Review

pubs.acs.org/CR

Selectivity between Oxygen and Chlorine Evolution in the Chlor-

Alkali and Chlorate Processes
Rasmus K. B. Karlsson and Ann Cornell*
Applied Electrochemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, SE-100 44 Stockholm,
Sweden

ABSTRACT: Chlorine gas and sodium chlorate are two base chemicals produced
through electrolysis of sodium chloride brine which find uses in many areas of industrial
chemistry. Although the industrial production of these chemicals started over 100 years
ago, there are still factors that limit the energy efficiencies of the processes. This review
focuses on the unwanted production of oxygen gas, which decreases the charge yield by
up to 5%. Understanding the factors that control the rate of oxygen production requires
understanding of both chemical reactions occurring in the electrolyte, as well as surface
reactions occurring on the anodes. The dominant anode material used in chlorate and
chlor-alkali production is the dimensionally stable anode (DSA), Ti coated by a mixed
oxide of RuO2 and TiO2. Although the selectivity for chlorine evolution on DSA is high,
the fundamental reasons for this high selectivity are just now becoming elucidated. This
review summarizes the research, since the early 1900s until today, concerning the
selectivity between chlorine and oxygen evolution in chlorate and chlor-alkali
production. It covers experimental as well as theoretical studies and highlights the relationships between process conditions,
electrolyte composition, the material properties of the anode, and the selectivity for oxygen formation.

CONTENTS 3.2. Extent of Oxygen Evolution from Different

Reactions 3019
1. Introduction 2982 3.3. Connection between Anode Stability and
1.1. Industrial Chlor-Alkali Production 2983 Selectivity 3020
1.2. Industrial Sodium Chlorate Production 2985 4. Conclusions 3021
1.3. Selectivity Concept in Chlor-Alkali and Author Information 3021
Sodium Chlorate Production 2986 Corresponding Author 3021
2. Selectivity for Oxygen and Chlorine Evolution in Notes 3021
Chlor-Alkali and Chlorate Processes 2986 Biographies 3021
2.1. Studies on Oxygen Formation during De- Acknowledgments 3022
composition of Hypochlorous Acid Species 2986 Nomenclature 3022
2.1.1. Uncatalyzed Decomposition 2986 References 3022
2.1.2. Catalyzed Decomposition 2987
2.2. Studies on Selectivity during Electrolysis 2988
2.2.1. Academic Research from 1900 to 1969 2988
2.2.2. Academic Research during the 1970s 2990 1. INTRODUCTION
2.2.3. Research during the 1980s 2991
Chlorine gas and sodium chlorate are base chemicals, with yearly
2.2.4. Research during the 1990s 2997
production rates of 50−60 million tonnes1,2 and over three
2.2.5. Research during the 2000s 3000
million tonnes,3 respectively. Chlorine gas is used in a wide
2.3. Electrochemical Studies Concerning the
variety of applications, including in production of construction
Relationship between Selectivity and Stabil-
materials such as polyvinyl chloride (PVC), in organic synthesis,
ity 3009
in metallurgy, and in water treatment.4 Sodium chlorate finds its
3. Discussion 3015
use almost exclusively for bleaching of pulp and paper products.3
3.1. Factors Affecting the Selectivity between
Both products are produced predominantly through electrolysis
Chlorine and Oxygen Evolution in the
of sodium chloride brine. Although the charge yields of both the
Production of Chlorine and Chlorate 3015
chlor-alkali process, in which chlorine gas and sodium hydroxide
3.1.1. Influence of Process Conditions 3015
are produced, and chlorate processes are quite high, ≥ 95%,5,6 the
3.1.2. Influence of Additions and Contami-
fact that both chlorine gas and chlorate are bulk chemicals,
nants in the Electrolyte 3017
3.1.3. Influence of the Anode Structure and
Composition 3017 Received: July 6, 2015
Published: February 16, 2016

© 2016 American Chemical Society 2982 DOI: 10.1021/acs.chemrev.5b00389

Chem. Rev. 2016, 116, 2982−3028
Chemical Reviews
produced in large quantities, means that losses of even a few
percent are costly. The yearly electricity consumption in chlor-
alkali production alone is about 150TWh,1 which makes it clear
that improvements in energy efficiency of these processes could
yield significant reductions in world energy consumption. The
main side reaction in industrial electrolytic cells is the production
of oxygen. In the chlorate process, the unwanted oxygen
combines with hydrogen in the cell gas and may form explosive
gas mixtures, which also makes oxygen a safety hazard. Further
study of the factors deciding the selectivity between chlorine or
chlorate and oxygen production in industrial chlor-alkali and
chlorate cells is therefore warranted. However, there is no review
of the scientific literature that focuses specifically on the
selectivity issue. This review aims to bridge that gap.
The electrolytic production of chlor-alkali and sodium chlorate
is performed in either divided, for production of chlor-alkali, or
undivided, for production of sodium chlorate, electrochemical
cells using, for example, steel or activated Ni cathodes (Ni
cathodes are only used in chlor-alkali production) and
dimensionally stable anodes (DSA, dimensionally stable anode,
is a trademark of Industrie De Nora S.p.A., Italy.).1,7 DSA are
mixed ruthenium−titanium oxide (RTO) coatings of rutile RuO2
and TiO2 deposited on Ti. The usage of DSA to describe anodes
in the present review is primarily used to refer to anodes of the
typical industrial “Beer 2” (30% RuO2 and 70% TiO2 coated on
Ti) formulation.8 Commercial DSA electrodes most often
contain one or more other additional dopant materials. RTO is
used in the present review as a more general term for anodes with
coatings containing varying amounts of RuO2 and TiO2. In these
coatings, the RuO2 and TiO2 components form solid solutions,
where RuIV and TiIV are part of the same rutile lattice.9−11 While
rutile RuO2 has a high electronic conductivity,12 pure rutile TiO2
is a semiconductor with a band gap of 3 eV.13 Nevertheless, the
mixed oxide has a high electronic conductivity, enabling its use as
an electrode, as the doping with RuIV introduces new electronic
states in the region of the TiO2 band gap.14,15 The preparation
and usage of dimensionally stable anodes was patented by Beer in
a series of patents in the 1960s (Britain) and 1970s (United
States).8,16−23 The discovery of DSA has been called “one of the
greatest technological breakthroughs of the past 50 years of
electrochemistry”.24 Since then, the usage of DSAs in these
processes has led to significant energy savings due to their lower
potentials at industrial current densities.24,25 However, as the
name implies, their most important advantage over previous
graphite electrodes is their stability, with modern DSAs being
able to operate at industrial current densities for more than 10
years.24 The literature concerning DSAs and RTOs in general is
summarized in several reviews.23−33 The recent reviews of Over
concerning the chemistry and catalysis of pure RuO212 and
concerning correlations and contrasts between liquid phase
electrochemical and gas phase chemical reactions on RuO2 and
related metallic oxide materials,34 as well as the review of
Diebold35 concerning the surface chemistry of TiO2, should also
be mentioned.
The oxygen evolution side reaction (OER) in chlor-alkali and
sodium chlorate production is connected to catalytic processes
ongoing both in the electrolyte and on the anode surface, where
oxygen might be evolved both electrochemically and chemically
through water or hypochlorous acid (or hypochlorite)
decomposition. Therefore, to get a complete picture of the
selectivity issue in these industrial processes, compositions of
both the electrolyte and the anode are important. Furthermore,
other process conditions, such as current density and temper-
2983
Review
ature, affect reactions both in the bulk electrolyte and on the
anode surface. This review therefore discusses all three aspects:
electrolyte composition, anode composition, and the process
conditions. The focus of this review is on the selectivity issue in
general, without limitation with regard to the anode material
used. Since there are connections between some mechanisms of
electrode decomposition and oxygen production, the stability of
DSA will also be discussed.
The following section of the introduction constitutes a brief
overview of the chlor-alkali and chlorate processes, as well as the
most important and well-known main and side reactions. It gives
the necessary basic information to describe effects of various
process, electrolyte, and anode properties on the selectivity. The
selectivity in the chlor-alkali and chlorate processes is not a
simple concept, as it involves both direct formation of oxygen on
the anode as well as oxygen resulting from bulk reactions.
Therefore, the selectivity concept as applied for industrial chlor-
alkali and sodium chlorate production, as well as some of the
methods that have been used to explore it, will be described in
section 1.3. Afterward, in section 2, the literature relevant to the
selectivity is described, in chronological order from the early
1900s until today. The literature is described in three main
sections, covering research on oxygen-evolving reactions relevant
to the electrolyte processes, electrochemical studies (both
experimental and theoretical), and studies on the link between
stability and selectivity. Finally, a discussion of the results and
trends found in literature is given, as well as some conclusions
regarding future research needs.
1.1. Industrial Chlor-Alkali Production
Chlorine gas and sodium hydroxide are produced in chlor-alkali
production according to the following overall reaction1
2NaCl + 2H 2O → Cl 2 + H 2 + 2NaOH (1)
The electrochemical formation of chlorine gas at the anode
(DSA) occurs according to the following reaction
2Cl− → Cl 2 + 2e− (2)
with an associated equilibrium potential of E° = 1.3583 V versus
SHE, where the standard potentials used are those of Bard et
al.,37 unless otherwise indicated. The evolved chlorine gas is
collected and processed in a number of steps. As chlorine is being
evolved at the anode, hydrogen (except in the mercury cell
process) forms at the cathode
2H 2O + 2e− → H 2 + 2OH− (3)
a reaction with E° = −0.8277 V. The anode compartment is kept
separated from the cathode compartment, and the way in which
they are separated constitutes the main characteristic of the
different processes used to produce chlor-alkali. The mercury cell
process, the diaphragm process, and the membrane process
dominate industrial production of chlor-alkali. In a membrane
cell, a cation-selective membrane separates the anode and
cathode compartments, whereas a microporous diaphragm is
used in the diaphragm process. The first industrial process was
the mercury cell process, in which a mercury amalgam is
produced at the cathode instead of hydrogen. The amalgam is
then later decomposed in a separate reactor to yield hydrogen gas
and sodium hydroxide. Today, the mercury cell and diaphragm
processes are being replaced by the membrane process for both
environmental and technical reasons.38,39 By the end of year
2013, the total installed chlorine capacity in Europe consisted of
59% membrane technology, 25% mercury cells, and 14%
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Chemical Reviews Review

diaphragm cells.39 The usage of mercury cells in the European Table 2. Some Important Dissolved and Gaseous Chlorine
Union is scheduled to be discontinued in 2017.39 Typical Species and Their Cl Oxidation States.42
conditions applied in the membrane process are shown in Table
species name Cl oxidation state
1, and more detailed descriptions of the three technologies can be
Cl− (aq) chloride (ion) −1
Table 1. Typical Conditions for Chlor-Alkali Production in Cl−3 (aq) trichloride ion −1, 0
Membrane Processes1,2,36 HCl (g) or (aq) hydrochloric acid −1
Cl2 (g) or (aq) chlorine gas 0
cell voltage (V) 2.4−2.7 HOCl (aq) hypochlorous acid +1
current density (kA m−2) 1.5−7 [or chloric (I) acid]
temperature (°C) 90 ClO− (aq) hypochlorite (ion) +1
NaCl concentration in the anolyte (g dm−3) 200 [or chloric (I) ion]
anolyte pH 2−4 Cl2O (g) chlorine monoxide +1
NaOH concentration in the catholyte (wt %) 32 HClO2 (aq) chlorous acid +3
ClO−2 (aq) chlorite (ion) +3
found in, for example, Wendt et al.40 or Schmittinger et al.1 A ClO2 (g) chlorine dioxide +4
small percentage of the total chlorine production is based on ClO−3 (aq) chlorate (ion) +5
electrolysis of 17 wt % HCl in either diaphragm or membrane ClO−4 (aq) perchlorate (ion) +7
cells.1 The energy cost for the production is usually given in
terms of kWh t−1 NaOH produced, with 886 kg Cl2 being
produced per tonne of NaOH. In membrane cells, the specific
electrical energy requirement is approximately 2100 kWh t−1
NaOH.1
Dissolved chlorine may hydrolyze according to the dynamic
equilibrium in reaction 4. Formed hypochlorous acid is involved
in another equilibrium with water, reaction 5. The impact of the
pH value on the relative concentrations of Cl2, HOCl, and ClO−
is significant, as is indicated in Figure 1.
Cl 2 + H 2O ⇌ H+ + HOCl + Cl− (4)

HOCl + H 2O ⇌ ClO− + H3O+ (5)

Hypochlorous acid and hypochlorite react to form chlorate, Figure 2. Pourbaix diagram for aqueous species in the chlorine-water
ClO−3 , according to reaction 6. system, indicating the stable equilibria at 25 °C and unit activity of the
dissolved species. Figure prepared using pymatgen45−47 and thermody-
2HOCl + ClO− → ClO−3 + 2H+ + 2Cl− (6) namic data from Wagman et al.48

Figure 1. Percentages of active chlorine species Cl2, HOCl, and ClO− as

a function of anolyte pH at 90 °C and 200 g NaCl dm−3. The
percentages are calculated using equilibrium constants for Cl2 hydrolysis
and HOCl deprotonation. Reprinted with permission from ref 41.
Copyright 1990 Springer Science and Business Media.
Cl−, HOCl, ClO−, and ClO−3 are the main species of interest
during chlor-alkali and chlorate production, but the chlorine-
water equilibrium in aqueous solution is significantly more
complex. Table 2 shows some of the known dissolved and
gaseous species that might occur during electrolysis.42,43 The
stability of these species at different electrode potentials and pH
values is indicated in Figures 2 (stable species), 3 (metastable
chlorate species), 4 (metastable chlorite species), and 5
(metastable hypochlorite species). The trichloride ion, Cl−3 ,
2984
Figure 3. Pourbaix diagram for the aqueous metastable chlorates
(excluding ClO−4 ) in the chlorine-water system, indicating the equilibria
at 25 °C and unit activity of the dissolved species. Figure prepared using
pymatgen45−47 and thermodynamic data from Wagman et al.48
which is in equilibrium with Cl2 (aq) under chlor-alkali
conditions (chloride activities between 2 and 6),44 is not seen
in the figures, as its window of stability is very small.
In addition to chlorate ions, hypochlorite (or hypochlorous
acid) may also form oxygen as will be described in the next
section. Both chlorate ions and oxygen gas are highly undesired
in chlor-alkali cells, and thus, the formation of the reactant
hypochlorite species should be suppressed. In the membrane and
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Chemical Reviews
Figure 4. Pourbaix diagram for the aqueous metastable chlorites
(excluding ClO−3 and ClO−4 ) in the chlorine-water system, indicating the
equilibria at 25 °C and unit activity of the dissolved species. Figure
prepared using pymatgen45−47 and thermodynamic data from Wagman
et al.48
Figure 5. Pourbaix diagram for the aqueous metastable hypochlorites
(excluding ClO−3 , ClO−4 , HClO2, and ClO−2 ) in the chlorine-water
system, indicating the equilibria at 25 °C and unit activity of the
dissolved species. Figure prepared using pymatgen45−47 and thermody-
namic data from Wagman et al.48
diaphragm cells, small amounts of hydroxide ions may pass
through the separator, dividing the acidic anolyte and the alkaline
catholyte, and increase the pH close to the separator in the anode
chamber, with subsequent oxygen and chlorate generation.
Careful acidification of the anolyte can counteract the increase in
pH related to the hydroxide leakage, resulting in oxygen levels in
the chlorine gas of <0.5%. Oxygen levels in the chlorine gas are
typically up to 4% in a diaphragm cell49 and 1.5−2% in
membrane cells with no anolyte acidification.49 Mercury cells,
with no separator but where the alkali is formed in a secondary
reactor, do not have this problem and the chlorine gas contains
<0.5% oxygen.49 Bilayered membranes, with perfluorosulfonate
facing the anode and perfluorocarboxylate facing the cathode
side, are state-of-the-art today in membrane cells.1 The loss in
charge yield for alkali is 3−7% due to the migration of hydroxide
ions through the membrane, while the loss of chloride ions to the
catholyte is extremely low. About 0.14 kg ClO−3 produced per
tonne NaOH is to be compared to 3.5 to 5.2 kg ClO−3 per tonne
NaOH in the absence of acidification.50
1.2. Industrial Sodium Chlorate Production
Sodium chlorate is also produced using electrolysis of sodium
chloride solutions. The following overall reaction describes the
formation:
2985
Review
NaCl + 3H 2O → NaClO3 + 3H 2 (7)
The energy requirement in kWh per tonne sodium chlorate
produced in the industrial process can be estimated using (with a
typical cell voltage of 3.1 V)51
Pe = 1511 Ah t−1 × 3.1V ≈ 4700 kWh t−1 (8)
The same electrode reactions that occur in the chlor-alkali
process, reactions 2 and 3, are also believed to be the first steps in
chlorate production.51 Dimensionally stable anodes and
cathodes of either low carbon steel or titanium are used in the
electrolysis cell.6 The chlorate cells are undivided, and the bulk
electrolyte pH is 6−7. However, the ongoing anode and cathode
reactions make the pH at the anode more acidic, while the pH at
the cathode is alkaline. Thus, a pH gradient is set up across the
cell, and this means that the hydroxide ions that form in the
cathode reaction 3 can hydrolyze the chlorine that forms in the
anode reaction 2.6,7,51,52 This gives the following dynamic
equilibrium
Cl 2 + 2OH− ⇌ ClO− + H 2O + Cl− (9)
Alternatively, water can hydrolyze the chlorine gas according to
reaction 4.6
Hypochlorite is formed through reactions 4 and 5, or through
reaction 9, and then chlorate is formed according to reaction 6.51
This reaction is a purely homogeneous chemical reaction, which
has a maximum rate around pH 6.1−6.4 under industrial
conditions and 80 to 90 °C.7 The pH that is used in the chlorate
process is chosen to prevent chlorine gas formation, which
increases in rate at lower pH, and oxygen gas formation, which
increases in rate at higher pH. Chlorate cells usually have a large
volume tank through which the reaction solution flows to allow
reaction 6 to reach high conversion.6,40,53 The process
temperature is kept high to increase the rate of reaction 6
(enabling the usage of a smaller reaction vessel) and of the
electrode reactions (lowering the cell voltage).6,53−56 However,
the rate of parasitic oxygen evolution also increases with
increasing temperature, meaning that the temperature chosen
is a balance between minimizing the rate of oxygen evolution and
maximizing the reaction rates of the desired reactions.57
A number of anodic reactions limit the charge yield,
particularly for chlorate production but also for chlor-alkali
production. One of the more well-known is the following anodic
side-reaction in which both oxygen and chlorate are formed:58,59
6ClO− + 3H 2O → 2ClO−3 + 4Cl− + 6H+ + 1.5O2 + 6e−
(10)
54
with E° = 1.14 V. The reaction is generally called anodic
chlorate formation and must necessarily be a sum of several
substeps.
Apart from reaction 10, the oxidation of water, hydroxide, and
chlorate can also occur.
2H 2O → O2 + 4H+ + 4e−, E° = 1.229 V (11)
1
2OH− → O2 + H 2O + 2e−, E° = 0.401 V
2 (12)
ClO−3 + H 2O → ClO−4 + 2H+ + 2e−, E° = 1.189 V
(13)
By comparing the standard potentials of reactions 11 and 2
(chlorine evolution), it is seen that the OER is thermodynami-
cally favored versus the chlorine evolution reaction. However,
high chlorine evolution reaction (ClER) selectivity is still
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Chemical Reviews
obtained on modern electrocatalysts due to the significantly
more favorable kinetics of the ClER. Oxidation of water
dominates if the anode potential is below that required for
chlorine formation, and if there is no hypochlorite in the
solution.54,60 The reaction is also dependent on the anode
material, chloride concentration, and the pH of the electrolyte
and can largely be controlled by adjusting these factors.7 When
discussing the effects of pH, it is necessary to keep in mind that
the conditions in the bulk of the electrolyte might differ
significantly from those at the electrode surface, where the
electrochemical reactions occur.44,53,61 Due to the parasitic
formation of oxygen gas (reaction 11) and the hydrolysis of Cl2
(reaction 4, less important in chlor-alkali production), the pH
close to the anode surface will be more acidic than in the
electrolyte bulk.44 For this reason, reaction 12 is very minor.
Additionally, as described above, migration of OH− through the
separator in chlor-alkali cells results in locally increased pH
values in the anolyte close to the membrane. In turn, this
increased pH results in local formation of hypochlorous acid and
hypochlorite, enabling subsequent homogeneous chlorate
formation and possibly also decomposition of hypochlorous
acid species to form oxygen. Chlorate oxidation, by reaction 13,
will occur under conditions of high chlorate concentration and
low chloride concentration, and although DSA yields very small
amounts of perchlorate, significant concentrations may accumu-
late over time in closed mode operation.5,7
Apart from reactions occurring electrochemically at the
electrodes, there is also the possibility that hypochlorite is
decomposed in the bulk of the electrolyte, or heterogeneously on
the electrodes, according to reaction 14:6,54
2HOCl → 2HCl + O2
Reaction 14 is slow62 but may be catalyzed by metal ions and
light. The literature on catalysis of this reaction in hypochlorite
solutions is discussed in section 2.1 of the present review.
The reactions above dictate the design and operating
conditions used in chlorate production. To maximize the
chemical formation rate of chlorate (reaction 6), the volume of
electrolyte in the electrolysis compartment or in the interelec-
trode gap is minimized, and the formation of chlorate then
mostly occurs in a large either internal or external reactor.7 The
electrolyte is circulated, either by gas lift in the electrolysis cell or
by pumping, and the temperature of the electrolyte is kept
constant by use of heat exchangers.6 The composition, pH, and
temperature of the electrolyte as well as the current density and
cell voltage need to be optimized for high current efficiency.
Some typical operating conditions for sodium chlorate cells are
shown in Table 3.
Table 3. Typical Operating Conditions in Sodium Chlorate
Production6,7,51
cell voltage (V) 2.9−3.7
current density (kA m−2) 1.5−4
temperature (°C) 65−90
NaCl concentration (g dm−3) 70−150
NaClO3 concentration (g dm−3) 450−650
NaOCl concentration (g dm−3) 1−5
Na2Cr2O7 concentration (g dm−3) 1−6
electrolyte pH 5.5−7
Review
1.3. Selectivity Concept in Chlor-Alkali and Sodium Chlorate
Production
The desired reactions in chlor-alkali and sodium chlorate
production is first the anodic ClER (reaction 2, the first and
only desired anodic reaction in chlor-alkali production), followed
by, in the case of chlorate production, chemical conversion of Cl2
into ClO−3 (reactions 9 or 4 followed by reaction 6). In other
words, in chlor-alkali production, the current efficiency for
chlorine formation is the primary measure of selectivity, while the
charge yield for chlorate production is the measure of selectivity
in the chlorate process. The selectivity between anodic chlorine
evolution (reaction 2) and oxygen evolution (reaction 11) on the
anode surface is related to the intrinsic selectivity of the anode
material used. Here, the properties (surface structure and
composition) of the anode are the deciding factors, and its
importance is reflected in the large number of studies that have
been focused on the relationship between the anode and the
selectivity. However, especially in the case of the chlorate
process, it is only a part of the overall selectivity issue, for which
secondary reactions in the bulk (decomposition of hypochlorous
acid species, reaction 14) and reactions involving decomposition
of hypochlorous acid species on the anode are of key importance.
The study of the selectivity in these processes thus requires
methods that can account for both anode reactions and bulk
reactions and reaction products in both liquid and gas phase. The
anode reactions have mostly been explored using conventional
electrochemical measurements (e.g., voltammetry and polar-
ization curves), but theoretical methods have also been applied to
study the intrinsic selectivity of anodes.63−65 The composition of
evolved gases are usually determined using, for example, gas
chromatography (GC)66−69 or absorption of O2 in, for example,
pyrogallol.36,41,54,70−74 Considering that decreases in anodic
(14) selectivity primarily occur either through direct formation of O2
on the anode, or by formation of O2 by decomposition of HOCl
or OCl− in the electrolyte, it is reasonable to quantify the anodic
current efficiency (the percentage of the anodic current used for
production of the desired products) based on oxygen in the
evolved gases. Since the 1990s, differential electrochemical mass
spectroscopy (DEMS) has been used in several studies.75−84
This method enables a highly sensitive determination of reaction
products formed on an anode. In the electrolyte, the
concentrations of hypochlorite, chloride, and chlorate can be
determined using titration methods.
2. SELECTIVITY FOR OXYGEN AND CHLORINE
EVOLUTION IN CHLOR-ALKALI AND CHLORATE
PROCESSES
2.1. Studies on Oxygen Formation during Decomposition of
Hypochlorous Acid Species
Before considering the selectivity in the electrochemical
environment, the literature concerning reactions in the bulk
will be presented. Both the uncatalyzed and catalyzed
decomposition of hypochlorous acid or hypochlorite to form
oxygen, reaction 14, will be discussed in this section.
2.1.1. Uncatalyzed Decomposition. The uncatalyzed
decomposition of hypochlorous acid species to form oxygen
has been discussed less than the main reaction (6) forming
sodium chlorate. It appears that this reaction has long been
known,85,86 although which is the earliest discussion of the
reaction is unclear. Indeed, the reaction of
2NaOCl ⇌ 2NaCl + O2 (15)
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Chemical Reviews
occurring together with homogeneous sodium chlorate for-
mation, is mentioned already in 1897, in the work of Bhaduri87
who studied the decomposition of NaOCl in darkness at 100 °C.
Returning to research from the 20th century, it seems that
Lister88 is the first to consider the side reaction in much detail, in
a paper from 1952. It was suggested that the oxygen evolution
reaction is first order in HOCl but independent of the OCl−
concentration. The first-order rate constant was found to be 4.65
× 10−4 min−1 at 30 °C, increasing to 12.9 × 10−4 min−1 at 40 °C.
The associated activation energy for oxygen formation was 80 kJ
mol−1. As a comparison, the rate constant for the slow first step in
the formation of chlorate, found to occur in two steps via ClO−2 ,
was 0.95 M−1 s−1 at 40 °C. Two more papers were later
published86,89 by the same author and a co-worker. Both of these
papers were focused on attempts to completely remove any
impurities, such as of copper, that might catalyze the formation of
oxygen. Indeed, in the later paper of Lister and Petterson,89 it was
concluded that the uncatalyzed decomposition of hypochlorite is
of second order in OCl−, with a rate constant of 7.5 × 10−6 M−1
min−1 at an ionic strength of 3.5 and 60 °C. On the basis of an
evaluation of activation energies, and comparison with the
chlorate formation reaction, it was suggested that the two
reactions had activated complexes with the same stoichiometry,
90
Cl2O2−2 , but with different arrangements. In 1994, Church again
considered the uncatalyzed oxygen evolution side reaction
during hypochlorite decomposition, finding results in line with
those of Lister and Petterson.89 In 1999, Adam and Gordon91
measured a second-order rate constant in OCl− of 8.9 × 10−10
M−1 s−1 for uncatalyzed hypochlorite decomposition. Sandin et
al.92 studied the decomposition of hypochlorite in 2015,
determining the rate dependence on pH in dilute hypochlorite
solutions. The study combined mass spectrometry with ionic
chromatography to study both gas phase and liquid phase
concentrations during decomposition. It was found that the
uncatalyzed O2 formation reaction has a pH dependence that is
very similar to that of chlorate formation, with a maximum rate at
about pH 6.5. This could further support the suggestion of Lister
and Petterson,89 that the two pathways of chlorate formation
(main reaction) and oxygen formation (side reaction) share an
intermediate. The oxygen evolution rate was found to be third
order in total hypochlorite concentration (cHOCl + cOCl−) at pH
6.5, a higher order than that found previously in the alkaline
range.89,91 The third-order rate constant for uncatalyzed oxygen
formation by hypochlorite decomposition in this pH range was
found to be 0.046 M−2 s−1, compared with that for chlorate
formation of about 0.73 M−2 s−1.
2.1.2. Catalyzed Decomposition. Compounds that are
able to decompose hypochlorous acid species have been known
ever since the early 19th century. Howell93 lists six studies from
the 1800s and notes that earlier researchers have found that silver
oxide, powdered pyrolusite (a MnO2-containing mineral), oxides
of Co, Ni, Cu, and Fe, and barium peroxide are able to,
catalytically or otherwise, decompose hypochlorous acid species
in solution. White94 quotes a study from 1834 in which it was
found that irradiance could decompose hypochlorous acid
species to form oxygen. The same study also found that both
Sn and Cu would be converted to oxychloride form, with
concomitant production of small amounts of oxygen.
In 1903, White94 studied the effect of metallic Fe, Sn, Cu, As,
Ni, Co, Al, Mg, Sb, Pb, Zn, and Cd on alkaline bleaching powder
(calcium hypochlorite) solutions at “ordinary temperatures”. Co,
Ni, and Fe were found to give high production rates of oxygen.
These metals were all found to be converted into hydroxide form.
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Slow rates of O2 production were noted for Sn, Cu, and As. Al
and Mg were instead found to yield hydrogen production. Sb, Pb,
Zn, and Cd were found to be inactive. The effect of sunlight on
hypochlorite solutions was also studied, and a correlation
between sunlight and formation of small amounts of oxygen
was noted.
In 1914, Hofmann and Ritter95 compared the effects of a
number of oxides on calcium hypochlorite solutions and sodium
hypochlorite solutions. They found oxides of Co, Ni, and Ir to be
active for the decomposition of both solutions. Salts of Ru and Rh
were found to decompose the bleaching powder solution but not
the sodium chlorite solution. Oxides (the specific type of each
oxide was not mentioned) of Cr, Fe, Mn, U, W, Pd, Os, Tl, and V
were found to be inactive in both solutions.
In 1923, Howell93 studied the effect of Co peroxides (prepared
by precipitating CoSO4 with NaOH and NaOCl) on sodium
hypochlorite solutions and found that they catalyze the
decomposition. Addition of NaCl was found to accelerate the
decomposition.
In 1926, Chirnoaga96 again studied the effect of Co peroxide,
Ni peroxide, CuO, Fe2O3, MnO2, HgO, and alumina on sodium
hypochlorite solutions. Co and Ni peroxides (both prepared
using precipitation of CoCl3 or NiCl2 with NaOH and NaOCl)
had the highest activity for decomposition, while activities of
CuO, Fe2O3, MnO2, or HgO were lower, and alumina was
inactive. Alumina was found to promote the action of CoII
hydroxide.
In two articles published in 1927 and 1930,97,98 Lewis studied
the catalyzed decomposition of NaClO by solutions of CuSO4,
FeSO4, CoSO4, and suspensions of cobalt peroxide (prepared in
a similar way as in the studies of Howell93 and Chirnoaga96),
CuO, and Fe2O3. In the first article, it was shown that the
peroxide suspension and sulfate solution of Co were most active
for hypochlorite decomposition, while the corresponding CuO
suspensions and solutions were less active. Data for the iron
oxide suspension alone was not reported. Instead, a mixed
suspension of Fe2O3 and CuO was used, which was reported to
be more active than the CuII suspension and solution. This was
said to be due to a promoter effect by Fe2O3. In the second
article,98 a promoting effect of magnesium hydroxide on the
hypochlorite decomposition activity of CuO was reported. It was
argued that the promotional effect was caused by Mg hydroxide
particles preventing the CuO particles from agglomerating.
In 1952, as a part of a study on the properties of Ru in its + VI,
+ VII, and + VIII oxidation states published, Connick and
Hurley99 presented results indicating a catalytic effect of the
−
ruthenate ion RuO2− 4 on decomposition of ClO
H 2O + 2RuO24 − + ClO− ⇌ 2RuO−4 + Cl− + 2OH−
(16)
RuO2−
4 was then thought to be reformed through a reaction with
OH−:
1
2RuO−4 + 2OH− ⇌ 2RuO24 − + O2 (g) + H 2O
2 (17)
100
In 1954, Patel and Mankad presented experimental
measurements on oxygen evolution due to hypochlorite
decomposition and studied the effect of CoII, NiII, and FeII
sulfates and chlorides, as well as of CoII and NiII nitrates and ferric
ammonium citrate on the decomposition rate. The rate of oxygen
evolution was not determined directly and was instead found by
thiosulfate titration after 3 h of reaction to determine amount of
reacted hypochlorite. This means that the formation of chlorate
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due to decomposition of HOCl was disregarded in the analysis.
In any case, CoII sulfate, chloride, and nitrate were found to
catalyze the decomposition, while the analogous FeII and NiII
species were either completely inactive (sulfates) or only
increased the decomposition rate slightly versus the experiment
conducted without catalyst. Ferric ammonium citrate also
significantly increased the decomposition rate of HOCl.
In two papers by Ayres and Booth101,102 published in 1955, the
decomposition of 2 M NaCl-containing hypochlorite solutions
by dissolved Ir metal, in the form of Na2IrCl6, was studied. The
effect of initial pH on the catalyzed decomposition was reported
extensively in the first paper. In the second paper, the kinetics of
the catalyzed decomposition was investigated. The reaction rate
was found to be first order with respect to hypochlorite
concentration. Rate constants at temperatures between 20 and
40 °C were found, increasing from 3.92 × 10−4 to 2.35 × 10−3 s−1,
and an energy of activation of 69 kJ mol−1 was calculated. As
active catalysts only need to be present in small quantities, it was
problematic that the Ir metal that was used as the raw material to
prepare Na2IrCl6 in the studies101,102 contained trace amounts of
several other metals (Pt, Rh, Cu, Ag, Mg, and Ca).
In 1956, Lister103 reported the catalytic effect of salts of MnII,
FeIII, CoII, NiII, and CuII on the decomposition of sodium
hypochlorite. Apart from FeIII, which was added as a nitrate salt,
chloride salts were used. CoII, NiII, and CuII were found to
catalyze the formation of oxygen, while MnII and FeIII were
inactive. None of the materials catalyzed the formation of
chlorate. Reaction orders and activation energies were
determined. In the case of NiII and CoII, the reaction order in
hypochlorite concentration was found to be zero, while in the
case of CuII, the reaction was first order in hypochlorite
concentration. For both NiII, CoII, and CuII, the reaction rate was
proportional to the added amount of catalyst.
In 1977, Gray et al.104 reported the catalytic effect of CuII
hydroxide complexes on the decomposition of hypochlorite and
hypobromide in alkaline solution at 25 °C. Since only high
NaOH concentrations of above 2 M were considered, the results
are less relevant for industrial chlorate production.
In the same year, Hamano and Mori105 presented results on
the catalytic effect of CuO, NiO, and Co3O4 on NaOCl and H2O2
decomposition. The catalyst materials were calcined at three
different temperatures (300, 500, and 700 °C), and Brunauer−
Emmett−Teller measurements were performed to enable the
activity of the different materials to be normalized by the specific
surface area. It was found that the reaction rate constant for
NaOCl decomposition, normalized by the specific area, was
highest for NiO and lowest for CuO. Whether the NiO catalyst
was stable under the reaction conditions, or was oxidized to a
higher oxide, does not appear to have been studied.
In 1994, Church90 reexamined the catalytic effect of CuII on
the decomposition of NaClO solutions. Rate constants for both
the uncatalyzed and catalyzed decomposition of NaClO were
determined. The kinetics for the catalyzed decomposition was
found to be well-described as first order in both CuII and ClO−
concentration.
In 1998, Hamano et al.106 presented results of the pH effect on
the catalytic decomposition of NaOCl solutions by Co3O4 at 25
°C. In the absence of a catalyst, no oxygen was evolved at pH
values in the range of 7−10, in opposition to what Lister and
Petterson,89 Church,90 and Sandin et al.92 had found. However,
when cobalt oxide was added, oxygen was evolved even at pH 12.
Increased decomposition rates were noted as the pH was
decreased down to 7. At pH 7−9, both O2 and chlorate were
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detected, whereas no chlorate was formed at the higher pH
values. A first-order rate constant for oxygen evolution by
decomposition of NaOCl was calculated and found to exhibit a
maximum at around pH 5. This calculated rate constant agreed
with experimental data for pH > 7, below which the production
of chlorine gas made comparisons impossible.
In 2015, Sandin et al.92 reported results of the catalyzed
decomposition of hypochlorite. The pH value was controlled
during the experiments, allowing the effect of pH to be
decoupled from the effect of the catalysts. The potential catalysts,
which were tested at pH = 6.5, were the salts AgCl, CeCl3, CoCl2,
FeCl3, IrCl3, and RuCl3, and the oxides Fe3O4, Al2O3, Na2Cr2O7,
Na2MoO4, and RuO2. IrCl3, Na2Cr2O7, and RuO2 were also
tested at pH ≈ 11. Of these, only IrCl3 and CoCl2 were found to
catalyze the formation of oxygen. Additionally, IrCl3 was found to
catalyze the formation of sodium chlorate.
2.2. Studies on Selectivity during Electrolysis
2.2.1. Academic Research from 1900 to 1969. Chlorine
gas was first produced by Scheele in 1774, using chemical
methods. Industrial electrolytic chlorine production was first
performed in Germany in 1890,107 when both the diaphragm and
mercury cell technologies were introduced.1 The earliest
research concerning chlorine production was summarized long
ago by Kershaw,108 Müller,109 and Baldwin.107 Industrial chlorate
production has been performed ever since 1886, with research
starting even earlier than that, as was reviewed by Ibl and Vogt.62
Focusing presently on the chlorate production process, it is
well-known that, among others, Oettel110−112 and Foerster and
co-workers58,113−124 studied the fundamentals of chlorate
formation during electrolysis of chloride solutions at the turn
of the 20th century. This work might be traced to early German
investigations into industrial-scale chlor-alkali electrolysis for
production of, for example, caustic soda, which is said to have
started in 1884.108 This early research found that formation of
Cl2 is the first step in production of sodium chlorate, since a solid
product of Cl2, chlorine hydrate, is formed at the anode if
electrolysis is performed at low temperature.58 It was also found
that hypochlorite is the intermediate compound in the
production of chlorate from chlorides and that the formation
of chlorate probably occurs through reaction 6.114 Furthermore,
Oettel110 and Foerster et al.114 found that the production of
chlorate occurs not only through reaction 6 but also through
anodic oxidation of hypochlorite. Foerster and Müller also tried
to find the overall reaction formula for anodic chlorate formation,
identifying eq 10 as the most fitting with their experimental
data.125 Both reactions 6 and 10 are referred to as Foerster’s
reactions in the literature. During this time, it was also suggested
that both reaction 10 and direct oxidation of ClO−,
ClO− + 2O → ClO−3 (18)
the so-called primary chlorate formation, with no accompanying
chloride formation, occurred simultaneously in alkaline solution,
both reactions forming chlorate (the reaction is written as given
by Foerster59). This early research was conducted mainly using
polished Pt electrodes, but experiments were also done with
graphite electrodes,123,126 rough Pt electrodes,121 and Pt−Ir alloy
electrodes.117,123 Foerster123 recommended the Pt−Ir electrode,
rather than graphite, in chlorate and chlor-alkali production,
based on its superior stability. These early studies were often
careful and detailed studies of the chemistry, often including
measurements of both evolved oxygen gas and liquid phase
hypochlorite, chlorate, and perchlorate. Perchlorate formation
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Chemical Reviews
was studied in detail by Oechsli.127 Furthermore, the effects of
temperature, pH,121 chloride concentration,121,128 current
density, and current concentration129 (the ratio between the
total current and the volume of the electrolyzer cell) were
reported in some detail in several of these publications. Even at
this time, the possibility that oxygen produced during chlorate
formation might not only be the result of anodic chlorate
formation (reaction 10) or water oxidation but also due to
oxidation of HOCl or OCl− was discussed.116,121 Much of this
early research is summarized in English by Foerster59 and Ibl and
Vogt.62
Building on these early German studies, Knibbs and
Palfreeman130 published an article in 1920 concerning the
chlorate and perchlorate formation reactions in industrial cells
using platinum electrodes. The main part of the work was
focused on finding the proper process parameters for chlorate
and perchlorate formation. However, the different electro-
chemical pathways to oxygen formation in chlorate cells were
also examined. Experiments with addition of NaOH to an
operating chlorate cell were performed to see if the oxygen
evolution rate followed the addition of hydroxide or if it followed
the concentration of NaOCl. It was found that increasing
concentrations of HOCl led to a linear increase in the percent of
oxygen in the cell gas. Furthermore, it was found that the oxygen
evolution rate was diffusion limited at higher current densities.
The conclusion was that the main source of oxygen evolution is
the discharge of the OCl−.
In 1936, Joffe131 published results on the selectivity between
the OER and the ClER on graphite and magnetite electrodes in
concentrated chloride solutions. A way of calculating approx-
imate selectivities directly from the polarization curve was
presented, where the current densities at a certain potential in
H2SO4 (to obtain the polarization curve for OER) and in
concentrated NaCl were used to obtain the selectivity for
conditions under which both reactions occur. The selectivity for
Cl2 was seen to increase with current density during electrolysis
of neutral 5 M NaCl solutions.
In 1945, further results were published by Rius and Llopis,132
who performed a number of experiments, using Pt electrodes and
volumetric analysis of the formed gases as well as analyses of
chloride, chlorate, and hypochlorite in the electrolyte solution, to
increase the understanding of the reaction mechanisms of
chlorate formation. They claimed results contrary to those of
Foerster, and proposed a new overall stoichiometry for anodic
chlorate formation
5ClO− + 8H 2O → 3ClO−3 + 2Cl− + 2O2 + 16H+
+ 16e− (19)
accompanied by
1 to the surface of the anode. Additionally, the oxidation loss
2OH− → H 2O + O2 + 2e−
2 (20)
In 1956, de Valera133 presented a model for sodium chlorate
formation, based on the idea that the stoichiometry for
electrochemical chlorate formation according to Foerster (eq
10) could be replaced with simpler reactions, if the processes
occurring in the anode diffusion layer are taken into account. de
Valera proposed that the only electrolytic processes occurring are
oxidation of Cl− and OH− and that chlorate and hypochlorite
forms chemically in the diffusion layer. It was found that a model
based on these considerations would also agree with
experimental observations but without the need for chlorate
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Review
formation through an electrochemical oxidation of hypochlorite.
Oxygen evolution during electrolytic chlorate formation is, in the
model of de Valera,133 a consequence of decomposition of H2O2
formed through oxidation of OH−.
Hammar and Wranglén54 examined the oxygen evolution side
reaction in chlorate production in an early experimental study
from 1964, in which graphite anodes were used. The effects of
current density, temperature, concentrations of chloride,
hypochlorite, and chlorate, pH, and cathode type (steel, iron,
or graphite) on both oxygen evolution and on cathodic losses
were reported.
It was found that the oxidation loss (determined as the
percentage of oxygen in the evolved gas) increased linearly with
hypochlorite concentration from 0 to 250 mM (see Figure 6).
Figure 6. Dependence of the oxygen losses (%O2 in the off-gas) on the
hypochlorite concentration, as found and reported by Hammar and
Wranglén54 using graphite anodes. ● represent data for solutions
without sodium chlorate, and × represent data for solutions with 273 g/
dm3 NaClO3. The temperature was 25 °C, cNaCl = 150 g/dm3, and j = 0.4
kA/m2. Reprinted with permission from ref 54. Copyright 1964 Elsevier.
This suggests that the oxygen evolution rate due to hypochlorite
decomposition is mass transfer controlled. It also increased
slowly with temperature (about 2%/K), which was related to an
increase in the diffusion coefficient for hypochlorite. Additions of
chlorate (273 g NaClO3/dm3) decreased the oxygen evolution
rate somewhat. In a similar way as with the effect of temperature,
this was thought to be related to an increase in electrolyte
viscosity that decreased the rate of mass transfer of hypochlorite
decreased with increasing current densities. This dependence
was approximately linear if the volumetric percentage of oxygen
was corrected for the varying thickness of a Nernst diffusion layer
during gas evolution at the anode. On the basis of these results
and an analysis of possible alternative reactions to 10, Hammar
and Wranglén54 concluded that reaction 10, anodic chlorate
production according to Foerster, was the mass transfer
controlled oxygen evolving reaction.
In 1969, Jaksić et al.55 published a study where the Foerster
reactions were used to model the overall current efficiency of the
chlorate process. Experiments were carried out in a stirred flow
reactor where pH, total available chlorine (the sum of
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hypochlorous acid and hypochlorite) in the inlet and outlet, as

well as chlorine and oxygen in the off-gas were measured
simultaneously. A good agreement between the model and the
results at different flow rates, current densities, and temperatures
was obtained, in turn supporting the Foerster reactions as
suitable for describing electrochemical chlorate formation. The
mathematical treatment by Jaksić et al.55 was further developed
by Despić et al.134 to extend its applicability to concentrated
electrolytes. In the same year, Jaksić et al.135 also suggested that
the current efficiency of the homogeneous chlorate formation
reaction should be dependent on the pH, through the activity of
the hypochlorous acid/hypochlorite pair. They thought that
Hammar and Wranglén54 had neglected the effect of CO2
absorption in the electrolyte when they reached their conclusion
that pH does not influence the efficiency of the chlorate process
in the pH = 6.5−11 range.
The most important development of the 1960s related to the
chlor-alkali and sodium chlorate processes was the invention by
Henri Beer of the DSA. However, Beer’s patents do not give any
detailed description of selectivity between chlorine and oxygen
evolution on DSAs.8,16−22 A relevant comment from the patents
is that other film-forming metal supports (Ta, Zr, W, or alloys of
these) than Ti or Nb are preferable for oxygen evolution. One of
the example compositions, that of (TiO2−IrO2−PtO2) on Ta, is
said to be “operated excellently in electrolytic processes for the
preparation of chlorine, oxygen, oxidation of organic compounds
and in galvanic baths” (“Example III” in U.S. patent 3,933,616).22
2.2.2. Academic Research during the 1970s. To our
knowledge, in 1972 Kuhn and Mortimer70 published the first
study of current efficiency for the ClER using metal oxide Figure 7. Gas-tight rotating disc electrode setup used by Kuhn and
Mortimer:70 “Diagram of the rotating disc apparatus: 1, carbon brush; 2,
electrodes, sodium chloride solutions of varying concentrations
drive pulley; 3, collar fixed to shaft; 4, spring; 5, teflon bearing, sliding fit
and at varying temperatures. The electrode materials used were on shaft; 6, teflon bearing, fixed to glass stem (8); 7, gas inlet to balance
RuO2 and IrO2 on Ti. A flow-through cell was used to keep the hydrostatic head of electrolyte; 8, glass stem; 9, titanium shaft; 10, teflon
electrolyte concentration constant. Current efficiency measure- bearing fixed to glass stem; 11, teflon cylinder screwed to the shaft end;
ments were performed at T = 20 °C and t = 70 °C, pH ≈ 2, with 12, electrode slug, secured to shaft by (11); 13, brine inlet”. Reprinted
stationary and rotating electrodes. A gastight rotating disc with permission from ref 70. Copyright 1972 Springer Science and
electrode (RDE) setup was used, which is shown in Figure 7. The Business Media.
current efficiency was calculated based on assuming that only
reactions 10 (anodic chlorate formation) and 11 (water example, gas composition. What is worth noticing from the
oxidation) occurred. Both these reactions yield the same amount point of view of selectivity is that bubbles of what was thought to
of oxygen per electron, allowing the current efficiency to be be oxygen were noticed at the rest potential when pure RuO2
calculated based on analysis of the amount of oxygen formed. electrodes were inserted into a chlorine-saturated NaCl solution
The results of the experiments showed that the current with low Cl− concentration. This was thought to result from a
efficiency for chlorine evolution at t = 20 °C on a nonrotating combined reduction of Cl2 and oxidation of hypochlorite species
electrode was increased from 97% to 99% as the chloride to form chlorate by the electrochemical reaction 10.
concentration was increased from 1 to 5 M at controlled current Again in 1972, Jaksić et al.137 published data about the effects
− −
densities. At both concentrations, increasing current density of Cr2O2− 3− 2−
7 , PO4 , NO3 , SO4 , and F on the anodic part of the
from about 3 to 20 kA/m2 had no effect on the current efficiency. chlorate process, using Pt and DSA anodes in an electrolyte of
At concentrations below 1 M, the current efficiency was lower. At 310 g/dm3 NaCl and 1 g/dm3Na2Cr2O7 at 25 °C, using the same
the lowest concentration of 0.13 M, the current efficiency system as in their previous work.55 Additions of anions were
decreased with increasing current density. When instead of the made at concentrations of 0.01 M ≤ canion ≤ 0.2 M. It was seen
−
stationary electrode a rotating disc electrode was used, it was that increasing concentrations of Cr2O2− 3−
7 , PO4 , and NO3 all
found that increased current densities, from 3 to 50 kA/m2, yielded higher percentages of oxygen in the off-gas. This
increased the current efficiency, up to a certain point at which the dependence seemed to level off at higher anion concentrations.
mass transport of chloride to the surface of the electrode became The effect was highest with dichromate addition and lowest with
limiting. However, it was noted that the rotation of the electrode nitrate addition. No effect on the oxygen evolution was seen from
drew evolved gases to the axis of the electrode, which would addition of sulfate or fluoride. Furthermore, since NO−3 has a no
result in blockage of the electrode area and possibly negatively pH buffering effect and phosphates have a higher buffering
affect the quality of the results at high current densities. In capacity than dichromate species, the effect on the oxygen
comparison with RuO2-coated Ti electrodes, IrO2-coated Ti evolution was thought to relate to adsorption of the anions,
electrodes exhibited higher efficiencies in dilute 0.5 M NaCl. rather than to a buffering effect on the hydrolysis of Cl2 formed at
In 1973, Kuhn and Mortimer136 reported further results from a the anode. Other factors, such as the similarity to an adsorption
purely electrochemical study without measurement of, for isotherm of the increase in oxygen percentage with increasing
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concentration of anion, and the higher effect on oxygen
percentage of Pt (which operates at a higher anode potential
than DSA), were also suggested as supporting the hypothesis of
adsorption of anions. It was thought that the adsorption of
dichromate, phosphate, and nitrate increased the oxygen
evolution rate since they might increase the availability of the
surface for oxidation of hypochlorite species and that they also
might catalyze the electron transfer reactions involved in anodic
perchlorate production.
In 1974, Jaksić56 reported the effects of several process
parameters on the current efficiency of the chlorate process. The
paper discussed the optimal current density, temperature, and
pH of the chlorate process without a stated specific focus on the
selectivity between chlorine or chlorate and oxygen.
In the same year, Bondar et al.138 reported on the electrolysis
of chloride-sulfate solutions using RTO anodes. Their most
relevant finding for the selectivity between oxygen and chlorine
was that the presence of H2SO4 decreased the current efficiency
for chlorine evolution. This points to the importance of
competitive adsorption of other ions than Cl− on RTO.
However, the result disagrees with that of Jaksić et al.,137 who
found no effect from addition of sulfate. In the same year,
Veselovskaya et al.139 showed that a decrease in RuO2 in the
RTO coating decreased the current efficiency for oxygen
evolution.
In 1976, Agapova and Kokhanov140 reported on electrolysis of
concentrated brine using Co3O4-coated Ti, finding a high
selectivity for chlorine evolution. At 2 kA/m2, low pH and 90 °C,
the current efficiency for chlorine evolution was above 99.8%.
Also in 1976, Shlyapnikov141 found that titanium anodes coated
with Pt or RuO2 exhibited higher chlorate production efficiencies
than graphite or Ti coated with MnO2 or PbO2. The higher
chlorate current efficiencies of Pt or RuO2 was associated with a
lower oxygen evolution current efficiency. The optimal pH for
chlorate production was similar for all anode materials.
In 1977, Buné et al.66 reported the selectivity between oxygen
and chlorine evolution on titanium−ruthenium oxide anodes in
solutions as a function of applied current density. Buné et al. used
one Tafel expression for the current density for each reaction.
These expressions could then give the ratio of Tafel slopes for
two different reactions. By measurement of polarization curves at
a high current density, when one of the two reactions is
dominating, the Tafel slope of that reaction could be decided.
With the use of the ratio between Tafel slopes, the Tafel slope of
the other reaction could then be determined. Experimental
measurements were performed using anodes composed of 30%
RuO2 and 70% TiO2, in acidic (pH ≈ 2) NaCl solutions with
different concentrations (300, 100, and 10 g/dm3), at 87 °C. The
oxygen and chlorine content of the gas evolved was measured
using GC and then converted into partial current density. It was
found that the oxygen content of the evolved gas decreased as the
applied current density was increased from 25 A/m2 to 25 kA/m2
and that the current efficiency for chlorine evolution increased as
the concentration of NaCl was increased. It was suggested that
the reason for the decrease in oxygen evolution was due to a
decreased surface coverage by intermediates in the OER as the
concentration of adsorbable Cl− increased (competitive
adsorption).
One year later, Uzbekov et al.142 reported on the possibility of
decreasing the active surface area of electrode coatings to
increase the local current density on the active sites of the
electrode, thereby increasing the selectivity for chlorine
evolution. In the same year, Kazarinov and Andreev143 reported
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Review
that HSO−4 and H2PO−4 adsorbed preferentially, displacing Cl−
on RTO electrodes, elucidating the reason for the reduction in
current efficiency upon addition of sulfate that Bondar et al.138
observed. However, their measurements only covered the range
of potentials from 0 to 0.7 V versus SHE, lower than anode
potentials expected during ClER, and were performed in dilute
solutions. Additionally, some of the experiments had been
performed at pH below 0, where formation of Ru(OH)2+ 2 is
predicted,47 possibly complicating the analysis.
In 1979, Fukuda et al.144 studied the effect of F− addition on
the anodic behavior of DSAs (Ti/RuO2, Ti/IrO2, Ti/RuO2−
TiO2, Ti/PtO2, Ti/Pd−PdO, Ti/Co3O4, and Ti/Rh2O3) in an
aqueous solution of H2SO4 and (NH4)2SO4. The behavior was
studied at current densities in the range from 0.1 to 1000 A/m2
(potentials between 1.5 to 2.5 V vs SHE). The addition of
increasing amounts of F− (1 × 10−3 to 1 M NH4F) decreased the
current efficiency of O2 formation on the Ti/RuO2, Ti/IrO2, and
Ti/RuO2−TiO2 electrodes, instead promoting S2O2− 8 formation.
It was shown by a photographic method that F− adsorbed on the
surface of these electrodes. Fukuda et al. rationalized the results
by suggesting that F− deactivated the surface sites used for
oxygen evolution but not the sites used for S2O2− 8 formation.
However, these results regarding the selectivity for S2O82−
formation versus oxygen formation cannot be considered a
direct analog to the selectivity between chlorine and oxygen
evolution, as the standard potential for S2O2−8 formation is 2.08 V
versus SHE,37 a significantly higher anode potential than that
applied for industrial chlorine evolution. Earlier studies by Jaksić
et al.137 found no effect of F− on the current efficiency for the
chlorate process. Furthermore, Kelsall and Robbins145 have
predicted, based on thermodynamic considerations, that F−
addition should result in dissolution of TiO2, which might
complicate the analysis of the work of Fukuda et al.
In the same year, Iwakura et al.146 presented anodic
polarization curves using a number of mixed metallic oxides,
coated on Ti, in 1 M KOH and 3 M NaCl. They compared the
characteristics of the RuO2 coating with coatings of SnO2−RuO2,
SnO2−PtOx, and SnO2−PdOx. Relatively low current densities
between 0.01 and 100 Am2 were applied. The mixed SnO2−
RuO2 coating exhibited a higher overpotential for oxygen
evolution in 1 M KOH than the pure RuO2-coating, while
showing a similar overpotential for chlorine evolution. This same
trend was also observed for the SnO2−PtOx and SnO2−PdOx
coatings, although the SnO2−PtOx coating exhibited a steep
increase in chlorine evolution overpotential as the current
density exceeded 10 A/m2. These results indicate that Sn-doped
RuO2 coatings and mixed Sn−Pd and Sn−Pt oxide coatings
exhibit a higher selectivity for chlorine evolution than pure RuO2.
The stability of the coatings were not discussed, although
Pourbaix diagrams45−47 predict instability of Ru at high pH and
anodic potentials in chloride solutions.
2.2.3. Research during the 1980s. In 1980, Caldwell and
Hazelrigg147 reported on the properties of cobalt spinel anodes
for chlorine evolution. The properties of pure cobalt oxide,
Co3O4, were contrasted with those of ZnII- and ZnII−ZrIV-doped
cobalt oxide. The Co−Zn−Zr oxide exhibited a significantly
higher surface area than the pure cobalt oxide or the Zn-doped
cobalt oxide. The Zn−Zr−Co oxide exhibited a higher chlorine
gas current efficiency (more than 99.5%) than either a Ru−Sn−
Ti oxide coating (about 99%) or a RTO coating (about 98%) in a
laboratory H-cell with concentrated NaCl on the anode side.
In the same year, Saito148 presented results of work on the
properties of a PdO-based anode coating (no details were given
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Chemical Reviews
about the composition) for chlorine evolution. It was found that
the PdO anodes had higher OER overpotentials, and lower ClER
overpotentials, than conventional RTO electrodes. The off-gas
from a laboratory cell operated with a PdO anode and 5.4 M
NaCl showed significantly lower oxygen concentrations (less
than 0.5% at a concentration of 50 mM active chlorine) than an
RTO (about 2% at 50 mM active chlorine) or pure RuO2 (about
2.5% at 50 mM active chlorine). The lifetime of the PdO coating
exceeded that of an RTO in an accelerated lifetime test. This is
unexpected, considering the low stability of PdO in chloride-
containing electrolytes at pHs below neutral.149
Again in 1980, Bergner150 presented work on the current
efficiency for chlorate and oxygen formation during chlorine
evolution in a membrane cell. It was observed that the sum of the
current efficiency for chlorine, oxygen, and sodium chlorate in
the membrane cell equals 100%. If anodes which exhibit
decreased oxygen evolution selectivity are used in membrane
cells, they seem not only to decrease the oxygen evolution
selectivity but also to yield an increase in chlorate production.
This agrees with the earlier study of Shlyapnikov.141
In 1981, Ibl and Vogt62 devoted a chapter in their overview of
inorganic electrosynthesis to chlorate production. Apart from a
detailed analysis of the overall efficiency of chlorate processes
based on process parameters such as reactor volume, current
density, and temperature, there is also a discussion of the sources
of oxygen in the chlorate process in the chapter. This discussion
is based on previously described sources, such as Hammar and
Wranglén,54 and also on several articles by Jaksić et al.55 (such as
refs 55, 56, 135, and 137). A general discussion about the
influence of different process parameters on the overall efficiency
of chlorate production is also given. A higher temperature,
current density, and volume of the reactor for the homogeneous
reaction was reported to increase the current efficiency, based on
expressions similar to those Jaksić et al.55 developed. Increasing
flow rate through the system had both a positive effect and a
negative effect. The positive effect was due to an increased
volumetric flow rate and thus a decreased concentration of
hypochlorite species in the cell, increasing the current efficiency.
The negative effect was due to the higher flow rate increasing the
rate of mass transfer to the anode and thereby increasing the rate
of anodic chlorate production. Ibl and Vogt62 believed the
negative effect is more important than the positive effect in
industrial systems.
In the same year, Gorodetskii et al.151 discussed the selectivity
between chlorine and sodium chlorate in a study that was mainly
focused on stability. The paper will be discussed more fully in
section 2.3, but it should be noted here that Gorodetskii et al.151
found that the amount of oxygen formed during chlor-alkali
electrolysis increased with pH in the range from 0 to 5. This effect
might be related to a decrease in the equilibrium potential for the
OER as the pH is increased. Furthermore, they noted that the
chlorate formation also increased significantly. The authors
suggested that the chlor-alkali anolyte should be kept at low pH
(below 3) to maximize selectivity and minimize the formation of
sodium chlorate.
In 1982, Pecherskii et al.67 continued the work of Buné et al.,66
examining the parallel between the rate of oxygen evolution and
the corrosion of electrodes during electrolysis through combined
gas phase oxygen and chlorine measurements and radiometric
corrosion rate measurement. Three different types of electrodes,
all on Ti supports, were studied. The first type only had
ruthenium galvanically deposited on the surface. The next type
had the same deposit but was subsequently heat treated in an
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argon stream containing low concentrations of oxygen. The last
type was prepared with the same galvanic ruthenium deposit and
heat treatment but with an added galvanostatic anodic
polarization in a sulfate solution. The polarization was stopped
when a sharp increase in the electrode potential was detected.
Auger electron spectroscopy showed the presence of titanium on
the surface of electrodes of the third type, while on the second
type Ti was only found deeper inside the bulk of the coating.
Pecherskii et al. thought that electrodes of the third type had a
Ru−Ti mixed oxide surface composition similar to that of DSA
produced by conventional means. The results of measurements
in chloride solutions was that the corrosion rate was highest on
type one and lowest on type three electrodes. The oxygen
evolution rate followed the same trend, being lowest on
electrodes of type three. Both the rate of oxygen evolution and
the rate of corrosion increased with increasing applied current
densities. Increased pH increased the rate of oxygen evolution,
but the slope of the increase was lower on electrodes of type
three. The decreased rate of oxygen evolution on type three
(RTO-like) electrodes was rationalized by the increased Ti oxide
amount in the surface separating the active ruthenium sites. The
authors stated that chlorine evolution takes place from a single
site, through an Erenburg mechanism,152 while oxygen evolution
requires two “paired” sites (something that was suggested by
O’Grady et al.153 and Buné et al.66). Therefore, the rate of oxygen
evolution would be decreased significantly as the surface
coverage of Ru decreased, while the chlorine evolution reaction
rate would not be decreased as much.
In 1983, Denton et al.154 presented an overview of research
concerning chlor-alkali anodes performed at Imperial Chemical
Industries (ICI), now Ineos Chlor-Chemical Ltd. Data for the
relationship between the Ru content of an RTO coating and the
oxygen content of the cell gas, as well as the chlorate
concentration in the anolyte, in an industrial diaphragm cell
were presented. The amount of oxygen in the off-gas increased,
and the chlorate concentration decreased, with increasing Ru
concentration in the anode. The increase in oxygen percentage
was associated with a decrease in overpotential for OER with
increasing Ru concentration. The overpotential also decreased
with increasing coating loading.
In 1984, three articles describing the development of a
selective titanium anode were published.71−73 The electrodes
were developed for increased selectivity for chlorine evolution,
for applications in chlorate cells, and seawater electrolysis. The
electrode was a mixed coating of RuO2−TiO2−PdSn2, forming a
compound of Sn, which has a high oxygen evolution over-
potential, and Pd, which was thought to increase the stability of
Sn in hypochlorite-containing solutions. Mixing the more
expensive Pd with RuO2−TiO2 was done to increase the stability
further, at a lower cost (Ti and Ru being less expensive than Pd).
The preparation of the anodes was done by standard thermal
decomposition of chloride precursors mixed in suitable ratios. X-
ray diffraction (XRD) was used to find ratios where more stable
PdSn2 was formed in one phase, with solid solution RuO2−TiO2
making up the other phase in the surface.73 There was apparently
no reference data for the PdSn2 phase identified by XRD, and the
stable form of such a phase according to Pourbaix diagrams,
during both the preparation and during ClER or OER
conditions, should be that of a mixed oxide rather than a Pd−
Sn alloy.45−47
Electrodes with varying compositions were tested in 300 g/
dm3 NaCl at pH = 2 and t = 80 °C at current densities up to 1 kA/
m2. It was found that, to keep the same high activity as standard
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Figure 8. Oxygen content of the cell gas as a function of cNaClO, corrected for cathodic inefficiencies, from Spasojević et al.71 Open circles represent
standard DSA anodes, and filled circles the modified coating. The dilute solution contained 30 g/dm3 NaCl, was kept at 25 °C, pH ≈ 7−9 and
electrolyzed at a current density of 1 kA/m2. Reprinted with permission from ref 71. Copyright 1984 Catalysis Research Center, Hokkaido University.
RuO2−TiO2, at least 30 atm % noble metals were needed in the
coating. The activity of a mixed coating of 14 atm % Ru, 35 atm %
Ti, 17 atm % Pd, and 35 atm% Sn showed the same activity as that
of a 40 mol % RuO2−60 mol % TiO2 anode.73
Selectivity measurements on both electrodes of the new
composition and of standard composition were performed. The
result for oxygen content of the gas evolved at j = 1 kA/m2 in
dilute brine is shown in Figure 8, which indicates the existence of
multiple mechanisms for oxygen formation. The first occurs at
low concentrations of hypochlorite, when mass transport is
limiting the rate of electrochemical oxidation of hypochlorite
(reaction 10). Under these conditions, electrochemical water
oxidation is the dominating source of oxygen. The second
oxygen-evolving mechanism is said to be hypochlorite oxidation.
This reaction is mass transfer limited, which explains its gradual
rise with the hypochlorite concentration. Figure 8 shows that the
new anode coating decreased the volumetric percentage of
oxygen in the formed gas by about 4% in dilute NaCl.71,72
The measurements under chlorate conditions (sodium
dichromate-buffered concentrated NaCl) showed that the
oxygen evolution rate was mass transfer limited for both the
new coating and the standard coating.71,72 In concentrated brine,
the new electrode coating did not exhibit a decrease in the rate of
oxygen evolution. However, addition of phosphates to the
electrolyte decreased the oxygen concentration in the gas when
the new coating was used, explained by strong adsorption of
phosphates on Pd.71 The authors presented further results
concerning phosphate addition in their third paper.72 In this
paper, they reported the influence of pH on the current efficiency
of the new coating and a standard coating, with dichromate
buffering or phosphate buffering. It was found that a high activity
was maintained in a broader pH range around pH 6.5 when the
phosphate buffer was used with the new coating. A high current
efficiency could be maintained up to pH ≈ 7.5. They also
commented that while normal DSA is destabilized by phosphate
addition, the modified coating with PdSn2 was not. Both the new
and the “standard” coating had similar long-term stability and
efficiency. The improvement in selectivity at chlorate process
conditions by using the new coating only appears if phosphates
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are added to the solution. Only at low chloride concentrations,
where water oxidation is the dominating source of oxygen, did
the modified coating in itself yield a decreased selectivity for
oxygen evolution.
In 1984, Kokoulina and Bunakova155 published results on
oxygen evolution currents in chloride-containing solutions at
applied current densities between 0.1 and 1000 kA/m2 and at
pHs between 1.4 and 2.1. The electrodes used were RuO2 and
RuO2 + TiO2, both with loadings of 5.5 g/m2. The electrolyte
used was either 1 M NaCl or 4 M NaCl at 70 °C. Kokoulina and
Bunakova first determined whether any oxygen evolution
occurred without electrode polarization. The electrolyte was
saturated by Cl2, and under such conditions (i.e., when ECl2/Cl− >
E > EO2/H2O), only the following two reactions were assumed
likely to occur on the electrode:
2H 2O → O2 + 4H+ + 4e− (21)
2Cl 2 + 4e− → 4Cl− (22)
As these two reactions occur, 1 mol of gaseous oxygen and 4 mol
of HCl forms. Thus, titration of the electrolyte was performed to
measure the change in concentration of HCl a certain time after
the RTO electrode was immersed in the solution. However, it
was found that the change in pH corresponded directly to the
amount of Cl2 that had been decomposed and that only a very
small amount of ClO−3 had formed. The change in pH did not
support spontaneous evolution of O2 under these conditions.
This contrasts with the results of Kuhn and Mortimer,136 who
noted oxygen evolution from NaCl solutions even without
polarization, when RuO2 electrodes were used.
Kokoulina and Bunakova then applied two methods to study
the oxygen evolution under electrode polarization.155 First,
titration was used to determine the amount of HCl formed
during electrolysis, using this amount to then calculate the
amount of oxygen formed. It was concluded that the oxygen
evolution rate decreased with increasing Cl− concentration. The
second method used potential compensation to obtain jO2, the
partial current density for oxygen evolution, at different electrode
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Figure 9. Voltammograms of DSA measured at increasing temperature from Kotowski and Busse.159 Reprinted from ref 159. Copyright 1986 John
Wiley & Sons Ltd. All Rights Reserved. The figure may not be reproduced, stored in a retrieval system, or transmitted, in any form or by any means,
electronic, mechanical, photocopying, recording or otherwise, without the permission of Ellis Horwood Limited, Market Cross House, Cooper Street,
Chichester, West Sussex, England.
potentials. The method is based on the assumption that if the
electrolyte is continuously saturated with Cl2-gas at a certain
partial pressure, the electrode potential can be maintained at the
reversible potential versus a RHE in the same solution. However,
electrochemical oxygen evolution will cause the electrode
potential to change from the reversible value. If a current is
applied to maintain the electrode potential at Eanode = E0,Cl2, the
current that is applied will be the same as that used for the side
reaction. Under such conditions, the OER current is
compensated by an equal and opposite current. To measure
the OER current at different electrode potentials, the chlorine
pressure of the gas above the electrolyte was decreased to lower
and lower values, decreasing the equilibrium chlorine potential.
The current that is applied is said to be the jO2(Eanode), yielding a
polarization curve for oxygen evolution. The results showed 40
mV lower overpotentials for oxygen evolution at RuO2 than on
RuO2+TiO2, indicating an increase in Cl2 selectivity for the
mixed oxide. Effects on the overpotential of changes in pH were
also noted. The results from both the titration and the potential
compensation methods compared favorably.
Also in 1984, Trasatti156 reported results of several studies of
the oxygen and chlorine evolution on oxide materials, primarily
pure oxides such as RuO2 or Co3O4. The bulk of the article
discussed the interplay between surface area (q*) and point of
zero charge in determining the activity of oxides in the relevant
reactions. In the concluding part of the article, Trasatti correlated
oxygen evolution overpotentials and chlorine evolution over-
potentials for several oxide materials. He found that the slope
between the two was close to unity. On materials, such as RuO2,
where the overpotential for chlorine evolution is low, the
overpotential for oxygen evolution is also low. He thought that
this indicated that the selectivity between chlorine and oxygen
evolution largely was not determined by the oxide material itself.
While the activity for both oxygen evolution and chlorine
evolution shows differences between different materials, the
selectivity does not.
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In the same year, Buné et al.157 published results on the effect
of the electrolyte composition on the kinetics and selectivity for
OER and ClER on RTO anodes of the typical 30% RuO2-70%
TiO2 composition. The measurements were carried out at a
current density of 2000 kA/m2 in either 4.27 or 0.71 M NaCl, at
87 °C and pH 1.6. Effects of addition of either phosphate, sulfate,
or perchlorate to the electrolyte were reported, continuing the
work of Bondar et al.138 and Kazarinov and Andreev.143 After
addition of phosphate, even at low concentrations of 0.004 to 0.1
M NaH2PO4, significant increases in anode potential were noted.
The addition of 0.1 M of phosphate resulted in an increase in the
selectivity for oxygen evolution, as measured by GC. Smaller
effects were noted upon addition of similar amounts of sulfate,
and no effect on the anode potential was noted upon addition of
perchlorate. It was therefore concluded that phosphates and
sulfates adsorb competitively, limiting the number of electrode
surface sites accessible for chloride. The addition of increasing
concentrations of phosphates also increased the electrode
potential during oxygen evolution from solutions containing
4.27 M NaClO4, indicating the effect of competitive adsorption
also on the oxygen evolution reaction.
In 1986, Cairns et al.158 presented further work on ICI anode
coatings for use in chlor-alkali membrane cells. It was noted that
the “classical” method to prevent oxygen evolution was brine
acidification, while modification of anodes was less frequently
used. However, data for a modified “low oxygen” coating was
presented, although without any details regarding the
composition of this anode. It is probable that the coating was
similar to those discussed earlier by Denton et al.154
In the same year, Kotowski and Busse159 presented research
on the oxygen evolution side reaction in membrane cells. The
results were based on measurements in both a diaphragm cell and
in a membrane flow cell. Kotowski and Busse discussed the
relative influence of reactions 10 (anodic chlorate production),
11 (water oxidation), 12 (hydroxide oxidation), 14 (bulk
decomposition of hypochlorite), and also the reaction (first
proposed by Wranglén160)
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HOCl + H 2O → 3H+ + Cl− + O2 + 2e− (23) Based on these results, Kotowski and Busse159 concluded that
in industrial cells, oxygen is evolved in reactions 10, 11, and 23.
which is a combination of HOCl reduction (E° = 1.482 V) and Two of the three reactions occur when hypochlorite reaches the
H2O oxidation, making it relevant in the potential range 1.23 to anode. All three reactions involve water, leading the authors to
1.48 V versus SHE. suggest that the oxygen evolution overpotential measured in
Reactions 10 and 11 were found to make up between 20 and sulfuric acid could be used to predict the oxygen selectivity of the
60% of the total oxygen evolved in a membrane cell. Reaction 12 anode materials. The idea was supported by measurements on
was not seen as important, since the pH at the anode surface is RTO anodes with decreasing amounts of RuO2 in the coating.
likely quite acidic when the electrode is anodically polarized. The For these electrodes, a linear relation between the logarithm of
amount of oxygen evolved due to reaction 11 was estimated the oxygen content in the membrane cell gas and the
based on data from amalgam cells, in which very little overpotential for oxygen evolution, measured in sulfuric acid
hypochlorite is formed. The amount of oxygen evolved due to solution, was found (see Figure 10).
reaction 10 was estimated based on the amount of chlorate that
formed and the assumption that all chlorate formed in the
membrane cell was formed due to oxidation of hypochlorite at
the anode.
Based on these initial experiments, Kotowski and Busse
reached the conclusion that a large percentage (between 40 and
80%) of the total oxygen formed had to be formed in reactions
involving hypochlorite, reactions 14 and 23. All other reactants
for oxygen formation, such as Cl2O, ClO−2 , or HClO2, were
excluded based on spectrophotometric data, leaving only
hypochlorite species as reactants for oxygen evolution.
Voltammograms of DSA were then measured in 200 g/dm3
NaCl and 3 to 5 g/dm3 NaClO. The voltammograms exhibited
peaks at 400 to 500 mV and around 1000 mV (see Figure 9), with
increasing intensity at increasing temperatures, which led to the
hypothesis of a coupled redox reaction occurring at the anode.
Kotowski and Busse thought it likely that concurrent oxidation,
according to reaction 23, and reduction of hypochlorite
2e− + H+ + HOCl ⇌ Cl− + H 2O (24)
occurred on the anode. The net result would then be production
of oxygen according to
2HOCl → O2 + 2H+ + 2Cl− (25)
To quantitatively test this hypothesis, further experiments
were then performed at room temperature and high pH (pH ≈ Figure 10. Relationship between the overpotential for the OER and the
10, to prevent chlorine evolution), at which only reactions 10 and volume percent of O2 in the off-gas, as found by Kotowski and Busse.159
23 were thought to occur. The electrolyte contained 30 g/dm3 The slope of the relationship between ηOER and log %O2 was found to be
NaCl and approximately 5 g/dm3 NaClO. Since the number of −169 mV per decade. Reprinted from ref 159. Copyright 1986 John
electrons released per mole of O2 formed is different for the two Wiley & Sons Ltd. All Rights Reserved. The figure may not be
reactions (2 electrons for reaction 23 and 4 electrons for reaction reproduced, stored in a retrieval system, or transmitted, in any form or
by any means, electronic, mechanical, photocopying, recording or
10), the percentage of the charge due to each of the reactions
otherwise, without the permission of Ellis Horwood Limited, Market
could be calculated. Three different anode coatings were used, a Cross House, Cooper Street, Chichester, West Sussex, England.
“normal”, a “special” (only said to be containing another
platinum-group metal together with Ru and Ti), and a Pt/Ir
coating. In industrial membrane cells, the gas evolved from the
cell using the normal coating contained 0.45 vol % oxygen, the Again in 1986, Buné et al.68 published results using GC to
special coating gave a gas containing 0.17 vol % oxygen, and the measure the selectivity for oxygen formation using DSA. This
Pt/Ir coating gave a gas containing 0.09 vol % oxygen. For the time, the composition of the anode was changed; previous
standard coating, the percentage of the oxygen evolved due to selectivity studies66,67 had examined the effect of current density,
reaction 10 constituted 21% of the overall oxygen formation. For chloride concentration, and pH. The molar percentage of Ru in
the special and the Pt/Ir coatings, the percentages of oxygen the coating was varied from 10% to 100%, similar to what was
generated from the same reaction were 0% and 69%, respectively. done in the study of Kotowski and Busse. The experiments were
In each case, the rest of the oxygen was accounted for by reaction done in a similar way as in previously described articles by the
23, the coupled hypochlorite reduction/water oxidation reaction. same group.66,67 The conclusion from the measurements was
Reaction 14, homogeneous decomposition of hypochlorite, was that the selectivity for chlorine formation increased as the
not considered to be important. Kotowski and Busse159 had done amount of Ru in the coating decreased, especially as the amount
previous experiments that confirmed that several heavy metal of Ru was decreased below 30%. The rationale was similar to that
ions promote the rate of this reaction. However, they did not find of Pecherskii et al.,67 that oxygen evolution is dependent on
that solids, such as DSA or solid Pt/Ir, increased the rate of adjacent Ru sites, while chlorine evolution is not. Their results
reaction. are summarized in Figure 11.
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Chemical Reviews
Figure 11. Dependence of the oxygen content (vol %) of the cell gas on
RTO anode composition obtained by Buné et al.68 (plotted using data
from the article68). The NaCl concentration was 4.27 M, pH ≈ 1.6, and
the current density was 1.2 kA/m2. Adapted with permission from ref 68.
Copyright 1986 Springer Science+Business Media.
In 1987, Spasojević et al.161 presented the optimization of a
RuO2−TiO2 anode for use in chloride electrolysis. Optimal Ru−
Ti ratios, loadings, and calcination temperatures to achieve an
active, selective, and stable anode were presented. Of interest to
the question of selectivity is that results (very similar to those of
Buné et al.68) indicating a clear decrease in partial current density
for OER for coatings with Ru content below 40% were given. The
lifetime of the anode during electrolysis of a dilute chloride
solution was also maximized at around 40% Ru.
Two years later, Tilak et al.69 published an article examining
the selectivity in the chlorate process. Tilak et al.69 derived a
mathematical expression, based on Tafel slopes, for the current
efficiency of a main reaction when two competing reactions are
occurring simultaneously. The equations are valid when both
reactions are activation controlled. Tilak et al. believe that the
relevant oxygen-evolving side reaction in the chlorate process is
anodic oxidation of water (reaction 11). They disregard the
reaction discussed by Kotowski and Busse,159 reaction 23, since
they did not think it was “satisfactorily demonstrated”. The
approach in developing the equations was similar to that of Buné
et al.66 However, a more extensive set of equations was
developed. The central one was
1 of O2 in the gas phase, from the study of Tilak et al.69 Reproduced with
em =
1 + δem−ϵI −ϵ (26)
where I is the overall current density, em the current efficiency for
the main reaction,
j0, p
δ= × e(k ′×ΔE) × j0,m A ·ϵ
j0,m (27)
and
k − k′
ϵ=
k (28)
k and k′ are the inverse of the Tafel slopes for the main reaction
(chlorine evolution) and the “parasitic” reaction (oxygen
evolution), respectively. ΔE is the difference in reversible
potential between the main reaction and the parasitic reaction.
A is the effective surface area of the electrode. The main
implication of the expressions is that the selectivity for the main
reaction (chlorine evolution in the case of chlorate and chlor-
alkali production) could be increased if materials with a lower j0,p
(j0,oxygen evolution) were used (eq 27). Furthermore, for chlor-alkali
and chlorate processes, k > k′ since the Tafel slope for chlorine
evolution on DSA is around 40 mV while the Tafel slope for
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oxygen evolution is around 130 mV. This means that ϵ > 0 (eq
28), so that an increase in current density yields an increase in
current efficiency for chlorine evolution (eq 26). That this is the
case for chlorine evolution on DSA has been shown many times
(refs 54, 56, 57, 62, 66, 69, 70, 75, 131, 154, and 162−164).
Tilak et al. then went on to perform experiments to test these
equations. The experiments were performed at T ≈ 95 °C using
an electrolyte of 5 M NaCl and 2 M NaClO4 saturated with
chlorine at pH ≈ 4. Coatings with decreased j0,oxygen evolution
(RuO2 coatings doped with different amounts of HfO2 or SnO2)
were tested using polarization measurements, showing that the
overpotential for chlorine evolution was usually higher on such
electrodes than on standard DSA. On the basis of galvanostatic
selectivity measurements at 2.32 kA/m2, the selectivity for
chlorine evolution was decreased for most of the Hf- or Sn-
containing coatings. It was also found that the current efficiency
for chlorine evolution increased with increasing current density.
The percentage of oxygen in the off-gas using anode materials
with increasing roughness factor (increasing Areal/Ageometric) was
then measured at the same current density. The results are shown
in Figure 12. The roughness factor was changed by using
Figure 12. Relationship between surface roughness and the percentage
permission from ref 69. Copyright 1988 The Electrochemical Society.
different coating deposition methods (brushing or spraying),
different drying and calcination temperatures, and by varying the
number of coating layers applied. The measurements showed
that an increase in roughness factor gives an increase in the
oxygen percentage in the off-gas. This seems to support the idea
expressed by Uzbekov et al.142 and Trasatti and Lodi,165 that an
increase in surface area yields a decrease in local current density
and thereby a decrease in selectivity for chlorine evolution.
In 1989, Hardee and Mitchell162 published an article regarding
the selectivity for oxygen evolution at chlorate conditions,
examining the effect of process conditions on the percentage of
oxygen in the gas phase, using an undivided cell with a DSA. The
electrolyte contained NaCl (either 50 or 200 g/dm3) and 2 g/
dm3 sodium dichromate at pH = 6.5 and 60 °C.
Hardee and Mitchell found that hypochlorite decomposition
was the main source of oxygen evolved. The percentage of
oxygen in the evolved gas was dependent on the hypochlorite
concentration at both sodium chloride concentrations. At the
higher NaCl concentration, the dependence was approximately
linear (see Figure 13). Extrapolation to cNaClO = 0 indicated that
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Figure 13. Dependence of hypochlorite concentration on the percent
oxygen evolved as found by Hardee and Mitchell.162 The concentration
of sodium dichromate was 2 g/dm3, the temperature was 60 °C, and the
current density was 2.5 kA/m2. DSA were used. Reproduced with
permission from ref 162. Copyright 1989 The Electrochemical Society.
the background oxygen production level, due to water oxidation,
would be equivalent to 0.3% oxygen in the gas phase, for the 200
g/dm3 NaCl electrolyte. To determine the rate of homogeneous
oxygen evolution, the cell was also operated in the same way but
without the electrodes inside. A nitrogen flow, of similar
magnitude to the hydrogen evolved in normal operation, was
led through the cell to remove the formed oxygen. It was seen
that the oxygen evolution was dependent on the NaClO
concentration also in this case. The sum of the oxygen
percentages from water oxidation and homogeneous hypochlor-
ite oxidation was not enough to cover the total percentage of
oxygen in the gas phase. Thus, the remaining part of the oxygen
evolved was thought to be produced in reaction 23, as proposed
by Kotowski and Busse.159
Hardee and Mitchell162 also examined the effect of some other
process parameters. Increasing NaCl concentrations, from 50 to
300 g/dm3, were seen to reduce the oxygen evolution rate. The
oxygen percentage in the off-gas decreased linearly with
increasing NaClO3 concentrations between 0 and 400 g/dm3.
It was thought that this might be due to competitive adsorption
of chlorate onto the anode. There was no consideration of the
explanation of Hammar and Wranglén,54 who showed that the
increased viscosity of the electrolyte with increasing chlorate
concentrations was a likely reason for the decreased oxygen
evolution rate. Higher temperatures were seen to yield higher
rates of oxygen evolution. This was partly explained by improved
kinetics for homogeneous hypochlorite oxidation and partly by
hypochlorite oxidation having a higher increase in rate with
temperature than chloride oxidation. pH apparently had no effect
in the 5−7 range, but an increased oxygen evolution rate was
noticed at higher pH. This was thought to be related to the
increasing prevalence of the deprotonated hypochlorite species
at higher pH. The selectivity for oxygen evolution was seen to
decrease with increasing current density. This was thought to be
related either to difference in Tafel slope between the chlorine-
and the oxygen-evolving reactions or due to a limiting current
density for hypochlorite oxidation being reached. Hardee and
Mitchell also examined the effect of dichromate concentrations
between 0 and 5 g/dm3. At 0 g/dm3, the oxygen percentage
increased significantly. However, this was due to the large
decrease in cathodic current efficiency that is associated with
complete removal of dichromate from the electrolyte. When this
effect was corrected for, the dichromate amount was said to have
no effect on the oxygen evolution rate. This contrasts with the
results of the work of Jaksić et al.,137 who saw increase in oxygen
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evolution rate at increasing concentrations of dichromate.
Looking at the data presented by Hardee and Mitchell, a slight
increase in the percentage of oxygen with increasing concen-
tration of dichromate can be seen. Finally, long-term data for two
anodes were reported: one of standard DSA and one with a secret
modified composition. The modified coating, which had been
adjusted based on the importance of the hypochlorite oxidation
at the anode, showed a significantly lower percentage of oxygen
in the off-gas.
In the same year, Zhinkin et al.163 contributed a study mainly
focused on stability of DSA. The work will be discussed in more
detail in section 2.3, but it will be noted here that the authors
showed that during chlor-alkali electrolysis using the conven-
tional DSA and concentrated NaCl solution, the amount of
oxygen in the off-gas increased with pH in the range of 2−5
(possibly related to the pH dependence of the O2/H2O
equilibrium) and decreased with increasing current density in
the range from 2 to 10 kA/m2.
2.2.4. Research during the 1990s. In 1990, Boodts and
Trasatti166 published an article investigating the activity of
Ru0. 3Ti(0.7−x)SnxO2 coatings for oxygen evolution from 1 M
HClO4. The selectivity was not investigated per se but rather the
activity and surface charge of this ternary oxide. Boodts and
Trasatti found that the activity, measured as j(1.43 V vs RHE)/q*
(current normalized by the surface charge), for oxygen evolution
is increased by increasing Sn addition. In contrast to the
suggestion of Krstajic et al.,73 Boodts and Trasatti believed
addition of Sn to the coating should decrease the selectivity for
chlorine evolution, and they proposed that it was PdSn2 rather
than Sn itself that promoted the selectivity for chlorine evolution
seen in the study of Krstajic et al.
Also in 1990, Couper et al.167 reported further data for an ICI
membrane chlor-alkali process anode coating. The coating, with
unnamed composition, was an improvement of the previous low
oxygen coatings154,158 and had been developed for a high oxygen
evolution overpotential. Experimental data comparing the new
low oxygen anodes with previous coatings indicated significantly
lower oxygen percentages in the off-gas when using the new
anode coating, at least up to pH ≈ 4.5. The results were explained
using eq 29,
log(oxygen content) = −Aη(O2 ) + B pH (29)
which describes the oxygen evolution in membrane cells where
the oxygen content of the cell gas is related partially to the pH
and partially to the overpotential for oxygen evolution. A and B
are introduced simply as fitting parameters without any physical
interpretation.
In the same year, Bergner et al.41 reported data for HCl
addition to membrane chlor-alkali cells. This addition is done to
neutralize any OH− that might migrate from the cathode side of
the membrane. Bergner attempted to obtain data on suitable acid
additions to the brine inlet of an industrial membrane chlor-alkali
cell. The study did not attempt to decide the magnitude of
different oxygen-producing reactions but presented suggestions
for HCl addition that were shown to reduce the oxygen levels
significantly, from just below 2% to 0.4% (see Figure 14). These
results agreed with those previously obtained by Gorodetskii et
al.151
Also in 1990, Wanngård57 reported results concerning the
oxygen forming reactions in chlorate electrolysis in a pilot scale
system, with industrially relevant current densities and temper-
atures and using a RTO anode and a steel cathode. Wanngård
found, in agreement with other studies,54,162 that the oxygen
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Chemical Reviews
Figure 14. Effect of anolyte acidification with HCl on current
efficiencies in chlor-alkali production, from Bergner.41 Original caption
reads “Current efficiencies of products and by-products in brine pH
range from −0.8 to 2.0. The points (×) at pH 2 correspond to the means
of Figure 5.”. Reprinted with permission from ref 41. Copyright 1990
Springer Science and Business Media.
concentration in the off-gas was related to the concentration of
hypochlorite species (the sum of [HOCl] and [ClO−]). In turn,
the concentration of hypochlorite species was found to be
dependent on pH, temperature, ionic strength, and the cubic
root of the current concentration (total current divided by the
total electrolyte volume in the system). Furthermore, Wanngård
found that the oxygen percentage was independent of the flow
velocity in the electrode gap. This contrasts with results obtained
in studies at low temperature,53,54 where the oxygen evolution
rate was mass transport limited and indicates that the oxygen
evolution was kinetically limited at the higher temperatures used
industrially. Wanngård called
%O2,off − gas
= SR
[HOCl + OCl−]electrodegap (30)
a “selectivity ratio” (SR) when discussing the results. Linear
relationships (indicating that the rate of oxygen evolution is
linearly proportional to the amount of hypochlorous acid species
in the cell) were found when plotting SR versus (1/t), where t is
the temperature in degrees centigrade. The same slope was found
in all cases, except for when the electrolyte was contaminated by
compounds active for hypochlorite decomposition. Wanngård
claimed that this linear dependence implied reaction control of
the oxygen evolution under chlorate conditions. Neither
changing the electrode gap from 2 to 3 mm nor increasing the
height of the electrode blades (i.e., changing from rectangular
blades with 0.333 m height and 0.379 m width to rectangular
blades with 0.8 m height and 0.3 m width) altered the slope of the
linear dependence. However, the increase in height decreased the
value for SR, implying that the electrode height (or possibly the
total area, as the higher blades had a higher geometric surface
area) had an impact on the oxygen formation. Wanngård
cautioned that the effect on SR that higher electrodes exhibited
could point to a difficulty in drawing conclusions relevant for full
scale cells from laboratory scale data. Wanngård further claimed
that experimental studies performed at the same company, at
similar temperatures (50 to 90 °C), had shown that only 5−10%
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of the oxygen evolved originated from homogeneous hypochlor-
ite decomposition (reaction 14).
In 1992, Wanngård168 published a report concerning impurity
effects in the chlorate process, where it was noted that electrolyte
concentrations of Pb, Mn, Sn, F, Al, Si, and BaSO4 should be
minimized to prevent deactivation (due, for example, to
blockage) of the anode. Tests of hypochlorite decomposition
catalysts under chlorate conditions at 70 °C had also been carried
out, finding that Ni, Cu, Co, and Ir increased the oxygen
percentage in the cell gas upon addition, while Pt, Ru, and Fe had
no effects on the oxygen percentage (the form of the metal, i.e.,
salt, metallic, or oxidic, was not indicated). Wanngård also
pointed out some important areas for further studies of the
selectivity, such as studying the amounts of oxygen forming at the
anode versus in the bulk electrolyte, deciding criteria for
sufficient electrolyte purity and regarding demands on analysis
methods used to detect impurities, and finally further studies of
which current concentration gives the optimum selectivity.
Also in 1992, Traini and Meneghini169 presented experimental
data for the percentage of O2 in a chlor-alkali membrane cell off-
gas for a De Nora “Low-oxygen coating”, which decreased the
percentage of O2 by about 0.4% at pH 4.0 in comparison with
that of a conventional DSA coating. No information was given
about the composition of the low-oxygen coating, although it was
pointed out that an improved distribution of chlorides at the
surface of the anode could be used to prevent local low brine
concentrations leading increased rates of oxygen evolution.
In the same year, Czarnetzki and Janssen170 presented a study
of hypochlorite production by galvanostatic electrolysis (j = 2.76
kAm−2 or j = 5.54 kAm−2) of dilute NaCl solutions (6 to 90 g/
dm3) in a lab-scale membrane cell at alkaline pH (in the range 8−
10), using a commercial RTO anode. The study focused
specifically on the initial behavior of the cell, with measurements
covering about 1 h of electrolysis. It was found that increasing the
hypochlorite concentration resulted in a linear increase in oxygen
formation rate, although an extrapolation of the trend to zero
hypochlorite concentration resulted in a significant background
oxygen formation rate. Increasing the initial NaCl concentration
instead resulted in decreased oxygen formation rates. Fur-
thermore, increasing the current density resulted in a slight
increase in oxygen formation rate. It was concluded that the rate
of chloride oxidation was mass transport limited in the study, and
therefore, the effect of adding nonreactive anions was attributed
to their effect as supporting electrolytes. The addition of
supporting electrolytes reduced the migration mass transfer of
chloride to the electrode surface, thus further reduced the
limiting current density for chloride oxidation. However, it was
also noted that the addition of ClO−3 , ClO−4 , or SO2−4 seemed to
catalyze the oxygen formation, as a concomitant decrease in
anode potential was measured. The authors also estimated that
the pH at the anode during electrolysis was about 2.0, based on
the formation rate of oxygen and an assumed concomitant
production of H+ ions. Based on this, they concluded that the
electrochemical oxidation of ClO− should be negligible and
suggested that HOCl should be the dominating species at this
pH. However, according to Figure 1, it is more probable that at a
pH of 2, HOCl will be converted to Cl2 and water. Finally, the
authors suggested that their chlorate formation results could be
explained if the formation of chlorate occurred through both the
conventional chemical conversion of hypochlorite, as well as
through a direct electrochemical oxidation of Cl− to ClO−3 .
In 1993, Bergner and Hartmann36 published an article
concerning oxygen evolution in membrane chlor-alkali cells.
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Results were presented for oxygen and chlorate production in
industrial membrane cells, operated at industrially relevant
process parameters over a period of several years. The cells were
either equipped with “low oxygen” or “high oxygen” anodes, with
unnamed compositions. The results confirmed the previous
trends141,150,154 in that the anode designed for lower oxygen
production exhibited a lower oxygen production but also a higher
chlorate production.
In the same year, the first research, to our knowledge, that
employs mass spectrometry (MS) for detection of Cl2 and O2
formed during electrolysis using DSA was published. Takasu et
al.171 adapted DEMS for use with a titanium net coated with
different compositions of RuO2, TiO2, and IrO2. The potentials
where chlorine and oxygen, respectively, were first detected by
the MS were termed the threshold electrode potentials. The
difference between the two threshold potentials was proposed as
a measure of the selectivity for the two reactions (see Figure 15).
Figure 15. Threshold electrode potentials of (a) oxygen and (b)
chlorine evolution on RuO2−TiO2 electrodes of varying composition.
Reprinted with permission from ref 171. Copyright 1993 Elsevier.
Also, the ratio between chlorine evolved and the total gas evolved
at a certain potential (above the threshold potential for both
reactions) was proposed as a measure of selectivity. Based on the
results, the authors conclude that a 20% RuO2 + 80% TiO2
coating shows the highest selectivity for chlorine evolution. The
applicability of the results to actual anodes in industrial
production is uncertain, since DEMS studies are always done
at low current densities. In this case, the maximum current
density reached during the sweep was about 40 A/m2.
In the same year, Nakajima et al.172 presented a study on the
properties of Ru−Ti−Sn oxide and Ru−Sn oxide electrodes used
for chlorine evolution in a laboratory-scale membrane cell. XRD
indicated that the Ru−Sn oxide was of the rutile type, but the
structure of the other electrodes was not clearly stated. The Ru−
Sn oxide electrodes exhibited lower anode potentials than both
Ru−Ir−Ti, Ru−Ti, and Ru−Ti−Sn electrodes. Similarly to
conventional RTO electrodes, the volume percent O2 in the off-
gas increased with the amount of Ru in the Ru−Sn oxide coating.
Lower Ru percentages in the mixed Ru−Sn coating also led to
longer coating lifetimes, which also matches the behavior of
RTO.
In 1994, Trasatti’s latest extensive review of DSA and related
conductive metal oxides was published.26 While the review
discussed both chlorine and oxygen evolution on DSA and other
materials, there is very little said about the selectivity between the
two reactions. The main reference is to the studies of Krstajic et
al.73 and Spasojević et al.71 on a selective water electrolysis and
chlorate production anode, which has been described previously
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in this review. Furthermore, Trasatti reviewed some data that
points to the importance of a connection between surface redox
reactions of electrocatalyst materials (e.g., changes the oxidation
state of Ru in the surface coating of DSA) and the redox
potentials of reactants. Trasatti comments that the reason why
Tilak et al.69 and Spasojević et al.71 claim that Sn addition
increases the selectivity for chlorine evolution is that “...the redox
transition leading to oxygen evolution on RuO2 is pushed to
more positive potentials by the presence of the inactive
component. This is also the case for RuO2+TiO2 electrodes”.
In 1994, further lab-scale research concerning the current
efficiency in the chlorate process was presented by Baolian and
Wenhua.173 The main contribution of the study was a new
formula for calculating the current efficiency for a chlorate cell
utilizing an oxygen cathode instead of the conventional hydrogen
cathode. The study again reconfirmed previously seen trends
regarding optimal pH for chlorate production (finding an
optimum at around pH 6.5−6.75), sodium chloride concen-
tration (increased efficiency with increasing NaCl concentra-
tion), and sodium chlorate concentration (a slight increase in
current efficiency with increasing NaClO3 concentration).
However, the study also examined the effect of additions of
Na2HPO4, Na2Cr2O7, or NaF to the electrolyte at two different
concentrations of NaCl (either 200 g/dm3 or 50 g/dm3).
Additions of increasing amounts, up to 7 g/dm3, of Na2HPO4 or
Na2Cr2O7 resulted in a slight decrease in current efficiency for
chlorate formation. However, the addition of NaF resulted in
increases in current efficiency of about 1% at the high NaCl
concentration and about 3% at the low NaCl concentration.
These results agree with the general conclusion of Fukuda et
al.,144 who found that F− addition could reduce the OER
selectivity of DSAs, while they disagree with those of Jaksić et
al.,137 who found no effects on current efficiency for chlorate
formation from fluoride addition.
In 1997, Eberil et al.164 examined the selectivity issue in a
chlorate system, calculating the efficiency for chlorate electrolysis
based on the equation
ΦeNaClO3 = 100 − 2V (O2 ) − V (Cl 2) − 2.5
(31)
where 2.5 was a previously determined efficiency for cathodic
reduction in the cell and V are volume fractions. Experiments
under chlorate conditions showed that ηNaClO3 increased with
potential, reaching a plateau at anode potentials E > 1.37 V versus
SHE. The efficiency was constant at pH 6−7 at potentials above
1.365 V versus SHE. At potentials lower than the plateau value,
the efficiency was significantly higher for solutions with pH 6−
6.5. The maximum ΦeNaClO3 was found at potentials close to the
so-called “critical potential”, Ecr. This potential has been
associated with a break in the Tafel line and an increase in the
rate of decomposition of the anode.165,174 Furthermore, they
found that the efficiency of chlorate production decreased with
increasing temperature but increased with increasing current
density. Thus, a high current efficiency can be maintained at a
higher temperature if the current density is increased.
In 1998, Arikawa et al.75 published DEMS results on the
selectivity between oxygen and chlorine evolution on RTO and
RuO2. Several known effects, regarding NaCl concentration,
oxide loading, and RTO composition, were reconfirmed by their
experiments. The experiments using different concentrations of
NaCl showed that the selectivity for chlorine evolution increased
with increasing concentration of NaCl. Additionally, the
selectivity increased with increasing anode potential (and current
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Chemical Reviews
density) in solutions with high chloride concentrations (2 M). A
number of measurements were also carried out at a lower
chloride concentration of 0.3 M. At this concentration, the
selectivity for ClER in general decreased with increasing anode
potential. The decrease was more severe when the oxide loading
of RuO2 was increased from 0.1 to 0.9 mg/cm2. For a fixed oxide
loading of RTO, it was found that the selectivity for ClER was
improved over that of pure RuO2 when the RuO2 content in the
coating was between 20% (the lowest concentration) and 60%.
2.2.5. Research during the 2000s. This section is divided
into one part describing experimental studies and one part
devoted to a more detailed description of the first-principles
modeling of chlorine and oxygen evolution on metallic oxides.
This latter field has seen a large growth during the past few years.
In the present review, these studies are described after the
experimental studies, although the approach used in some of the
experimental studies has been inspired by recent results from
first-principles calculations.
2.2.5.1. Experimental Studies. In 2000, Eberil et al.74
published a thorough examination of the current efficiency for
chlorate production, by measuring the evolution of chlorine and
oxygen, using both DSA (30 mol % RuO2 + 70 mol % TiO2) and
Ir-containing DSA (15 mol % RuO2 + 15 mol % IrO2 + 70 mol %
TiO2). The maximal ΦeNaClO3 was again found at potentials E ≈
1.4 V versus AgCl/Ag, close to Ecr (see Figure 16). This
coincided with the minimum in ΦeO2. Depending on whether the
anode potential was below or above the critical one, the
dependence of the efficiency for oxygen evolution, ΦeO2, on the
anode potential, Ea, was different. At Ea < Ecr, ΦeO2 decreased with
Figure 16. Current efficiencies for O2 and Cl2 formation as a function of
anode potential, determined under different conditions. Unfilled, half-
filled, and filled symbols depict measurements at 60, 80, and 90 °C,
respectively. The series of symbols (circles, squares, triangles, and stars
with increasing number of points) depict measurements done at
different current densities from 0.15 to 1.7 A/cm2. Original caption
reads (Eberil et al.74 used the symbol η to signify current efficiency,
rather than using the conventional Φe175): “Dependences of ηCl2 and ηO2
on Ea of ORTA at different ia and T in solution containing 150 g l−1 NaCl
and 350 g l−1 NaClO3; pH 6.5.” ORTA is an abbreviation meaning
ruthenium−titanium oxide anode (RTO). Reprinted with permission
from ref 74. Copyright 2000 Springer Science and Business Media.
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increasing temperature. At Ea > Ecr, ΦeO2 increased with increasing
temperature. The efficiency for chlorate production was
determined largely by ΦeO2. A higher temperature, a lower pH
and a higher concentration of NaCl increased ΦCl e
. The
2
measured efficiencies were also compared to those obtained in
the system164 with directed circulation and a holding tank for
chlorate formation. The system with the holding tank had higher
efficiencies and showed similar trends in efficiency at E < Ecr. No
experiments at E > Ecr had been done in the system with the
holding tank and directed circulation. Furthermore, a difference
between the Ir-containing DSA and the standard DSA was noted.
For the standard DSA, the maximum ΦeNaClO3 was moved to
higher anode potentials (higher applied current densities), and
ΦeO2 increased overall, when the chloride concentration was
decreased. This could be interpreted as resulting from
concentration limitations of Cl− at the anode surface. However,
when Ir-containing DSA were used, ΦeO2 did not increase as the
chloride concentration was decreased. The reason for the
increase in oxygen evolution at standard ruthenium−titanium
DSA, once the critical potential is reached, was supposed to be
the formation of volatile RuO4. As IrO2 increases the stability of
the coating, it was proposed that this process is hindered on Ir-
DSA. The Ir-DSA coating showed other advantageous character-
istics, such as somewhat lower ΦeCl2 and higher ΦeNaClO3, at most
current densities.
In 2001, Byrne et al.176 published a tertiary model of current
distribution in the chlorate cell, including mass transport through
diffusion, migration, and convection for relevant species, using
the Nernst−Planck equation. Butler−Volmer expressions were
used to model reactions 2, 11, and 23 on the anode. The last
reaction was modeled for oxygen formation through both
electrochemical oxidation of hypochlorite and electrochemical
oxidation of hypochlorous acid. The possibility of different type
of heterogeneously catalyzed, nonelectrochemical, decomposi-
tion of hypochlorite on the surface of the electrode was not
considered. Byrne found that electrochemical water oxidation
was an insignificant source of oxygen when compared with that of
anodic decomposition of hypochlorous acid or hypochlorite. The
latter reactions were the dominating source of oxygen at the
anode. Two different trends were seen for the anodic
decomposition of hypochlorous acid and the hypochlorite ion.
While the decomposition of hypochlorous acid was highly
dependent on the flow rate, the rate of decomposition of
hypochlorite ions was found to be relatively independent of the
flow rate. This agreed well with the results of Wanngård,57
indicating that hypochlorite, rather than hypochlorous acid,
might be the main reactant in the anodic decomposition of
hypochlorite species in the chlorate process. The model was
experimentally validated using a cell with segmented electrodes
in a vertical column.177 It was found that the model corresponded
well to the experimental data only at low flow velocities between
0.25 and 0.75 m/s and near the inlet inside the column.
The same year, Jirkovský et al.76 published a study concerning
sol−gel-prepared RuO2 coatings on Ti meshes. The study was
focused on the selectivity for chlorine and oxygen evolution on
coatings made up by crystals of different sizes. The particle sizes
increased with the annealing temperature used during the
preparation. The DEMS technique was used to measure the
oxygen and chlorine evolution during cyclic voltammetry (CV)
measurements. The study focused on examining the activity of
different crystal edges on RuO2 nanocrystals. The electrolyte was
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a dilute solution of 0.1 M HClO4 and 0.3 M NaCl. For the
coatings with the smallest particles, Jirkovský et al. found that the
onset potential for chlorine evolution was more positive than that
for oxygen evolution, as opposed to what was found in the study
of Takasu et al.171 However, Arikawa et al.75 also made
measurements at cNaCl < 0.5 M, finding that the threshold
potential (or onset potential) of oxygen evolution was lower than
that of chlorine evolution. Furthermore, Jirkovský et al.76 found
that the Tafel slopes of both oxygen and chlorine evolution were
114 mV/dec. These values are, like in the previous studies using
DEMS,75,171 much higher than what is normally reported for
RuO2. For coatings prepared at high temperature, with larger
particles, the threshold potential for oxygen evolution shifted to a
higher potential than that for chlorine evolution. The selectivity
for chlorine evolution was higher on coatings prepared at these
higher temperatures and showed a linear dependence on the
annealing temperature. The authors rationalized the increased
selectivity for chlorine evolution based on the types of crystal
edges that were more prevalent at the larger particles that formed
at these temperatures. However, the specific surface area of the
coating was about half as large on the electrodes prepared at 900
°C. It is known from previous studies that an increase in current
density increases the selectivity for chlorine evolution. Whether
this had any effect does not appear to be considered in the article.
Also in 2006, Santana and De Faria178 presented research on
the electrolytic production of Cl2 and O2 using DSA doped with
CeO2 and Nb2O5. Their conclusions were that Nb2O5 had no
effect on the activity or selectivity of the coatings. However,
introduction of even 1 mol % CeO2 into DSA decreased the low
Tafel slope for O2 evolution to 30 mV/dec from 40 mV/dec, but
only at current densities lower than 10 A/m2. On the other hand,
CeO2-doping did not seem to affect the Tafel slope for Cl2
evolution. CeO2-doped DSA thus exhibited higher O2-selectivity
at low current densities.
In 2007, Panić et al.179 presented stability and selectivity data
on RTO deposited, by use of a sol−gel procedure, on a ternary
titanium carbide, Ti3SiC2. It was thought that this carbide would
be much more stable as a support material than Ti. Instead of the
more usual 30% RuO2 + 70% TiO2, a coating with equimolar
amounts of ruthenium oxide and titanium oxide was used.
Experimental results suggested that the selectivity for chlorine
evolution was more favorable for anodes on the Ti3SiC2 support
than on Ti. However, the new support was shown to be much less
stable in an accelerated lifetime test than the standard Ti support.
In 2008, Macounová et al.77 published DEMS results on the
selectivity between further DEMS research examining the
selectivity between oxygen and chlorine evolution on
Ru1−xNixO2−y, where x was between 0.02−0.3, coated on Ti
meshes. Similarly to the study by Jirkovský et al.,76 the coatings
were characterized using XRD and energy-dispersive X-ray
spectroscopy (EDX) and evaluated using DEMS and CV in
solutions containing 0.1 M HClO4 and 0.3 M NaCl. This time,
the coatings were all heat treated at 400 °C for 20 min. The
DEMS study indicated a complicated dependence of the
selectivity on the Ni content of the coating. The selectivity was
dependent both on the applied potential and the Ni content. The
maximum selectivity for chlorine evolution was found at x = 0.1.
The Tafel slope for chlorine evolution was found to be around 35
to 40 mV/dec, while that for oxygen evolution assumed its lowest
value of 40 mV/dec at x = 0.02 and then had a maximum of 100
mV/dec at x = 0.1. A model was presented to explain the activity,
based on there being four types of active sites, with increasing
numbers of adjacent Ni atoms. Sites with no Ni atoms were
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thought to be active for oxygen evolution, sites with one nickel
atom were thought to be active for chlorine evolution, and sites
with two Ni atoms were imagined to be selective for oxygen
evolution. The third type was thought to be less active for oxygen
evolution than the first type. This model could describe some
trends observed in the experimental data but was unable to
account for the low activity for chlorine evolution that coatings
with the highest Ni content exhibited. There was no comment on
the stability of the coating, but Pourbaix diagrams45−47 indicate
that Ni2+ might dissolve from the coating.
Also in 2008, Macounová et al.180 also presented results for Fe-
doped RuO2 (Ru0.98Fe0.02Ox and Ru0.7Fe0.3Ox) prepared using
sol−gel synthesis. XRD indicated that the Fe dopants entered
into the overall Ru rutile lattice. Selectivity measurements using
DEMS indicated that the selectivity was affected strongly by the
gas present in the 0.15 M NaCl−0.1 M HClO4 electrolyte. In the
Ar-saturated electrolyte, the selectivity for Cl2 was high for both
electrode compositions, whereas in oxygen-saturated electrolyte,
oxygen evolution was the dominating process for the
Ru0.7Fe0.3Ox electrode. The authors suggested that the trend
could be explained by oxidation of the Fe sites in oxygenated
solutions.
The same group also published an article concerning the
Ru0.8Co0.2O2−x material in 2008.78 The electrodes were prepared
by sol−gel synthesis onto Ti meshes. The study used X-ray
photoelectron spectroscopy (XPS) and TEM to draw con-
clusions regarding the connection between the surface
morphology and the selectivity between chlorine and oxygen
evolution on this material. DEMS measurements were done in
the same way as the previous articles from the same group, by
using CV and DEMS. This time, the solution not only contained
0.1 M HClO4, but also (like in refs 76 and 77) 0.3 M NaCl. The
addition of chlorides shifted the onset potential for oxygen
evolution to more anodic potentials. The particle size did not
have any effect on the rate of oxygen evolution, but an increased
selectivity for chlorine evolution (due to an increased rate of
chlorine evolution) was noted on coatings with larger (d > 40
nm) crystals. The onset potential for the chlorine evolution
reaction was about 1.1 V versus SCE, while the onset potential for
OER was approximately 1.2 V. At higher potentials, the chlorine
evolution current was almost constant, while the oxygen
evolution current continued to increase. The Tafel slope for
the chlorine evolution was 120 mV/dec below 1.2 V and a very
high value of about 600 mV/dec at higher potentials. The change
in Tafel slope at 1.2 V was thought to be related to a change in the
number of active sites for chlorine evolution at that potential.
Makarová et al.78 claimed that this supported the Krishtalik
mechanism, in which an oxidation of the surface is the first step in
the chlorine evolution reaction. The oxygen evolution reaction
was thought to be retarded on the mixed Ru−Co oxide, due to
stabilization of the surface oxygen intermediate by Co.
Two papers concerning ZnII-substituted RuO2 were published
in 2010 and 2011.181,182 The coating was prepared by use of
freeze-drying, with subsequent high temperature annealing and
deposition onto Ti meshes. The coating was characterized by use
of DEMS (in 0.1 M HClO4 and 0.15 M NaCl), X-ray absorption
spectroscopy (XAS), X-ray absorption near-edge spectroscopy
(XANES), extended X-ray absorption fine-structure spectrosco-
py (EXAFS), EDX, scanning electron microscopy (SEM), and
transmission electron microscopy (TEM). XAS and EXAFS data
showed that addition of Zn into the structure obstructed the
stacking of Ru coordinatively unsaturated sites (CUSs). On the
basis of refined EXAFS data, it was proposed that Zn gathered in
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ilmenite defects on the surface, similarly to how Fe impurities in
rutile TiO2 gathers. A graphical representation of rutile and
ilmenite RuO2 and Ru0.9Zn0.1O2 from the article by Petrykin et
al.182 can be seen in Figure 17. The EXAFS function for ilmenite
Figure 17. Graphical representations of rutile and ilmenite RuO2 and
Ru1−xZnxO2 from Petrykin et al.182 It is seen that the ordered
arrangement of Ru CUSs (indicated by adsorbed O in the figure) is
obstructed in the ilmenite structure. Reprinted from ref 182. Copyright
2011 American Chemical Society.
structure Ru1−xZnxO2, based on the structure of ZnTiO3 ilmenite
but with Ti atoms replaced with Ru atoms in the optimization of
the structure, fit the measured Ru-EXAFS function well. Since no
ilmenite structures were indicated in XRD or electron diffraction
patterns, it was thought that they should be present in small
domains distributed in the catalyst crystallites. No information
was given regarding the stability of Zn in the coating, but
Pourbaix diagrams45−47 indicate that ZnII might leach from RuO2
at low pHs.
DEMS data showed that in solutions without chlorides, the
activity of Ru0.9Zn0.1O2 was higher than that of RuO2, based on a
lower onset potential and a higher current density at three
potentials above the onset potential. However, at higher levels of
Zn addition, the activity started to decrease while staying slightly
higher than that of pure RuO2. In DEMS measurements in
solutions containing chlorides, the activity for concurrent oxygen
and chlorine evolution was lower than that of pure RuO2. While a
similar maximum of activity for 10% substitution was observed
also in this case, the current density was lower than that of RuO2
for all degrees of substitution and at all applied potentials.
However, the ZnII-substituted coating had a much improved
selectivity for oxygen evolution and the selectivity increased with
increasing substitution by Zn. The increased selectivity was
rationalized based on the presence of ilmenite structures in the
surface of Ru1−xZnxO2. The formation of peroxo groups, found
to precede the formation of Cl2 on RuO2 according to the work
by Hansen et al.183 (see the following section), is not favorable
since CUSs and bridge sites are distributed randomly on the
ilmenite structures (see Figure 17). However, this blocks the
formation of precursor intermediates for both chlorine and
oxygen evolution. This would conflict with the observation that
the activity for oxygen evolution was improved by substitution
with Zn in chloride-free solutions. Therefore, Petrykin et al.182
thought that oxygen evolution could take place via crystal edge
recombination of surface oxygen intermediates on the ilmenite
structures. The higher activity of Ru0.9Zn0.1O2) in chloride free
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solutions could then be explained by concurrent oxygen
formation via both the peroxo route suggested by Rossmeisl et
al.184 and by recombination of oxygen intermediates on crystal
edges in the ilmenite structures on the surface of the coating. It
was proposed that at x < 0.1, the recombination mechanism
could make up for the lost rutile structure peroxo species
formation.
In two articles published in 2011 and 2012, Chen and co-
workers studied the seawater electrolysis performance of RuO2−
Sb2O5−SnO2 electrodes with and without IrO2 in the coat-
ings.185,186 The Ir-doped coatings were found to be smoother,
and their stability in an accelerated life test was found to be
higher. Current efficiencies were similar for both electrodes.
In 2012, Neodo et al.187 compared the electrolytic behavior of
RuO2−SnO2-coated Ti electrodes with platinized Ti electrodes.
The study was performed in dilute NaCl solutions (0.07 M).
Current efficiencies for active chlorine, O2, chlorate, and
perchlorate were determined. It was found that the current
efficiency for oxygen formation increased with increasing
temperature (tests were performed at 10, 25, and 65 °C),
consistent with a change in activation energy for oxygen-evolving
reactions. Furthermore, the current efficiency for oxygen
formation was slightly higher for the platinized Ti electrode.
In the same year, Spasojević et al.60 presented current
efficiency and stability studies for a RTO electrode with an
overlayer of Pt and rutile IrO2 nanoparticles. The electrode was
prepared on Ti, by first thermally depositing a 10 g/m2 40%
RuO2-60% TiO2 layer, and then thermally depositing a second
layer with a loading of 6 g/m2 from 60% H2PtCl6 and 40% IrCl3
solution. This electrode was compared with an electrode with
only the first RTO layer. The double-layer electrode was found to
exhibit 50 mV higher overpotentials for oxidation of dilute pH 7
NaCl solutions than the more standard RTO electrode.
Furthermore, the double-layer electrode had a much smoother
surface and a significantly lower electrochemically active surface
area. The anodic current efficiency for active chlorine formation
(evaluated based on the gas composition) was some 4% higher
for the double-layer coating than for the single-layer RTO
coating (see Figure 18). By extrapolating to zero hypochlorite
concentration, it could be concluded that OER is the dominating
source for oxygen evolution for both coatings. Furthermore, the
stability, as evaluated by the time before a steep increase in
electrode potential after galvanostatic electrolysis at j = 10 kAm−2
of a 0.5 M H2SO4 solution, was found to be significantly higher
for the double-layer coating than for the single-layer RTO
coating and several times higher than for a DSA electrode of
conventional composition.
In 2013, Xiong et al.188 presented research on DSA coatings
and Sn−Sb-substituted DSA coatings deposited either on Ti or
on TiO2 nanotubes (TNT). In the substituted DSA coating, half
of the Ti content had been replaced by Sn and Sb to obtain
coatings of the nominal structure Ru 0.3Ti0.34Sn0.3Sb0.06O2
(Ru0.33Ti0.4Sn0.18Sb0.08O2 according to EDX). SEM imaging
showed that the coatings deposited on TNT were smooth, in
contrast to the usual mud crack structure of coatings on Ti.
Determination of the voltammetric surface charge for the
coatings, including one coating of overall composition
Ru0.3Ti0.34Sn0.36O2, showed that the Sn−Sb-substituted coating
deposited on TNT had the highest electrochemically active
surface area, slightly higher than that of both RTO deposited on
TNT and Ru0.3Ti0.34Sn0.36O2 deposited on TNT. It was
suggested that the introduction of Sb possibly retards crystallite
growth, yielding a higher electrochemically active surface area.
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Figure 18. Anodic current efficiency for active chlorine (hypochlorous
acid and hypochlorite) production, based on measurements of O2 in the
cell gas, as a function of hypochlorite concentration, from Spasojević et
al.60 ■ are a conventional 40 mol % RuO2-60 mol % TiO2 coating, while
● represent the Pt-IrO2 double-layer coating. Experiments were carried
out in a 30 g/dm3 NaCl solution at 25 °C and a current density of 1
kAm−2. Reprinted from ref 60. Copyright 2012 Elsevier.
Linear sweep voltammetry indicated that the onset potential
difference between Cl2 and O2 evolution was highest for the Sn−
Sb-substituted coating deposited on TNT, followed by the Sn−
Sb-substituted coating deposited on Ti, indicating an enhanced
Cl2/O2 selectivity. The increased Cl2 selectivity is thus a result of
the introduction of the tin−antimony component into the
coating, rather than an effect of the smoother electrode surface.
Since previous studies have found Sn-doping to increase the Cl2
selectivity, it is possible that this component (and not the Sb
component) is the main origin of the selectivity increase.
The work of Krtil and co-workers continued in 2013 and 2014,
now in cooperation with Rossmeisl and co-workers.82,83 The
focus was now on RuO2 doped with small quantities (up to 20
mol %) of Co, Ni, or Zn. In the initial experimental study of Co-
doped RuO2, the structural and electrochemical properties of this
mixed oxide were tested using XRD, XAS, EXAFS, and DEMS
experiments examining both chlorine and oxygen evolution in
0.1 M HClO4 with 0.01 to 0.3 M NaCl. Refinement of the EXAFS
functions indicated that the rutile structure was maintained, with
Co occupying sites diagonally across the unit cell (i.e., with no
neighboring Co CUS). The selectivity for oxygen evolution was
found to increase with increasing concentration of Co in the
coating. The relationship between the selectivity trend and the
structure of the mixed oxide electrocatalyst was examined in the
following study by Halck et al.83 In this study, electrochemical
selectivity measurements on Co- and Ni-doped RuO2 electro-
catalysts were combined with first-principles DFT calculations
(see also the following section) based on EXAFS-refined
structures. The calculations showed that the presence of Ni or
Co dopants serve to activate the bridge site oxygen, allowing it to
accept a hydrogen adsorbate. This modification of the OER
mechanism, which on rutile materials involves the formation of
an *OOH intermediate adsorbed on, for example, Ru alone,
stabilizes the *OOH intermediate. The binding energy of the
*OOH intermediate is determined by, for example, Ru alone on
pure rutile materials, but in these doped materials, it can be tuned
by both the main constituent cation and by the dopant cation.
This stabilization of the *OOH species decreases the overall
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reaction barrier for OER, offering a potential explanation for the
trend in selectivity observed for Co- and Mn-doped RuO2.
Later the same year, Krtil and co-workers also examined Co,
Ni, and Zn-doped IrO2 in an analogous way.189 On the basis of
XRD and EXAFS measurements, it was concluded that Zn and
Co were doped into the cationic positions of the rutile lattice,
while Ni formed clusters embedded in the overall structure. The
concomitant evolution of oxygen and chlorine during electrolysis
was characterized using DEMS in experiments where either the
concentration of NaCl or the anode potential was varied.
Increasing the chloride concentration yielded the expected
increase in selectivity for chlorine evolution. The pure IrO2
material showed a higher selectivity for chlorine evolution than
any of the three-doped materials. Whereas the doped materials
showed decreasing Cl2 selectivity at potentials between 1.55 to
1.65 V versus RHE and the highest NaCl concentration of 0.05
M, the pure material showed 100% Cl2 selectivity up to the
maximum 1.65 V versus RHE potential. At 0.01 M NaCl,
however, all materials showed similar and decreasing Cl2
selectivities of around 10−20% at potentials above approximately
1.6 V versus RHE. At potentials between 1.4 to 1.6 V versus RHE,
the Cl2 selectivity of the pure IrO2 material was significantly
higher than that of the doped materials.
In 2015, Le Luu et al.190 studied the selectivity between Cl2
and O2 evolution in acidic 5 M NaCl solution, comparing IrO2
and RuO2 electrodes. The electrochemically active surface areas
of the electrodes, which were prepared by conventional thermal
decomposition, were determined using CV. The IrO2 electrodes
were found to exhibit a 40% larger active surface area.
Electrochemical measurements at pH 2, 4, and 6 showed that
the current efficiency for chlorine evolution was higher for the
RuO2 electrodes. The current efficiency for both electrodes
decreased as the NaCl concentration was decreased, but the
RuO2 electrode in all cases exhibited a higher current efficiency.
The authors suggested surface oxygen deficiency, XPS d-electron
binding energies, differences in point-of-zero charge, electrical
conductivity, and hydrophilic properties as reasons behind the
increased selectivity of the RuO2 electrodes. However, it is
perhaps more likely that the difference in selectivity was the result
of the significantly lower electrochemically active surface area
which the RuO2 electrodes were found to exhibit (see section
3.1.3 for further discussion).
In 2014, Spasojevic et al.191 presented a new chlorate
production current efficiency model. The chlorate cell was
modeled as either an ideal tubular reactor or an ideal stirred tank
reactor. The model only included losses due to water oxidation
(reaction 11) and anodic chlorate formation (reaction 10). A
DSA and a Ti plate cathode were used as electrodes. Experiments
were performed in a pumped laboratory chlorate setup, using a
conventional small-volume electrolysis cell connected to a larger
holding tank, to get experimental data for the model. The
conditions for the experiments were close to those used in
industrial cells. The model was verified by comparing predicted
and measured inlet and outlet active chlorine concentrations, for
two different inlet concentrations and for electrodes of different
sizes, yielding good agreement. This means that only the loss
reactions of water oxidation and of anodic chlorate formation
were enough to account for current efficiency losses in a
laboratory chlorate production setup.
In the same year, Zeradjanin et al.192 presented experimental
results for the selectivity between chlorine and oxygen evolution
on Ti−Ru−Ir mixed metal oxide electrodes. DEMS was used to
determine the evolved gas composition. The DEMS measure-
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Chemical Reviews
ments were performed at 4 kA/m2, 25 °C, pH = 3 and NaCl
concentrations varied between 1 and 4 M. Scanning electro-
chemical microscopy (SECM) was used to study the impact of
the microstructure of the electrode on the activity and selectivity
for the two reactions. DEMS indicated that oxygen was evolved
even at NaCl concentrations of 3 M, over which the current
efficiency for chlorine evolution reached almost 100%. EDX
measurements found local Ru enrichment after electrochemical
testing. SECM measurements, sensitive only to the evolved Cl2,
found the current distribution over the electrode surface was
inhomogeneous on the micrometer scale. The SECM tip current
(which is due to the reduction of Cl2 formed at the electrode
surface) varied from −500 to −3000 nA, and it was estimated
that the local electrode potential at the most highly active site was
1.41 V versus AgCl/Ag and at the least active site 1.63 V versus
AgCl/Ag. It was thus deemed possible that Cl2 could be formed
at certain active parts of the electrode, only to be reduced at
other, less active, parts. That this was possible despite the high
anodic potentials was explained based on an increase in the Cl2/
Cl− redox potential due to the combination of a high
concentration of formed Cl2 and a low concentration of Cl−
(due to concentration limitations).
In 2015, a purely experimental study on Mg-doped RuO2 was
also published.193 From the group of Krtil, the work employed
many of the same techniques as previously (XRD and EXAFS
measurements for structural studies and DEMS for electro-
chemical studies). The authors concluded that Mg was unevenly
distributed in the overall RuO2 rutile structure, and that the local
environment surrounding the Mg dopants was ilmenite-like,
similar to what was found for Zn-doped RuO2,182 except for the
lowest dopant concentration. The Mg-doped material was found
to exhibit improved Cl2 selectivity. This effect was most
significant for the lowest dopant concentration of 5 mol %.
The authors believed that the structure of this Ru0.95Mg0.05O2
electrode could be most similar to that of undoped RuO2,
indicating that a significant improvement in selectivity could
occur when Ru is replaced by Mg in the rutile lattice. Also higher
concentrations of Mg dopant resulted in higher chlorine
selectivity, but the rationale given was then the broken CUS
stacking in the ilmenite structure.182
In the same year, Macounová et al.84 studied anodic oxidation
of hypochlorite in 0.1 M NaClO4, at pH values of at least 9.5,
using DEMS and a Pt mesh electrode. It was suggested that, at an
anodically polarized Pt electrode, hypochlorite is decomposed in
a radical reaction involving formation of ClO•. Once this species
has formed, it was suggested that it should react with OH− to
form the superoxide radical •OO−, which could either react with
water to form H2O2 and O2 or with HOCl to form O2 and OH·.
The latter radical was suggested to regenerate ClO−, closing a
catalytic loop resulting in conversion of water into O2. On the
basis of the electrical charge transferred per mol of O2 generated
on the Pt electrode, which was lower than expected during OER,
it was suggested that the reaction via ClO•, •OO−, and OH• was
occurring on the electrode. This pathway does not involve
formation of H2O2 and results in accumulation of Cl− in the
system. However, H2O2 was detected, suggesting that also the
reaction between •OO− and water was ongoing. Furthermore,
measurements of chloride concentrations before and after an
experiment did not indicate accumulation of Cl− and none of the
suggested radical species were detected experimentally. Whether
the suggested radical mechanism is relevant for industrial chlor-
alkali or sodium chlorate production using DSAs remains an
open question.
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2.2.5.2. Research Based on First-Principles Modeling
Concerning Chlorine and Oxygen Evolution on Metal Oxides.
The number of articles using first-principles approaches to
understand electrochemical processes has increased substantially
since the turn of the century. The majority of studies performed
so far fall into the group of computational free energy (or ab
initio thermodynamics) studies,194 where only the overall
thermodynamics of the elementary steps of surface reactions
are characterized. The two articles which laid the groundwork for
the first theoretical works on the selectivity between oxygen and
chlorine evolution on metal oxides are those of Rossmeisl et al.184
and Hansen et al.,183 published in 2007 and 2010, respectively.
The first article models oxygen evolution on a few metallic
oxides, while the second one continues the work by also
including chlorine evolution in the model. Both studies
employed the “computational hydrogen electrode” (CHE)
method of Nørskov et al.195 This method allows results from
first-principles calculations in which only adsorption energies of
intermediates on, for example, metal oxide slabs in vacuum are
calculated to be used to describe electrochemical reactions in
solution, by correcting the adsorption energies in vacuum using
standard thermodynamic relationships and reference data. This
significantly simplifies the computational expense and complex-
ity of the modeling, as neither the charge transfer process nor the
effect of polarization on the binding energies of intermediates
have to be modeled explicitly. However, this also means that the
full kinetics of electrochemical processes cannot be captured in
the model. For this to be possible, methods including explicit
polarization of the model surface, such as those of Filhol and
Neurock,196 Otani and Sugino,197 or Rossmeisl et al.198 have to
be used. Nevertheless, the existence of Brønsted−Evans−
Polanyi (BEP) relationships in heterogeneous catalysis and
electrocatalysis,199−201 which show that the activation energy for
an elementary reaction step in general is correlated with the
reaction free energy of the same step, does indicate that the
conclusions from computational free-energy studies give a
qualitatively correct description of the full thermodynamics
and kinetics of surface reactions. Indeed, the successful
predictions of more active electrocatalysts for a variety of
reactions that have resulted from computational free-energy
studies support this conclusion.202,203
The computational free-energy study of Rossmeisl et al.184
used DFT calculations to calculate the stability of intermediates
in the oxygen evolution reaction on the (1 1 0) surface of RuO2,
IrO2, and TiO2. The (110) surface of rutile oxides has two
different sites on which reactions can take place, bridge sites or
CUSs. The nature of the (1 1 0) surface of RuO2 was studied
previously by Over et al.,204 and the importance of CUS for the
activity of oxide materials was conjectured already by, among
others, Mars and van Krevelen.205 A model of the (1 1 0) surface
of RuO2 is found in Figure 19. Rossmeisl et al.184 calculated the
adsorption free energies of all intermediates that could result in
oxygen evolution. The calculations showed that oxygen
evolution on rutile oxides occurs via the following steps, where
HOc, Oc, and HOOc are adsorbates bound to the CUS:
H 2O → HOc + H+ + e− (32)
HOc → Oc + H+ + e− (33)
Oc + H 2O → HOOc + H+ + e− (34)
HOOc → O2 + H+ + e− (35)
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Chemical Reviews
Figure 19. A model of the (1 1 0) surface of RuO2. Ruthenium cations
are green, while oxygen anions are red. The Ru CUSs and the O bridge
sites (binding to Ru bridge sites) are indicated with arrows.
Rossmeisl et al. found oxygen evolution through recombination
of two oxygen atoms (a Volmer−Tafelmechanism) to have a too
high activation energy to be plausible, based on previous DFT
calculations by the same group.199 This means that the traditional
view of OER on rutile oxides as being dependent on O−O
recombination on neighboring Ru CUS67,68 is likely incorrect. In
the case of RuO2 and IrO2, the largest ΔG was found for the third
step in the mechanism above, the decomposition of the second
water molecule. Therefore, for RuO2 or IrO2, the calculated ΔG
for this third step was used as the measure of the overpotential.
The overpotential (ΔGstep 3 − ΔG0 = ΔGstep 2 −1.23 V) was
determined to be 0.37 V for RuO2 and 0.56 V for IrO2. In the case
of TiO2, the step associated with the highest change in free
energy was the second one, formation of O* from HO* on the
surface. The overpotential, based on ΔG for this step, was 1.19 V.
The adsorption energies for the intermediates (Oc, HOc, and
HOOc) for different levels of surface coverage of Oc and HOc on
the surfaces of the oxides were also calculated. A linear
relationship, a scaling relation, was found between the adsorption
energy for O on the surface and the adsorption energy of HO or
HOO. In other words, surfaces that bound O strongly also bound
HO and HOO strongly. This also implied that, for all three oxide
materials treated, the rate of the oxygen evolution reaction is
given by the adsorption energy of oxygen on the surface. The
scaling relation was then applied in the calculation of the free
energy of reaction for the different steps of the reaction. This
yielded a volcano plot, as shown in Figure 20. The volcano plot
qualitatively agreed with experimental data (mainly that
described by Trasatti27,156).
The topic of the present review is the selectivity between
chlorine (or chlorate) formation and oxygen evolution, and thus
all studies on ways to improve the OER on metallic oxide
materials will not be included here. However, it is interesting to
compare the results of the study of Rossmeisl et al.184 with the
later theoretical study of Fang and Liu.206 In 2010, Fang and
Liu206 studied the OER on RuO2 (110), now also calculating the
kinetic barriers for both the Volmer−Tafel pathway (recombi-
nation of two Oc) and a water dissociation pathway, similar to
that suggested by Rossmeisl et al.184 The study represents a step
forward as the calculation of kinetic barriers allows for an explicit
account for both reaction thermodynamics and kinetics. Fang
and Liu206 found, in agreement with the assumption of Rossmeisl
et al.,184 that the Volmer−Tafel pathway was less energetically
favorable than the water dissociation mechanism. A difference
between the mechanisms of Rossmeisl et al.184 and Fang and
Liu206 resided in whether the Obr sites were protonated. In both
cases, a protonated bridge site was found to reduce the
thermodynamic reaction barrier, but Rossmeisl et al.184
concluded that bridge sites will be deprotonated at anodic
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Review
Figure 20. Volcano plot for oxide materials obtained by Rossmeisl et
al.184 The different lines represent the negative of the free energy of
reaction of each step. These lines each limit the reaction rate, based on
the binding energy of oxygen on the surface of the three oxides and the
surface coverage. The most active type (based on surface coverage) of
each oxide is included as ● in the diagram. Reprinted with permission
from ref 184. Copyright 2007 Elsevier.
potentials above 1.4 V versus SHE. However, Fang and Liu206
found that a mixed HObr-Obr phase was slightly more stable than
a fully deprotonated RuO2 surface at potentials up to about 1.6 V
versus SHE, enabling the HObr-stabilized pathway. Interestingly,
in 2014, a type of Obr stabilization was suggested by Halck et al.83
to explain the improved OER activity of Ni- and Co-doped RuO2.
In that case, it was suggested that the dopant cations
predominantly occupied the cationic bridge sites, allowing the
Obr sites to stabilize the HOObr intermediate in the mechanism of
Rossmeisl et al.184
In 2010, Hansen et al.183 applied DFT calculations to treat
chlorine evolution at rutile (1 1 0) surfaces. The transition metal
oxide surfaces considered were IrO2, RuO2, PtO2, and TiO2. It
was found that the bridge sites were covered by oxygen for most
conditions, so that the CUSs were active in OER while, for
example, in the case of RuO2, O-covered Ru CUSs were active for
ClER. The energy of adsorption of the different intermediates
(Clc, OHc, Oc, Oc2, Cl(Oc)2, and ClOc) were then calculated, and
a number of Pourbaix diagrams were determined. The Pourbaix
diagram for RuO2 is reproduced in Figure 21. In each area of the
Pourbaix diagram, the predominant species is the one which has
the most negative free energy of adsorption versus a suitable
reference state (e.g., gas phase Cl2 in the case of the Cl
adsorbate). The Pourbaix diagrams indicated under which
conditions chlorine or oxygen evolution would be more
probable. Furthermore, as was the case for oxygen evolution,184
it was found that the binding energy of the intermediates
(including the Cl-containing species) all scaled with ΔE(Oc)
(the adsorption energy of Oc). Application of the scaling
relations allowed a general phase diagram, where U and ΔE(Oc)
decide which surface state is most stable, to be constructed (see
Figure 22). This phase diagram is correct for all pure rutile oxide
(110) surfaces, as long as all relevant intermediates have been
considered. The diagram was constructed for pH = 0 and aCl− = 1,
to make the diagram relevant at conditions where chlorine gas
forms, but it can be adapted for other conditions as well. Only the
areas which allow formation of stable chloride-containing
intermediates are likely as chlorine evolution sites, since their
stability likely makes the sites abundant on a real electrocatalyst.
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Figure 21. Phase diagram calculated by Hansen et al.183 The only area
(at the pH and potentials included in the diagram) where the surface has
a stable Cl-containing intermediate is at U > 1.55 V at pH < 1.3. Since the
only stable chlorine intermediate is Cl(Oc)2, Hansen et al. believe that
the reaction mechanism that yields Cl2 on real RuO2 surfaces includes
the Cl(Oc)2 intermediate. Reproduced with permission from ref 183.
Copyright 2010 PCCP Owner Societies.
Figure 22. General phase diagram, with the dominant surface
compounds indicated for each predominance area, of Hansen et al.183
The background is a visual representation of the surface and the
compounds, where metal ions are blue, oxygen is red, hydrogen is white
and chlorine is green. Reproduced with permission from ref 183.
Copyright 2010 PCCP Owner Societies.
Three reaction mechanisms, one for each of the stable surface
chloride compounds (ClOc, Cl(Oc)2, or Clc), were proposed
based on the calculated adsorption energies. The effects of
applied potential, pH, chloride concentration, and electrode
material were considered, using the computational hydrogen
electrode (CHE) model,195 when determining under which
conditions each of the three reaction mechanisms would become
spontaneous. The reaction mechanisms are the following
Oc + Cl−(aq) → ClOc + e−
ClOc + Cl−(aq) → Oc + Cl 2(g) + e−
c
for the ClO intermediate,
Cl−(aq) +c → Clc + e−
c − c −
Cl + Cl (aq) → Cl 2(g) + +e
c
for the Cl intermediate, and
− −
Occ c
2 + Cl (aq) → Cl(O )2 + e
Review
Cl(Oc )2 + Cl−(aq) → 2Oc + Cl 2(g) + e− (41)
c c
for the Cl(O )2 intermediate. In these reactions, signifies a bare
CUS and Occ 2 is an adsorbate with molecular oxygen-like
geometry bound to two neighboring CUSs. For each reaction, an
expression for the electrode potential where all steps are
spontaneous, as a function of ΔE(Oc), can be written and
entered into the general Pourbaix diagram (Figure 22). The
resulting diagram is shown in Figure 23, which contains the
Figure 23. General phase diagram, with thick lines indicating the
“volcano” for chlorine evolution activity, taken from Hansen et al.183
Actual oxide materials are indicated as red dots with error bars. Dotted
lines are the lines for the chlorine evolution reaction involving each
chloride surface species (ClOc, Cl(Oc)2, or Clc). The volcano is limited
by the reaction that requires the lowest applied potential to occur, for
each ΔE(Oc). It is also limited by predominance areas where chloride
containing compounds are stable, and therefore common, on the
surface. The horizontal line is the equilibrium potential for chlorine
evolution. It is seen that RuO2 has an activity that is close to the optimal
one in the volcano plot. The blue dashed line is the line for oxygen
evolution. It is seen that the potential necessary for chlorine evolution is
always lower than the potential necessary for oxygen evolution.
Reproduced with permission from ref 183. Copyright 2010 PCCP
Owner Societies.
volcano plots. The volcanoes are limited both by the areas where
chloride-containing intermediates are prevalent and where the
chlorine evolution reaction involving these intermediates is
spontaneous. Hansen et al. conclude their work by supposing,
based on Figure 23, that there is room to find an oxide material
which has an optimal ΔE(Oc), at which the ClER would progress
with a lower applied potential and with a higher selectivity for
chlorine evolution. No similar analysis at conditions for chlorate
production has been published so far.
In 2014, Exner et al.207 performed a complete reevaluation of
the theoretical Pourbaix diagram for chlor-oxy species on the
(110) surface of RuO2. All relevant intermediates were
considered. The Pourbaix diagram produced, shown in Figure
24, mostly agreed with that of Hansen et al.,183 even though
Exner et al. performed their study using the PBE exchange-
correlation functional instead of RPBE. However, a key
(36) difference was that Exner et al.207 did not find that the Occ 2
(oxygen molecule-like) adsorbate was the most stable adsorbate
(37) on the surface of RuO2 at applied potentials and pH below those
required for ClER or OER, instead identifying 2 Oc as the most
stable configuration. Still, the intermediates present at pH and
(38) potentials required for both ClER and OER on RuO2 were found
to be the same in both the study of Exner et al.207 and the study of
(39) Hansen et al.183 Furthermore, the difference in stability between
the Occ c
2 and 2 O was within the errors expected from GGA-level
DFT calculations. Nevertheless, the results of Exner et al.207
(40) agreed with the GGA-level DFT study of Wang et al.,208 who also
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Figure 24. Theoretical Pourbaix diagram for OER and ClER on RuO2
(110) according to Exner et al.207 (excluding solvation effects). The
areas in which ClER and OER can occur are marked in the figure. The
conditions (aCl− = 1 and T = 298 K) are the same as those in Figure 21,
the Pourbaix diagram according to Hansen et al.183 The diagram is
similar to that of Hansen et al.183 in most respects, but the key difference
resides in Exner et al.207 finding that Occ
2 is unstable on the surface and
that both CUSs are covered by Oc at potentials and pH values below
those where ClER and OER can occur. Reprinted with permission from
ref 207. Copyright 2014 Elsevier.
found that the Occ
2 adsorbate on RuO2 should dissociate into 2
Oc. The authors also took a step further by including the effect of
solvation, by use of a continuum solvent model. This had a clear
effect on the Pourbaix diagram and also made the 2 Oc
configuration significantly more stable than the Occ 2 config-
uration. However, the effects of solvation on the adsorption
energies of the different intermediates were found to be much
larger than what was found in the first-principles studies of both
Rossmeisl et al.184 and a later more thorough study by
Siahrostami and Vojvodic.209 The latter calculation, in which
water was considered explicitly, found that the effect of up to 2.5
monolayers water molecules on the adsorption energies of the
OER intermediates (HOc, Oc, and HOOc) is minor for RuO2
(110).209 However, the effects of water molecules on the
adsorption energies of chlorine species was not considered,
warranting future study of the effects of solvation on such species.
Figure 25. Model structures considered by Karlsson et al.64 (a) is a side view of the structure of Ru-doped TiO2, (b) indicates is a side-view of the
structure of the DSA model system, and (c) is a three-dimensional image of the surface formed by the system indicated in (a). In (a and b), the surface
normal is in the z direction, upward in the figure. Reprinted with permission from ref 64. Copyright 2014 Elsevier.
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Exner et al.210 continued the theoretical study the year after, by
considering the effect on the chlorine evolution activity of
applying overlayers of other metal oxides on RuO2 (110). A
significant finding was that deposition of a monolayer of PtO2 on
RuO2 (110) should yield increased activity for ClER. Addition-
ally, in 2015, Exner et al.211 reported results on the effects of
doping another transition metal (either Cr, Ir, Mn, V, Au, Rh, Co,
or Pd) in either the active CUS or the cationic bridge site next to
the active site in RuO2. It was found that either doping Ir into the
active site, or doping Cr, Ir, Mn, Zr, or V into the neighboring
cationic site, could improve the activity for OER. However, in
neither study was the selectivity between OER and ClER
considered.
Later in 2014, two theoretical studies of chlorine evolution
selectivity, a study focusing on RTO by Karlsson et al.64 and a
study focusing on monolayers of TiO2 on RuO2, by Exner et al.,63
were published. The study of Karlsson et al.64 was based on the
previous volcano plot of Hansen et al.183 The adsorption energy
of atomic oxygen on the CUS of TiO2, RuO2, and both Ru-doped
TiO2 and Ti-doped RuO2, as well as on a structure with the same
overall stoichiometry as that of conventional DSA (30% RuO2
and 70% TiO2) were studied (see Figure 25). The adsorption
energy of oxygen had been found by Hansen et al.183 to serve as a
descriptor for both OER and ClER on rutile oxides. The
approach used by Karlsson et al.64 allowed the effect of the local
structure of an electrode (i.e., the position of the dopant relative
to the surface-active CUS) on the electrocatalytic properties of
the mixed oxide to be studied. It was found that while doping
RuO2 with Ti has a relatively minor effect, doping TiO2 with Ru
serves to activate Ti CUSs. These activated Ti sites had oxygen
adsorption descriptor values in the range optimal for highly
selective and active chlorine evolution. If the dopant Ru atom was
situated in the CUS, the descriptor value was the same as for pure
RuO2, indicating that the properties of Ru were maintained even
in the mixed oxide. These results are shown in Figure 26. The
study indicated that the improvement in ClER selectivity that
RTO electrodes exhibit, when compared with electrodes of pure
RuO2, is related to activation of surface Ti atoms by nearby Ru
dopant atoms. The study also indicated that even electrodes with
monolayers of TiO2 on RuO2 should exhibit improved selectivity
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Figure 26. Trends in oxygen adsorption energy descriptor values as the position of the dopant atom is changed, indicating an activation of Ti sites by
dopant Ru atoms. This could explain the improved selectivity for ClER that RTO electrodes exhibit. Reprinted with permission from ref 64. Copyright
2014 Elsevier.

Figure 27. Results of doping rutile TiO2 with other dopants, in either the CUS (left side) or the bridge site (right side). The vertical lines correspond to
descriptor values for pure TiO2 (thin green), optimal selectivity and activity for ClER (thick red), maximum OER activity (thick blue), and for pure
RuO2 (black). Reprinted with permission from ref 65. Copyright 2015 Elsevier.

for ClER, while maintaining a similarly high activity as pure
RuO2. Interestingly, the study of Exner et al.,63 building upon the
results from their previous study,207 also concluded that a
monolayer of TiO2 on RuO2 should optimize the selectivity for
ClER. Thus, the two studies were in basic agreement in spite of
being based on two independent sets of calculated surface
3008
Pourbaix diagrams and volcano plots and used two different
exchange-correlation functionals and assumptions related to
effect of the electrolyte on the reaction. The reason for the
improvement in selectivity is the decrease in Oc adsorption
energy that occurs when applying a monolayer of TiO2 on
RuO2.63,64
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Figure 28. Pourbaix diagram for Ru in concentrated chloride solution, from Loučka.214 Original caption reads: “Potential-pH diagram for the Ru−
H2O−Cl−, system at 25 °C in a solution of 264 g/dm3 NaCl. Activities of other ions are 1 × 10−6 M”. Reprinted with permission from ref 214. Copyright
1990 Springer Science and Business Media.
In a publication from 2015, Karlsson et al.65 expanded their
theoretical studies of doped rutile TiO2.65 The method was
analogous to the one used in Karlsson et al.,64 but now included
38 dopants, mainly transition metals. A general study of the effect
of the dopant either as active site, or located close to a Ti site, was
performed, suggesting a number of possible dopants that would
activate TiO2 either for OER or ClER. The results are shown in
Figure 27. Arsenic was suggested as a dopant that would result in
maximal ClER activity regardless of position. The dopants Bi, Co,
Ir, Mn, Pd, Ru, or V were predicted to result in a doped oxide
with optimal ClER selectivity and activity, while doping with Mo
or Re was predicted to result in an oxide with high OER activity.
However, it was found that the local structure of the active site is
key to achieving these effects. The properties of some ternary
oxides were also studied, finding that the combined effect of two
dopants located next to a Ti-active site was close to the average
effect of the dopant in their respective binary Ti oxides.
Furthermore, it was found that under OER conditions, but not
under ClER conditions, there is a driving force for most dopants
to segregate toward the active CUS. One of the highest driving
forces was noted for Ru-doped TiO2, indicating that the
deactivation of Ru-based DSAs might occur through segregation
of Ru toward the active site, followed by formation of RuO4.212
However, the process after segregation toward the active site
(e.g., formation of RuO4) was not studied in the paper.
2.3. Electrochemical Studies Concerning the Relationship
between Selectivity and Stability
There are many studies of Ru metal oxide degradation and
decomposition. A complete discussion of this literature would
necessitate a full review. Therefore, in this section a selection of
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works that have clarified the relationship between selectivity for
Cl2 or ClO−3 and O2 and the stability of the electrode material will
be considered. As will be seen, the decomposition of RTO
electrodes is connected with the removal of Ru from the
electrode in reactions related to the OER. For this reason, studies
of both Ru metal, RuO2, and mixed Ru oxides will be considered
in this section. The discussion will start from the Pourbaix
diagram for Ru, which was published in 1966,213 and the review
will then discuss papers published from 1966 and onward.
The Pourbaix diagram for Ru213 indicates the regions of
stability of the pure metal (see Figure 28 for the Pourbaix
diagram for Ru in chloride solutions of Loučka214). The
conversion from Ru, to Ru(OH)3, RuO2, and finally volatile
RuO4 at potentials above 1.5 V versus SHE at pH 0 is central to
the understanding of the stability of Ru and its oxides. The
potential required for conversion of RuO2 to form RuO4
decreases with increasing pH, until the final product of the
oxidation of RuO2 becomes RuO−4 and then RuO2− 4 at pH > 9−
12.
Around the same time, Llopis and Vázquez215 and Llopis et
al. studied the corrosion of Ru. In the first study, anodic and
216
cathodic charging curves for Ru in HClO4 and HCl solutions
were measured. On the basis of these results, the electrode
potentials where oxidation of Ru to form Ru2O3, RuO2, and
RuO4 occurs were found. In Llopis et al.216 a radiochemical
technique, which allowed for the detection of very small amounts
of dissolved Ru, was applied to study the potentiostatic corrosion
of Ru in 2 or 4 M HCl, at 50 °C. The technique was based on
detecting a radioactive Ru isotope, which is formed after neutron
irradiation of the electrodes in a nuclear reactor. The potential in
the electrochemical measurements was kept constant at a
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number of potentials in the range from 0.95 to 1.25 V versus SCE
during more than 10 h. The Coulombic corrosion yield (the
percentage of the current resulting in the corrosion of Ru)
decreased sharply as the potential was increased above 1.0 V
versus SCE. At these potentials, a passivating Ru surface oxide
grows on the metal, decreasing the rate of Ru cation transport
through the film. At potentials approaching 1.4 V, formation of
RuO4 started.213,216
In 1973 and 1976, Gorodetskii et al.217 and Pecherskii et al.,218
respectively, presented further work on the anodic behavior of
Ru. The studies examined the anodic dissolution behavior of Ru
in the potential range from 0.8 to 1.4 V versus SHE. A
radiochemical technique was again used to determine the
amount of dissolved Ru. In the first study, the anodic behavior of
the electrode was studied in both 3 M HClO4, where oxygen
evolution is the dominating anodic process, and in 3 M HCl,
where chlorine evolution is the dominating anodic process. In the
former solution, the total current density as well as the rate of Ru
dissolution increased as the potential was increased above 1.2 V
versus SHE. The slopes for both processes were equal, at about
30 mV per decade in either corrosion rate, measured in g/cm2 s
or current density. The authors concluded that the rate of the
OER was connected with the rate of Ru dissolution, possibly due
to the existence of shared surface intermediates. However, in 3 M
HCl at the same potentials, although the rate of Ru dissolution
did increase with increasing electrode potential, the slope of the
Ru dissolution rate was significantly lower than that of the total
current density. It appeared that during chlorine evolution,
increasing current density resulted in a decreasing current
efficiency for Ru dissolution. Furthermore, Gorodetskii et al.
studied the effect of increasing Cl− concentration from 0.01 to 1
M at an anode potential of 1.4 V versus SHE, finding a 4-fold
decrease in the Ru dissolution rate together with an increase in
overall current density by a factor of 300. The authors suggested
that electrodes, specifically RTO, with increased selectivity for
the ClER thus should also exhibit improved corrosion resistance.
Pecherskii et al.218 performed a deeper study of the effect of pH
on the Ru dissolution rate. The overall anodic current density
and the Ru dissolution rate were determined in solutions of
HClO4, H2SO4, or HCl at a constant ionic strength of 3 M and
acid concentrations from 0.01 to 3 M. In the sulfate and
perchlorate solutions, both the overall current density and the Ru
dissolution rate increased with increasing pH, again indicating
the connection between Ru dissolution and the OER. In the HCl
solution, the overall current density decreased slightly with
increasing pH, and the Ru dissolution rate increased.
In 1974, Veselovskaya et al.219 published a study of the anodic
behavior of metallic Ru including measurements conducted in a
number of solutions, including 300 g/dm3 NaCl at pH 3. All
measurements were performed at 80 °C. The authors noted that
the regions of Ru dissolution at lower anodic potentials (below 1
V vs SHE) are followed by regions of lower Ru dissolution rate
(due to the formation of hydrous RuO2) at potentials above 1 V
versus SHE. The Tafel slope for electrolysis in the chloride
solution at these higher potentials coincided with the typical 40
mV/dec Tafel slope for ClER on a DSA electrode, supporting the
idea that a hydrous RuO2 layer covers the surface under these
conditions. The paper is perhaps most notable due to its
introduction of the “critical anode potential”, Ecr, here given as
approximately 1.45 V versus SHE, as the potential where
conversion of RuO2 into volatile RuO4 becomes favorable.
In 1977, Iwakura et al.220 presented research on possible
mechanisms for OER and for Ru dissolution from Ru, suggesting
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that Ru oxides form on the surface of the electrode during OER
and that ruthenates are released into the solution.
In 1978, Uzbekov et al.221 presented a radiochemical study of
decomposition of RTO electrodes prepared using thermal
decomposition to achieve the standard composition of 30%
RuO2 and 70% TiO2. The electrodes were polarized anodically in
5 M NaCl, kept at pH 7, at several potentials during 10 to 80 h.
Initially, measurements were conducted at an anodic current
density of 2 kA/m2 and an anode potential of 1.34 V versus SHE.
The authors found that the corrosion rate, as measured by the
radioactivity of dissolved Ru in the solution measured during the
experiment, decreased from more than 10 × 10−6 g/cm2 h to
around 10 × 10−7 g/cm2 h over the first few hours and then
steadily decreased further over time. Although the solution was
continually stirred, the radioactivity measured when draining the
cell after the end of the experiment was higher than that
measured in the circulating solution. This indicated to the
authors that a part (10 to 40%) of the degradation of the anode
took place by detachment of solid particles from the surface. Ru
was also dissolved in the electrolyte, indicated by the deposition
of Ru on the counter electrodes and released into the gas phase as
RuO4. It was estimated that 5−15% of the Ru was released into
solution and that 10% was released into the gas phase.
Furthermore, it was noted that the corrosion rate increased 2−
5 times upon current interruption of even a few seconds. After
several hours of electrolysis, the corrosion rate again decreased to
a low value. Finally, the authors examined corrosion rates at
several different anodic potentials. A significant increase in the
corrosion rate was noted at potentials above 1.3 V versus SHE.
Increasing the anode potential increased the rate of corrosion,
but the specific rate (per mole Cl2 produced) decreased.
In the same year, Kokoulina et al.222 presented polarization
measurements on conventional RTO anodes measured in 1 N
H2SO4 at different pH in the range of 0.5−13 and temperatures
between 20 and 80 °C. An increase in the Tafel slope was noted
at 1.5 V versus RHE at 20 °C and 1.4 V versus RHE at 80 °C. The
potential at which this bend occurs was termed the critical
potential (a term first introduced by Veselovskaya et al.219) at
which the change in Tafel slope might signal an increase in
corrosion rate due to formation of RuO4. Increasing the pH
decreased the critical potential, which would agree with the
Pourbaix diagram.213
Also in 1978, results based on anodic polarization measure-
ments conducted in buffered sulfuric acid solutions using pure
RuO2/Ti electrodes was presented by Bondar and Kalinovskii.223
The authors determined the critical current density (the current
density at the critical potential,219,222 at which the change in Tafel
slope of the polarization curve occurs) as a function of pH at 20
and 60 °C. This indicated the current densities which should not
be exceeded for RuO2 electrodes, at various pH values. As an
example, the critical current density for oxygen evolution on
RuO2 in sulfuric acid at pH 0 was approximately 1 kA/m2.
In 1979, Gorodetskii et al.224 examined the effect of current
density on the corrosion rate of DSA. Again, electrodes with the
standard 30:70 Ru:Ti composition were prepared by thermal
decomposition. Electrolysis was performed at 87 °C in 5 M NaCl
at a pH of around 2, and the corrosion rate of Ru was determined
using a radiochemical method. Results for one measurement
carried out at a current density of 2 kA/m2, giving an anode
potential of 1.33 V versus SHE, was shown. As in Uzbekov et
al.,221 the corrosion rate decreased slowly over several hours and
increased for a short time after shutdowns when the electrode
had been removed from the solution. It was estimated that 14%
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of the corrosion was due to detachment of particles and that 12%
was due to formation of gas phase RuO4 (apparently being
produced at an anode potential below 1.4 V vs SHE). A
comparison between the corrosion rate of pure RuO2 and of the
RTO electrodes indicated that the corrosion rate of the pure Ru
oxide was 1 order of magnitude higher than that of the RTO
material. The total corrosion rate of the RTO anode was also
shown as a function of the current density, once more indicating
that the rate of RTO degradation increases with increasing
current density but that the specific (per mol Cl2 produced)
corrosion rate decreased with increasing current density.
In 1980, Barral et al.225 published results on the deactivation of
RuO2 and RTO during OER in 1 M H2SO4 at 40 °C. The
deactivation was determined indirectly, by measuring the time
required to reach an anodic potential of 4 V versus the saturated
mercury sulfate electrode. Interestingly, it was found that pure
RuO2 electrodes had a longer lifetime than RTO electrodes at 10
kA/m2. However, the electrodes had been prepared by thermal
oxidation at 500 °C for only 10 min with no final prolonged
heating. This is significantly shorter than the conventional time
of about 1 h for the final oxidation of the coating. Indeed, Gerrard
and Steele11 note that for pure RuO2, about 5 min is needed to
achieve a stable value for the electrical conductivity, but an oxide
coating of 30:70 Ru:Ti needed more than 1 h to reach a stable
conductivity. Therefore, it is possible that the results of Barral et
al.225 disagree with the majority of other work since their mixed
oxide coatings were not sufficiently stabilized during preparation.
Still, they noted a trend for the pH dependence of the
deactivation of pure RuO2 that seems to contradict that of
Bondar and Kalinovskii.223 Barral et al. found that the lifetime
was essentially constant in the range of pH from 0 to 13 at a
current density of 5 kA/m2. At higher pH, the lifetime increased
significantly. The authors suggested that the reason for the
constancy in lifetime is related to the difference between bulk and
anode surface pH. Because of the ongoing OER, the pH at the
anode is lower than in the bulk. Only at very large pH values (e.g.,
−
a bulk pH > 11.5 at a current density of 100 Am 2), does this
change, they argue. Nevertheless, the fact that the corrosion rate
was not determined directly by measurement of the corrosion
products limits the utility of the study. Determining the lifetime
based only on an increase in anode potential means that the
deciding factor for the lifetime might be the formation of a
nonconductive interlayer between the Ti substrate and the
coating, rather than decomposition of the coating itself. It is
therefore difficult to disentangle the various mechanisms of
deactivation when using only the potential as the deciding factor.
Still, it will be indicated much later in the works of Tilak et al.226
and Eberil’ et al.227 that the appearance of an insulating TiO2
layer might not be an important mechanism for DSA
deactivation.
In 1981, Gorodetskii et al.151 published a study of the effect of
pH in the range from 0 to 5 on both the corrosion rate and on the
rate of the OER on DSA. Some corrosion measurements were
also carried out at lower pH values. Again, standard DSA
electrodes were studied at 87 °C in 300 g/dm3 or 100 g/dm3
NaCl. Once more, electrolysis was carried out at a current density
of 2 kA/m2. The same radiochemical method as used previously
was employed. However, the O2 formed was now quantified by
GC. Corrosion measurements were started after the system had
reached steady state (after about 200 h), and measurements with
different pH and NaCl concentration were then performed.
Again, about 14% of the corrosion was the result of detachment
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of particles, independent of the pH value of the solution. The
results indicated that the connection between the OER and the
rate of corrosion is not necessarily as simple as was previously
indicated. At pH below zero, the corrosion rate was said to
decrease significantly when increasing the pH up to 0. In the pH
range from 0 to 3, the rate of corrosion of the DSA was essentially
constant at a value of about 1 × 10−8 g/cm2 h in the concentrated
NaCl solution. The corrosion rate was somewhat higher in the
100 g/dm3 NaCl solution, here showing a minimum at about pH
1, and then increased with increasing pH for both concentrations.
However, the OER rate showed a clear increase when increasing
the pH from 0 to 2, and then again when increasing the pH from
4 to 5, in the 300 g/dm3 NaCl solution. Increases in the OER rate
was also noted when increasing the pH from 2 to 4 in the 100 g/
dm3 NaCl solution. The results thus indicate a region of maximal
stability around pH 0 to 3 in the 300 g/dm3 NaCl solution at
industrially relevant current densities. Furthermore, the total
percentage of Ru released as gaseous RuO4 was determined as a
function of pH at both NaCl concentrations. In both cases, at a
−
current density of 2 kAm 2 and anode potential of 1.33 V versus
SHE, the percentage released as RuO4 increased significantly
when increasing the pH, from about 10% at pH 0−1 to about
60% at pH 4 in the 100 g/dm3 NaCl solution and 40% at pH 5 in
the 300 g/dm3 NaCl solution.
The work of Pecherskii et al.67 from 1982 has already been
described in section 2.2.3, but the corrosion results will here be
discussed in more detail. Again, the study in question examined
the properties of three types of electrodeposited coatings on Ti
substrates. The first type consisted of Ru only, the second of Ru
which was then heat-treated for several hours, and a third which
was treated the same way as the second but was then polarized
anodically in sulfate solution until the electrode potential
increased sharply. The first electrode could thus be considered
to consist of a Ru hydroxide or metal, the second of RuO2, and
the third of RuO2 mixed with TiO2. Auger electron spectroscopy
was performed, indicating that Ti was present in the surface layer
of the third type of electrode but not in the second type. The
same trend as was noted for the oxygen production rate was seen
also for the corrosion rate. Electrodes of the third type not only
produced less oxygen but also exhibited significantly lower
corrosion rates than the second type. The corrosion rate at 1 kA/
m2 was about 1 × 10−5 g/cm2 h for the first type of electrode,
about 1 × 10−6 g/cm2 h for the second type of electrode, and
about 1 × 10−9 g/cm2 h for the third type of electrode. The pH
dependence of the corrosion was also studied. Electrodes of the
third type exhibited the behavior seen by Gorodetskii et al.,151 of
essentially constant corrosion rate up to pH 3, followed by an
increase in corrosion rate. Corrosion rates increased with anode
potential at potentials positive of 1.3 V versus SHE for all three
types of electrode. The slopes of the increase in corrosion rate
with electrode potential was similar to the Tafel slope of the
oxygen evolution reaction.
In 1982, Burke et al.228 presented results for OER using RuO2.
As in the study of Barral et al.,225 the lifetime was estimated based
only on a steep increase in anode potential. Nevertheless, it was
again seen that increasing current density results in a significant
decrease in lifetime in both acid and base. The lifetime of the
anode decreased significantly with acid concentration in H2SO4
solutions, while in alkaline solution of NaOH the lifetime
increased significantly with increase in concentration above 1 M
NaOH. Mechanisms for both OER and Ru corrosion were
suggested.
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In 1983, Denton et al.154 presented results from radiochemical
experiments using RTO electrodes used for chlorine evolution in
either membrane or diaphragm cells, finding a direct relationship
between the rate of Ru loss from the coating and the oxygen
percentage in the cell gas. It was also claimed that increased pH of
the anolyte resulted in increased anode wear, that increased cell
temperature or current density resulted in increased anode wear,
and that increased chloride concentration was associated with a
decrease in anode wear rate.
In 1984, Kötz et al.212 contributed a detailed study of the
corrosion of RuO2, in which CV was combined with in situ
differential reflectance spectroscopy, finding that during OER in
H2SO4, RuO4 is the only corrosion product. Furthermore, the
release of RuO4 started at the same potential as the OER. This
study clearly shows the mechanistic link between the OER and
the corrosion of RuO2.
In 1985, Uzbekov and Klement’eva229 published a study
employing radioactive isotopes of Ru and Ti in the salts used to
prepared a DSA coating, so that both Ru and Ti corrosion
products (regardless of oxidation state) could be detected during
electrolysis. The experiments were conventional chlorine
evolution experiments, conducted in 5 M NaCl and 90 °C,
with a current density of 2 kA/m2. The effect of pH, in the range
from 0 to 11, was studied. The electrode potential was essentially
constant at about 1.33 to 1.38 V versus SHE in all experiments,
indicating the constancy of the activity of the electrode during
corrosion, over time, and at all pH values. It was found that there
are clear differences in the dissolution of Ru and Ti from RTO
electrodes. During a long-term electrolysis experiment at pH 2,
during the first 30 h, removal of Ru from the coating was the
dominating process. Although the ratio between Ru and Ti were
0.45 to 1 in the coating, during the first 30 h, the selectivity for
dissolution of Ru over Ti decreased from values between 4 and 2
toward equal dissolution. After 30 h, the selectivity was close to 1,
indicating equal rates of Ru and Ti dissolution. This means that
during electrolysis, the surface layers of RTO lose Ru and
become more concentrated in Ti. Measurements of the steady
state corrosion rate of Ti and Ru as a function of pH were also
performed. At low pH (around and just under 0), the corrosion
rates of Ru and Ti were both elevated, but the selectivity for Ru
dissolution was less than 1, indicating a higher rate of Ti
dissolution. As the pH then was increased, the dissolution rate of
Ti decreased, reaching stable values above 2 and up to a pH of
5.4. One measurement was apparently then made at pH 11.3, at
which the rate of dissolution of Ti had increased significantly.
The dissolution rate of Ru showed a minimum at about pH 2
then increased. The resulting trend in the selectivity for
dissolution of RuIV versus TiIV is an increase from less than 1
at the lowest pH, increasing to almost 9 at pH 5.4. Due to the
clear increase in Ti removal rate at pH 11, the selectivity
decreased to 4. Aside from the lowest pH values below pH 2, the
dissolution rate of Ru was up to 9 times higher than the
dissolution rate of Ti. It was proposed that both Ti and Ru
dissolve due to formation of soluble metal chlorides at the lowest
pH values, while Ru removal could also occur due to the
electrochemical conversion of RuO2 to RuO4 at higher pH
values. At high pH values, Ti would be converted into soluble Ti
oxyhydroxides, in agreement with the Pourbaix diagram.230
Further work from the same group appeared in 1985, this time
focusing on the corrosion of RTO during sodium chlorate
production.231 DSA were used, prepared using the conventional
thermochemical method and with the standard 30:70 Ru:Ti
composition. Measurements were conducted using an anodic
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current density of 2 kA/m2 at 60 °C. Corrosion rate
measurements were conducted using the same radiochemical
method as previously applied. The effect on the anode potential
and corrosion rate of changing the electrolyte concentration
from 5 M NaCl to 6 M NaClO3 was examined, finding a clear
increase in anode potential as the NaCl concentration was
decreased. At the same time, the corrosion rate increased. The
mechanism involved is likely the same as has been seen in several
other studies, that the rate of OER increases significantly when
the Cl− concentration decreases, resulting in an increased
corrosion rate.
In 1986, Kötz and Stucki232 presented results on stability of
mixed Ir−Ru rutile oxide coatings. While the corrosion rate was
only determined based on the standard accelerated lifetime test
(as determined by an increase in the anode potential) in H2SO4,
the authors indicated that mixing RuO2 and IrO2 results in
stabilization of the material, although at the cost of a decrease in
activity for OER.
In the same year, Kolotyrkin233 presented a review of the
relationship between corrosion and kinetics for anodes. For
RuO2 and DSA, the results essentially mirror the discussion thus
far: for RuO2 both the rate of OER and rate of corrosion decrease
in a similar way as a chloride solution is acidified. For DSA, the
dissolution rate exhibits a minimum in the pH range 1−3, as seen
by Gorodetskii et al.151 and Uzbekov and Klement’eva.229
In 1987, Lyons and Burke234 presented a study of the
stabilization of RuO2 by addition of SnO2 in which the lifetime
was evaluated by a standard accelerated lifetime test during OER
in concentrated NaOH at 80 °C.
In 1989, Zhinkin et al.163 presented results on the corrosion
behavior of standard DSAs, focusing on current densities
exceeding 2 kA/m2 and several temperatures in the range from
70 to 90 °C. The pH range was 2 to 5. Measurements were
conducted in 300 g/dm3 NaCl. The same radiochemical method
as had been used in several previous Soviet studies was again
applied. The authors analyzed the gas phase and solid phase
particulate losses of Ru, finding that the gas phase loss made up
20−40% of the total loss and that the solid particulate losses were
less than 1% of the total corrosion. A clear increase in the
corrosion rate was noted as the pH was increased above 4. This
increase was concomitant with a clear increase in the percentage
of O2 in the off-gas as the pH was increased. The connection
between Ru corrosion and the rate of the OER was thus again
seen. Increasing the current density from 5 to 10 kA/m2 also
increased the corrosion rate but less significantly. There was a
clear effect of temperature on the corrosion rate, with higher
corrosion rates noted at 90 °C than at 70 °C. Still, the effect of
increasing the pH from 2 to 5 was more significant than both the
effect of current density and of temperature.
In 1990, Manli and Yanxi235 presented results on corrosion of
DSA, prepared using the conventional method, during
electrolysis at 10 kA/m2 in saturated NaCl solution at 80 °C.
The corrosion rate was evaluated based on when the electrode
passivated, resulting in a high anode potential. Secondary ion
mass spectrometry (SIMS) results indicated that Ru is being
selectively removed from the surface layer of the electrode during
electrolysis. This agrees with the results found by Uzbekov and
Klement’eva.229
In 1990, Loučka214 presented a Pourbaix diagram for Ru in
concentrated chloride solution, as relevant for chlor-alkali
production. The main detail important to notice from this
Pourbaix diagram is the supposed existence of soluble Ru
chlorides at low pH and anodic potentials. Interestingly, the
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diagram of Loučka only includes a very small pH range of RuO2
stability above the Cl2/Cl− equilibrium potential, between pH
2.3 and 3.0. It was pointed out that this pH range roughly agrees
with that found to give the highest stability of DSA electrodes.151
In accordance with the Pourbaix diagram of Loučka,214 at lower
pH, formation of soluble Ru chlorides was predicted to become
favorable, while at higher pH, formation of (per)ruthenates
becomes favorable.
In 1998, Hardee and Kus236 reported on studies of passivation
of DSAs through formation of an interlayer between the coating
and the substrate. Electrodes deactivated either in the industrial
setting or by using accelerated aging regimes exhibited changes in
impedance phase angle at low frequencies (around 1 Hz) as well
as in high-frequency regions (around 1000 Hz). These changes
were attributed to formation of a TiO2 interlayer, although no
direct detection of this interlayer was presented. A DSA coating
with a number of TiO2 layers deposited on the surface showed
changes only in the low-frequency region. Using XPS and atomic
emission spectroscopy (AES), removal of Ru in the outer layers
of DSA after deactivation was noted. This was not deemed to be
the reason for the deactivation, as such removal was also noted
for electrodes that still functioned with lower anode potentials.
Furthermore, a pure IrO2 electrode was deactivated in a sulfate
electrolyte, after which changes particularly at high frequencies
were noted. Also on the basis of this observation, it was
concluded that formation of an interlayer was the mechanism of
deactivation, as a significant amount of IrO2 still remained on the
electrode.
In 2001, Tilak et al.226 presented an electrochemical
impedance spectroscopy (EIS study of the deactivation of DSA
electrodes. An accelerated aging process was employed, wherein
the potential was changed from 1.35 to −0.32 V versus SCE at 60
Hz. These results support those reported several times before,
that during electrolysis, corrosion results in the selective removal
of Ru from the surface layers of the electrode. Tafel, CV and EIS
results indicated that deactivated electrodes (as determined by
the standard passivation test of an increase in anode potential)
behave similarly to fresh electrodes prepared with a 5% Ru
content. Furthermore, the authors note that fresh electrodes with
5% Ru behave the same way in the low frequency region as aged
30% Ru electrodes, indicating that the deactivation process of
DSA electrodes is due to removal of Ru from the surface, rather
than formation of an insulating TiO2 layer between the Ti
substrate and the coating.
In the same year, Eberil’ et al.227 presented results on aging of
DSA electrodes under standard chlorate production conditions.
It was seen that the anode lifetime increased with the amount of
Ru in the electrode, indicating the relationship between anode
lifetime and the dissolution of Ru from the coating. Furthermore,
as Tilak et al.226 did in the same year, Eberil’ et al. also performed
tests to examine the proposed deactivation mechanism of
formation of a TiO2 layer between the coating and support. It was
seen that a slight improvement in anode lifetime resulted from
the insertion of a Pt sublayer between the support and the
coating. However, introducing Pt into the coating itself resulted
in a significantly improved lifetime. This also indicates that the
reason for DSA deactivation is the removal of Ru from the
coating, rather than the formation of a nonconductive interlayer.
Also in 2001, Bommaraju et al.237 presented results on
deactivation of DSA electrodes. Much of the work was presented
in Tilak et al.,226 but the authors also showed SIMS results
agreeing with those of Manli and Yanxi.235
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Review
In 2003, Cornell et al.174 studied the critical anode potential
using commercial DSA for chlorate electrolysis. It is known from
industrial practice that during the first months of industrial
operation in a chlorate cell, the anode potential decreases
simultaneously with an increase in chlorate selectivity. From
laboratory studies, it was concluded that a new, relatively
compact DSA operates at a potential higher than Ecr. When in
production, the real surface area of the electrode increases
(probably due to corrosion of the coating) and the electrode
potential thus decreases to a stable value at, or below, Ecr. The
critical current density, at which the anode operates at Ecr,
depends on factors such as the chloride concentration. Later
work by Nylén and Cornell238 concluded that process conditions
in industrial chlorate production leads to a higher risk of
exceeding Ecr than the conditions in the chlor-alkali process,
where the chloride concentration is higher, pH lower, operating
temperature higher, and there is no chromate in the electrolyte.
In 2004, Gajić-Krstajić et al.239 presented the application of a
spectrophotometric method to determine low concentrations of
dissolved Ru species on the corrosion of RuO2 deposited on Ti.
The method was based on the catalytic action of Ru on the As−
Ce redox reaction in sulfuric acid. This method is of a comparable
sensitivity (1 × 10−9 M Ru) as the radiochemical methods
employed in several studies mentioned previously in this section.
The experiments were conducted in 0.5 M H2SO4 solution, at a
current density of 5 kA/m2. The service life, determined in the
standard way, increased exponentially with decreasing applied
current density (and thus with decreasing rate of OER). By
performing measurements at several potentials in the range from
1.52 to 1.67 V versus SCE, a constant dependence of the current
density for oxygen evolution, jO2, on the current density for Ru
dissolution, jRu, was found
jRu
= 8 × 10−6
jO (42)
2
In 2014 and 2015, a number of papers of Mayrhofer and co-
workers240−243 were published. In all papers, an in situ method to
measure transition metal degradation products was applied, in
which an electrochemical flow cell is coupled to an inductively
coupled plasma-mass spectrometer (ICP-MS).244 First, Zer-
adjanin et al.242 reported results on the connection between
RuO2−SnO2 mixed oxide surface morphology and OER activity
and stability. Electrodes with two types of surface morphology,
either cracked or smooth, were prepared using thermal oxidation
of sol−gel-synthesized precursors onto Ti substrates. The usage
of more dilute solutions of the Ru and Sn precursors in
isopropanol, together with repeated coating application cycles,
enable the formation of smooth surfaces. Electrolysis was
performed in a 0.1 M H2SO4 electrolyte at 25 °C. The sensitivity
of the ICP-MS instrument, allowing detection of nanograms of
Ru per square centimeter of electrode area, is such that
dissolution of Ru from the RuO2 component of the mixed
coating during cycling of the potential in the range from 1 to 1.6
V versus RHE could be measured. For an industrial catalyst, the
current density is normally kept constant, apart from at
shutdown, so these results are not directly comparable to a
steady-state dissolution rate during industrial electrolysis.
Furthermore, it is unclear what the ratio between RuIV and
SnIV components in the mixed coatings were. Still, it was found
that the dissolution rate of Ru increased as the potential was
increased over the reversible potential for OER of about 1.25 V
versus RHE, and became especially high above 1.45 V versus
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Table 4. Effects of Process Conditions on the Selectivity between Oxygen and Chlorine or Chlorate Formation Identified in
Literaturea
selectivity for oxygen
factor evolution refs comment
low pH (chlorine production) decreased 41,151,154, and 163 effect of pH is complex
pH for chlorate conditions optimum pH value exists 56, 67, 141, 162, and 173
higher cCl− decreased 66, 70, 75, 76, 121, 128, 154, 155, 162, 170, and 173 especially if cCl− < 100 g/dm3
increased j decreased 54, 56, 57, 62, 66, 69, 70, 75, 131, 154, and 162−164 increase at low cCl−170
higher cHOCl increased 54, 55, 57, 71, 116, 121, 130, 162, and 170
higher cNaClO3 decreased 6, 54, 162, and 173 related to viscosity?
increased cell temperature increased 54, 57, 74, 154, 162, and 164
anode potential (chlorate production) optimal anode potential exists 74 and 164
higher anode (changed geometry) decreased 57
larger holding volume decreased 55 and 62 current efficiency not directly measured
irradiance increase 6 and 94
a
The table focuses on trends described in concentrated NaCl solutions. This table gives a simplified view of the factors involved. The trends are
described in more detail in section 3.1.1.

Table 5. Effects of the Electrolyte Composition on the Selectivity between Oxygen and Chlorine or Chlorate Formation Identified
in Literaturea
selectivity for oxygen
factor evolution refs comment/contradictory results
F− possible decrease 137, 144, and 173 137
found no effect
PO3−
4 increase 137, 157, and 173 not with Pd71
137
SO2−
4 increase 138 and 157 found no effect
NO−3 increase 137
Na2Cr2O7 increase? 137 no effect,92,95,162 slight decrease173
Al no effect peroxide,96 oxide92
Ag increase oxide sources cited in ref 93 salt92 has no effect
As increase metal94
Ce no effect salt92
Co increase salt/ionic,86,92,94,97,100 metal,94 oxide93,95−97,105,106 and sources
in,93 unspecified168
Cr no effect salt,92 oxide95
Cu increase salt/ionic,90,97,103 metal,94 oxide,94,96,97,105 unspecified168 less active than Co, Ni
Fe increase? metal,94 oxide sources in93,96 salt,86,92 metal,93 oxide92,95 or unspecified form168
has no effect
Hg increase? oxide96
Ir increase salt/ionic,92,101,102 oxide,95 unspecified168
Mn increase? oxide sources in93,96 salt,86 metal93 has no effect
Mo no effect oxide92
Ni increase salt/ionic,103 metal,94 oxide95,96,105 and sources in93 unspecified168
Pt no effect unspecified168
Sn increase? metal94
RTO, Pt/Ir no effect particulates159 Ir increase according to ref 62
Ru no effect salt/ionic,92,95 oxide,92 unspecified168
Rh no effect salt/ionic95
U, W, Pd, Os, no effect oxide95
Tl, V
Sb, Pb, Zn, Cd no effect metal94
a
Several of the sources are studies of decomposition of bleach (sources cited in refs 93−95) or hypochlorous acid solutions (refs 90, 92, 93, 96, 97,
100, 102, 103, 105, and 106, which differ significantly from the electrolytes used in industrial chlor-alkali or sodium chlorate production. This table
gives a simplified view of the factors involved. Sources cited in ref 93 are published before year 1900. Each factor is discussed in more detail in section
3.1.2.

RHE, where the conversion of RuO2 to RuO4 can start.
Dissolution was also noted at potentials below 1.23 V versus
RHE, during cycling between 1.23 to 0 V versus RHE. It was
found that the crack-free coating experienced a higher rate of
decomposition in all potential ranges studied. Cherevko et al.240
then reported results on dissolution of metallic electrodes of Ru,
Ir, Rh, Pd, Pt, and Au, finding a clear correlation between a low
Tafel slope for OER and a high dissolution rate. Shortly
3014
thereafter, Cherevko et al.241 reported on the dissolution of IrO2
films, prepared using spin-coating onto Ti substrates and
conventional thermal oxidation, during OER in 1 M HClO4. It
was found that the stability of the films increased with increasing
calcination temperature, in the range from 250 to 550 °C, except
for electrodes prepared at 350 °C which was found to be the least
stable. During constant-current experiments, performed at 20 A/
m2, it was found that dissolution of both Ir and Ti occurred, with
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Table 6. Effects of the Anode Composition on the Selectivity between Oxygen and Chlorine or Chlorate Formation Identified in
Literaturea
selectivity for oxygen
factor evolution refs comment
modified composition decrease 36, 158, 162, 167, 169, and several modified coatings exist
173
increased surface area increase 69 related to decrease in jloc?
larger coating crystallite decrease 78 related to increase in jloc?
particle size
higher oxide loading increase 75
less Ru in RTO coating decrease 67, 68, 75, 139, 154, 161, same effect as decreased j0 for reaction 11? Connected to increased chlorate
and 171 formation36,141,150,154
decreased j0 for reaction 11 decrease 69, 150, 159, and 167 but reaction 11 not only source
IrO2 substitution decrease? 74 doped into RTO; dorrosion products might increase selectivity in practice
Co substitution decrease? 78 doped into RuO2;82,83,189 saw increase
SnO2 substitution decrease 69, 71, 147, and 172 doped into RuO269,172 or together with Pd71
HfO2 substitution increase 69 doped into RuO2
Zn substitution increases 181, 182, and 189 doped into RuO2
Ni substitution decrease 77 doped into RuO2
Mg substitution decrease 193 doped into RuO2
Fe substitution decrease? 180 doped into RuO2, high Cl2 selectivity in Ar-saturated solutions
overlayer material decrease 60 overlayer of Pt mixed with IrO2
support material possible effect 8 and 179
a
The table is limited to oxides based on RuO2. “Modified composition” signifies studies where details about the composition or physical properties
of the electrodes were not given. Each effect is described in more detail in section 3.1.3. The table only includes studies where selectivity was
measured directly [i.e., not only by comparing differences in electrochemical behavior (e.g. Tafel slopes) in solutions with and without chloride ions].

the dissolution rates of both components decreasing with time. 3. DISCUSSION

In 2015, Reier et al.243 reported a combined OER activity and
stability study of Ir−Ni oxides (rutile-like at Ni contents below
21% and of a layered brucite-like structure at higher Ni contents)
in 0.1 M HClO4. It was found that coatings containing 67% Ni
(as measured by inductively coupled plasma atomic emission
spectroscopy) were most active for OER, which was related to a
higher active surface area of this composition. However, the Ir
dissolution rate of the coating with this composition was 34 times
higher than the dissolution rate of pure IrO2, even at a low
current density of 10 A/m2.
Also in 2014, Frydendal et al.245 presented a study where
electrochemical quartz crystal microbalance (EQCM) and ICP-
MS measurements were combined to monitor corrosion of rutile
RuO2 and amorphous MnOx. The electrodes had been prepared
using sputter deposition on Au or EQCM Au quartz crystals.
Constant potential, at 1.8 V versus RHE for RuO2 and 1.8 and 1.9
V versus RHE for MnOx, and constant current, at 300 A/m2 for
RuO2 and 200 A/m2 for MnOx, measurements were carried out
in either 0.05 M H2SO4 in the case of RuO2 or 1 M KOH in the
case of MnOx. Constant mass loss rates were noted in both types
of measurement, which were carried out for 2 h. These electrodes
thus did not exhibit any stabilization during electrolysis, in
contrast with what has been found for both pure and mixed rutile
oxides in other studies. A year later, Frydendal et al.246 found a
that the stability of MnO2 coatings for OER in 0.05 M H2SO4
could be improved by codeposition of other transition metals. A
combination of theoretical and experimental results indicated
that mixed MnO2−TiO2 coatings, prepared by cosputtering,
exhibited an improved stability at the cost of a slight decrease in
activity.
3.1. Factors Affecting the Selectivity between Chlorine and
Oxygen Evolution in the Production of Chlorine and
Chlorate
The research literature portrays some general trends in the
selectivity between chlorine and oxygen evolution. Some factors
have been examined in several articles and can be considered
well-understood. Others have been reported only once, or, in
some cases, with different authors finding different results.
Sections 3.1.1, 3.1.2, and 3.1.3 will discuss the selectivity from the
point of view of process, electrolyte, and anode factors, while
section 3.2 will discuss the relative importance of the different
reactions that can lead to formation of oxygen. Tables 4, 5, and 6
summarize the different factors, related to process conditions,
electrolyte contents, and electrode composition, respectively,
that have been found in literature, as well as the literature
references for each factor. The purpose of the discussion is to
highlight the trends that have been reported, as well as to point to
factors that have been reported to have opposing effects in
different studies. The discussion focuses specifically on the trends
that are relevant for chlor-alkali and sodium chlorate formation
and is thus limited to concentrated NaCl solutions. In some
cases, the trends in dilute solutions are different, as shown by, for
example, the study of Czarnetzki and Janssen.170 Finally, the
connection between anode stability and anode selectivity will be
discussed in section 3.3.
3.1.1. Influence of Process Conditions. There are two
factors that, at first, seem relatively straightforward to consider:
the thermodynamics of the two main competing reactions 2 and
11 (written again below) and the effect of the current density on
the selectivity.
The equilibrium between chloride ions and chlorine is
described by
1
Cl− ⇌ Cl 2 + e−
2 (2)

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For the OER, the equilibrium can be written as
1
H 2O ⇌ O2 + 2H+ + 2e−
2 (11)
It is obvious that the latter equilibrium is dependent on the pH of
the solution. The reversible potential of the first reaction is also
influenced by the chloride concentration, as will be discussed.
Oxygen evolution is increasingly unfavorable as the pH
decreases, keeping other conditions (e.g., current density)
unchanged, due to the pH dependence of the electrode potential
for oxygen evolution, unlike that for chlorine evolution.41,151,165
Only in chlor-alkali processes with HCl addition can oxygen
evolving reactions be ruled out almost completely.41,151 This
would imply that oxygen evolution is a more severe problem in
chlorate processes, in which the pH of the process solution bulk
is higher (pH 5.5−7). However, Trasatti and Lodi165 point out
that if water oxidation occurs at the anode, the water oxidation
reaction 11 acidifies the electrolyte close to the anode. Even if no
water oxidation occurs, the formation of hypochlorous acid,
reaction 4, acidifies the electrolyte. It is therefore considered
reasonable that, even in processes where the bulk pH is high, the
pH at the anode surface is in the acidic range. However, this
reasoning is not sufficient to actually rule out any of the oxygen-
forming reactions, since the pH is probably not sufficiently acidic
at the anode surface to fully prevent water oxidation. Indeed,
several studies54,56,67,162,165 have shown clear correlations
between pH and the oxygen evolution rate. The disagreement
between different studies of the influence of pH also highlights an
important difficulty in studying pH effects in chlorate electro-
lytes. Hammar and Wranglén54 did not find any influence of pH
on the oxygen evolution rate between pH = 6.5 and pH = 11.
However, Jaksić56 later found that the optimal pH for chlorate
production should be in the pH = 6−6.5 range. Jaksić believed
this disagreement to be the result of improper handling of the
buffering effect of carbonates from absorption of CO2 from the
air. Moreover, Hardee and Mitchell162 only found an influence of
pH at pH > 7, and no effect of pH on the rate of oxygen evolution
in the range of pH = 5−7. However, Hammar and Wranglén54
used graphite anodes. Nevertheless, chlorate electrolytes are
buffered both by dichromate species and hypochlorite species,
and several reactions in the process involve H+, making the study
of pH effects in chlorate electrolytes somewhat difficult.
Eq 2 also shows the influence of chloride concentration.
Several studies and reports66,70,75,76,121,128,154,155,162,170,173 note
that increasing concentrations of Cl− increase current efficiencies
for chlorine or chlorate production and decrease the selectivity
for oxygen evolution. However, this might not only be related to
the decrease in the reversible electrode potential for chlorine
evolution but also due to increased rates of mass transfer of
chloride to the anode surface as well as competitive adsorption of
chlorides on the surface of the anode, preventing anodic oxygen-
evolving reactions.66,165
The next fundamental factor that needs to be considered is
that of the current density on the selectivity. It is simple to
consider the effect of current density on two separate reactions,
such as reactions 2 and 11. If Tafel expressions are written for
both reactions, with the respective subscripts m and p for the
main (ClER) and the parasitic (OER) reaction, the following
expressions are obtained
ηm = A m + bm × log(j) (43)
for the main reaction and
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Review
ηp = A p + bp × log(j) (44)
for the parasitic reaction. If the Tafel slope b for the main reaction
is lower than the Tafel slope of the parasitic one, it is clearly seen
that the overpotential for the parasitic reaction increases more
quickly with the current density. This is the case for the
competition between the chlorine evolution and water oxidation
reactions. This simplified treatment assumes that the reactions
take place on separate active sites, an assumption that might be
questionable if the two reactions compete for the same active
sites. It also neglects the effects of both mass transport of
reactants to the anode surface, and of the formation of
bubbles,247,248 on the local concentrations of reactants at the
anode.247,248 Both of these effects will become important at the
high current densities employed industrially. As several different
reactions yield oxygen, especially under chlorate production
conditions, and since the effect of competitive adsorption is
important, this Tafel treatment of the influence of current density
gives a limited understanding of the effect of current density. A
more quantitative variant of this type of analysis is that by Tilak et
al.,69 as given by eqs 26−28.
Nevertheless, studies performed so far have found that
increasing current densities decrease the selectivity for oxygen
evolution (refs 54, 56, 57, 62, 66, 69, 70, 75, 162, 164, and 165).
This could indirectly imply that the most important anodic side-
reactions that yield oxygen have higher Tafel slopes than the
chlorine evolution reaction. However, this effect is likely tangled
with the effect of a decreasing pH at the anode surface with
increasing current density. The effect of current density is
probably that exhibited also by electrodes with decreased surface
area,69,78,79 which yields an increase in local current density.
Moreover, it is important to also recall that Eberil et al.74 found a
maximum in chlorate formation efficiency close to the critical
anode potential (for RuO4 formation), meaning that increased
current density increases the selectivity only up to a certain point
at chlorate conditions. Although several studies have seen effects
of current density on the selectivity, further study of this factor
under chlorate conditions is warranted.
The effect of increasing concentration of hypochlorite species
is related to the decomposition of hypochlorite species to form
oxygen (refs 54, 55, 57, 71, 116, 121, 130, 162, and 170). This
reaction will be discussed in more detail in section 3.2.
An effect of chlorate concentration, due to competitive
adsorption of chlorate on the electrode, on the oxygen evolution
side reaction has been shown.54,162 However, Hammar and
Wranglén54 made estimations that showed that the increase in
electrolyte viscosity that chlorate brings could be the main reason
for the decrease in oxygen evolution rate. This increase in
viscosity would result in a decrease in the mass transfer rate of
hypochlorite to the anode surface and a decrease in oxygen
produced through decomposition of hypochlorite.
The effect of temperature is probably complicated to elucidate
in a detailed way, since it has effects on both thermodynamics and
kinetics. This is true especially at chlorate cell conditions, since
several reactions are involved in the main reactions yielding
chlorate and the side reactions yielding oxygen. Several studies
have found that increasing temperatures yield increased rates of
oxygen evolution at chlorate conditions.54,57,162,164 This has been
suggested to be related to increasing rate of diffusion of
hypochlorite species to the anode surface at increasing
temperatures54 and to increased rates of anodic and homoge-
neous decomposition of hypochlorite species at higher temper-
atures.162 Eberil et al.74 found a complicated temperature
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dependence under chlorate conditions, at which the temperature
had different effects at anode potentials on different sides of Ecr.
Furthermore, the critical anode potential was associated with a
maximum in current efficiency for chlorate production and a
minimum in oxygen evolution current efficiency. This shows that
it is imperative that further study of the selectivity issue is
performed with equipment that allows precise correction of iR
drop, since the critical anode potential is reached only at high
applied current densities. Using such equipment makes it
possible to determine the effect of Ecr clearly.
The effects of anode geometry that Wanngård57 found is likely
related both to a decrease in local current density, due to the
increased geometric surface area of the higher electrode blades,
and a change in the concentration gradient in the electrolyte flow
across the blade for the higher type of blade (the “lower” blades
were 0.333 m high and 0.379 m wide, while the higher blades
were 0.8 m high and 0.3 m wide).
Increasing the external holding volume has been found to
increase the charge yield for chlorate formation.55,62 This is likely
related to the increased residence time for the electrolyte
afforded by a larger holding volume, enabling a higher conversion
in the homogeneous chlorate formation reaction.
3.1.2. Influence of Additions and Contaminants in the
Electrolyte. There have been comparatively few studies on the
effect of contaminants and additions to the electrolyte on the
oxygen evolution side reaction. In some cases, the species that
have been studied have been found to have opposing effects. The
great majority of studies are performed on systems that differ
greatly from industrial chlorate or chlor-alkali conditions (e.g., on
bleach or hypochlorous acid solutions), again indicating the
importance of performing further studies under conditions
similar to those used industrially.
Fluoride was found by both Fukuda et al.144 and Baolian and
Wenhua173 (based on the overall chlorate cell current efficiency)
to decrease the rate of oxygen evolution. On the other hand,
Jaksić et al.137 found essentially no influence of fluoride on the
oxygen evolution rate under chlorate conditions. The difference
between the study of Fukuda et al. and Jaksić et al. might be
possible to rationalize based on the differences between the
electrolytes studied (Jaksić et al. studied a chlorate electrolyte
while Fukuda et al. studied an acidic electrolyte), if the results of
Baolian and Wenhua were ignored. Still, the results might be
reconciled by noting that the effect seen by Baolian and Wenhua
was significantly smaller (about 1%) at 200 g/dm3 NaCl than at
50 g/dm3 NaCl. Furthermore, the measurements of Jaksić et al.
were performed with a NaCl concentration of 310 g/dm3.
However, Wanngård168 notes that F− needs to be avoided since it
also has the effect of deactivating the anode. Kelsall and
Robbins145 have predicted, based on thermodynamic calcu-
lations, that F− addition should result in dissolution of TiO2 to
−
form TiF2− 6 . Still, it might be concluded that the effect of F
addition on selectivity essentially is that of competitive
adsorption on the electrode surface, reducing the rate of oxygen
formation in dilute electrolytes, but also possibly competing with
the adsorption of Cl−.
Phosphates have been found to increase the rate of oxygen
evolution.137,157,173 In contrast, the PdSn2-containing coating
devised by Spasojević et al. made use of the adsorption of
phosphates on Pd to prevent oxygen evolution. Sulfates have
been reported to decrease the efficiency of chlorine evolu-
tion.157,165 Kazarinov and Andreev143 concluded that both
phosphates and sulfates adsorb strongly on RTO, displacing
chlorides. However, Jaksić et al.137 saw no effect on oxygen
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Review
evolution under chlorate process conditions, but they found that
addition of nitrates resulted in increased oxygen evolution rates.
The effects of all of these species seem to be related to
competitive adsorption on the anode surface, and these effects
might become less important at high chloride concentrations.
Dichromate has been reported to both increase137 and
decrease173 the selectivity for oxygen evolution. Interestingly
enough, other studies have seen only minor effects.162 All three
studies were performed at chlorate process conditions. Studies of
dilute hypochlorous acid solutions have not found any effect of
dichromate on the selectivity for oxygen evolution.92,95
A small number of metals, salts, and oxides of the elements
have been shown to exhibit catalytic effects on hypochlorite
decomposition. These are Co, Ni, Ir, and Cu. The effects of Fe,
Mn, Hg, and Sn are less clear, with some (especially very old
studies) reporting acceleration of hypochlorite decomposition.
Connick and Hurley99 suggested that ruthenate ions might
catalytically decompose hypochlorite ions (eqs 16 and 17).
However, considering that the window of stability for the
ruthenate ion is at high pH values of about 13−14 and potentials
less than 1 V versus SHE,214 the prevalence of this reaction as an
explanation for the oxygen evolution side reaction in either the
chlor-alkali or the chlorate process is deemed quite low. No
studies have been performed to compare the effects of different
elements under industrial chlorate conditions. Some materials
have not been studied since the 1800s, and a more general study
of the heterogeneous activities of different metals, and possibly
combinations of different metals, could serve to settle these
issues. An important aspect to consider in such studies is the
speciation of the metallic compounds, as it is possible that salts
that are added will be oxidized to form metallic oxides active for
decomposition of hypochlorite.92 It is clear that the influence of
many different possible electrolyte contaminants and additives
has not yet been examined fully under industrial conditions.
3.1.3. Influence of the Anode Structure and Compo-
sition. The effect of the anode properties on the oxygen
evolution side reaction has been studied by many. Unfortunately,
many studies lack important details regarding the properties of
the anode. For example, proprietary coatings of unnamed
composition that lead to lower oxygen evolution rates have been
used in several experimental studies.36,162,167,173 Most studies
have focused only on the selectivity between oxygen and chlorine
formation under chlor-alkali conditions. An exception is the
study of a modified coating with decreased selectivity for oxygen
evolution at chlorate conditions performed by Spasojević et
al.71−73 Additionally, detailed characterization, such as of the
actual composition of the final coating has usually not been
reported in literature, even if studies on proprietary anodes are
excluded. This is a problem, especially since the preparation of
anodes used for research usually is a manual process where the
coating is, for example, brushed onto a substrate. Furthermore, it
is known that the deposition efficiency of different compounds
can vary widely depending on which precursors and which
preparation conditions are used.249 This lack of detailed materials
characterization could explain some of the conflicting results in
literature. This does not necessarily imply that the studies are
poorly done, since many of the studies were performed when
characterization methods that are common today, such as SEM,
XRD, XPS, and atomic force microscopy (AFM), had not
entered general use. Furthermore, the usage of other X-ray
spectroscopies (e.g., XAS), which allow a deeper understanding
of factors such as the local structure, were not as accessible as
today. Nevertheless, even studies conducted today often do not
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make use of the possibilities afforded by modern characterization
methods.
All the same, some overall factors can be identified. One effect,
that of the active surface area of the electrode, is likely primarily
connected to its effect on the local current density, as discussed in
section 3.1.1. While a large active surface area is obviously
important to achieve a high utilization of the coating, an
increased electrode surface area is also associated with a
decreased local current density and resulting increased selectivity
for oxygen evolution. An increased electrode active surface area is
often achieved by decreasing the size of the particles making up
the coating. The selectivity effects from doping RuO2 or RTO
that are found in many studies are most likely due to this effect.
Arikawa et al.75 found that the selectivity is affected by the RTO
loading on the anode, with increasing loading resulting in
increased selectivity for OER. This effect is possibly also
connected to an increase in active surface area, especially since
Arikawa et al.75 studied electrodes with comparatively low
loading.
The atomic-level electronic effect of using different combina-
tions of cations in mixed oxide electrodes (e.g., the combination
of Ru and Ti in Beer-type DSA) is more complex. Certain trends
that are valid for Ru-based oxides might not apply for, for
example, Ir-based oxides, as has been shown by, for example,
Kuznetsova et al.189 (pure IrO2 being more Cl2-selective than any
of the doped oxides considered, while Ti or Sn-doped RuO2
oxides are more Cl2-selective than pure RuO2). Even if one
focuses only on “Ru-based” electrodes, the electronic structure
and therefore also the electrochemical properties of materials
containing low concentrations of RuIV are significantly different
from materials containing high RuIV concentrations.64 However,
it is important to consider the cautionary observation of
Trasatti156 that the selectivity of different anode materials does
not generally exhibit varying selectivities for chlorine evolution
versus oxygen evolution. Materials highly active for chlorine
evolution are usually also highly active for oxygen evolution. A
first fundamental understanding for this behavior has been
provided by the DFT studies of Hansen et al.,183 showing that
ΔE(Oc) determines the activity for both chlorine and oxygen
evolution reactions on several metallic oxide materials. The
fundamental factor that governs the selectivity is the descriptor
value placing each material in a certain part of the activity volcano
relevant for a certain set of linearly scaling reactions.183,199,250
Nevertheless, while the same factor governs both reactions, there
is some room for optimizing the selectivity for chlorine evolution
over oxygen evolution even on conventional rutile oxide
electrodes, as has been explored theoretically63−65 and as
experimental studies also indicate (see Table 6).
The effect of altering the relative amounts of Ru and Ti in RTO
coatings will be discussed first. A decrease in the Ru content has
consistently been shown to result in decreased selectivity for
oxygen evolution (refs 67, 68, 75, 159, 161, 165, 167, and 171).
Similar trends regarding Ru content and OER selectivity have
been noted for Ru−Sn oxide electrodes.172 This might be
another aspect on the observation that an increased overpotential
for oxygen evolution of an anode material (i.e., a decreased j0 for
reaction 11) has been linked to a decreased selectivity for oxygen
evolution in chloride-containing solutions.69,150,159,167 These
factors have been related to mechanistic differences between the
oxygen-evolving reaction and the chlorine-evolving reaction. It
has been proposed that both reactions need Ru sites to progress,
but that the oxygen-evolving reaction needs two Ru adjacent
sites.67,68 Here an interesting new insight can be gained from the
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DFT studies by Rossmeisl et al.,251 Hansen et al.,183 and of Exner
et al.207,210 In these studies, the importance of adjacent CUSs on
the anode surface were considered. First, it has been found that it
is not only the metal CUSs themselves (found by Hansen et al.183
to be the active sites on weaker-binding oxides) but also O-
covered CUSs183,207 that are active sites for both ClER and OER.
Second, it has been found that the mechanism for OER does not
necessarily involve O−O recombination,183,207 thus not being
dependent on paired CUSs. The finding that the adsorption
energy of O on CUSs on the surface is the deciding factor for
both chlorine and oxygen evolution activity might at first be hard
to reconcile with experimental studies that show that materials
with increased overpotential for oxygen evolution also show an
increase in selectivity for chlorine evolution. This can be
understood by studying Figure 23, which shows that there are
ΔE(Oc) values which allow decreased selectivity for oxygen
evolution, compared with RuO2, with maintained low over-
potential for chlorine evolution.64 Indeed, Karlsson et al.64 have
built upon the results of Hansen et al.183 to conclude that the
increased selectivity exhibited by RTO electrodes likely is caused
by an electronic activation of Ti by Ru. The effect on selectivity
from changing the relative amounts of Ru and Ti in the binary
coating is thus not a matter of separation of active Ru sites67,68
but related to the fundamental electronic properties of the mixed
oxide coating and its effects on the activity of Ti sites.
Much work has been devoted to improving the selectivity by
using other materials than RTO, or by doping RTO. Studies
which examine the effect of IrO2 have found it to have a lower
selectivity for oxygen evolution than pure RuO2,70 and Ir-doped
RTO have also shown decreased O2 selectivities.74,165 At the
same time, the dissolution of Ir compounds from the anode
might yield an increase in oxygen evolution in the industrial
setting due to catalysis of homogeneous hypochlorite decom-
position. However, RuO2−Sb2O5−SnO2 electrodes have been
found to exhibit similar selectivities in dilute solutions regardless
of Ir doping.185,186 PdO has been reported to be a stable and
highly selective ClER anode.148 Shlyapnikov141 found that Pt and
RuO2 exhibited higher current efficiencies for chlorate formation
than graphite, lead oxide, or manganese oxide anodes. On the
other hand, platinized Ti has been reported to have a lower
chlorine evolution efficiency than RuO2−SnO2-coated Ti.187
Co3O4 and related compounds have also been reported to have a
lower selectivity for oxygen evolution.78,140,147,165 However, also
in this case, Co corroded from the surface of the electrode might
yield increased oxygen evolution due to homogeneous
hypochlorite decomposition. Combining Ru with Sn in oxide
electrodes has been found to have generally similar effects as the
combination of Ru and Ti in RTO electrodes.172 However,
studies have found that Ru−Sn oxide electrodes are less selective
for OER than RTO electrodes.69,188 Tilak et al.69 noted similar
effects when combining Ru and Hf in mixed oxide electrodes.
Doping RuO2 with Zn, Ni, or Mg have also been found to yield
lower selectivities for oxygen evolution, in comparison with those
of pure RuO2.77,181,182,193
The insights from DFT63−65,183,184,207,210 are also interesting
when discussing the recent study of Spasojević et al.60 They
found that Pt-IrO2 overlayer coatings on RTO show decreased
selectivity for OER as a side reaction in both chlor-alkali and
chlorate electrolytes.60 The overlayer electrodes exhibited a
significantly lower electrochemically active surface area (in-
creased local current densities), which is likely part of the reason
for the improvement in selectivity (see section 3.1.1). However,
the work might also be reflective of the same fundamental effects
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discussed in several theoretical works.63−65,183,210 Doping TiO2
with Ru changes the descriptor value of the doped oxide toward
the part of the volcano optimal for chlorine evolution,64 and it is
possible that Spasojević et al.60 is noting a similar effect when
mixing IrO2 with Pt. PtO2 and IrO2 are located on opposite sides
of the volcano tip optimal for selective and active chlorine
evolution.65,183,210
Some have found effects on the selectivity for chlorine
evolution based of the support material.179 This influence is also
hinted at in the original Beer patents.8,22
Less attention has been devoted to the possibility that the
electrode might heterogeneously catalyze the decomposition of
hypochlorous acid species. While certain compounds (such as
Co) are generally not considered as electrode components, due
to their well-known catalytic effect as electrolyte contaminants
(see the previous section), there are fewer studies of
heterogeneous hypochlorite decomposition. When it comes to
metallic and oxidic materials (see Table 5), Co, Ni, Ir, and Cu are
materials which have been found to catalyze the bulk
decomposition. Still, Kotowski and Busse159 did not find that
Pt/Ir particles were active for hypochlorite decomposition,
despite the Ir content. Kuhn and Mortimer136 did see indications
that RuO2 heterogeneously decomposes hypochlorite in a Cl2-
saturated solution, while Kokoulina and Bunakova155 and
Kotowski and Busse159 found no effect when RTO electrodes
were used. To get complete certainty in this matter, studies
where both RuO2, RTO and doped RTO or RuO2 electrodes are
tested under the same conditions, with the same equipment and
methods, are likely required.
Finally, some studies36,74,141,150,154 indicate that for the chlor-
alkali process, it might not be enough to simply optimize anodes
for minimal oxygen selectivity, as this is then associated with
increased rates of chlorate production. This might partly be a pH
effect, as the OER decreases pH at the anode and therefore also
decreases the rate of chlorate formation.154 A reduced rate of the
OER with a low-oxygen anode might thus require additional
anolyte acidification,36 although this might yield an increase in
cell voltage due to decreased conductivity of the cation-
permeable membrane.2 Whether the effect could be associated
with changes in activity or selectivity for electrochemical chlorate
formation on the surface of the anode is yet to be determined.
3.2. Extent of Oxygen Evolution from Different Reactions
We now change focus to discuss the relative importance of the
different reactions thought to result in oxygen production. Only a
few studies have attempted to quantify the five most probable
oxygen-evolving reactions, reactions 10, 11, 12, 14, and 23, that
are present in varying degrees at chlorate and chlor-alkali
conditions. Due to the low pH at the anode surface, anodic
hydroxide oxidation, reaction 12, is generally assumed to be an
unimportant source of oxygen. The importance of the other
reactions is less clear.
The influence of the first reaction, the anodic chlorate
formation reaction, is controversial. Studying chlorate process
conditions, Hammar and Wranglén,54 Ibl and Vogt,62 and Jaksić
et al.55 thought it was the most important oxygen-evolving
reaction. Recent modeling studies make the same assumption.191
These models describe the overall current efficiency of the
process well. However, Hardee and Mitchell162 seem to think it
has a small influence. Studying a membrane cell chlor-alkali
system, Kotowski and Busse159 thought it could make up
anywhere from 20% to 60% of the oxygen evolved in the system.
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Finally, Tilak and Chen5 believe it has an insignificant influence
under chlorate production conditions.
The influence of the water oxidation reaction, reaction 11, is
also uncertain. It is known that this reaction dominates at low
chloride concentrations and low electrode potentials,54 but at
actual industrial current densities and concentrations, the
influence is unclear. Kotowski and Busse159 think it makes up a
significant amount of the oxygen evolved in the membrane chlor-
alkali process, while Hardee and Mitchell162 and Spasojević et
al.71,72 find it to be insignificant at chlorate conditions. Tilak and
Chen5 believe it is the only important source of oxygen at
chlorate conditions. The studies of Spasojević et al.71 and
Spasojević et al.60 indicate that a majority of the oxygen is formed
through water oxidation (see Figures 8 and 18) in dilute
solutions with similar hypochlorite concentrations as in chlorate
production. It seems that the rate of water oxidation is
significantly lower in concentrated chlorate solutions with
chromate buffering,57,71,72,162 making it a less important source
of oxygen than the decomposition of hypochlorite in sodium
chlorate production. The water oxidation reaction is likely
kinetically controlled, while the oxidation of hypochlorite species
is diffusion controlled,60,71,72 at least at the current densities
applied in industrial chlor-alkali and chlorate production.
The homogeneous decomposition of hypochlorous acid to
form oxygen gas, reaction 14, is well-known. The catalytic effect
of different electrolyte contaminants on this reaction has been
discussed in section 3.1.2. Hypochlorite does decompose to form
oxygen even in the absence of any catalyst, although the rate is
significantly lower than that of chlorate production.89,91,92 There
are indications that both reactions share an intermediate.89,92
While measures to control the electrolyte pH can be applied to
prevent the formation of hypochlorous acid species in the chlor-
alkali process,36 this is obviously not a possible recourse in the
chlorate process. Further research is needed to elucidate the
connection between oxygen and chlorate formation, so that
measures might be found to influence the selectivity in the
direction of chlorate formation. More studies of this reaction are
needed to fully understand its importance in chlorate production.
Still, it can be said that purification of the electrolyte to remove
metallic contaminants should minimize the importance of
homogeneous hypochlorite decomposition in both chlor-alkali
and sodium chlorate production.
Finally, the influence of anodic decomposition of hypochlorite
species, resulting in formation of oxygen but not chlorate, is
controversial. Kotowski and Busse159 have suggested one
mechanism for this reaction, eq 23. Older studies consider the
anodic decomposition of hypochlorite a possible source of
oxygen,116,121,130 but most studies performed before 1980 seem
to conclude that it is a minor source of oxygen. Several studies
performed since the end of the 1980s have shown it to be an
important factor for oxygen evolution in chlorate sys-
tems.54,57,159,162,177 The fact that the anodic decomposition of
hypochlorite was not thought to be an important side reaction at
chlorate process conditions until the second half of the 1980s
shows that indirect methods used to measure current efficiency
for chlorate production are insufficient to give a full under-
standing of the process. It took studies where the proper
detection of the oxygen evolved was performed to find that other
reactions might also be important sources of oxygen. Never-
theless, some still do not agree that anodic decomposition of
hypochlorite species is important,5,167 warranting further studies
of how hypochlorite is actually decomposed at the anode. The
relative importance of heterogeneous chemical decomposition
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Chemical Reviews
and electrocatalytic decomposition of hypochlorite species on,
for example, the RTO electrode surface, is also an open question.
Furthermore, in studies where the influence of anodic
hypochlorite decomposition has been considered under
chlorate-process-like conditions, some studies find that the rate
of oxygen evolution shows characteristics of mass transport
limitations (even on graphite),54 while others find it shows
characteristics of kinetic limitations (on RTO).57 Studies have
found that the reaction could make up as much as 40−80% of the
overall oxygen production, even in membrane chlor-alkali
cells.159 Wanngård57 found that if the homogeneous decom-
position reaction can be avoided (reaction 14), the anodic
decomposition of hypochlorite (the reaction where hypochlorite
is decomposed electrochemically on the anode surface, proposed
by Kotowski and Busse159 to proceed via reaction 23) is the main
contributor to the oxygen evolved under chlorate conditions.57
However, the actual mechanism of the decomposition, whether
hypochlorous acid or hypochlorite is the main reactant, is still not
known. Physics-based macroscopic modeling has suggested that
hypochlorite (OCl−) is the most probable reactant,176 while
estimations based on a probable low pH at the anode surface
suggest that HOCl should be the reactant.170 The recent study of
Macounová et al.,84 suggesting the possibility of radical reactions
involving ClO· during oxidation of hypochlorite, also indicates
the need for further research on the topic.
3.3. Connection between Anode Stability and Selectivity
The literature clearly shows the connection between the rate of
DSA degradation and the rate of the OER. However, it must be
pointed out that the relationship is more complex than it may
seem. In chloride-containing electrolyte, at very low pH values
below 2, degradation due to the formation of soluble chlorides is
likely a dominating mechanism of anode degradation.213 At these
pH values, the corrosion rate of Ti has been found to exceed that
of Ru.229 The rate of corrosion of DSA has been found to be
minimal in the pH range of 2−3,151 which agrees with the area of
maximal stability according to the Pourbaix diagram.214 As the
pH is increased, the rate of corrosion increases in a similar rate as
the OER.163,217,218 In this area, the corrosion rate of Ti has been
found to be constant, but the Ru corrosion rate increases
significantly.229 It may be noted that this increase coincides with
the chlorine-hypochlorite equilibrium being pushed toward
hypochlorite, see reaction 4 and Figure 1. The oxidizing power of
hypochlorite, and the fact that hypochlorite, as opposed to
chlorine, does not form gas bubbles in the electrolyte, may
accelerate the oxidation of ruthenium. There is a clear link
between OER and RuIV corrosion in the pH range relevant to
especially industrial chlor-alkali production (pH 2 to 4). While
less data is available under pH values suitable for chlorate
production, it is likely that the trend is maintained even there.231
However, there is no clear link between the rate of ClER and that
of RuIV corrosion in the pH range relevant for chlor-alkali or
chlorate production. At higher pH values (above 10), the rate of
corrosion of both TiIV and RuIV increase,229 possibly the result of
formation of metal oxyhydroxides.142,213,230
Literature indicates that the surface layers of electrodes used in
chlor-alkali or sodium chlorate production will be stripped of
RuIV. This has been shown directly both radiochemically229 and
by, for example, selective ion mass spectrometry or
AES,235−237,252 and indirectly by other means.226,227 This is in
agreement with thermodynamic predictions,214 which indicate
that soluble Ru compounds should form during anodic
polarization of pure RuO2 in concentrated chloride solutions,
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at both acidic, neutral, and alkaline pH values, while the solubility
of pure TiO2 is predicted to be low under such conditions.145
Despite these predictions for the pure oxides, the lifetime of
industrial RuO2−TiO2 mixed-oxide DSAs is about 10 years.253
Additionally, the anode potential of electrodes in operation does
not change until the RuIV content has become very low.226 The
constancy in activity during corrosion could perhaps be seen as
support for our recent suggestion that also Ti sites can be active
in DSAs and that only low concentrations of Ru are necessary to
achieve these effects.64 Perhaps it might even be conceivable that
the last sites that are active on DSA are Ti sites activated by Ru, as
these sites might be more stable.65
While not directly relevant to the selectivity issue, some
conclusions can be mentioned regarding the supposed
deactivation of DSA due to formation of a nonconductive
interlayer of TiO2, between the support and the coating, during
electrolysis.223,236,237,239,254 This deactivation mechanism is
frequently mentioned, but there seems to be little direct proof
of it being an important deactivation mechanism for electrodes
used in chlor-alkali or sodium chlorate production. It has been
suggested that the deactivation is more likely the result of
complete removal of Ru from the surface layers of the
coating.226,227 Indeed, the fact that reactivation by Pt deposition
onto the surface of used industrial electrodes seems to be
possible supports this claim.2
We would like to point out that much of the detailed
knowledge about the connection between selectivity and stability
has resulted from the radiochemical studies performed almost
exclusively by scientists in the Soviet Union between 1960 and
1990. These methods have allowed the corrosion of the anode to
be studied in situ during electrolysis at industrially relevant
current densities and electrolyte composition and not only based,
for example, on an increase in potential in accelerated lifetime
tests. The latter type of stability test, which gives very little
understanding of the character of the degradation during
electrolysis, has been the dominating one employed in the
West even up until year 2015. The reason is perhaps the practical
challenge in employing the radiochemical method, as proper
safeguards must be employed, and possibly also the long time
periods needed to study anode degradation at industrially
relevant conditions. The study of Gajić-Krstajić et al.,239 which
employed a spectrophotometric method to allow similarly
sensitive detection of Ru as afforded by the radiochemical
method, could perhaps be used to avoid handling radioactive
materials and give time-resolved understanding of the degrada-
tion process. Furthermore, the recent studies of Mayrhofer and
co-workers240−243 and Chorkendorff and co-workers245,246 have
shown how ICP-MS and EQCM can be used to monitor
degradation of DSAs during use as OER catalysts. Nevertheless,
long-term tests in the correct conditions, so that the effect of the
relevant reactions are studied, are still necessary. Additionally, the
clear link between OER and degradation that the literature
indicates means that, for example, an accelerated lifetime test in
sulfuric acid, where OER is the only reaction occurring,
constitutes a test of a completely different property than what
is relevant for an anode which is to evolve almost exclusively
chlorine gas.
As seen in several studies (refs 74, 164, 174, 219, 222, 223, 231,
and 238), there is a change in the Tafel slope for OER and ClER
on Ru-based anodes at the critical anode potential, Ecr. This
potential is still not well understood but has been related to the
formation of RuO4.219 Indeed, the Pourbaix diagram indicates
the connection between Ecr and the start of formation of
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Chemical Reviews
ruthenate species.214 Furthermore, an increase in the rate of Ru
dissolution from DSA has been noted at electrode potentials
above Ecr.231 Thus, operation at anode potentials higher than Ecr
should be avoided to limit DSA corrosion. From an industrial
perspective, the risk of exceeding Ecr is higher in the chlorate
process than in the chlor-alkali process.238 This is partly
connected to the decrease in Ecr which occurs as pH is
increased223 and which in turn likely is related to the pH effect on
the potential required for ruthenate formation, which follows the
same trend.214 Interestingly, Eberil et al.74 found an optimum in
selectivity for chlorate production close to Ecr. Another
important industrial aspect is the finding that Ru corrosion
increases by repeated interruptions in the electrolysis.224 Thus,
repeated starts and stops should be avoided.
In closing, we would like to provide a discussion of how the
lifetime of industrial DSA can be maximized in the intermediate
pH range relevant for chlor-alkali and sodium chlorate formation.
The difference in corrosion behavior between the Ru and Ti
component of DSA in the intermediate pH range is most likely
due to the possibility of forming ruthenates and perruthenates.213
Ti does not form such compounds.230 The formation of gaseous
RuVIII products during electrolysis using DSA is well-known both
in literature (see, for example, refs 151, 154, 221, 224, and 229)
and in industrial chlor-alkali and sodium chlorate production.
This aspect has devoted significant experimental work, with, for
example, the study of Kötz et al.212 clearly showing the
connection between the onset of OER and the onset of RuO4
formation on pure RuO2 electrodes. It is reasonable to assume
that the formation of RuO4 occurs via an intermediate that is
shared with the OER, as surface oxides need to form in both
cases. Both the rate of OER and the percentage of the Ru released
into the gas phase increases with pH.151,154 Furthermore, it was
clearly shown by Pecherskii et al.67 that Ru electrodes that exhibit
improved selectivity for ClER also exhibit improved stability.
Even for other Ru mixed oxides, such as Ru−Sn oxides, improved
chlorine evolution selectivity69,71,172 is associated with improved
stability.234 RuIV corrosion rates have been found to decrease
significantly with increasing Cl− concentration.154,218,231 As has
been discussed in the preceding sections, increasing the Cl−
concentration is a very simple way of increasing the current
efficiency for Cl2. Increasing the current density is another way of
improving the current efficiency for Cl2, at least as long as the
density is not so high as to, for example, result in mass transport
limitations, and this also results in decreased current efficiency
for corrosion.154,221,224,231 Increasing the temperature decreases
the selectivity for chlorine evolution and increases the rate of
corrosion of DSA.154,163 However, a higher temperature might
still be viable, as it improves the kinetics of the chlorine- and
chlorate-producing reactions and decreases the cell potential
difference. At pH values relevant for industrial chlor-alkali and
sodium chlorate formation, high oxygen production rates are
indicative of a high rate of RuIV corrosion due to the formation of
ruthenates or perruthenates. Thus, chlor-alkali production
should operate in the pH range of 2−3 to achieve a maximal
chlorine current efficiency41,151 and anode lifetime.151 For
chlorate production, the optimal pH for current efficiency of
chlorate production is significantly higher, at about pH 6−7. In
this pH range, it is not possible to maximize both chlorate
production efficiency and DSA stability in the same way, and
both factors are connected to the critical potential. Anodes in
both processes should be operated below the critical potential.
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4. CONCLUSIONS
It is clear that the issue of the selectivity between the main
reactions in chlor-alkali and chlorate processes and the oxygen-
evolving side reactions requires further study, as has also been
recommended by Wanngård168 and Tilak and Chen.5 While the
effect of several factors, most importantly of the current density,
are relatively well-known, the details of the effects of process
parameters, electrolyte composition, and electrode character-
istics on the selectivity issue, as well as the mechanisms and
relative importance of the suggested oxygen-forming reactions,
are still not well-elucidated. Several studies have been conducted
under conditions similar to those used in industrial chlor-alkali
production, while fewer studies have examined the selectivity
under conditions similar to those used during industrial chlorate
production. For chlor-alkali production, a practical way of
increasing the selectivity through acidification of the electrolyte is
available for state-of-the-art membrane cells. However, a higher
pH is necessary to facilitate chlorate formation, thus excluding
the method of acidification in industrial chlorate production, and
oxygen evolution still accounts for about 5% current efficiency
loss. Additionally, the possible influence of the critical anode
potential, Ecr, on the selectivity for chlorate production is still not
well understood. Its appearance at high, industrially relevant,
current densities makes it imperative that future studies employ
accurate iR compensation methods. Such methods could then be
combined with measurements of both the gas and the liquid
phase composition which might also give further understanding
for the relative importance of the different oxygen-evolving
reactions.
For both processes, modern experimental and theoretical
methods should be used to gain a deeper understanding of the
interplay between anode activity and selectivity, composition,
and structure. The combination of theoretical modeling and
modern characterization methods (e.g., the different X-ray
spectroscopic methods available today) is well-suited to
exploring the details of heterogeneous and homogeneous
(electro)catalytic reactions. These tools now allow for detailed
understanding of the electronic structure of practical catalysts,
whereas before mostly macroscopic parameters regarding
structure and composition of electrodes have been possible to
study in detail. The understanding resulting from studies
combining theory and experiments could then be used to
improve the selectivity and activity of electrodes used in chlor-
alkali and sodium chlorate production. They could also be used
to start exploring the details of the relatively poorly understood
bulk-phase reactions, where catalytic processes are involved both
in unwanted oxygen evolution reactions as well as in the
formation of sodium chlorate. The latter aspect is especially
interesting, as an understanding of the catalysis of sodium
chlorate formation could result in new ways of accelerating the
reaction, with important consequences for sodium chlorate
process design.
AUTHOR INFORMATION
Corresponding Author
*E-mail: amco@kth.se.
Notes
The authors declare no competing financial interest.
Biographies
Rasmus K. B. Karlsson received his Master’s degree in Chemistry and
Chemical Engineering in 2011 and his Ph.D. in Chemical Engineering in
DOI: 10.1021/acs.chemrev.5b00389
Chem. Rev. 2016, 116, 2982−3028
Chemical Reviews Review

2015, both from KTH Royal Institute of Technology. His Ph.D. thesis CV cyclic voltammetry
research was primarily focused on combining experimental and differential electrochemical mass spectrosco-
theoretical methods to elucidate the fundamental mechanisms deciding DEMS py
the selectivity between chlorine and oxygen evolution in the chlor-alkali DSA dimensionally stable anode
and chlorate processes. EDX energy-dispersive X-ray spectroscopy
Ann Cornell received her MSc in Chemical Engineering in 1987 and EIS electrochemical impedance spectroscopy
then worked for 15 years in industry with research and development EQCM electrochemical quartz crystal microbalance
within electrochemical engineering, mainly related to industrial chlorate EXAFS extended X-ray absorption fine-structure
electrolysis. She completed her Ph.D. in 2002 at KTH with a thesis on spectroscopy
electrode reactions in the chlorate process and has, since 2003, worked GC gas chromatography
in the group of Applied Electrochemistry at KTH. Ann is now an ICP-MS inductively coupled plasma mass spectrome-
associate professor and still conducts research related to industrial try
electrolysis but has also broadened her interests to areas such as MS mass spectrometry
cellulose-based Li-ion batteries. OER oxygen evolution reaction
ORTA ruthenium−titanium oxide anode, abbrevia-
tion frequently used in Soviet and Russian
ACKNOWLEDGMENTS literature
The financial support of the Swedish Energy Agency and of RDE rotating disc electrode
Permascand AB are hereby acknowledged. Furthermore, the RHE relative hydrogen electrode, the SHE value
constructive comments given by Dr. John Gustavsson adjusted for the pH of the solution (i.e., that
(Permascand AB) on a draft of this review are gratefully measured with a SHE immersed in the same
acknowledged. Staffan Sandin is acknowledged for bringing some solution as the working electrode)
of the papers on decomposition of hypochlorous acid species to RTO ruthenium−titanium oxide
our attention. Professor Kiyotaka Asakura (the Catalysis SCE saturated calomel electrode
Research Center of Hokkaido University, Japan) is acknowl- SECM scanning electrochemical microscopy
edged for assistance with providing a high-resolution version of SEM scanning electron microscopy
Figure 8. Professor Lars G. M. Pettersson (Stockholm SHE standard hydrogen electrode
University) is gratefully acknowledged for constructive com- SIMS secondary ion mass spectrometry
ments on section 2.2.5.2. TEM transmission electron microscopy
TNT TiO2 nanotube
NOMENCLATURE XANES X-ray absorption near-edge spectroscopy
η overpotential, V XAS X-ray absorption spectroscopy
Φep current efficiency (or charge yield) of product XPS X-ray photoelectron spectroscopy
p XRD X-ray diffraction spectroscopy
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3028 DOI: 10.1021/acs.chemrev.5b00389

Chem. Rev. 2016, 116, 2982−3028