hr. J. Hydrogen Energy, Vol. 20, No. 10, pp.

835-844, 1995
Copyright @ 1995 International Association for Hydrogen Energy
Elsevier Science Ltd
036&3199(95)00014-3 Printed in Great Britain. All rights resrved
036@3199/95S9.50+ 0.00

ELECTROCHEMISTRY AND ENVIRONMENT:

THE ROLE OF ELECTROCATALYSIS*

S. TRASATTI
Department of Physical Chemistry and Electrochemistry, University of Milan, Via Venezian 21, 20133 Milan. Italy

(Receivedfor publication 10 Jar~uury 1995)

Abstract-After an introductory discussion of the conceptual meaning of electrocatalysis and its technological
significance, the impact of electrochemistry on the environment is illustrated with two major examples: Hg cells in
chlor-alkali technology and electric cars. The problems of fossil fuel exhaustion and pollution call for a resort to
renewable energy sources. Electrochemistry can help to alleviate environmental issues with appropriate technological
strategiesinvolving processes and products. In this context, research on electrocatalysis has been focused on a number
of major targets which are discussed and illustrated by means of examples: intermittent water electrolysis; destruction
of organic pollutants; ozone, hydrogen peroxide and chlorine dioxide electrosynthesis; cathodic conversion of CO,;
anodic oxidation of SO,; cathodic destruction of NO,; replacement of chromates; desulfurization of natural gas, etc.

INTRODUCTION where AE is the thermodynamic decomposition potential

Electrocatalysis is the term used to indicate the catalysis
of electrode reactions. This can be accomplished by the
action of the electrode material Cl] or alternatively by
the action of species in solution [2, 3) or both. Thus,
under the term electrocatalysis, a number of phenomena
are grouped which may have little in common. This
generalization can be avoided by distinguishing between
homogeneous and heterogeneous electrocatalysis. In har-
mony with the field of heterogeneous catalysis [4],
heterogeneous electrocatalysis deals with the effect of the
electrode material on the rate and the mechanism of
electrode reactions. This is the significance more usually
attached to “electrocatalysis” in practical fields [S].
That of electrocatalysis is the electrochemical field
where fundamental aspects have a most direct impact on
applications, and where people from universities and from
industry best understand each other on the grounds of
a common language [6, 71. Nevertheless, a substantial
difference in research targets is to be pointed out.
Fundamentals vs applications
Industry is interested in keeping energy consumption
as low as possible. This entails working at high current
and low voltage. The voltage AV applied to an electrolysis
cell comprises several contributions [8]:
AV=AE+Q+AV,+AE, (1)
*From a lecture first delivered at the 43rd Meeting of the
International Society of Electrochemistry (ISE), 2&25 September
1992,Cordoba (Argentina).
difference determined by the nature of the electrode
reactions, Cq is the sum of the overpotential terms, i.e.
the extra voltage required to drive the electrode reactions
at a practical rate, AV, includes all ohmic drops in the
electrode structure and the interelectrode gap and AV, is
what is usually called “stability”, i.e. the voltage increase
due to degradation of the electrode material with time.
The evaluation of this term calls for long-term electrolysis
tests (sometimes replaced by less accurate but more
practical “accelerated” tests).
Fundamental research is usually focused on the evalu-
ation of the term Xv, the target being the study of material
structure/activity relationships. In applications the con-
cept of electrocatalysis is to some extent distorted to
include all the terms in equation (l), in that it is the total
value of AV which bears upon the energy efficiency of
an electrolysis cell. Thus, substantial energy savings can
be achieved by reducing the value of AE. This is the
reason for the introduction of (sometimes called) “de-
polarized” electrodes: (i) 0: cathodes replacing H, evol-
ution [9, lo]; (ii) H, anodes replacing 0, or Cl, evolution
[ 111; and(iii) oxidation ofcarbonaceous materials instead
of 0, evolution [12], etc.
AV, is also of great practical interest. It includes any
ohmic loss due to an eventual poor conduction of
electrode materials, any ohmic barrier at the support/
overlayer boundary of activated electrodes, as well as the
ohmic drop in the interelectrode gap. While the first two
events are related to the properties of electrode materials
and are often discussed in fundamental research [13], the
third one is an engineering problem, although it may
happen to be indirectly alleviated by acting on the nature

835
836 S. TRASATTI
of the electrodes [14]. Typical is the example of dimen-
sionally stable anodes (DSAs): most of the AV diminution
achieved with their use in chlor-alkali cells is in fact a
consequence of the possibility of minimizing the interelec-
trode gap [ 151.
The term which is very often neglected or under-
estimated or superficially evaluated in fundamental re-
search is AK, i.e. the stability. From a practical point of
view this is very often more important than the electro-
catalytic term Cs. The reason is simple: operational
discontinuities due to frequent maintenance to rearrange
or replace electrodes add to investment and operational
costs. Many very good electrocatalysts have not yet found
applications due to their poor stability.
In conclusion, from a broad point of view electrocataly-
sis can be regarded as the search for new materials and/or
new operating conditions in order to (i) improve activity,
efficiency and selectivity of electrodes; (ii) reduce invest-
ment and operational costs; (iii) increase the electrode
(cell) lifetime; and (iv) avoid pollution.
ELECTROCHEMISTRY AND ENVIRONMENT
The development of industrial applications depends on
three main factors: technological innovation; economical
convenience; and environmental safety. Unfortunately,
these factors do not move in the same direction. Until
the 196Os, technological progress and profit prevailed
over environmental concerns. At present, the two first
factors must comply with safety requirements. The tech-
nological attitude has thus changed, nevertheless com-
pliance with safety rules is not often observed sponta-
neously.
The impact of technology on the environment also
bears upon and conditions fundamental research. Tech-
nology, if not unhealthy products, produces waste. If these
are subjected to safe disposal, no problems arise, other-
wise the impact of waste on the environment may arouse
public alarm. Technology may react directly and correct
the production, otherwise political action may be necess-
ary to constrain industry to solve the problem. Since
research and technology are in close relation, any action
on technology has a reflection on the policy of research.
Three major examples will illustrate the above argu-
ments, and are presented below.
The “mercury” story [16]
In the 1960s the Japanese chlor-alkali industry was
growing, more than 90% of the plants being based on
Hg cells. Loss of Hg in the environment created major
problems as a disease (called minamata) suddenly ap-
peared. The public alarm triggered a political action:
industries were invited to convert Hg plants. The alter-
native technology available at that time was diaphragm
cells which soon proved inefficient. This forced industries
and reasearch centers to find an alternative technology:
in 1977 the new membrane cells appeared, and in 1986
the conversion of the Hg plants was completed.
While this example proves that new technologies can
be stimulated by environmental constraints, other
examples show that political action is not always so
strong, so that environmental problems persist.
The “electric car” story [17, 181
After the invention of the first electrochemical power
source (“pile”) by Alessandro Volta in 1799, the first
electric carriage appeared in 1837. In the 1890s the
growth of the electric car industry was at its top with up
to 60% of the market. With the invention of the
self-starter for internal-combustion engine vehicles in the
1920s the electric car production dropped becauses of
evident technical limits. Interest reappeared in the 1970s
with the energy crisis, and it became more acute as the
environmental concern grew to a critical issue. Now-
adays, with the Clean Air Act in California, local political
action is trying to force a change in technology which
otherwise would not be attempted owing to the evident
uneconomical and poor technical situation of the electric
car industry [19]. The prospects of decisive success are
poor because the car industry has not yet found a viable
technological solution.
Fossil fuels
The actual technology (economy) is based on fossil
fuels: coal, oil, natural gas. Fossil fuels suffer from two
shortcomings, they are polluting and they are not renew-
able, i.e. they are doomed to exhaustion.
Pollution. Environmental concerns related to fossil fuels
stem from their releasing pollutants upon combustion
[ZO]. Besides various metals, they contain 15P200/& of
sulfur and 1&12“~, of nitrogen which produce SO, and
NO,, respectively [Zl]. In addition, CO, is quantitatively
produced from carbon oxidation. The fate of these
pollutants is different: SO, can be oxidized in the air and
washed out giving rise to acid rains [22]. NO, is toxic
by itself and together with CO, is responsible for the
greenhouse effect [23, 24).
Exhaustion. Exhaustion is a more futuristic but well
predictable event [23, 251. All projections converge to
indicate that we are in the descending branch of the coal
wave, and at the top of the oil wave. Natural gas
consumption is still growing but it does not solve
pollution problems. Exhaustion may still take a century
for completion, but since a change in technology requires
5@70 years to become operative [26], the time to start
has already come.
Hydrogen economy. There are several candidates as
alternatives to fossil fuels: alcohols, hydrogen, biomass
[27], etc. Hydrogen is indicated as the cleanest fuel both
for production and for combusion residues [28]. Hydro-
gen can be produced in several ways, including electro-
lysis [29]. Technology based on hydrogen is mature in
many respects, but its success is retarded by the lack of
concerted world political action in this direction [30].
 ELECTROCHEMISTRY
ELECTROCHEMISTRY: IMPACT ON
ENVIRONMENT
Electrochemistry can offer much for solving or alleviat-
ing environmental issues [31]. It is usual to claim that
electrochemical technology is cleaner by itself [32] since
electrochemical reactors do not need high temperatures
and collateral services. Thus, the options offered by
electrochemistry are: (1) alternative industrial processes;
(2) environmental protection; (3) pollution monitoring;
and (4) non-polluting energy sources.
While the claim for (1) is justified in principle, it clashes
with the following practical aspects: a technology cannot
be cleaner than the energy source to drive it. This means
that as long as electrochemical technology uses energy
produced from fossil fuels, pollution is simply moved from
one site to another. If, for instance, all cars were changed
into electric vehicles, the increasing demand of electricity
to recharge batteries would in fact increase the degree of
pollution from fossil fuels, although conceivably away
from cities.
It follows from the above that a really non-polluting
electrochemical technology should be driven by an energy
system which does not possess the shortcomings of the
fossil fuels. In particular, an ideal energy system should
be inexhaustible, clean, abundant and economical. The
only possibility is to resort to renewable energy sources
[33] which meet at least the first three requisites: solar,
wind, tidal, ocean-thermal, biomass, geothermal and
nuclear (fusion). None of them offer a developed technol-
ogy, however sparse applications of solar energy conver-
sion are already a reality [34]. The others are still in the
distant future. In any case, all of them require energy
storage and transportation.
Although solar energy is the most promising source
with a technology in an advanced state (photovoltaics),
it suffers from a number of shortcomings: it is intermit-
tent, away from consumption centres, not for transpor-
tation by itself, not storable by itself, not transportable
by itself and dilute. From an electrochemical point of
view, solar energy conversion can take place directly in
photoelectrochemical cells [35] or in photovoltaicelec-
trolytic cell systems [36]. While the former technology
is not ready, the latter is available for small on-site
production.
ENVIRONMENTAL STRATEGIES
In the last section electrochemistry was said to be able
to alleviate environmental problems with an environ-
mental protection strategy. This involves changing pro-
cesses, products, or converting polluting species into
useful materials.
Chlorine has long been one of the major products of
the large electrochemical industry [37]. Due to the
dangers of its transportation and its inherent toxicity, the
demand for chlorine is declining [38]. Since the produc-
tion of chlorine is joint to that of NaOH in chlor-alkali
plants, the problem of an inbalance in the demand of the
two co-products is being solved by designing electrolysis
AND ENVIRONMENT 837
processes producing NaOH without chlorine, e.g. sulfate
electrolysis.
Chlorine has long been used in the disinfection of water.
It now seems that chlorinated hydrocarbons formed
during the treatment may possess some carcinogenic
action [39]. For this reason chlorine is being replaced
by ozone or hydrogen peroxide, whose production must
thus be increased and improved. In the particular case
of pulp and paper bleaching, there is an increasing
demand for chemical alternatives to Cl, to avoid trans-
portation problems: one of these is chlorine dioxide
(CQ) c401.
Other problems which can be tackled electrochemically
are: the presence of organic pollutants and metal ions in
wastewater; the elimination of chromate in spent liquors;
the recovery of H,S from natural gas; and the destruction
of cyanide from electroplating baths. The role of elec-
trocatalysis in all the issues thus far described will be
illustrated with examples in the next section.
ISSUES FOR ELECTROCATALYSIS
The main aim of this paper is to outline the scenario
on which electrochemistry is acting or will act to solve
environmental problems. In this context, research areas
where electrocatalysis is the main target will be identified
and illustrated with examples.
Intermittent wter electrolysis
Hydrogen can be produced in small quantities on-site
by feeding an electrolytic cell with photovoltaic cells 1361.
The main problem is that the solar energy source is
intermittent owing to its natural day/night cycle. In
addition, in certain latitudes, further problems may arise
due to the occasional presence of clouds. During an
illumination cycle, the current density can vary from zero
up to 1 A cm-‘(Fig. 1) [41]. This poses serious problems
of stability which are less crucial for constant current
electrolyzers.
1,000
;
: 800
E
‘2 600
s
?a
D 400
E
2
2 200
.
time of the day
Fig. 1. Current density vs time sequence simulating a day/night
cycle of intermittent water electrolysis. Data from Ref. 1411.
838 S. TRASATTI

observed with monopolar cells [43, 441. The reason is

750 continuous intermittent
that, as the current is disconnected, the two faces of a
Ni bipolar electrode are short-circuited through the tubes
z
_ 650 connecting two cells. Thus, the potential of Ni is pushed
3 NiO, into the region of free dissolution while the short-circuit
= ---_<____----.---A
current may reach several milliamps per square cen-
timeter. This is a typical case where material problems
are more crucial for the stability of electrodes than for
their activity. On the other hand, monopolar cells are
technologically less convenient.
Destruction of organic pollutants
250-
100
The aquatic environment can be polluted by organic
150
0 50
chemicals from municipal and industrial sources [45].
electrolysis time / hours Many industries, such as oil refineries, coke plants,
Fig. 2. Modification with time of electrolysisof theoverpotential chemical and plastic plants are characteristic sources of
for 0, evolution. Data from Ref.[44]. phenolic pollutants. Organic pollutants are usually con-
trolled by means of biological treatments of wastewater.
Someof the chemicals, e.g.phenolic compounds, are very
The typical material for alkaline water electrolysis is poorly degradable biologically and they can accumulate
nickel [7]. It is prepared in a special form (Raney-nickel) in the environment.
to increase its cathodic activity while it is mainly used Electrochemistry offers two options for the treatment
as such anodically. Raney-nickel is an alloy of Ni with of theseorganic pollutants with the aim of oxidizing them,
Zn or Al or both plus additives which are then leached if not to CO,, to biodegradable products: mediated and
out to leave a very porous and active surface [42]. direct electrochemical oxidation.
Raneyynickel does not resist intermittent electrolysis: its
overpotential increases dramatically with time [43]. Mediated electrochemical oxidation. This is accom-
Day/night cycles are usually reproduced in the labora- plished by a strong chemical oxidant in the homogeneous
tory with pulsed electrolysis which represents an accel- liquid phase,which is then regeneratedelectrochemically.
erated test of stability. Attempts to improve the stability A typical oxidant has long been in situ generated
and to maintain or increase the activity have been made Cl,(ClO-), but this is being replaced becauseof the risk
by activating Ni electrodes with transition metal oxides of forming chlorinated hydrocarbons. Alternative pro-
[44]. Figure 2 shows that for anodes mixed Ni + Fe cedures have been proposed based on the use of Co(II1)
oxides lead to improved performances. For cathodes the [46], Ag(I1) [45], Ce(IV) [47] and Ru(VII1) [48]. There
best performances are given by Co,O, doped with is little of electrocatalysis in these processes,except the
transition metals (Fig. 3). LaNiO, with or without Fe search for an electrode material where 0, evolution
has also been tested. proceeds at high overpotential so as to allow the reoxi-
A major problem with thesecells is the heavy corrosion dation of the mediator which usually requires high
of the Ni supports with bipolar cells, which is not potentials. The anode material has almost invariably
been Pt.

continuous intermittent
6001 2.5

\*_=
NiO,+ Flu Co,O, + lr
___--.
____ -.-.---
: _____----
r_-___----
co,o, + Ru

O( 1’
0 50 100 150 -6 -5 -4 -3 -2 -1
electrolysis time I hours log (j/Acm-*)

Fig. 3. Modification with timeofelectrolysisof the overpotential Fig. 4. Current&potentialrelationship for 0, evolution on
for H, evolution. Data from Ref.[44]. differentelectrodes.Adaptedfrom Ref.[SO].
 ELECTROCHEMISTRY
OLA
0 10 20
charge, Q / Ah
Fig. 5. Charge required for destruction of organics on different
electrodes. Adapted from Ref. [105].
Direct electrochemical oxidation. The oxidation of the
organic compounds occurs on the anode surface by an
electrochemical mechanism. This involves either interac-
tion of the pollutant with surface OH groups generated
at high potentials, or direct electron transfer from the
organic molecule to the electrode. The anode material
must exhibit a very high oxygen overpotential in this case
as well. Pt, PbO,, and more recently SnO,, have been
proposed as electrocalysts [49, SO].
Figure 4 shows a comparison between Pt, PbO, and
SnO,. The overpotential for 0, evolution increases in
the samesequence.Nevertheless,the efficiency for organic
oxidation is almost the samefor Pt and PbO, and much
higher for SnO,. This is clearly shown in Fig. 5 where
destruction not only of benzene,but also of all the organic
content, is reached more easily with SnO, than with Pt
and PbO,.
Electrosynthesis of ozone
Ozone is a strong oxidant which does not give rise to
undesirable products. For this reason it is finding increas-
ing use for paper bleaching in place of chlorine, in water
purification and sterilization, in disinfection of living
spaces and as disinfectant of purified water loops in
electronic and pharmaceutical industries.
Electrocatalysis offers a convenient route to the syn-
thesis of ozone [Sl]. Requisites of the anode material are
a high overpotential for 0, evolution and a high stability.
Natural candidates have thus traditionally been Pt and
PbO, [52], but glassy carbon [53] and Ti suboxides [54]
have recently beeninvestigated. The competition between
0, and 0, formation can be shifted in favor of 0, by
suppressing 0, evolution by operating on a number of
variables, in particular the composition of the electrolytic
solution [Sl]. It has been found that the strong absorp-
tion of such anions as F- and BF, increases the
overpotential of 0, evolution thus improving the effi-
ciency of 0, electrosynthesis [52, 531. A commercial
generator based on a solid polymer electrolyte (SPE) cell
with a PbO, anode has been proposed [55].
AND ENVIRONMENT 839
300
;
: EbonexlPbO,
E 200.
o;-=/L~//
3 4
EvsSCEIV
Fig. 6. Current-potential curves for 0, generation on different
electrodes. Data from Ref. 1543.
The reaction of 0, formation has a standard potential
of 1.51V (SHE) while for that of 0, evolution E” = 1.23
V (SHE) [52]. However, 0, synthesis requires a lower
activation energy than 0, formation, therefore the com-
petition between the two reactions is influenced by a
number of variables. Figure 6 shows that 0, generation
on PbO,/Ebonex (Ebonex is a commercial material based
on Ti suboxides) takes place at lower potentials compared
with Ebonex alone and glassy carbon [54]. The superior
performance of PbO, is also shown in Fig. 7 where a
difference between /I- and +PbO, is also visible, while
DSAs and other metals are inefficient [Sl].
The effect of anions on the current efficiency for 0,
generation is illustrated in Fig. 8 where anions are arranged
according to an empirical electronegativity scale.Although
F- is the most studied anion in this respect, the figure
shows that other anions are more effective. On account
of the higher activation energy,0, evolution is suppressed
at low temperature[51]. A lower temperatureof electrolysis
is thus favorable for 0, formation. Researchis addressed
to a further increasein the efficiency of the process.
‘01
d
Au, Pd, DSA
ON
)------t-
0 0.4 0.8 1.2 1.6 2
i I A cm-2
Fig. 7. Current efficiency for 0, generation for different electrode
materials. Data from Ref. [Sl].
840
25.
20
z _*’
7715~ SF;
CIO,-
.-5
,’
,=-
; IO-
,,‘. ,-” HSO,
F-. ,,,*’ H,PO,-
5~ ,’
,’ ,’
l OH-
0
0 5 10 15
electronegativity
Fig. 8. Dependence of current efficiency for 0, generation on
the electronegativity of the anions of the supporting electrolyte.
Adapted from Ref. [Sl].
H,O, direct electrosynthesis
Peroxide solutions find use as oxidizing or bleaching
agents in many sectors of industry. Environmentally, the
use of H,O, is safer than many other oxidants since its
reduction product is water and the unreacted compound
can be easily degraded catalytically. Traditionally, the
electrochemical production of H,O, was an indirect
process where sulfate was anodically oxidized to persul-
fate and the latter hydrolyzed in solution to sulfate and
H,O, [56]. An on-site electrolytic process with particular
advantages for the pulp and paper industry is based on
the electrolytic reduction of 0, [57, 581.
Cathodic 0, reduction has long been an active research
topic for its direct impact on fuel cells, air batteries and
air cathodes [9, 593. In these processes the target is,
however, to reduce 0, down to water in a four-electron
reaction with full recovery of the chemical energy. 0,
reduction to H,O, is a two-electron reaction customarily
regarded as a shortcoming in fuel cell electrocatalysis. In
the environmental context, H,O, synthesis becomes a
priority target which thus requires an opposite strategy
of search for electrocatalysts. In other words, materials
unsuitable for fuel cells or batteries are primary candi-
dates for the direct synthesis of H,O,, particularly some
forms of carbons and graphite [59]. Some other com-
pounds can be used to activate carbon, but their opti-
mization calls for reverting the research strategy since
fuel cell-oriented research has thus far been privileged.
Electrosynthesis of ClO,: a great challenge
Cl, production has been traditionally concentrated in
large plants with consequent need of chlorine transpor-
tation to the sites of utilization. Hazards connected with
the handling of Cl, are discouraging the transport of this
gas. Although the membrane cell technology is now more
suited to smaller production in on-site plants, replace-
ment of Cl, with less hazardous chemicals is being
pursued. ClO, is one of these [60].
S. TRASATTI
ClO, is produced by chemical reduction of chlorate
by SO,, methanol or H,O, in strongly acid environment
PF; .
[61]. Electrochemically, ClO, can be obtained by oxida-
tion of chlorite which is not a common chlorine com-
pound [40]. An attractive electrochemical alternative
,,,,’ n
would be to reduce ClO, to ClO, since chlorate is a
L’,’ .
AsF, readily available precursor. This reaction is, however,
HSiF; very challenging since ClO, is in turn readily reduced,
according to thermodynamics [62]. Thus, it would be
necessary to find appropriate conditions ensuring the
suppression of ClO, reduction.
To date, only two attempts have been proposed. In a
patent [63] ClO, is reduced to ClO, on an oxide cathode
20 25 30 based on RuO,/Rh,O,. However, in view of the strong
acidity necessary for the reaction to occur, it is doubtful
whether the reduction proceeds electrochemically rather
than chemically. Another attempt was based on an
autoocatalytic process using carbon electrodes [40].
Starting with a small amount of ClO, already in solution,
the product builds up while the electrode potential is
cycled in an appropriate potential range. Further studies
in this direction would be welcome.
Cathodic reduction of CO,
CO, is regarded as the main culprit responsible for
the greenhouse effect [23], although its involvement is in
fact lower than for other gases [64]. Its impact is, however,
greater because of the large amount continuously released
in the atmosphere. In view of the dispersity of the sources
of CO, it is unrealistic to think that electrochemical
fixation of CO, can be a means of alleviating the problem.
The electrochemical route becomes attractive in view
of the exhaustion of fossil fuels, since CO, reduction
can become a viable route to the synthesis of higher
organic compounds no longer available from natural
sources.
CO, reduction is one of the most intriguing reactions
from an electrocatalytic point of view. From a synthetic
point of view, selectivity is a major problem, first of all
because of the competing H, evolution, and secondly for
the large variety of products which can be formed.
It is possible to identify four main reaction routes
leading to CH, (and higher hydrocarbons), CO, CH,OH
(and higher alcohols) and HCOOH, respectively. Selec-
tivity depends substantially on the electrode material.
Thus sp-metals with high H, overpotential give prefer-
entially HCOOH. Au and Ag give CO, Cu produces CH,,
whereas transition metals such as Fe and Ni do not
activate CO, but evolve H, [65, 661.
While the detailed mechanisms are complex, it is
possible to envisage the main factors governing selectiv-
ity. sp-Metals do not adsorb atomic hydrogen or CO,.
Thus CO, is probably reduced by a primary electron
transfer with the formation of a radical anion which in
turn can scavenge an atomic H formed by the parallel
H+ discharge to produce formiate [67].
Ag and Au are located at the borderline of the
appropriate properties. They adsorb hydrogen weakly
while chemisorption of oxygen is possible. Thus, one
 ELECTROCHEMISTRY
4
, 5
0.001 I
0 IO 20 30 40
temperature, t / “C
Fig. 9. Current efficiency for CO, reduction to hydrocarbons
on Pd as a function of temperature. The figures by the lines
indicate the number of carbon atoms of hydrocarbons. Data
from Ref. [76].
oxygen can be ultimately extracted from the CO, mol-
ecule to give CO [68].
Cu is known to chemisorb both oxygen and hydrogen,
although not so strongly as transition metals. Thus, the
CO, molecule can be chemisorbed and totally reduced
by the surface hydrogen to methane [69].
The critical nature of these surface parameters is well
illustrated by the fact that the state of the surface of Cu
can influence the nature of the products. Thus, superfi-
cially oxidized Cu gives, preferentially, CH,OH [70],
which is evidence for a less reducing surface action.
Methanol is also the main product with MO which
possesses high affinity for oxygen [71].
The great amount of data in the literature [72-751
indicates that the following properties of the catalyst are
important: position of the potential of zero charge;
surface availability of H atoms; and oxygen adsorbability.
In fact, the catalyst surface should be a sink of 0 and a
jj \\ __ . SO, on pyrolized Co phthalocyanines [84]. Waste gases
0
-2 -1.7 -1.4 -1.1 -0.8 -0.5
EvsSCElV
Fig. 10. Conversion of CO, by cathodic reduction on an alloy
compared with the pure metals. Data from Ref. [7X].
AND ENVIRONMENT 841
50 2oo 1 2 3 4 5
H,SO, concentration / mot dm-3
Fig. 11. Effect of NO, on the efficiency of the electrocatalytic
abatement of SO, from gases, as a function of H,SO, content
in solution. Adapted from Ref. [84].
source of H. The mode of adsorption of the intermediate
is thus a crucial factor.
A very interesting possibility is the reduction of CO,
to higher hydrocarbons, since this would be a way to
synthesize organic chemicals. This has been proved for
Pd electrodes (Fig. 9) [76]. Another interesting route is
the production of CH,OH since this is a potential
candidate for the substitution of fossil fuels. Besides that
with oxidized Cu and MO, methanol has also been
observed with some transition metal oxides (DSA) [77].
The range of materials investigated for CO, reduction
is impressive. The efficiency and selectivity of electro-
catalysts can also be modulated by using surface alloys
of variable composition (Fig. 10) [78]. The effect of H
present in subsurface regions (absorbed) of Pd has been
reported [79]. The effect of the crystallographic orienta-
tion has also been investigated [SO].
Finally, the reduction of CO, to methanol has recently
been achieved with perovskite electrodes by means of a
gas diffusion electrode [81]. Perovskites are inactive if
Cu is not present in their structure, which stresses the
crucial role of this element in CO, reduction.
Anodic SO, conuersion
SO, formation is essentially concentrated in thermal
power stations and chemical plants where fossil fuels are
burned [21]. To avoid dispersion in the environment with
related corrosion problems [82], SO, can be collected in
aqueous solution and oxidized to H,SO, by HBr; the Br,
formed is then reconverted to HBr electrochemically [83].
A fully electrochemical route makes use of gas diffusion
electrodes where SO, is electrocatalytically oxidized to
-0.2 usually also contain NO,. It has been observed [84] that
NO, can poison the Co macrocycle thus lowering the
efficiency of SO, removal from the waste gas (Fig. 11).
This entails the use of larger surface area electrodes to
maintain the same efficiency of SO, abatement.
842 S. TRASATTI
-!I% 0
EvsRHEIV
0.5 1
Fig. 12. Efficiencyof cathodic NO, destruction to N, on Pt
electrodesas a function of potential. Adaptedfrom Ref.[87].
Cathodic destruction of NO,
NO, is a noxious component of waste gases; in
particular it is produced by internal combustion engines
[20]. It is responsible for the greenhouse effect and is not
decomposed in the atmosphere, therefore it must be
abated at the producing site [SS].
In view of the dispersity of its formation, it is difficult
to envisagean electrochemical method for its destruction.
Nevertheless, some electrocatalytic studies have shown
interesting prospects. NO, is easily reduced on Pt in the
potential range of hydrogen adsorption [86]. The current
efficiency can be as high as 100% if a gas diffusion
electrode is incorporated in the cell (Fig. 12) [87].
Recently, interest in the electrochemical treatment of
other nitrogen compounds, particularly nitrates and
nitrites, has stemmed from the problem of processing
liquid radioactive waste, and the development of electro-
chemical sensors for environmental pollution. Although
Pt is the most efficient catalyst since adsorbed hydrogen
plays a definite catalytic role, other materials have been
found to be active, in particular Pd, Rh and Ni [88, 891.
Efficient reduction has also been observed with transition
metal macrocycles [90].
Replacement of chromates
While chromates are obviously used in the electro-
plating industry, which is facing environmental con-
straints, the case of interest in the present context is
related to the use of chromates as additives in the solution
of chlorate cells. The addition is made to minimize the
reduction of intermediate ClO- on the cathode with a
drop of current efficiency [91].
Recent studies [92] have shown that the role of
chromates is not simply to form a mechanical barrier to
diffusion of speciesfrom the solution, but also to provide
some electron transfer inhibiting effects.In other words,
electrocatalytic effects are involved. Since chromates are
environmentally unhealthy, their replacement is a must.
This constitutes another challenging problem of electro-
catalysis. Replacement with a simple mechanical barrier
has not given the expected effect, therefore this remains
an open point for research.
Desulfurization of natural gas
Natural gas contains H,S in small amounts. In view
of the growth of natural gas utilization, the products of
H,S combustion cannot be discharged in the atmosphere.
An electrolytic route has been proposed recently [93] to
recover and convert H,S into H, and S. The gas is
bubbled in an alkaline solution where H,S is dissolved
as sulfide. Electrolysis takes place between a cathode of
Ni or graphite and an anode of Ti, graphite, Ni or Ni-Cr.
The main problem is the deposition of sulfur at the anode
with the possibility of passivation.
Other items
These include CN- destruction in exhausted electro-
plating bath [94], as well as problems related to small
electrolytic units for on-site hypochlorite generation,
which are still produced [95]. In addition, electrochemical
promotion of catalysts is an emerging field called
NEMCA (non-faradaic electrochemical modification of
catalytic activity) by its discovers, Vayenas et al. [96].
These reactions usually proceed at intermediate tempera-
tures thus involving solid electrolyte cells [97].
It is necessary to mention that some of the reactions
discussed above are also possible via a photoelectro-
chemical (or photochemical) route. This introduces the
field of photoelectrocatalysis [98], which is also a broad
field. For instance, organic compound destruction can be
achieved at photoanodes or photochemically in short-
circuited photocells constituted by small particles disper-
sed in solution [99, 100). Other casesare H, generation
[loll or CO, reduction [102, 1033in photoelectrochemi-
cal cells, although from a technological point of view these
systemsare not at the samestageas electrolytic cells [ 1041.
CONCLUSIONS
The aim of this article was to outline a strategy of
research in the field of electrocatalysis related to en-
vironmental problems. A number of researchtargets have
been identified which are still awaiting further insight.
Some of them are only nominally connected with prac-
tical solutions, while others have already found techno-
logical applications. All of them offer intriguing aspects
from the fundamental point of view.
The most appealing item for research is the cathodic
reduction of CO,, while the one closest to technological
application is the intermittent electrolysis of water. All
of them offer food for thought in that they illustrate the
many variables which can intervene in an electrocatalytic
reaction. The many systemsdiscussed have provided an
almost exhaustive picture of the problems faced from the
environmental point of view in the field of electrocatalysis.
From the analysis carried out, it should also be clear that
the attitude towards technology and the environment has
changed decisively.
 ELECTROCHEMISTRY AND ENVIRONMENT 843

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