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CHAPTER 6
6.1 Introduction
The search for new photocatalysts is driven by the desire to nd an ecient and
stable, yet inexpensive material that will be useful for carrying out photoelectrochemical (PEC) reactions. Currently the generation of hydrogen or fuels by
photoelectrolysis of water (water splitting) is of interest. However, 40 years
of experience in this eld has shown that photocatalyst materials can be
fabricated from many elements in the periodic table, and the eciency for
conversion of photons to electrons and holes can depend on the composition of
the material, each involving 4 or more elements. Thus, the experimental
exploration to discover and optimize photocatalysts involves millions of
candidates. Rapid screening, involving the automated preparation of candidate
arrays and their testing, is a promising approach. Moreover, quantitative
comparisons of dierent elemental dopings of a given material can provide
useful data that can guide the formulation of theories and models as well as
indicate the compositional factors that are important in their behavior.
RSC Energy and Environment Series No. 9
Photoelectrochemical Water Splitting: Materials, Processes and Architectures
Edited by Hans-Joachim Lewerenz and Laurence Peter
r The Royal Society of Chemistry 2013
Published by the Royal Society of Chemistry, www.rsc.org
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6.2
Chapter 6
Figure 6.1
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followed by annealing to form the desired photocatalysts. Here, each spot has a
quantitatively dierent proportion of each photocatalyst component, and the
ratio of components is determined by the number of drops of each precursor
solution dispensed on each spot. The photocatalyst spots are typically created
using a piezo dispenser that delivers pL-drops of the appropriate precursor
solutions. These dispensers are computer-controlled to move and dispense
drops at precise locations. Typically, one precursor solution is dispensed at a
time. After one precursor solution is deposited, the solution is drained from the
dispenser and a second (and perhaps a third or fourth) precursor solution is
deposited at exactly the same position on the spot array electrode. The result is
an array of drops containing dierent pre-programmed amounts of each metal.
The distances between photocatalyst spots on the array are usually about
500900 mm, with a spot diameter of approximately 200500 mm as discussed in
Section 6.3. Multidispenser systems are also available, and these speed up array
preparation. With these, one must calibrate each dispenser drop size to establish each spot composition. Dispensers can have reproducibility problems
because they are easily clogged with particles and damaged by inadvertent
crashes with substrate. All solutions used in spot preparation should be ltered.
An example of dispensing equipment for creating spot array electrodes for
SECM is a CH Instruments model 1550 Dispenser (Austin, TX) with a
piezoelectric dispensing tip (MicroJet AB-01-60, MicroFab, Plano, TX) connected to an XYZ stage driven by a computer-controlled stepper-motor system
(Newport). The applied potential and the pulse duration are controlled to
change the amount dispensed from the piezo-dispensing tip. Typical drop sizes
are B100 pL. For example, to get B100 pL/drop with the above equipment, a
potential of 80 V is applied to the piezo-dispensing tip for 40 ms.15 The total
number of drops can vary depending on the resolution of concentrations
needed. For example, a total of 10 drops will give a 10% change/drop
in composition, while a total of 33 drops will give a 3% change/drop in
composition.
When creating spot array electrodes, great care must be taken when
producing the spots so that one can accurately compare their photocatalytic
behavior. To make accurate comparisons, it is important that each spot has the
same diameter and the same thickness. An example of an optical prole image
showing the uniformity of a good spot array electrode created by the piezodispensing technique is shown in Figure 6.2.13
Here the optical prole image was measured by white light vertical scanning
interferometry using a commercial optical surface proler (NT9100, Veeco,
New York).16 The color in Figure 6.2 represents the surface height of the spot
array electrode. In this example, each spot has a uniform thickness of 440 nm
and uniform diameter of 230 mm.
To create high-quality spot array electrodes for which accurate comparisons
between the spots can be made, one must consider several factors: the support
electrode material, the photocatalyst precursors, the solvents for the photocatalyst precursors, pretreatment of the support electrode, the spot deposition
method and conditions, spot size and spacing, and annealing of the electrode.
Here we provide guidelines for each of these factors for creating spot array
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Figure 6.2
Chapter 6
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17,19
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Chapter 6
Figure 6.3
(a) Diagram of a spot array and resulting SECM image of the array
involving W doping of BiVO4. Brighter yellow spots indicate higher
photocatalytic activity of the specic composition.21(b) Schematic diagram of scanning electrochemical microscope (SECM) with the ber optic
for photoelectrochemical screening of a photocatalytic material array.14
Reprinted with permission from J. Lee, H. Ye, S. Pan, A. J. Bard, Anal.
Chem., 2008, 80, 7445; and H. Ye, J. Lee, J. S. Jang, A. J. Bard, J. Phys.
Chem. C, 2010, 114, 13322. Copyright 2008 and 2010 American Chemical
Society.
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21
photoactivity can be found (Figure 6.4). The size of the ber optic, the dimension of the spots on the array, and the scan rate are important to ensure
high resolution of the SECM. Although a smaller irradiated area can provide
higher geometric resolution, the intensity of the light through the smaller
diameter optical ber decreases the photocurrent, making fast scanning more
dicult.
Figure 6.4
(a) Schematic view of the ber optic and the array substrate in the SECM
setup. (b) An image of spot array and (c) corresponding current vs.
distance plot. Peaks in (c) represent photoactivity of each spot. The
resolution of the peaks in (c) depends on dimensions in (a).
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Chapter 6
When designing the spacing of a spot array electrode and the positioning of
the ber optic cable, it is important to determine the signal resolution. The
signal resolution (Rs) can be determined by considering the geometry of the
SECM system assuming that (1) the photocurrent is sucient to resolve the
peak current from the background current and (2) the tip scan rate (ber optic
movement distance per unit time) is slow enough to a get steady state photocurrent at all points on the scan. We will discuss the dependence of pixel
resolution on scan rate below.
RS
ds2 ds1
ds2 ds1
ws2
ws1 ws2 = 2
6:1
In equation (6.1), ds1 and ds2 are the positions of two adjacent spots, spot 1
and spot 2, respectively along a line of spots, and ws1 and ws2 are the average
peak width of spot 1 and spot 2, respectively. The average peak width can be
approximated as the spot diameter (Dspot) when the spot diameter is larger than
the irradiation diameter (Dirr). When the irradiation diameter is larger than the
spot diameter, the average peak width can be approximated to the irradiation
diameter.
ws2 Dirr ;
Dirr 4 Dspot
6:2
Dspot ;
Dspot 4 Dirr
When the signal resolution is 1 or less, peaks are not well resolved, and a
resolution of at least 1.5 is recommended for direct comparison of photocurrents generated at individual spots on a spot array electrode.
The actual irradiation diameter (Dirr) depends on the specications of the
ber optic (core diameter (Dfo) and numerical aperture (NA)) and the height
(Hfo) (i.e. the distance between the ber optic and the substrate). The irradiation diameter on the electrode surface can be calculated by,
Dirr Dfo 2 Hfo tan y
6:3
6:4
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Figure 6.5
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6.3.2
Guidelines
The SECM cell for photocatalyst rapid screening consists of a Teon cell body,
an O-ring, the spot array electrode, and a plastic piece that holds the array
against the O-ring and in contact with electrolyte in the cell (Figure 6.7). All
components are tightly assembled with screws. The cell body has one small
chamber for the counter electrode and a larger chamber for the reference
electrode. The O-ring limits the size of the array and is consistent with the
moving range of the stepper motors in the SECM. The size of the array should
be designed to this limitation.
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Figure 6.6
Chapter 6
The electrolyte for the screening is determined by the nature of the desired
photoreaction. If the goal of the experiment is to screen for the maximum
photoactivity of an n-type material, one can use a sacricial reagent (e.g. SO32)
as an electron donor that undergoes an irreversible reaction. If one is interested in
a specic reaction (for example water oxidation with an n-type semiconductor),
the corresponding solution would be water with buer electrolyte at a particular
pH. In this case, recombination of photogenerated carriers with reaction
intermediates will often produce a smaller photocurrent than that seen with a
sacricial donor. If the photoreaction at the semiconductor involves the
production or consumption of protons, the electrolyte should be adequately
buered to prevent signicant pH changes at the electrode surface.
The adhesive copper tape attached FTO of the array electrode substrate is
placed between the cell body and the back of the cell. The holes for working and
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Figure 6.7
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Photos of an SECM cell for PEC array screening. From the top,
assembled cell, cell body, O-ring, spot array electrode substrate with
adhesive copper tape attached, bottom side of the cell and screws.
reference electrodes prevent them from interfering with the movement of the
SECM tip, i.e. the ber optic and its holder. The optical ber is positioned 100
to 200 mm above the substrate to prevent it from touching the substrate while
screening. This is accomplished by rst touching the ber optic to the FTO of
the substrate, tightening the ber in the SECM tip holder, and then withdrawing the ber away from the substrate to the desired distance using the
piezoelectric or stepping motor actuator. The array can be irradiated with the
full light of the Xe lamp or at a given wavelength by inserting a bandpass lter
between the ber optic aligner and the Xe lamp.
Many factors aect the image quality and current magnitude of the screened
array. Light intensity must be constant during the scanning. Thus, one needs to
wait until the Xe lamp has stabilized to prevent drifting of the light intensity
with time. Higher light intensities generally provide better signal to noise ratios.
Generally, screening is carried out under chronoamperometric conditions.
The potential of the substrate should be selected at a position where the dark
current is near zero while the photocurrent reaches its maximum level. For
example, for the current-potential prole of the photocatalyst shown in
Figure 6.8, holding the potential at 0.2 to 0.3 V vs. Ag/AgCl for screening
produces a high photocurrent while the dark current is small. The current scale
for the color-coded image needs to be adjusted for a good signal-to-noise ratio
and contrast between the dierent spots.
Even when the potential is set where the dark current is small, the background current from the substrate should be minimized. This often requires
adjusting the potential and allowing the background current to stabilize by
holding it in the dark for a signicant time before scanning. For spots of the size
described here, a typical background current is on the order of 108 to 107 A.
If the background current is signicantly larger, leakage of solution to the
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Chapter 6
Figure 6.8
contact might be the cause. An unusually small background current, e.g. 109 A,
might indicate bad contact to the FTO.
6.3.3
Data Analysis
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Figure 6.9
Figure 6.10
Spot array with the same component and the same concentration.
Although the rst spot shows less photocurrent due to slight mismatch
of thickness, the actual photocurrent dierence is only about 40 nA,
which is not signicant.
Figure 6.2), one can evaluate spot thickness by white light interferometry or
atomic force microscopy. It is also possible to obtain absorbance spectra of
spots in an array with a ber optic light source and a detector.13
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Chapter 6
photolysis, i.e. the hydrogen evolution and oxygen evolution reactions (HER
and OER). Both are heterogeneous, multi-electron inner-sphere reactions,
which can limit the overall water photolysis rate because of slow kinetics.25
Consequently, electrocatalysts are often required to achieve reasonable reaction rates. Extensive studies have been done to nd good electrocatalysts for
the HER and OER on both conductor and semiconductor electrodes. For
example, Pt, Pd, Ru, Ni, Ni-Mo, MoS3, and many other materials have been
studied as HER catalysts2629 and have been deposited on Si, Cu2O, SrTiO3,
and other photocathodes.3032 Similarly, Co3O4, RuO2, MnO2, IrOx, Pt and
many other metal (hydr)oxides and complexes have been reported as good
OER electrocatalysts3335 and have been applied to Fe2O3, BiVO4, TaON,
WO3, TiO2, and many other photoanodes.3641 Thus, it is of interest to screen
dierent electrocatalysts on semiconductor photocatalysts. The existence of
catalyst-support interactions as well as molecular interactions between electrocatalysts and adsorbates (e.g. hydroxides and protons) can aect the activity
of the electrocatalysts. This implies that the activity of a given electrocatalyst in
a PEC system may be dierent than that of the same electrocatalyst on a
conductive support in the dark.34,42,43
Rapid screening of photocatalysts with electrocatalysts is a valuable approach to nding a good combination of electrocatalyst and photocatalyst. For
example, the rapid screening of the electrocatalyst arrays prepared on photoelectrodes has been demonstrated using SECM to study the OER activity of
several electrocatalysts on W-doped BiVO4.17 In this study, the OER activity of
cobalt oxide electrodeposited from a phosphate medium (Co-Pi), Co3O4, Pt,
and IrOx on W-doped BiVO4 arrays were investigated (Figure 6.11).17 These
included Ir/Co oxide electrocatalyst arrays with dierent atomic ratios of Ir/Co
deposited using the piezoelectric dispenser on the photoanode substrate
(Figure 6.11(a)). The deposition and heat treatments were similar to those
described previously for the photocatalyst arrays, but a photoanode was used
in place of the conducting substrate. Moreover, photochemical deposition was
used to deposit Pt electrocatalyst arrays on the W-doped BiVO4
(Figure 6.11(b)). This was accomplished by placing an optical ber over the
photocatalyst substrate to generate electron-hole pairs, where the metal precursor, H2PtCl6, was reduced to form the electrocatalyst while the generated
hole was consumed by a sacricial electron donor, MeOH. From the rapid
screening, Co3O4 and Pt were found to be good electrocatalysts with W-doped
BiVO4. In contrast, IrOx formed from nanoparticles showed weaker OER activity on W-doped BiVO4, although it is a good OER electrocatalyst on conducting substrates in the dark. Again, the results indicate strong interactions
between the electrocatalysts and the photocatalysts, which may signicantly
aect the kinetics of desired chemical reactions on the electrocatalysts.
Using the rapid screening technique, optimum compositions of the complex
electrocatalyst pairs, as well as the deposition conditions, can be studied on
photoelectrodes.
There are several advantages to using a photoelectrode as the substrate for
rapid screening of electrocatalyst arrays including: (i) the activities of the
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Figure 6.11
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Chapter 6
The fact that the preparation methods for electrocatalysts vary with the
nature of the electrocatalyst (e.g. direct application, photodeposition, electrodeposition) may limit the application of rapid screening. For example, if
dierent electrocatalysts cannot be prepared simultaneously on the same
photoelectrode using identical preparation methods or if the photoelectrodes
are degraded during the preparation of the electrocatalysts, rapid screening
cannot be used. The interactions between the catalyst precursor solution and
the photoelectrode substrates can also limit array preparation with a
piezoelectric dispenser. For example, if a drop of precursor solution is not
conned to a certain photocatalyst spot and spreads over the substrates, the
thickness or amount of electrocatalyst on the spots cannot be controlled.
Consequently, quantitative comparisons between the spots in an array
may not be possible. Thus, in screening arrays of the electrocatalysts on a
photoelectrode, it is important that they are properly prepared as described
in 6.2.
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Figure 6.12
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Figure 6.13
Chapter 6
proportional to the donor density. The dopants can also modify the electronic
states of the host semiconductor, e.g. the band-gap energy of photocatalysts as
reported for TiO2.59 In addition to the electronic modication of the semiconductor, heavily doped metal oxides show a deformation of the crystal
structure as shown in Figure 6.13(c) and (d) for BiVO4.15 In Figure 6.13(c) and
(d), the lattice parameters of monoclinic scheelite-like structures were changed as
the doping concentration of W and Mo increased in the BiVO4 with an improvement in performance. The relationship of doping with the crystal and
electronic structures and the activity of photocatalysts is discussed in depth in
reviews specically dealing with the water splitting reaction.15,6063
References
1. E. W. McFarland and W. H. Weinberg, Trends Biotechnol., 1999, 17, 107.
2. R. Potyrailo, K. Rajan, K. Stoewe, I. Takeuchi, B. Chisholm and H. Lam,
ACS Comb. Sci., 2011, 13, 579.
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