Guest Commentary
pubs.acs.org/JPCL
On the Solar to Hydrogen Conversion Eciency of Photoelectrodes
for Water Splitting
T he conventional denition of the solar to hydrogen
conversion eciency of photoelectrochemical solar cells
for water splitting is dicult to relate with three-electrode half-
cell measurements of photoelectrodes that cannot split water
without the support of additional bias from an external power
source such as a photovoltaic cell in tandem with the
photoelectrode. An alternative denition is proposed that
allows the estimation of the intrinsic (internal) solar to
chemical conversion eciency of the photoelectrode rather
than the overall eciency of the entire tandem cell. We show
how the photocurrent and photovoltage produced by the
photoelectrode can be extracted from three-electrode voltam-
mograms measured in the dark and under illumination. The
photocurrent photovoltage product yields the internal
photovoltaic power produced by the photoelectrode which,
upon multiplication by its electrolysis eciency, provides the
intrinsic solar to chemical conversion eciency. This analysis
yields the current and voltage that should be provided to the
photoelectrode by the external power source in order to
achieve optimal solar to chemical conversion eciency.
The solar to hydrogen (STH) conversion eciency of
photoelectrochemical solar cells for water splitting is dened
as1
|J (mA/cm 2)| 1.23(V)
STH = sc F
P(mW/cm 2)
AM1.5G (1)
where Jsc is the short-circuit photocurrent density, F the
Faradaic eciency for hydrogen evolution, and P the incident
illumination power density. All these parameters have to be
measured under standard solar illumination conditions
(AM1.5G), without any sacricial reagents and without any
pH or electrical bias between the working and counter
electrodes.1 It is noteworthy that eq 1 denes the STH
conversion eciency of the entire photoelectrochemical cell
including all of its components: working and counter
electrodes, electrolyte, separator, wires, and so forth. Each
and every one of them contributes to the overall loss because of
recombination, polarization, diusion, internal resistance, or
other losses.2 The cell eciency, as dened by eq 1, accounts
for all these losses altogether. So although it is an important
benchmarking parameter of the photoelectrochemical cell,1 it is
not necessarily an accurate measure of the intrinsic eciency of
the photoelectrode within the cell.
In order to measure the intrinsic eciency of the
photoelectrode excluding the parasitic losses that arise from
other components in the cell, the photoelectrode should be
tested in a three-electrode conguration that measures the
current between the working photoelectrode and a counter
electrode as a function of the photoelectrode potential against a
third electrode, that is the reference electrode.3 Indeed, three-
electrode half-cell measurements are frequently carried out
and many reports present the current density (J), measured in
the dark and under illumination, as a function of the
2014 American Chemical Society
photoelectrode potential (U) against a reference electrode
such as the saturated calomel electrode (SCE)4 or the reversible
hydrogen electrode (RHE).5 It is noteworthy that the STH
conversion eciency, as dened by eq 1, cannot be obtained
from three-electrode measurements because the short-circuit
condition is ill-dened. Although in principle one could
measure the potential drop, that is the voltage (V), between
the working and counter electrodes using an electrometer and
thereby determine when short-circuit (V = 0) occurs, this
would only bring it back to square one with the parasitic losses
in the cell.
Another problem arises from the fact that electrolysis is an
endergonic reaction that requires work expenditure. The
minimum voltage that must be exerted in order to split water
is higher than the reversible potential of the water
decomposition reaction, Urev = G/nF = 1.23 V (under
standard conditions). In practice, a voltage of 1.6 V or above is
typically applied in state-of-the-art electrolysis cells in order to
drive the water splitting reaction at a suciently high rate.6
This voltage can be reduced by substituting metal electrodes
with semiconductor photoelectrodes that produce photovoltage
upon illumination. The photovoltage produced by the photo-
electrode adds up to the external voltage from the power source
such that the two of them together provide sucient voltage to
drive the water splitting reaction. Thus, the photoelectrode can
save power from the power source.
Ideally, the photovoltage produced by the photoelectrode
would suce to split water all alone without another power
source. But in practice, there are hardly any photoelectrodes
that can provide such a high photovoltage all by themselves,
except for those made of wide band gap materials such as
SrTiO3 and KTaO3 that absorb only a small fraction of the solar
spectrum resulting in too low a STH conversion eciency.7
Tandem cells overcome this problem by combining the water
splitting photoelectrode in tandem with another photo-
electrode or photovoltaic cell that provides the additional
voltage that is needed to split water. The pursuit of such
tandem cell devices is a rather complicated engineering exercise
that requires careful integration and optimization of both the
optical and electrical coupling between the two photoelectrodes
or photocells.8,9 Moreover, because photovoltaics is already a
mature technology, whereas water photoelectrolysis is not; the
photoelectrodes impose the bottleneck, by far and large, toward
ecient tandem cell devices. Under the circumstances, it does
not make much sense to spend so much time and eorts in
integrating low-eciency photoelectrodes with high-end photo-
voltaic cells. It is rather premature given the wide gap in
performance between the two components. Indeed, except for
very few reports that have convincingly demonstrated that
building such tandem cell devices is possible,10,11 most of the
work is still at the single component photoelectrode level rather
Published: October 2, 2014
3330 dx.doi.org/10.1021/jz501716g | J. Phys. Chem. Lett. 2014, 5, 33303334
The Journal of Physical Chemistry Letters
than at the multicomponent tandem cell device level. With the
lack of the second photoelectrode or photovoltaic cell that
would provide the additional voltage to drive the water splitting
reaction in the tandem cell, the missing voltage is readily
provided by a potentiostat. This is the most convenient way to
test the photoelectrodes, and at present, this seems like the
most reasonable strategy to expedite progress in this eld.
However, it carries a toll, like any compromise does. The toll is
that the eciency of the tandem cell cannot be measured
without assembling it together in the rst place. Therefore, the
STH eciency dened by eq 1 becomes irrelevant when the
photoelectrode is measured alone, without the rest of the
tandem cell.
In an attempt to overcome this shortcoming, the so-called
applied bias photon-to-current conversion eciency has been
evoked1
|J | (1.23 V )
ABPE =
photo
P
AM1.5G (2)
where V is the voltage that is applied to the cell from an
external power source and Jphoto is the photocurrent measured
at this voltage. Although this equation is correct from the
thermodynamic perspective, it does not allow quantifying the
intrinsic eciency of the photoelectrode because of the very
same reasons that were mentioned above. Furthermore, it is
noteworthy that some of the champion photoanodes that have
been reported to date reached high photocurrents at potentials
above 1.23 VRHE (volts against the reversible hydrogen
electrode).1113 This means that they require a voltage V in
excess of 1.23 V in order to achieve high photocurrent, and
hence, according to eq 2, the ABPE is negative, implying that
there is no net chemical power produced from sunlight. Does it
mean that they should not be operated above 1.23 VRHE?
So, we see that the conventional eciency denitions are
made for the entire tandem cell, but they are less helpful when
it comes to examining the intrinsic eciency of the photo-
electrode alone, without the rest of the tandem cell. Without
knowing the intrinsic power characteristics of the water
splitting photoelectrode, namely, the photocurrent vs photo-
voltage relationship, it is dicult to design optimal coupling
with the rest of the tandem cell. Here, we show how the
intrinsic power characteristics of the photoelectrode can be
obtained, very simply, from current vs potential voltammo-
grams measured in three-electrode conguration in the dark
and under illumination. From the intrinsic power characteristics
we obtain the maximum power point, namely, the maximum
photocurrent photovoltage product wherein the photo-
electrode converts solar power to electrical power at its highest
internal power conversion eciency, thereby saving maximum
power from the external power source. The product of this
internal power conversion eciency with the electrolysis
eciency of the photoelectrode in converting electrical power
to chemical bonds yields the intrinsic solar to chemical
conversion eciency of the photoelectrode. The latter reaches
a maximum at some specic current and potential values that
dene the optimal conditions for achieving maximum internal
solar to chemical conversion eciency by the photoelectrode.
These conditions are essential for designing optimal coupling
between the photoelectrode and the other components of the
tandem cell, especially the second photoelectrode or photo-
voltaic cell.
3331
Guest Commentary
In order to demonstrate this concept, we use an iron oxide
(-Fe2O3) thin lm photoanode as a case study. This particular
photoanode comprises of a 50 nm thick -Fe2O3 layer
(undoped) that was deposited by spray pyrolysis on an FTO-
coated glass substrate using a standard recipe as reported
elsewhere.14 Figure 1 shows current density (J) vs potential (U)
Figure 1. Current density (J) vs potential (U) voltammograms
measured in 1 M NaOH aqueous solution in the dark (dashed black
line) and under AM1.5G solar simulated illumination (full black line),
obtained with a 50 nm thick -Fe2O3 layer deposited on FTO-coated
glass substrate. The dierence between the light and dark currents,
that is, the photocurrent, is shown by the blue dotted curve with the
blue open triangles.
voltammograms that were measured in 1 M NaOH aqueous
solution in the dark (Jdark, dashed line) and under AM1.5G
solar simulated illumination (Jlight, full line). The dierence
between the light and dark currents is the photocurrent, Jphoto =
Jlight Jdark, shown by the blue curve with the triangles.
Central to the construction of the internal power character-
istics of the photoanode is the photovoltage, Vphoto. Provided
that the internal resistance of the photoanode is small, as can be
seen by the steep slope of the dark voltammogram, the
photovoltage is simply the potential shift between the light
current and the dark current, as shown by the horizontal red
arrow in Figure 1. It arises from the photovoltaic eect at the
electried junction between the photoanode and the aqueous
electrolyte solution.15 Consequently, the photoanode behaves
like an anode connected in series to a photovoltaic cell,16 an
internal photovoltaic cell that corresponds to the photovoltaic
action of the photoanode. The latter produces a photovoltage
that adds up to the applied potential from the potentiostat
(U).17 Thus, under illumination, the photoanode is eectively
at a surplus potential with respect to the applied potential, Ulight
(the subscript light signies that this is the potential applied to
the photoanode under light). The eective potential that drives
the water oxidation current is Ueff,light = Ulight + Vphoto, where
Ulight is the applied potential and Vphoto is the photovoltage.
Because the current is an injective function of the eective
potential, J = f(Ueff), under light it reaches the same level as in
the dark at a lower applied potential (Ulight) than in the dark
(Udark). In other words, Jlight = Jdark = J requires that Ueff,light(J) =
Ueff,dark(J) = Udark(J); therefore, we get Vphoto(J) = Udark(J)
Ulight(J). This is illustrated by the horizontal red arrow in Figure
1, whose length is commensurate with the photovoltage at the
respective current density (J = 0.2 mA/cm2 in this case). The
dx.doi.org/10.1021/jz501716g | J. Phys. Chem. Lett. 2014, 5, 33303334
The Journal of Physical Chemistry Letters
vertical red arrow shows the photocurrent at the same current
density. Thereby, the photocurrent and photovoltage can be
extracted from the dark and light voltammograms, as illustrated
by the red arrows in Figure 1 for a current of 0.2 mA/cm2.
Now that we know what the photovoltage is and how to
extract it from the current vs potential voltammograms, we can
draw the photocurrent as a function of the photovoltage, as
shown in Figure 2a. This curve describes the intrinsic
Figure 2. Intrinsic photovoltaic power characteristics of the photo-
anode. (a) The photocurrent as a function of the photovoltage. (b)
The intrinsic photovoltaic power as a function of the photovoltage.
The secondary y axis on the right of the gures shows the potential
(Ulight) that was applied to the photoanode by the potentiostat, under
light, as a function of the photovoltage.
photovoltaic power characteristics of the photoanode, and the
photocurrent photovoltage product, shown in Figure 2b, is
the light-induced electric power produced, internally, by the
photoanode. In other words, this is the intrinsic photovoltaic
power of the photoanode. Also shown on the secondary y axis
of these gures is the potential, Ulight, that was applied to the
photoanode, under light, as a function of the photovoltage. The
intrinsic photovoltaic power reaches a maximum of 0.16 mW/
cm2 at a potential (Ulight) of 1.4 VRHE. This corresponds to a
power conversion eciency of 0.16% from solar-simulated light
power of 100 mW/cm2 to electric power of 0.16 mW/cm2. The
ll factor reaches 43% at the maximum power point.
Now there is an important dierence between the power
produced by the photoanode and that of a conventional solar
cell. The latter provides electric power to the load connected to
it, where the power is spend on carrying out an electrical work.
But the photoanode carries out a dierent sort of work, a
chemical work that is spent on splitting water in order to
produce oxygen and protons from water as well as electrons
3332
Guest Commentary
that depart as anodic photocurrent. Having the photovoltaic
power of the photoanode spent on splitting water at the
photoanode/electrolyte interface, the next question is how
ecient the water splitting process is. In other words, what the
electrolysis eciency, el, is. This question has a simple answer.
It is the eciency of the photoanode in converting electric
power to chemical power. The latter is given by the product of
the reaction rate, measured in terms of the Faradaic current of
the reaction, times the reversible potential of the reaction, that
is 1.23 VRHE for water oxidation, yielding el = F
1.23(VRHE)/Ueff(VRHE) wherein Ueff is the eective potential
which is the sum of the applied potential from the external
power source plus the internal photovoltage of the photoanode.
As noted earlier, Ueff(J) = Udark(J) at the same current (J).
Although we did not measure the Faradaic eciency of this
particular photoanode, it is safe to assume that it is 100% (or
very close to it) based on previous reports on -Fe2O3
photoanodes.18,19 So now the intrinsic solar to chemical
conversion eciency of the photoanode can be dened as
J (mA/cm 2) Vphoto(V)
ISTC = el
photo
P(mW/cm 2)
AM1.5G
2
1.23(VRHE) Jphoto (mA/cm ) Vphoto(V)
Udark(VRHE) 100(mW/cm 2)
AM1.5G
(3)
where Udark is the potential that must be applied to the
photoanode in order to reach the respective current in the dark.
Equation 3 denes the intrinsic solar to chemical (ISTC)
conversion eciency of the photoanode, not to be mistaken
with the solar to hydrogen (STH) conversion eciency of the
entire tandem cell that is dened by eq 1.
Using the ISTC denition in eq 3 and the results in Figure
2(a) we can nally obtain the ISTC eciency of the
photoanode as a function of any of the aforementioned
parameters, namely the current (J), photocurrent (Jphoto),
photovoltage (Vphoto), and applied potential in the dark (Udark)
or under light (Ulight). Figure 3 shows the ISTC eciency of
the photoanode as a function of the photocurrent density. Also
Figure 3. ISTC eciency of the photoanode, plotted by the full line
curve with respect to the primary y axis on the left, as a function of the
photocurrent density on the x-axis. Also shown is the photoanode
potential, under light, plotted by the dashed line curve with respect to
the secondary y axis on the right.
dx.doi.org/10.1021/jz501716g | J. Phys. Chem. Lett. 2014, 5, 33303334
The Journal of Physical Chemistry Letters
shown in the same graph is the applied potential under light
(Ulight), plotted by the dashed line curve. The maximum ISTC
eciency reaches 0.11% at a photocurrent density of 0.4 mA/
cm2 and a potential (Ulight) of 1.4 VRHE.
The way to understand the ISTC eciency of the
photoanode is as follows. When the photoanode is powered
by a power source, any power source for that matter, to its
maximum ISTC point, it produces, under solar-simulated light,
a photocurrent density of 0.4 mA/cm2 at an applied potential of
1.4 VRHE. In the dark it would have to be biased to a higher
potential of 1.8 VRHE in order to produce the same current (see
Figure 1). This means that the solar-simulated light power (100
mW/cm2) saves 0.4 V from the external power source, or a
power of 0.4(V) 0.4(mA/cm2) = 0.16 mW/cm2. But the
electric power saved from the power source is reduced by the
conversion eciency of the electrolysis reaction, el
1.23(VRHE)/Udark(VRHE), which is 68% at this current level
because Udark = 1.8 VRHE. Thus, the light-induced contribution
to the chemical power produced by the photoanode is 68%
0.16 (mW/cm2) = 0.11 mW/cm2, which corresponds to an
ISTC eciency of 0.11%. Figure 3 shows that this is the
maximum ISTC eciency of the photoanode. Drawing either
more, or less, current from the photoanode would necessarily
reduce the ISTC eciency. Therefore, the maximum ISTC
point denes the optimal conditions for operating the
photoanode.
It is noted, again, that the ISTC eciency of the photoanode
(dened by eq 3) is not the STH eciency of the tandem cell
(dened by eq 1). Nevertheless, there is a link between the two
of them. Suppose the photoanode is coupled in tandem with a
photovoltaic cell that provides just the right voltage and current
to produce a photovoltage Vphoto and photocurrent Jphoto by the
photoanode, and suppose there are no additional losses by the
other components in the tandem cell, including the counter
electrode, that is, the cathode where hydrogen evolves. Then
the ISTC eciency of the photoanode plus the ISTC eciency
of the photovoltaic cell, calculated using eq 3 with Vphoto of the
photoanode replaced by Vphoto of the photovoltaic cell (i.e.,
Vphoto = Ulight in this case), predicts what the STH eciency of
this tandem cell would be under these conditions. Hence, the
ratio between the ISTC of the photoanode and the STH of the
tandem cell, or interchangeably the ratio between the
photovoltage produced by the photoanode and the total
voltage of all the power sources in the tandem cell (including
the photoanode itself), corresponds to the partial contribution
of the photoanode to the chemical power produced by the
tandem cell.
Applying the same analysis to the mesoscopic -Fe2O3
photoanode reported by Warren et al.,13 Figure 4 shows the
ISTC eciency of this photoanode as a function of the
photocurrent that it draws. It reaches a maximum value of
0.94% at a photocurrent of 3.4 mA/cm2, which requires
applying a potential of 1.4 VRHE from the potentiostat, under
light. This means that this photoanode would be best coupled
to a power source that sets the photoanode potential to 1.4
VRHE, yielding a current of 3.4 mA/cm2 generated by the
photoanode under AM1.5G sunlight. The chemical power
produced under these conditions is 3.4(mA/cm2) 1.23(V) =
4.2 mW/cm2, out of which 0.94 mW/cm2, that is 22%, is
produced by internal solar power conversion at the photoanode
whereas the rest comes from the power source (which could be
a photovoltaic cell in tandem with the photoanode).
3333
Guest Commentary
Figure 4. ISTC eciency of the mesoscopic -Fe2O3 photoanode
reported by Warren et al. in ref 13, plotted by the full line curve with
respect to the primary y axis on the left, as a function of the
photocurrent density on the x axis. Also shown is the photoanode
potential, under light, plotted by the dashed line curve with respect to
the secondary y axis on the right.
To sum up, we have demonstrated how to extract the
internal photovoltaic power characteristics and the intrinsic
solar to chemical conversion eciency of iron oxide (hematite)
photoanodes from current vs potential voltammograms
measured in the dark and under illumination using the
ubiquitous three-electrode half-cell test conguration. This
analysis yields the current that can be drawn from the
photoanode and the potential that should be applied to it in
order to make it convert solar power to chemical power at its
maximum internal conversion eciency. These parameters are
essential for optimization of tandem cells for conversion of
solar power to hydrogen fuel. The analysis is self-consistent and
simple to pursue, and it should apply not only to iron oxide
photoanodes but also to other types of photoanodesas long as
their internal resistance is small. The extension to high internal
resistances will be discussed in a follow-up paper.
Hen Dotan
Nripan Mathews,
Takashi Hisatomi,
Michael Grat zel
Avner Rothschild*,
Department of Materials Science and Engineering,
TechnionIsrael Institute of Technology, 32000 Haifa,
Israel
Institute of Chemical Sciences and Engineering, Ecole
Polytechnique Federale de Lausanne, 1015 Lausanne,
Switzerland
AUTHOR INFORMATION
Corresponding Author
*A. Rothschild. E-mail: avner@mt.technion.ac.il. Tel.: +972-4-
829-4576. Fax: +972-4-829-5677.
Present Addresses
(N.M.) School of Materials Science and Engineering, Nanyang
Technological University, Nanyang Avenue, Singapore 639798.
(T.H.) Department of Engineering, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Notes
Views expressed in this Commentary are those of the author
and not necessarily the views of the ACS.
dx.doi.org/10.1021/jz501716g | J. Phys. Chem. Lett. 2014, 5, 33303334
The Journal of Physical Chemistry Letters Guest Commentary

The authors declare no competing nancial interests. (18) Sivula, K.; Le Formal, F.; Gratzel, M. Solar Water Splitting:

ACKNOWLEDGMENTS
The authors acknowledge support of this research by the
Progress Using Hematite (-Fe2O3) Photoelectrodes. ChemSusChem
2011, 4, 432449.
(19) Iandolo, B.; Wickman, B.; Seger, B.; Chorkendorff, I.; Zoric, I.;
Hellman, A. Faradaic Efficiency of O2 Evolution on Metal Nano-
European Commission (Nanostructured Photoelectrodes for particle Sensitized Hematite Photoanodes. Phys. Chem. Chem. Phys.
Energy Conversion, NanoPEC, contract number 227179), and 2014, 16, 12711275.
by Europes Fuel Cell and Hydrogen Joint Undertaking (FCH
JU) under Grant Agreement No. 621252 (PECDEMO
Photoelectrochemical Demonstration Device for Solar Hydro-
gen Generation).

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3334 dx.doi.org/10.1021/jz501716g | J. Phys. Chem. Lett. 2014, 5, 33303334