DOI: 10.1002/asia.
201701596 Focus Review
Heterogeneous Catalysis
Semiconductor-Based Photoelectrochemical Conversion of Carbon
Dioxide: Stepping Towards Artificial Photosynthesis
Hong Pang,[a, b] Takuya Masuda,[a, c] and Jinhua Ye*[a, b, d, e]
Abstract: The photoelectrochemical (PEC) carbon dioxide re-
duction process stands out as a promising avenue for the
conversion of solar energy into chemical feedstocks, among
various methods available for carbon dioxide mitigation.
Semiconductors derived from cheap and abundant elements
are interesting candidates for catalysis. Whether employed
as intrinsic semiconductors or hybridized with metallic coca-
talysts, biocatalysts, and metal molecular complexes, semi-
conductor photocathodes exhibit good performance and
1. Introduction
The anthropogenic exploration and utilization of fossil fuels
have led to the depletion of natural resources and massive
CO2 emissions.[1] Aimed at controlling the amounts of CO2 and
increasing new energy storage systems, CO2 conversion into
useful chemical feedstocks is a promising route to address the
problem.[2] Although the global carbon balance is based on af-
forestation, solar-driven CO2 conversion based on semiconduc-
tors making use of sunlight is believed to be one of the most
reasonable and attractive artificial approaches to alleviate ex-
cessive amounts of CO2 because of solar energy’s infinite reser-
voir and environmental benignancy.[3]
[a] H. Pang, Prof. T. Masuda, Prof. J. Ye
Graduate School of Chemical Science and Engineering
Hokkaido University, Sapporo 060-0814 (Japan)
E-mail: Jinhua.ye@nims.go.jp
[b] H. Pang, Prof. J. Ye
International Center for Materials Nanoarchitectonics (WPI-MANA)
National Institute for Materials Science (NIMS)
1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)
[c] Prof. T. Masuda
Research Center for Advanced Measurement and Characterization
National Institute for Materials Science (NIMS)
Tsukuba 305-0044 (Japan)
[d] Prof. J. Ye
TJU-NIMS International Collaboration Laboratory
School of Materials Science and Engineering
Tianjin University, Tianjin 300072 (P.R. China)
[e] Prof. J. Ye
Collaborative Innovation Center of Chemical
Science and Engineering (Tianjin), Tianjin 300072 (P.R. China)
The ORCID identification number(s) for the author(s) of this article can be
found under https://doi.org/10.1002/asia.201701596.
Chem. Asian J. 2018, 13, 127 – 142
low overpotential during carbon dioxide reduction. Apart
from focusing on carbon dioxide reduction materials and
chemistry, PEC cells towards standalone devices that use
photohybrid electrodes or solar cells have also been a hot
topic in recent research. An overview of the state-of-the-art
progress in PEC carbon dioxide reduction is presented and a
deep understanding of the catalysts of carbon dioxide re-
duction is also given.
Homogeneous catalysts, semiconductor suspensions, or het-
erogeneous photoelectrodes have contributed much to this
field.[4] Because the carbon atom in the CO2 molecule occupies
the highest valence, there are a variety of possible reduced
products in different oxidation states, ranging from gaseous
CO, CH4, and other multicarbon species (e.g., C2H4, C3H8) to
liquid chemicals, such as carboxylic acids (e.g., HCOOH,
CH3COOH) and oxygenated hydrocarbons (CH3OH), and so
forth.[5] However, the goal is not easy to realize from a techno-
logical point of view. Intrinsically, CO2 is a molecule of high sta-
bility with two symmetric C=O bonds in a short line, which re-
quires quite a high energy of about 750 kJ mol@1 to break the
initial carbonyl bond in CO2.[6] Moreover, proton reduction can
occur at potentials required for CO2 reduction, which results in
low selectivity and a low efficiency of the desired reaction. In
addition, although a great deal of literature has proposed vari-
ous materials that exhibit excellent performance, research into
CO2 reduction is still in its infancy. Not only is the solar-to-
chemical conversion efficiency from practical applications, the
durability, product selectivity, intermediate control of the cata-
lysts, and other related aspects remain scientifically challeng-
ing.[7] Because current research is at the fundamental stage,
various important processes, such as light harvesting and
charge separation/recombination, or those taking place at in-
terfaces, such as the adsorption/desorption of reactants, elec-
tron-transfer (ET) pathways, and formation/breakage of chemi-
cal bonds, are still not very clear and deserve more attention
and efforts from researchers.
First discovered by Halmann in 1978, the photoinduced re-
duction of CO2 into hydrocarbons was realized in the presence
of water under illumination.[8] In the following two decades,
the basic properties of the photoelectrochemical (PEC) reduc-
tion of CO2 over photocathodes based on semiconductors, es-
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pecially p-type semiconductors (p-SCs), such as GaP,[9] silicon,[10]
and CdTe,[11] were well investigated with or without roughly
deposited metals on the surface. However, during the next
decade, there was an apparent decrease in the number of
papers published in this field. After this period, with the exploi-
tation of environmental crises and the prospect of nanomateri-
als in the most recent decade, PEC CO2 reduction based on
semiconductors came back to the fore and an increasing
number of researchers are engaged in this field. At this time,
photoelectrocatalysts tend to be much smaller and of rich vari-
ety. Well-established efficient and earth-abundant nanostruc-
tures are also introduced to construct standalone devices for
CO2 reduction under sunlight.[12] A large amount of benchmark
results have emerged to push forward the development of ar-
tificial photosynthesis to a hot topic.
Different from previous reviews focusing on molecular metal
complexes[13] or electrocatalysts[5, 14] for CO2 reduction, herein,
we devote our attention primarily to the CO2 conversion pro-
cess on heterogeneous catalysts of semiconductor-based PEC
half-cells or standalone artificial leaves driven by solar light re-
ported recently. With electrolyte adjustment and hybrid modifi-
cation ranging from inorganic cocatalysts to biological or bio-
mimetic metal complexes, the products, selectivity, and current
efficiency have changed largely. Monolithic PEC cells com-
posed of a photocathode and a robust anode for solar fuels
are also introduced with an outlook towards artificial photo-
synthesis.
2. Fundamentals of PEC CO2 Reduction
2.1. Principles of Semiconductor-Based PEC CO2 Reduction
Generally, the PEC CO2 reduction is performed in single- or
two-compartment cells (H-type cell). Compared with the con-
ventional single-compartment cell, the H-type cell is recom-
mended and widely employed in the majority of current re-
search into electrochemical (EC) reactions, especially if taking
into consideration the accompanying severe proton penalty
and consequent solid/liquid junction change in the vicinity of
the electrode. In this regard, the H-type cell is made up of two
half-cells and a proton exchange membrane (Nafion), which
spatially separates CO2 reduction on the working electrode
and water oxidation on the counter electrode into different
chambers.[15]
Recently, instead of using a Nafion membrane, a bipolar
membrane (BPM) between the cathode and anode chambers
has been used to sustain steady pH values in each compart-
ment (Figure 1); this allows for the individual optimization of
each electrolyte at a suitable pH and a combined cell overvolt-
age.[16] BMP is composed of an AEL and CEL that allow protons
to transfer to the cathode and hydroxide ions to be transport-
ed to the anode; this balances consumed protons and hydrox-
ide ions, respectively, in the electrode reaction. For instance, if
CO2 reduction was conducted over a silver cathode in neutral
electrolyte with NiFeOx for the oxygen evolution reaction (OER)
in an alkaline environment, such design results in a total cell
voltage of more than 1 V, compared with the conventional cell
Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org
Focus Review
Figure 1. Ion transport through A) Nafion and B) BPM. Because the concen-
tration of K + far exceeds that of H + , K + is transported through Nafion. BPM
(B) consists of an anion-exchange layer (AEL) and a cation-exchange layer
(CEL) that block ions from the electrolyte and facilitate water dissociation at
the AEL–CEL interface. Reproduced with permission from ref. [17]. Copyright
2016 American Chemical Society.
with a platinum counter electrode and cation-exchange mem-
brane.[17]
Hong Pang received her B.S. in 2012 and M.S.
degree in 2015 from Tianjin University. She is
currently pursuing a PhD at Hokkaido Univer-
sity under the supervision of Dr. Jinhua Ye
and Dr. Masuda, concurrently working as a
Junior Researcher in National Institute for Ma-
terials Science (NIMS). Her interests mainly
focus on photofunctional materials for envi-
ronmental remediation and solar-to-chemical
energy conversion.
Takuya Masuda received his Ph.D. from Hok-
kaido University in 2006. He is now a Senior
Researcher at the National Institute for Ma-
terials Science (NIMS), and an Associate Pro-
fessor at the Graduate School of Chemical
Science and Engineering, Hokkaido Universi-
ty, Japan. His interest is in the development
of novel in situ characterization techniques
and their utilization for electrochemical pro-
cesses at solid–liquid interfaces.
Jinhua Ye received her Ph.D. from the Uni-
versity of Tokyo in 1990. She is now a Princi-
ple Investigator at the International Center
for Materials Nanoarchitectonics (MANA),
National Institute of Materials Science
(NIMS), and a Professor at the Graduate
School of Chemical Science and Engineer-
ing, Hokkaido University, Japan. Her research
interests focus on photocatalytic materials
and their applications in environment and
energy.
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Although CO2 reduction can occur at the surface of the sem-
iconductor electrode, semiconductors as photocathodes are
different from metals or other electrocatalysts in virtue of the
ability to absorb light and produce a photovoltage to supple-
ment the applied external potential, and even substitute the
total input.[3b] ET occurs at the semiconductor/electrolyte inter-
face to diminish the Fermi level (EF) difference between the
semiconductor and electrolyte if the semiconductor is im-
mersed in the electrolyte, which creates a space–charge region
at equilibrium, also called the depletion layer, which alters the
band diagram near the edges of the conduction (CB) and va-
lence band (VB). Typically, for an n-type semiconductor, of
which the Fermi level lies near the CB, electrons are the majori-
ty charge carriers that transfer from semiconductors to the
electrolyte, resulting in the upward band bending near the in-
terface, which favors the transfer of VB holes to the interface
and the oxidation reaction. On the other hand, downwards
band bending over the p-SC with an excess of holes, if the
Fermi level lies just above the VB (Ev), occurs to promote CB
electrons to the interface along the potential gradient to the
reduction reaction. With many holes in the VB and few elec-
trons in the CB, illumination can effectively increase the elec-
trons in the CB and the cathodic current.[3a, 8] Therefore, in PEC
reactions, p-SCs always serve as the photocathode, for exam-
ple, p-Si,[10] Cu2O,[18] GaP,[9] and ZnTe,[19] whereas n-type semi-
Figure 2. Energy band diagram of a p-SC photocathode and ET pathways during CO2 reduction in a) the equilibration state, b) the photochemical system,
c) the EC system, and d) the PEC system. NHE = normal hydrogen electrode.
Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org
Focus Review
conductors function as the anode.[20] In a PEC cell composed of
a p-SC cathode with a stable counter electrode, an external
positive electric bias applied on a semiconductor cathode will
move the band position upward. Instead of an external electric
potential, appropriate illumination can induce the transition of
semiconductor electrons from VB to CB; this produces a pho-
tovoltage that can also move the band position upward. The
band diagrams of an inherent semiconductor immersed in
electrolyte, with the application of an external electric field or
photoinduced voltage, as well as the photoelectric effect, are
illustrated in Figure 2. The Fermi level of the solution is gov-
erned by concentration and remains constant. As the semicon-
ductor is brought into the solution, ET occurred at the interface
until the Fermi levels of the semiconductor and liquid phases
are equal. Supposing Ev lies above the Fermi level of the redox
couple (Vredox), ET from the solution to semiconductor causes
the semiconductor to be negatively charged with respect to
the solution. A space–charge region in the range of 50–2000 a
and downward band bending occurs at the semiconductor/so-
lution interface.[3a] The consequent electric field will further en-
hance separation of the electron–hole pairs.
It should be noted that, by wiring the working electrode
with another auxiliary electrode, Schottky barriers occur at the
interface where the semiconductor is connected to the metal
wire to transfer electrons to the other site. Thus, an Ohmic
129 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

contact is required to lower the junction resistance and band
bending between the semiconductor and metal wire by de-
positing a layer of metals or alloys with an appropriate work
function.[15] As for the p-SC, the required work function of the
conductive layer needs to be larger than that of the semicon-
ductor, whereas the reverse is true for n-type semiconduc-
tors.[15] For example, a eutectic alloy of indium–gallium–zinc is
imperative for deposition between the back of the p-Si elec-
trode and the electrode holder to overcome the Schottky barri-
ers between the p-Si electrode and copper wire connected to
the EC workstation in the PEC experiment.[10c]
2.2. Thermodynamics and Kinetics of CO2 Reduction
The standard redox potentials for the transformation from CO2
to different C1-carbon fuel products, with respect to the stan-
dard hydrogen electrode (SHE), are given in Table 1.[6a, 14a, 21]
Table 1. Formal redox potentials (pH 7) for the reactions of CO2 reduction
to related products in aqueous media.
Reaction E8 vs. SHE [V]
2 H2O(l) + 2 e@ !H2(g) + 2 OH@(aq) @0.41
CO2(g) + 4 H2O(l) + 8 e@ !CH4(g) + 8 OH@(aq) @0.24
CO2(g) + 5 H2O(l) + 6 e@ !CH3OH(l) + 6 OH@(aq) @0.38
CO2(g) + 3 H2O(l) + 4 e@ !HCHO(l) + 4 OH@(aq) @0.48
CO2(g) + H2O(l) + 2 e@ !CO(g) + 2 OH@(aq) @0.52
CO2(g) + H2O(l) + 2 e@ !HCOO@(aq) + OH@(aq) @0.61
CO2(g) + e@ !CO2C@ @1.9
Based on the relationship of the Gibbs free energy change
(DG8) to the standard redox potential (E8), DG8 = @nFE8, it is
apparent that CO2 reduction is thermodynamically favored,
but, in practice, extra energy should be given to the electrode
to overcome kinetic barriers. Specialized catalysts can propa-
gate the reaction pathways by lowering the activation energy,
but semiconductors may go a step further than other electro-
catalysts in lowering the excess energy because of the photo-
voltaic effect. The low overpotential is not the result of one
factor. Other than band bending at the interface, it has rela-
tionship with CO2 adsorption and activation, intermediate sta-
bilization, and so forth because CO2 reduction is known to con-
sist of complicated multistep and multi-ET reactions.[22] Initially,
in pioneering work by Hori et al.,[23] it is prevalent that CO2 is
first reduced to the CO2C@ radical anion at approximately
@1.90 V versus NHE, which holds back subsequent reactions
with large kinetic barriers.[15, 23] Then CO2C@ proceeds to react in
different manner, according to the inherent characteristics of
the catalyst to form CO or HCOO@ . However, later such state-
ment became suspected because these reactions were more
likely to occur at a more positive potential than that of the
CO2/CO2C@redox potential. The detailed reaction steps are those
given in Equations (1)–(7):
CO2 þ e@ ! C CO2 @ ad ð1Þ
H þ e@ ! Had ð2Þ
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C CO2 @ ad þ Had ! HCOO@ ð3Þ
C CO2 @ ad þ H2 O þ e@ ! HCOO@ þ OH@ ð4Þ
HCOO@ þ e@ ! CO þ OH@ ð5Þ
C CO2 @ ad þ C CO2 @ ad ! 2 CO ð6Þ
C CO2 @ ad þ CO2 þ e@ ! CO þ CO3 2@ ð7Þ
These reactions suggest that water-mediated proton transfer
(PT) occurs to form HCOO@ [Eqs. (1)–(3)]. Subsequently, elec-
trons bind to the oxygen atom of CCO2@ for gold, silver, copper,
zinc, iron, nickel, and platinum, leading to HCOOH as the prod-
uct, but to the carbon atom of CCO2@ for heavy p-block metals
(In, Sn, Pb, Hg) to evolve CO. In nonaqueous solution without
a proton source, CO predominates as the main product.[15, 23] In
addition, CO2 reduction competes with H2 evolution at the
semiconductor electrode and might be the rate-determining
step. If CO2 reduction proceeds under mass transport control,
but H2 evolution occurs under activation control, the higher
energy of the CB of the semiconductor will lead to a higher H2
evolution current efficiency.[11b] From a more microview aspect,
the product distribution results from multiphysics, even includ-
ing the cathodic potential, electrode dimensions, geometry of
the cell,[24] and illumination intensity.[11a, 25]
From the kinetic perspective, typically, every chemical reac-
tion occurs stepwise and the electrons transfer one-by-one,
going through intermediate transition states. In each step,
there is a compromise in the binding strength of the reactant
to the catalyst, that is, it is necessary to find an optimal state
of the key intermediate that is neither too strongly nor too
weakly binding to the catalyst surface, according to the Sabati-
er principle.[26] The activity volcano model was hence devel-
oped to determine the optimal catalyst at or near the top.[22]
Different from the hydrogen evolution reaction (HER) with a
single intermediate, CO2 reduction undergoes multiple proton-
coupled electron transfer (PCET) steps, and there is more than
one intermediate in the reaction. Simultaneous transfer of mul-
tiple electrons means an extremely high intersection point of
the energy configuration of reactants and products in the reac-
tion coodinate. The PCET proceeds as sequential proton–elec-
tron transfer (SPET) pathways or concerted proton–electron
transfer (CPET) pathways, as determined by whether PT follows
ET or occurs in a concerted manner.[27] Although the majority
of surface reactions follow SPET pathways, it is assumed that
CPET is implicit in CO2 reduction. Generally, ET occurs in a re-
duction reaction if the intermediate has a high electron affinity,
whereas PT occurs in an oxidation reaction because the inter-
mediate has a low proton affinity. If the off-diagonal states are
energetically unfavorable and higher than the diagonal states,
CPET is predicted to be the only feasible pathway to avoid
high-energy intermediates. If PT and ET are decoupled, the cat-
alytic reaction features a strong pH dependence. For example,
CO2 reduction on a copper electrode shows a pH dependence
on different products. However, methane is not pH-dependent
on the reversible hydrogen electrode (RHE) scale, so it has
been suggested that the rate-determining step involves a
130 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Focus Review

CPET pathway. The formation of ethylene does not involve PT,

Table 2. Summary of recently reported representative PEC CO2 reduction
and hence, is not dependent on the SHE, but on the RHE; this reactions on semiconductor-based photocathodes.[a]
indicates that there is an intermediate in the rate-determining
step with suitable electron affinity.[28] We need to identify spe- Semiconductor Electrolyte Potential [V] Main product (FE Ref.
photocathode [%])
cific pathways on the basis of the direct observation of inter-
mediate species and products. Sn@Si NWs 0.1 m @0.875 (vs. HCOOH (88) [12a]
HCO3@ RHE)
Pt@TiO2/InP 0.02 m @0.77 (vs. CO (99 : 3) [36]
[EMIM]BF4 NHE)
3. PEC CO2 Reduction on Heterogeneous Semi- Cu@TiO2/InP nano- 0.5 m KCl @0.60 (vs. CH3OH (8.7) [37]
conductor Photoelectrodes pillars NHE)
InP/TiO2 NTs 0.1 m @1.35 (vs. CH3OH (41.17) [38]
CO2 reduction over light-harvesting semiconductor-based het- KHCO3 SCE)
erogeneous catalysts has been considered as a direct avenue Si/TiO2/Pt 0.1 m @0.8 CH3OH, C2H5OH, [39]
NaHCO3 C3H8OH (96.5)
to mimic the photosynthetic factory in nature to convert sun-
diamond 0.1 m @0.5 CO (> 90) [40]
light into high-energy solar fuels and has received substantial Na2SO4
interest.[29] By constructing a PEC cell with a suitable photoca- CdSeTe@TiO2 NTs 0.1 m @1.2 (vs. CH3OH (88) [41]
thode and anode to realize the carbon cycle, energized elec- KHCO3 SCE)
Au3Cu@Si NWs 0.1 m @0.20 (vs. CO (80) [12b]
trons induced by photoexcitation can be utilized to reduce
KHCO3 RHE)
CO2 directly. Semiconductors are introduced to cut down the Cu/p-Cu2O (stone- 0.1 m @2.0 (vs. Ag/ C2H4 (30.60) [18a]
electrical energy input and adjust the energy level of the pho- like) KHCO3 AgCl)
toelectrons. To satisfy these two points, semiconductors for a CuO/Cu2O NRs 0.1 m @0.2 (vs. CH3OH (95) [42]
photocathode base are required to have a band gap that Na2SO4 SHE)
Co3O4 0.1 m @0.9 (vs. HCOO@ (NA) [43]
matches well with the solar spectrum and have a sufficiently Na2SO4 SCE)
negative CB edge to supply sufficient overpotential for CO2 re- Cu/Co3O4 NTs 0.1 m @0.9 (vs. HCOO@ (100) [44]
duction for certain target products.[3c] Apart from the inherent Na2SO4 SCE)
SnO2/Fe2O3 NTs 0.1 m @1.1 (vs. Hg/ CH3OH (87.04) [45]
properties of the semiconductors (electronic structure, crystal-
KHCO3 Hg2Cl2)
line structure, shape, morphology, etc.), surface states and the p-CuInS2 0.1 m @0.54 (vs. CH3OH (97) [46]
reaction environment should be comprehensively balanced to Na2SO4 SCE)
determine a best practice. In this section, we discuss inherent CuInS2/graphene 0.1 m @0.59 (vs. CH3OH (95) [47]
Na2SO4 SCE)
semiconductors and hybrid photocathodes with modification
Mg:CuFeO2 0.1 m @0.9 (vs. HCOO@ (10) [48]
(metals, biological catalysts, metal complex catalysts, and poly- NaHCO3 SCE)
mers) to give a brief review of the semiconductor-based elec- CuFeO2/CuO 0.1 m @0.35 (vs. HCOO@ (> 90) [49]
trodes in this field. HCO3- RHE)
Fe@Cu oxide 0.1 m @0.4 (vs. Ag/ CH3COO@ (80 : 8) [50]
HCO3- AgCl)
Cu3Nb2O8 0.5 m @0.20 (vs. CO (9) [51]
3.1. Semiconductor Photocathodes NaHCO3 Ag/AgCl)
B:C3N4 0.5 m @0.40 (vs. C2H5OH (78) [52]
In early research, semiconductors with high CB position, such NaHCO3 Ag/AgCl)
as phosphites,[9, 11b, 30] tellurides,[11] and silicon,[10] electrodes ZnTe/ZnO/Zn 0.5 m @0.7 (vs. CO (22.9) [19a]
were selected to construct heterojunctions to perform PEC CO2 KHCO3 RHE)
reduction. In the following sections, the semiconductors are Au@ZnTe/ZnO NWs 0.5 m @0.5 (vs. CO (66) [19c]
KHCO3 RHE)
categorized into Groups III–V, IV, and II–V; oxide compounds; PPy/ZnTe 0.1 m @0.2 (vs. HCOOH (37.2), CO [19b]
and non-oxide compounds (Table 2) to give a specific descrip- KHCO3 RHE) (13.8)
tion of semiconductor-based photoelectrodes. The band posi-
[a] NW = nanowire, NT = nanotube, NR = nanorod, PPy = polypyrrole,
tions of the semiconductors are listed in Figure 3 and the EMIM = 1-ethyl-3-methylimidazolium, NA = not available, FE = Faradaic ef-
redox potentials for common reductive products are also pre- ficiency.
sented beside the band diagram.

pressure,[9b] solvents,[9c–e] and polymer modifications[9a] on the

3.1.1. Group III–V Compounds
Since the first attempt at PEC CO2 reduction was carried on
the p-type GaP photocathode,[8] more investigation have been
conducted on the III–V family. Except for GaN, common III–V
family members have a small band gap that can efficiently
absorb visible light, which provides extra charges for the redox
process. Halmann first reported that zinc-doped GaP generated
formic acid and trace amounts of formaldehyde and metha-
nol.[8] Afterwards, the effects of metal deposition,[9d, e, 31]
photoelectrodes have been investigated.
Recent studies of these materials have focused on the sur-
face properties, combined with DFT calculations and the modi-
fication of certain surfaces. MuÇoz-Garc&a and Carter clarified
the role of the p-GaP (110) surface surrounded by H2O mole-
cules in an EC reaction.[32] Both gallium and phosphorus atoms
have strong affinity for electrons and contact with electron
donors, such as pyridine. Hydride-like hydrogen atoms, as a
consequence of H2O dissociation, are bound to surface phos-

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Figure 3. CB and VB potentials of several commonly used semiconductors at
pH 0 versus NHE. Thermodynamic potentials for CO2 reduction and water
splitting into different products at pH 0 versus an NHE are shown beside the
band-edge positions of the semiconductors.
phorus atoms and may mediate CO2 reduction as an inter-
mediate.[33] This point was demonstrated on p-GaP in KCl as a
supporting electrolyte with 10 mm soluble pyridine compo-
nent; this could highly selectively produce methanol with a FE
of 100 % well below the thermodynamically required poten-
tial.[34] This material may undergo hydride transfer from the
pyridinium ring to CO2 to form a carbonate species that is elec-
troactive for reduction to methanol.
However, facile corrosion and the large band gap of p-GaP
limited its potential conversion efficiency. With optimal band
matching, p-GaAs (1.42 eV) has been extensively studied, since
the group of Halmann reported that photoassisted reduction
was also achieved over p-GaAs, but without a net gain in
energy conversion.[8, 9b, 30b, 35]
InP electrodes were systematically studied in carbonates, sul-
fates, phosphates, perchlorates of alkali salts, and tetraalkylam-
monium salts solvated in aqueous solution. Except for carbo-
nates (Na2CO3, Li2CO3, K2CO3), which supported the formation
of formic acid, other electrolytes (LiClO4, KClO4, NaClO4, Na2SO4,
Na3PO4, Na2HPO4, tetraethylammonium perclorate) facilitated
CO generation.[11b] Much corrosion takes place at the InP elec-
trode as a result of the hydrophilic nature of the electrode sur-
face and how the oxygen atom of H2O coordinates to a metal
site on the semiconductor.[36] With a well-aligned CB and large
VB offset between TiO2 and InP,[36] TiO2-passivated InP nanopil-
lars are in use as a photocathode.[53] Decorated with copper
nanoparticles, the selectivity of methanol production with
these nanopillars was improved to FE = 8.7 %. Furthermore,
oxygen vacancies on the TiO2 surface provided active sites for
CO2 adsorption.[37] In a similar case, constructing a heterojunc-
tion of worm-like InP and TiO2 NTs also achieved photoelectro-
catalytic CO2 reduction to methanol, with an enhanced FE of
41 % at @1.53 V; this was 1.53 times greater than that of CO2
reduction in the dark, as a result of the narrowed band gap
and facilitated charge transfer in such p–n junctions.[38]
3.1.2. Group IV Electrodes
Among widely used materials, silicon stands out because of its
abundance and narrow band gap (1.12 eV), which matches
best with the solar spectrum of semiconductors.[54] To date, the
unbreakable photocurrent record is still held by silicon-based
electrodes. With an absorption wavelength up to 1120 nm,
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nanostructured silicon can produce a photocurrent of several
tens of milliamperes per unit area. The p-Si material can pro-
vide a high photovoltage of 0.5 V, with an upward shift to
match the energy level of CO2 photoreduction and the solu-
tion reactants.[10b] Although silicon is the best candidate for
photocathodes with excellent conductivity and optical charac-
teristics, it suffers from easy oxidation. The introduction of a
TiO2 passivation layer is one approach to solve the aforemen-
tioned problem. Additionally, the n-TiO2/p-Si heterojunction
will promote the separation of electron–holes and transfer to
the surface for reaction. A Si/TiO2/Pt p–n junction was reported
to show good performance for methanol (0.88 mmol L@1), etha-
nol (2.60 mmol L@1), and acetone (0.049 mmol L@1) formation as
products in 90 min, with FE = 96 % at @0.8 V versus Ag/AgCl.[39]
Additionally, because the HER proceeds under fierce competi-
tion over unmodified silicon or poorly covered silicon, decora-
tion with appropriate metals or organic groups as cocatalysts
are expected to improve the reaction (details are given in Sec-
tion 3.2).
In the earliest reports on photocathodes in CO2 reduction, p-
type planar silicon is the primary choice of substrate.[10c–e] How-
ever, with a large surface area and long paths for light absorp-
tion and minor carrier collection, silicon NWs have been widely
employed in EC photosynthesis for either water splitting or
CO2 reduction. Tin-coupled p-silicon NW arrays displayed a sig-
nificant increase of formate production, which was five times
greater than that on the planar silicon electrode.[12a] Recently,
Yang et al. demonstrated a direct and facile way to assemble
well-dispersed bimetallic Au3Cu nanoparticles on the Si NW
surface, which served as a highly efficient photoelectrode for
the conversion of CO2 into CO, with FE = 80 % at @0.2 V versus
RHE and a large decrease of overpotential (up to 120 mV) com-
pared with that of the same catalyst coupled to a planar silicon
photoelectrode.[12b] In the presence of Si NWs as photosensitiz-
ers to harvest light and transfer electrons to [Co(tpa)Cl]Cl
(TPA = tris(2-pyridylmethyl)amine), the PEC CO2 reduction to
CO was conducted at much less negative potentials than that
on the Au/Si electrode. Both the photovoltage (580 mV) and
FE (69 %) induced by silicon NWs is higher than that by a
planar silicon electrode, for which the latter is only 320 mV and
57 %. The authors attributed the results to the multifaceted
nature of silicon NWs.[55]
A study on silicon photocathodes from another perspective
involves investigation of the illumination conditions for the re-
action. Spurgeon et al. showed that controlling the pulse fre-
quency of the applied bias in CO2 reduction led to a H2/CO
molar ratio ranging from about 32:1 to 9:16 for pulse times
between 10 and 80 ms.[56] In potentiostatic mode, the pulsed
mode provides additional time for CO2 diffusion to the catalyst
surface and promotes in situ oxidation and reduction of the
copper surface to create a copper oxide and oxide-derived
copper that favors CO production.
As another Group IV material with a CB at @5.2 V versus
SHE, the diamond electrode also appears to be an effective
material for CO2 reduction to CO under UV illumination. With
the H-terminated surface, diamond can excite electrons to the
CB and then, instead of combining reactants and forming the
132 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

intermediate on the surface, electrons inject into the adjacent
aqueous phase quickly and form solvated electrons or other
high-energy species.[40] This new pathway resulted in great
product selectivity of CO2 to CO (> 90 %) through a solvated
electron source of iodide ions.
3.1.2. Group II–VI Electrodes
With a sufficient CB position to initiate CO2 activation, Group
II–VI compounds are materials upon which early intensive re-
search has focused.[11] For this family, the influence of electro-
lyte has been clarified for a better understanding of effective
CO2 reduction. It was suggested that aprotic solvents (DMF,
propylene carbonate, tetraalkylammonium salts, CH3CN, DMSO,
ionic liquids, etc.) were able to increase the solubility of CO2 by
at least seven to eight and resulted in CO, but water could
serve as the proton source and favored formic acid formation
in aqueous solution.[11a, 57]
Although having a small band gap to match the maximum
absorption of the solar spectrum, CdTe and CdSe do not have
high CBs. In the form of quantum dots, however, ternary
CdSeTe showed feasible regulation of the band gap and an ex-
cellent optical response ability.[41] CdSeTe nanoparticles/TiO2
NTs generated the largest methanol yield of
18.57 mmol L@1 cm@2 and FE = 88 %.
With a more negative CB edge (@1.65 vs. RHE, pH 7.5), p-
ZnTe exhibits appreciable capability in CO2 reduction. When
zinc-blende ZnTe was directly formed on a Zn/ZnO NW sub-
strate through a simple microwave hydrothermal reaction in
tellurite and hydrazine, the electrode showed the stable forma-
tion of CO selectively with FE = 22.9 % at @0.7 V versus RHE
and a high incident-photon-to-current-efficiency (IPCE) of 85 %
at @0.8 V versus RHE.[19a] Gold nanoparticles coupled ZnTe/ZnO
NW arrays later developed by the same group were reported
to have a dramatic enhancement in CO FE of 68 % and the
IPCE increased to 98 % at @0.7 V versus RHE.[19c]
3.1.3. Oxide Compounds
When discussing oxide compounds for CO2 reduction, p-type
binary or ternary copper(I)-based oxide occupies a significant
position as an earth-abundant, nontoxic, and relatively stable
semiconductor with a high charge carrier mobility. Owing to
excitation from the 3 d10 VB to the primary 4 s CB, copper is
prone to suffer from self-reduction. As a result, adding another
metal with unfilled d orbitals will suppress self-reduction by
transferring excited electrons to an early transition state in the
CB.[58]
Electrodeposition from CuSO4 and Cu (NO3)2 can lead to p-
and n-type Cu2O thin films on Cu foil, respectively. Ba et al. ex-
perimented with the two types of electrodes, which demon-
strated much higher CO2 conversion efficiency over the Cu/p-
Cu2O electrode, especially in the conversion to C2H4.[18a] A basic
study of copper oxide nanoparticles on a copper electrode
(Cu/Cu2O) mapped the product evolution profiles, including
methanol, ethanol, formaldehyde, acetaldehyde, and acetone,
as a function of bias potential, electrolysis time, and pH. Meth-
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Focus Review
anol prevailed for a short period in the first 30 min; acetalde-
hyde and acetone were the main products after a longer accu-
mulation period over 2 h.[18b] The morphology of the deposited
layer will also make a difference. In the case above, stonelike
Cu2O exhibited a better performance than that of Cu2O nano-
belt arrays, mainly owing to the high coverage and amount of
Cu2O on the Cu substrate.[18a] Similarly, if Cu2O crystallites were
electrodeposited outside CuO, the p-type CuO/Cu2O core–shell
structure photocathode successfully resulted in methanol
being produced from CO2 reduction, with FE > 90 % at poten-
tials of 800 mV below the thermodynamic value.[18c, 42]
If Cu2O was set as a dark cathode, coupling with a TiO2 NR
photoanode could result in stable CO2 reduction, with FE =
87.4 % and a selectivity of 92.6 % for carbonaceous products.
The authors emphasized that direct exposure of Cu2O to the
electrolyte was the key to high selectivity and shaded Cu2O
could effectively inhibit deactivation of the Cu2O cathode by
suppressing the corrosion effect of generated holes.[59]
Co3O4 is a spinel semiconductor for which the CB is located
at @1.53 V and the band gap is 2.07 eV; it is also capable of
visible-light-driven PEC CO2 reduction. The formate yield over
an open hierarchical structure of Co3O4 microflowers on Co3O4
NRs was reported.[43] The high Co3 + -containing surface con-
structed from the {12̄1} facet enlarged the electrochemically
active surface area, and thereby, the PEC activity. If the mor-
phology of Co3O4 was converted into NT arrays decorated with
copper nanoparticles as cocatalysts, the system had a noticea-
bly high yield of 6.75 mmol cm@2 after 8 h and the selectivity
was approximately 100 % formate from a CO2-saturated aque-
ous solution.[44]
SnO2 NRs grown on the surface of Fe2O3 NTs permitted an
enhancement of CO2 photoreduction current by 7.48 times
that of Fe2O3 NTs at @1.1 V; this resulted in a CO2 to methanol
FE of 87.04 %.[45] Synergistic photo- and electrocatalytic effects
and good alignment of the band structure between SnO2 and
Fe2O3 account for the improvement.
Other than intrinsic semiconductors, a popular strategy to
change the band structure of the semiconductor is doping
with additional elements and introducing another energy level
to alter the optical properties or shift the band-edge positions
to harvest either visible or near-infrared light.[60] According to
this principle, some p-SC compounds with extended absorp-
tion to the visible-light region have been fabricated, for exam-
ple, CuInS2,[46] CuFeO2,[48] and Cu3Nb2O8,[51] to enhance the pho-
tocatalytic properties.
Because Fe 3 d dominates the CB edge at @0.9 V versus SCE
and divalent doping (i.e., Mg) can increase the bulk conductivi-
ty, Mg-doped CuFeO2 is a photocathode of interest. Gu et al.
tested the Mg-doped CuFeO2 photocathode with a small band
gap ( & 1.9 eV), which was active at irradiation wavelengths of
about 800 nm, and thus, capable of reducing CO2 to formate
at an underpotential of 400 mV with a maximum FE of 10 % at
@0.9 V versus SCE.[48] Although the efficiency is not sufficient,
this example opened up the possibility of using such semicon-
ductors and optimizing the performance through band-struc-
ture engineering. Mixed with CuO, the composite CuFeO2/CuO
photoelectrode exhibited a superior FE of up to 90 % for con-
133 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

version to formate over one week.[49] Wired with an inert plati-
num anode under no bias, the solar to chemical energy con-
version efficiency reached 1.2 %, which was even higher than
that in green plants. Furthermore, tuning the iron/copper
atomic ratio in the mixed CuFeO2@CuO phase can change the
selectivity of CO2 reduction from formate production to ace-
tate production with FE = 80 %.[50]
With a CB potential estimated to be @1.21 V versus NHE
(pH 7) and the capability of utilizing visible light (< 480 nm), p-
type Cu3Nb2O8 is an alternative photocathode for CO2 reduc-
tion, despite the low FE of 9 % for the only product, CO, in an
aqueous CO2-bubbled solution of NaHCO3 (pH 7.3) at @0.3 V
versus Ag/AgCl.[51]
3.1.4. Non-Oxide Compounds
Chalcopyrite p-SC, CuInS2, has a CB at @1.64 V and band gap
of 1.3 eV, which matches well with the solar spectrum. As a
thin film photocathode fabricated by Cu@In alloy electrodepo-
sition and sulfurization, it generated methanol during the CO2
reduction reaction, especially in the presence of pyridine. With
10 mm pyridinium ions as cocatalysts, it can produce methanol
with a current efficiency of 97 % at an overpotential of
20 mV.[46] If graphene was hybridized on the CuInS2 electrode
in the same system, the maximum methanol production oc-
curred at @0.59 V with FE = 95 % and was 1.4 times faster than
that over bare CuInS2 described above.[47] Instead of using solu-
tion-processed CuInS2, nanofibers fabricated by electrospinning
with polyacrylonitrile (PAN) as a template also showed a com-
pelling FE of (77 : 4) % for the reduction of CO2 to CO.[61]
In recent years, there has been much interest in and re-
search on graphitic carbon nitride (g-C3N4), a metal-free semi-
conductor, for its sufficiently negative CB edge and prominent
photolytic performance in water reduction[62] and CO2 reduc-
tion[63] under visible-light irradiation. DFT also predicted that g-
C3N4-supported single atoms of palladium or platinum pre-
ferred to reduce CO2 to HCOOH and CH4, respectively, with the
metal atoms as active sites and g-C3N4 as the photocatalyst
providing hydrogen.[64] Pristine g-C3N4 (n-type) and boron-
doped g-C3N4 (p-type BCN) were used in the PEC CO2 reduc-
tion reaction, despite a low photocurrent of < 10 mA, even
loaded with sputtered cocatalysts of gold, silver, and rhodium.
The BCN electrodes can produce ethanol as a main product. In
an optimum amount, the above cocatalyst improves ethanol
production in the sequence of gold, rhodium, and silver.[52]
Even the band energy level of semiconductors can be engi-
neered by doping to satisfy certain reaction steps; bare semi-
conductors are not able to adjust selectivity and are prone to
suffer from corrosion. Thus, an appropriate reaction environ-
ment and external modification of the semiconductors are
more important and popularly studied in the progress of this
field.
3.2. Hybrid Semiconductor-Based Photocathodes
If semiconductors are decorated with cocatalysts, the cocata-
lysts will introduce a local energy level and act as active sites
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Focus Review
to trap electrons and change the product distributions. Gener-
ally speaking, metals deposited as particles or incorporated
through a metal complex should have sufficient nucleophilicity
to bind CO2 at low overpotentials to break the C=O bond ef-
fectively.[15] A basic principle is that the Fermi level of the de-
posited metals, or the LUMOs, are located lower than the CB
of the semiconductors to allow ET from semiconductors to co-
catalysts prior to the absorption of reactive species. In this sec-
tion, hybrid photocathodes decorated with metals, small poly-
mers, biocatalysts, and metal complex are discussed.
3.2.1. Metallic Modification
With different work functions, metals change the extent of
band bending of semiconductors and polarization curves dif-
ferently because the electrode process rate is proportional to
band bending. In addition to forming a Schottky barrier to pro-
mote charge separation on the metal/semiconductor interface,
metals deposited on the semiconductor photocathodes also
result in different selectivities of the products.
The effects of deposited metals (Ag, Au, Pd, Pt, Rh, Cu) and
nonprecious metals (Zn, Ga, Cd, Pb, In, Sn, Bi, Ni, etc.) were ex-
amined in terms of CO2 conversion into carbon species.[15, 65]
Figure 4 depicts the product distribution of the majority of
metals in the periodic table when using electrocatalysts or co-
catalysts as semiconductors.[15, 65]
Figure 4. Section of the periodic table depicting the primary reduction prod-
ucts in CO2-saturated aqueous electrolytes on metal and carbon electrodes.
Reproduced with permission from ref. [15]. Copyright 2015 American Chemi-
cal Society.
Herein it worth mentioning that, as the cheapest noble
metal, copper is very special and considered to be the only
metal that can promote hydrocarbons. In acetonitrile with
3.0 m H2O, particulate Cu/p-Si could serve as a beneficial pho-
tocathode, providing a photovoltage of 0.75 V, primarily gener-
ating CH4 and C2H4, similar to the metallic copper electrode.[10f]
The p-type SiC surface decorated with Cu particles was found
to reduce CO2 into CH4, C2H4, and C2H6 upon illumination in an
aqueous CO2-saturated solution of KHCO3 and the hydrocarbon
formation rate varied with respect to electrolyte pH.[66] PEC
CO2 reduction over copper nanoclusters on single-crystal
(101̄0) ZnO photoelectrodes at @1.4 V versus Ag/AgCl can pro-
duce a mixture of CO, CH4, and C2H4, as well as liquid products,
such as methanol, ethanol, formate, methyl formate, and trace
134 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

levels of propanol, with a total current efficiency of approxi-
mately 55 %; this is comparable to that on the Cu (111) elec-
trode of 46 %, but the selectivity to alcohols (CH3OH and
C2H5OH) was improved by an order or magnitude.[67] Coupled
with copper nanoparticles as the cocatalyst, ZnO nanosheets/
GaN NWs n + –p Si junction can readily transfer energetic elec-
trons to Cu through the Cu@ZnO interface for activation and
reduction of CO2, resulting in syngas products with a CO/H2
ratio ranging from 2:1 to 1:4 and a remarkable turnover
number of 1330.[68] Copper-coupled GaN NW arrays on p-type
silicon substrate, with the surface doped as n-type, denoted as
Cu/GaN/n + –p Si, also produced CH4 selectively with a moder-
ate FE of 19 % at @1.4 V versus Ag/AgCl.[69] Suffering from easy
aggregation and low coverage on the silicon electrode, decora-
tion with particulate cocatalysts has inherent limitations. In-
stead of particulates, gold mesh-type cocatalyst over a silicon
photoelectrode was constructed; this exhibited excellent CO2
reduction performance, with over 90 % CO FE and a reduction
current of @2.94 mA cm@2 induced by the grain boundaries of
nanoparticles on the gold surface.[70]
As substitutes for precious metals, nanocarbon materials are
alternative cocatalysts. It was demonstrated that p-Si NWs with
nitrogen-doped graphene quantum sheets (N-GQSs) were ef-
fective as heterogeneous photoelectrodes for selective CO pro-
duction, with FE up to 95 % at @1.53 V versus Ag/Ag + in ace-
tonitrile.[12d]
Third, very recently, there has been increasing interest and
research into coinage metals, that is, gold, silver, and copper
Cu, that possess a surface plasmon resonance (SPR), which
opens up an avenue to develop light-driven systems by en-
hancing light absorption or lowering the activation energy.[71]
Kostecki and Augustynski first reported a surface plasmonic
photoeffect on a polycrystalline silver electrode in solutions
containing CO2 or nitrate ions.[72] The energy of surface plas-
mons at silver is close to 3.5 eV, which drives persistent CO2 re-
duction to CO with an increased rate and a cathodic onset po-
tential that is 0.5 V lower. However, the use of hot plasmonic
electrons for CO2 conversion is a compelling approach widely
adopted in photocatalysis, but rarely considered in electroca-
talysis. This is because hot plasmonic electrons can only be ex-
pected to participate in the electrocatalytic reaction with fast
enough plasmon-induced charge or energy transfer before
losing energy from particle to solvent as heat.[73]
3.2.2. Polymer Modification
Because modification of the silicon electrode with metal parti-
cles always leads to a low coverage of the surface, which
causes either corrosion or uninhibited HER activity, silicon elec-
trodes modified with organic moieties date back to the
1980s.[10a] Basically, to increase the adsorption of CO2 on the
semiconductor surface, polymers with ammonium groups are
favored. Polyethylenimine (PEI) and other chain polymers with
amine groups can capture CO2, stabilize the intermediate CO2C@
through hydrogen-bonding and electrostatic interactions, and
suppress HER.[74] Polyaniline (PANI) is another chain polymer
that can also enhance the chemisorption and protonation of
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Focus Review
CO2 through its nitrogen-containing groups.[75] Different from
PEI, PANI is a prominent organic semiconductor that can di-
rectly function as a photocathode responsible for PEC CO2 con-
version. The PANI cathode produced methanol and ethanol
with FE = 43 and 20 %, respectively, and a photocurrent up to
0.5 mA cm@2 at @0.4 V versus Ag/AgCl in the absence of coca-
talyst.[76]
Photoelectrodes modified with CdTe quantum dots and
polycations (polycations = poly(diallyldimethylammonium)
(PDDA), and poly(2-trimethylammonium)ethyl methacrylate
(PMAEMA)) by layer-by-layer electrostatic assembly were re-
ported for the reduction of CO2 into CO, CH3OH (with PDDA),
and HCOH (with PMAEMA).[77] These polycations influence the
photoelectrocatalytic effect mainly owing to their monomer
size and structure and the actual light applied on the indium
tin oxide (ITO) electrode.
Instead of enhancing the chemisorption of CO2, PPy is re-
ported to have a high work function value (4.6 to 5.2 eV) that
facilitates ET and charge separation. PPy-coated ZnTe (PPy/
ZnTe) demonstrated FE = 37.2 % for formic acid and 13.8 % for
CO at @0.2 V (total FE of 51.0 %) for overall CO2 reduction;
these values are both higher than that on the bare ZnTe elec-
trode of 24.9 % for formic acid and 8.8 % for CO at @0.1 V.[19b]
Usually, metal deposition is difficult on a silicon electrode
because the nanoparticle size and coverage affect the EC per-
formance severely. A continuous metal layer will lead to a high
Schottky barrier, whereas a scarce distribution of nanoparticles
will result in surface corrosion. A Si (111) electrode modified
with a viologen molecular layer as an ET mediator and various
metal complexes, such as [AuCl4]@ , [PdCl4]@ , and [PtCl4]@ , as
the catalyst can provide a compromise. Such an organic layer
between the metal and silicon surface can not only prevent
surface corrosion and the formation of charge recombination
centers, but also allow control of suitable Schottky barriers.[78]
3.2.3. Bio-Semiconductor Hybridized Photocathodes
The use of sunlight to close the carbon cycle entails the use of
light harvesters and catalytic components. This process was
first established in nature to fulfill the demand for the growth
of plants or microbes as photosynthetic biological catalysts.
The newly reported assemblies of CdS–Moorella thermoaceti-
ca[79] and Co@P–Ralstonia eutropha[80] enable the photosynthe-
sis of hydrocarbons from CO2, even exceeding the efficiency of
natural photosynthesis. An attractive research goal is to find
ways to incorporate the natural counterpart into artificial pho-
tosynthetic systems.
Chang et al. reported a biocompatible and earth-abundant
PEC HER catalyst, a-NiS nanoparticles, which performed water
splitting to electrochemically generate H2 by coupling with a
platinum cathode.[81] Generated H2 was then subsequently pro-
vided as an electron donor in situ by Methanosarcina barkeri
for CO2 conversion into CH4. Through a more facile HER reac-
tion, compared with the direct CO2 reduction reaction, such
bioinorganic hybrids demonstrated robust and efficient EC CO2
to CH4 conversion, with up to 86 % overall FE and a low over-
potential of 360 mV for more than a week. After further cou-
135 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Focus Review

pling to a TiO2 NW photoanode, the bioinorganic hybrid
system afforded a fully solar-driven system for methane gener-
ation from water and CO2.
Instead of stopping at simple carbon species, semiconduc-
tors with bacteria can even generate benzylic acid through
CO2 fixation by benzophenone; this resembles natural photo-
synthesis. The carboxylation reaction occurred at aromatic ke-
tones sites, yielding 98 % isolated a-hydroxyl acid product with
FE = 94 %.[82]
3.2.4. Metal Molecular Complex Assembled Heterogeneous
Photocathodes
Despite the sophisticated structures of biocatalysts for high
CO2 affinity and reduction efficiency, a great shortfall of such
cocatalysts is that they suffer from deactivation. Therefore,
metal complexes that mimic biocatalysts and function well as
catalysts free from decay and scarcity are in demand. They can
also be used to lower the overpotential of stabilizing the inter-
mediate in CO2 transformation to some specific products with
multiple binding modes.[13c] Changing the metal cores or the
ligand can change the reduction potential and improve the
fast kinetics and stability of the catalysts.[13c] Immobilization of
a suitable metal complex through a polymer or electropolyme-
rization on a semiconductor photocathode is promising to en-
hance charge transfer and the selectivity of PEC CO2 reduction.
Because there are many reviews focused on metal complexes
in carbon dioxide reduction,[13a, b, 91] only very recent publica-
tions related to assembly on semiconductors are summarized
herein (Table 3).
A third-generation conjugated polymer, with pyridinium or
pyridine groups, such as [Re(bpy)(CO)3Cl], and related deriva-
tives or analogues make up the largest population of effective
catalysts that drive CO2 reduction to CO with high efficiency
and stability over a long period.[92] When selecting the semi-
conductor base for immobilization of the molecular catalyst,
silicon is always the primary choice. First, through modification
with a rhenium-based molecular complex, [Re(v-bipy)(CO)Cl]
(v-bpy = 4-vinyl,4’-methyl-2,2’-bipyridine), the selective reduc-
tion of CO2 to CO took place at @1.0 V (vs. SHE) in acetonitrile,
with estimated faradaic yields of up to 100 %.[93] Recently,
Kumar et al. reported that the reduction of CO2 to CO occurred
at FE = (97 : 3) % with [Re(bipy-tBu)(CO)3Cl] anchored on hy-
drogen-terminated p-type silicon (p-type H@Si; Figure 5 a) at a
potential more than 600 mV lower than that required for a
platinum electrode with TBAH as the electrolyte (FE = (97 :
3) %).[83] A planar H@Si surface was selected because of its low
surface recombination and stability under reducing conditions
in deoxygenated acetonitrile. Later, through the addition of
water and variation in the concentration of [Re(bipy-tBu)-
(CO)3Cl], the heterogeneous cathode was able to generate
syngas (H2/CO = 2:1) with a total FE of (102 : 5) %; this was the
first example of the cogeneration of H2 and CO in a mixed
homo-/heterogeneous system.[84] Torralba-PeÇalver demon-
strated the performance of manganese-based carbonyl bipyrid-
yl complexes as molecular catalysts ([Mn(L)(CO)3(CH3CN)](PF6)
and [Mn(bpy)(CO)3Br] (L = bpy and 4,4-dimethyl-2,2’-bipyridine
(dmbpy)) bound to hydrogen-terminated silicon nanowire (Si
NW-H) photocathodes for CO2 reduction (Figure 5 b).[85]
[Mn(bpy)(CO)3(CH3CN)](PF6) coupled to Si NWs-H manifested a
superior catalytic current of more than 1.0 mA cm@2, as mea-
sured at @1.0 V versus SCE, compared with that measured on
planar Si@H and glassy carbon electrode, owing to the degree
of band bending and depth of the space–charge layer, which
was always greater for Si NWs-H. The energy conversion effi-
ciencies of [Mn(bpy)(CO)3(CH3CN)](PF6) and [Mn(dmbpy)-

Table 3. Summary of recent representative semiconductor photocathodes modified by metal complexes for CO2 reduction.[a]

Molecular catalyst Semiconductor Electrolyte (solvent) Potential [V] (Current Ref.

[mA cm@2])
[Re(bipy-tBu)(CO)3Cl] p-Si TBAH (acetonitrile) NA CO (97 : 3 %) [83]
[Re(bipy-tBu)(CO)3Cl] p-Si TBAH (0–5 % v/v @1.900 vs. Fc/Fc + (5.6) H2 + CO [84]
H2O + acetonitrile) (102 : 5 %)
[Mn(L)(CO)3(CH3CN)](PF6)[b] SiNWs-H 0.1 m Bu4NClO4 (CH3CN + 5 % @1.0 vs. SCE (1.14) CO [85]
H2O v/v)
[Ru(L@L)(CO)2]n[c] p-InP water @0.6 vs. Ag/AgCl (NA) HCOO@ [86]
(62.3 %)
[RuCE + RuCA][d] Cu2ZnSnS4 water @0.4 vs. Ag/AgCl (NA) HCOO@ [88]
(> 80 %)
RuRe NiO 0.1 m Et4NBF4 (DMF/TEOA, 5:1 @1.2 vs. Ag/AgNO3 (NA) 62 % (0–3 h) [89]
[Ru(bpy)2(MebpyCH2CH2bpyMe)Re(CO)3Br]2 + v/v) 98 % (3–5 h)
[Re(tBu-bipy)(CO)3Cl][e] TiO2-protected Cu2O 0.1 m Bu4NPF6 (acetonitrile + - @1.73 vs. Fc + /Fc (1.5) CO (100 %) [18f]
MeOH)
[Re(tBu-bipy)(CO)3Cl][e] mesoporous TiO2-protected 0.1 m Bu4NPF6 (acetonitrile) @2.05 vs. Fc + /Fc (2.5) CO (95 %) [18e]
Cu2O
MnP porous TiO2 0.1 m Bu4NPF6 (acetonitrile) @1.7 vs. Fc + /Fc (NA) CO (67 : 5 %) [90]
fac-[MnBr{4,4’-bis(phosphonic acid)2,2’-bipyri-
dine}(CO)3]

[a] bipy-tBu = 4,4’-di-tert-butyl-2,2’-bipyridine, TBAH = tetrabutylammonium hexafluorophosphate, NA = not available, Fc = ferrocene, TEOA = triethanola-
mine. [b] L = bpy = 2,2’-bipyridine. [c] L < C- > L is an diimine ligand. [d] RuCE = [Ru{4,4’-di(1H-pyrrolyl-3-propylcarbonate)-2,2’-bipyridine} (CO)(MeCN)Cl2,[88]
RuCA = Ru(4,4’-diphosphate ethyl-2,2’-bipyridine)(CO)2Cl2. [e] bipy-tBu.

Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org 136 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 5. Schematic illustration of the PEC CO2 reduction process on a) p-Si and [Re(bipy-tBu)(CO)3Cl] (reproduced with permission from ref. [83]), b) hydro-
gen-terminated silicon nanowires (Si NWs-H) and MnI-based carbonyl bipyridyl molecular catalyst (reproduced with permission from ref. [85]), c) Cu2ZnSnS4
(CZTS) and InP–metal complex hybrid photocatalyst (reproduced with permission from ref. [88]), and d) Cu2O photocathodes and a Re-based molecular cata-
lyst (reproduced with permission from ref. [18f]).
(CO)3(CH3CN)](PF6) were 3 and 2 %, respectively, and the elec-
trocatalytic activity was retained after grafted onto the semi-
conducting electrode.
Provided with a positive shift of 0.2 V for the required poten-
tial under visible light, p-InP modified with a ruthenium com-
plex grafted onto a polymer drove CO2 reduction selectively to
formate with a current efficiency of 62.3 % after the hybrid
electrode underwent cathodic photo-electropolymerization
and anodic electropolymerization.[86] Because InP contains a
rare metal, it is costly for industrial demand, so the InP has
been substituted by CZTS, which consists of relatively cheap
elements and demonstrates its high selectivity in CO2 reduc-
tion for formate (Figure 5 c). Selenium insertion into CZTS may
enhance the activity, presumably owing to enhanced carrier
mobility.[88]
Gr-tzel et al. demonstrated a low-cost single photocathode
paired with a rhenium bipyridyl catalyst, [Re(tBu-bipy)(CO)3Cl],
on TiO2-protected p-type Cu2O (Figure 5 d) in CO2-saturated
acetonitrile.[18f] A protic additive, such as methanol or n-propa-
nol, was used to remove the charge-transfer limitation be-
tween the TiO2 surface and catalyst. Selective CO evolution
with FE = 100 % over several hours was achieved with cathodic
photocurrent densities of 2.1 mA cm@2, which exceeded the
highest currents for CO2 reduction on all-oxide photocathodes.
They further improved the planar TiO2 overlayer as a low-tem-
perature-processed mesoporous scaffold and covalently immo-
bilized the catalyst onto TiO2 through phosphonate linking
Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org
Focus Review
groups. Enhancing the surface roughness and catalyst loading
enabled better photogenerated charge flux and a catalytic
photocurrent of 40-fold greater than that of the previous
planar TiO2-protected one.[18e]
A new hybrid photocathode, NiO immobilized with a ruthe-
nium(II)–rhenium(I) dimetal complex (RuRe) was an effective
photocathode for the conversion of CO2 into CO, with an aver-
age efficiency of 71 % and a maximum efficiency of up to
98 %.[89] Because the reductive potential of excited ruthenium
is more positive than that of the VB edge of NiO, electrons
from NiO will transfer to the excited ruthenium unit, which
then allows for intramolecular ET through an ethylene chain
from the reduced ruthenium unit to the rhenium unit,[94]
where CO2 reduction occurs.
Unlike ruthenium or rhenium complexes, which are rare and
expensive, porphyrins are usually simple and cheap, with
cobalt, iron, zinc, and nickel as the metal cores.[95] With the
presence of a sensitizer, [Ru(bpy)3]2 + , light of l = 425 and
525 nm caused a displacement instead of 625 nm. Another
iron porphyrin, meso-tetraphenylporphyrin iron(III) chloride
(Scheme 1 a), was also reported to driven by a hydrogen-termi-
nated silicon electrode for the photoelectrocatalytic reduction
of CO2 to CO in the presence of CF3CH2OH as a proton source,
with a current efficiency of more than 90 % at @1.1 V versus
SCE and 175 turnovers over 6 h. The p-Si photocathode result-
ed in a photovoltage of greater than 650 mV and achieved a
typical current of 3 mA cm@2.[96] Instead of using the porphyrin
137 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Scheme 1. a) meso-Tetraphenylporphyrin iron(III) chloride. Reproduced with
permission from ref. [96]. Copyright 2013 Wiley-VCH. b) ZnDMCPP-Re(-
bpy)(NHAc). Reproduced with permission from ref. [97]. Copyright 2013
Elsevier.
complex as a visible-light catalyst, its original role was as a
light-harvesting sensitizer. Inoue et al. attained CO2 reduction
to CO on a p-type NiO semiconducting electrode with a metal
complex dyad composed of a zinc porphyrin (Scheme 1 b) as a
sensitizer and a rhenium bipyridyl complex as a catalytic
moiety for reduction in CO2-saturated DMF.[97]
4. Standalone Artificial Leaf
Since Khaselev and Turner invented a photovoltaic–photoelec-
trochemical (PV-PEC) device, including a tandem photoanode
of GaInP2 on top of a GaAs p–n junction and a platinum coun-
ter electrode for water splitting,[98] more researchers have
tended to focus on the design of PV-PEC devices with light as
the only energy input for bias-unassisted artificial photosynthe-
sis. Only a handful of completely standalone PV-PEC devices
have been reported to date. Commonly used semiconductor
photoanodes include oxides, nitrides, and oxynitrides.
As a typical photocatalyst, TiO2 is most frequently selected
when establishing a photoanode-driven PEC cell.[59, 81, 99] Recent-
ly, one integration involved TiO2 NW arrays as the photoanode,
and a Si NW array functioning as a photocathode to harvest
light energy and generate reducing equivalents for the anaero-
bic bacterium Sporomusa ovata; this system produced acetic
acid with high FE (up to 90 %) and low overpotential (h <
200 mV) for nearly 200 h under aerobic conditions (21 % O2)
with merely solar energy input.[99]
With a higher CB, SrTiO3 is also used as photoanode. The
InP/[RuCP] (CP = complex polymer) system described by Arai
et al. was first hybridized with TiO2 photocatalysts in the
tandem configuration to achieve more than 70 % selectivity of
HCOO@ and 0.03–0.04 % solar energy conversion.[100] Then the
single photocathode was wired to a reduced SrTiO3 (r-STO)
photoanode to enlarge the difference in the band position be-
tween InP and the photoanode semiconductor (Figure 6 a).
With no external electrical bias, the solar energy to chemical
energy conversion efficiency reached 0.03–0.14 % in a PEC
device.[101] Reisner et al. wired a novel manganese complex
(MnP) anchored on mesoporous TiO2 with a CdS-sensitized
ZnO nanosheet photoanode (Figure 6 b). The light-sensitive
MnP molecular catalyst could be applied to the solar-light-
driven CO2 reduction system.[90]
Another exquisite example of using a perovskite solar cell
(Perov SC) involved triple-layered core–shell ZnO@ZnTe@CdTe@
Au NR photocathode (CZT-Au PC) and a CH3NH3PbI3 Perov SC
Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org
Focus Review
assembled in tandem (Figure 6 c). Front illumination resulted in
higher energy photons (> 2.14 eV) that could be absorbed by
the ZnTe electrode and relatively lower energy photons (>
1.5 eV) by the solar cell. With cost-effective cobalt bicarbonate
(Co@Ci) as the anode, instead of platinum for oxygen evolu-
tion, the standalone CO2 reduction device could work under
sunlight with no additional bias and a steady solar-to-CO effi-
ciency of over 0.35 %.[102]
Despite the high cost and not being earth-abundant, GaN, is
always incorporated into the PEC cell as a photoanode instead
of as the cathode. Wired to a tandem GaAs/InGaP/TiO2/NiOx
photoanode in 1.0 m KOH(aq) (pH 13.7) and a Pd/C nanoparticle
coated Ti mesh cathode in 2.8 m KHCO3(aq) (pH 8.0), the cathode
exhibited an overpotential less than 100 mV and FE > 94 % for
CO2 reduction to formate, and the anode exhibited an overpo-
tential of (320 : 7) mV for the OER. The total solar-to-fuel
energy conversion efficiency reached up to 10 %.[16] Taking into
consideration visible-light absorption, metal oxynitrides are
more suitable because many of them have an absorption edge
at l > 600 nm. Based on the as-described NiO electrode immo-
bilized with a RuRe complex, the group further coupled the
photocathode to a CoOx/TaON photoanode (Figure 6 d). Under
the assistance of an external electrical (0.3 V) and chemical bias
(0.10 V) produced by a pH difference between two electrodes,
the PEC cell performed CO2 reduction to CO selectively, along
with water oxidation in an aqueous solution of NaHCO3. The
authors claimed that this was the first use of water as a reduc-
tant based on the hybridization of a molecular complex with a
semiconductor electrode.[103]
In a two-compartment PEC cell, a higher cathode potential
is necessary for CO2 reduction, but raising the top band re-
quires the band gap to be widened, so less light can be uti-
lized by the photoelectrode. To compensate for this, a p–n
junction can be inserted on the backside of the photoanode
to raise the cathode potential. A conductive layer between the
photoanode and Si p–n junction guarantees Ohmic contact. If
the light illuminates the front side of the GaN photoanode,
transmitted light will fall onto the Si p–n junction and elevate
the Fermi level of n-Si and metal to same position (Fig-
ure 6 e).[104] Asadi et al also assembled two PV-a-si-3jn cells to
harvest light and wired tungsten diselenide nanoflakes (WSe2)
and cobalt(II) oxide/hydroxide on the anode side to mimic an
artificial leaf (as shown in Figure 6 f); this manifested a high
performance of about 4.6 % solar-to-fuel conversion efficiency
during 100 h of operation.[105]
It is worth mentioning another type of artificial leaf com-
prised of PV and EC cells that can provide more flexibility and
alternatives for materials, especially with the boom in solar
cells.[106] Recently, based on the PV–EC configuration, Gr-tzel
et al achieved a solar-to-CO conversion efficiency of 13.4 % by
using SnO2-modified CuO NW bifunctional electrodes prepared
by atomic layer deposition as both cathode and anode.[106b]
Electrocatalytic electrodes can be replaced by other materials
from semiconductors to metallic or nanocarbon materials.[14]
For more well-established electrodes without light harvesting
are beyond the scope of this review, readers can refer to more
specific reviews focused on each topic independently.
138 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Focus Review

Figure 6. a) Schematic illustration of PEC reduction of CO2 with a two-electrode configuration in the Z-scheme system with no electrical bias, comprising an
InP/[RuCP] photocathode and a r-STO photoanode. Reproduced with permission from ref. [101].Copyright 2015 The Royal Society of Chemistry. b) Schematic
representation and proposed mechanism for CO2 reduction by TiO2 j MnP (X = Br@ in the isolated compound). Reproduced with permission from ref. [90].
Copyright 2016 Wiley-VCH. c) Schematic diagram of a tandem cell comprising ZCT-Au PC–Perov SC–(Co@Ci) anode. Reproduced with permission from
ref. [102]. Copyright 2016 American Chemical Society. d) Schematic image of a hybrid PEC cell with the Z-scheme configuration. Reprinted with permission
from ref. [103]. Copyright 2016 American Chemical Society. e) Schematic illustration of the band structure under illumination. The potential gain owing to the
Si p–n junction is the key to enhancing the PEC reaction. Reproduced with permission from ref. [104]. Copyright 2015 AIP Publishing. f) Schematic illustration
of the amorphous silicon triple-junction photovoltaic (PV-a-si-3jn) cell design comprising WSe2 and cobalt(II) oxide/hydroxide. Reproduced with permission
from ref. [105]. Copyright 2016 American Association for the Advancement of Science.

5. Summary and Outlook light-harvesting semiconductors. Recently, many excellent

We have reviewed the development of PEC CO2 reduction
based on semiconductor electrodes. In addition to the basic
principles and concepts of CO2 reduction under illumination,
we have emphasized various types of photocathodic electro-
des based on compounds from Groups III–V and II–V, silicon
electrodes, oxides, and non-oxides. A brief summary of aprotic/
aqueous solvents and the effect of the electrolyte on the final
product distribution, as well as heterogeneous modification,
was also given. Based on efficient semiconductor-based hybrid
photoelectrodes, recent standalone PEC configurations to-
wards artificial leaves with only solar input are also listed
(Table 4).
Although remarkable results have been achieved in recent
decades, challenges still remain in solving difficulties in collect-
ing CO2 from air, the low efficiency of utilizing sunlight for
value-added products, the instability of the catalysts, the high
cost of some noble metals or the core in metal complexes, as
well as the deficiency of efficient reactors and detection meth-
ods in CO2 reduction investigations.
To find a reasonable approach to develop heterogeneous
catalytic electrodes towards CO2 reduction, one may consider
the following aspects: 1) Constructing a heterogeneous archi-
tecture by combining well-established nanomaterials with
works have emerged in electrocatalysis. Oxide-derived metals
(Cu,[109] Au,[110] Sn,[111] etc.), or even nanoparticles with high-
index facets[112] or alloys[113] can be developed on semiconduc-
tors for PEC CO2 reduction. 2) The use of nanocatalysts with di-
verse morphologies and dimensions, such as quantum dots,
NWs, and two-dimensional structures as electrodes. Owing to
discrepancies on the exposed surface or interface structure, dif-
ferent shapes may account for the diversity of products. 3) In-
troducing a plasmonic effect of coinage metals for photoelec-
trocatalytic reactions, especially for CO2 activation. The use of
the plasmonic effect to introduce light is another route for
photodriven reactions.[114] This effect has been demonstrated
for the HER[115] and OER,[116] and hence, is expected for the CO2
reduction reaction. 4) Finding organic materials that have more
compatibility and affinity for CO2 molecules, for better adsorp-
tion or activation of CO2 molecules. For example, grafting with
nitrogen-containing functional groups or polymers, such as
NH2 or carbene, can enhance the adsorption of CO2 and in-
crease the reaction probability.[117] Covalent– or metal–organic
frameworks with similar functional groups can also be consid-
ered for the assembly of semiconductor photoelectrodes for
PEC reactions. 5) Developing low-cost substitutions to reduce
the utilization of precious elements for the reaction. 6) Eluci-
dating the catalytic pathways by using advanced in situ char-

Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org 139 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Focus Review

curb the problem in either fundamental science or practical

Table 4. Summary of recent representative CO2 reductions with photoa-
node-driven PEC cells.[a] use. Not only single-carbon species, but also multicarbon
forms, are expected products from atmospheric CO2, water,
Cathode Anode Electrolyte[b] Current Product distribu- Ref. and solar light in the future of artificial photosynthesis. A deep
density tion (FE [%])
understanding of the essence of the CO2 reduction reaction
[mA cm@2]/
Bias [V] and the development of highly efficient catalysts will be re-
quired to reach this goal.
Pd@Cu CNTs/ 0.5 m KHCO3 NA/@1.2 CO (75) [107]
alloy Co3O4/
ZnO
NRs
Pt/RGO Pt/TiO2 A: 1 m NaCl NA/2 CO, HCOOH, [87] Acknowledgements
NTs C: 1 m CH3OH,
NaHCO3 CH3COOH, This work received financial support from the World Premier
C2H5OH (sum:
International Research Center Initiative (WPI Initiative) on Mate-
80.5)
Pt/RGO 5 % Pt/ A: 1 m NaCl 4/NA CO, HCOOH, [108] rials Nano-architectonics (MANA), MEXT (Japan), the National
TiO2 C: 1 m CH3OH, Basic Research Program of China (973 Program,
NTs NaHCO3 CH3COOH, 2014CB239301), and the National Natural Science Foundation
C2H5OH
of China (21633004).
Cu2O (dark) TiO2 0.1 m KHCO3 1.34/0.75 CH4, CO, CH3OH [59]
NRs (sum: 94.39)
Pd/C/Ti GaAs/ A: 1.0 m 8.5/NA HCOO@ (> 94) [16]
Keywords: carbon dioxide reduction · electrochemistry ·
[mesh] InGaP/ KOH(aq)
TiO2/ (pH 13.7) heterogeneous catalysis · photosynthesis · semiconductors
NiOx C: 2.8 m
KHCO3(aq)
(pH 8.0) [1] a) S. C. Roy, O. K. Varghese, M. Paulose, C. A. Grimes, ACS Nano 2010, 4,
Sporomusa TiO2 brackish 0.35/NA CH3COO@ (86 : 9) [99] 1259 – 1278; b) D. T. Whipple, P. J. A. Kenis, J. Phys. Chem. Lett. 2010, 1,
ovata/Si NW water 3451 – 3458.
arrays [2] a) G. A. Olah, G. K. S. Prakash, A. Goeppert, J. Am. Chem. Soc. 2011, 133,
RuCP/InP r-STO 0.1 m 0.15/NA HCOO@ (> 70) [100] 12881 – 12898; b) J. J. Concepcion, R. L. House, J. M. Papanikolas, T. J.
NaHCO3, Meyer, Proc. Natl. Acad. Sci. USA 2012, 109, 15560 – 15564.
phosphoric [3] a) A. J. Bard, J. Photochem. 1979, 10, 59 – 75; b) R. E. Blankenship, D. M.
acid (pH 7.7) Tiede, J. Barber, G. W. Brudvig, G. Fleming, M. Ghirardi, M. R. Gunner,
MnP/TiO2[c] CdS/ 0.1 m 0.010/NA CO (26) [90] W. Junge, D. M. Kramer, A. Melis, T. A. Moore, C. C. Moser, D. G. Nocera,
ZnO Bu4NBF4, A. J. Nozik, D. R. Ort, W. W. Parson, R. C. Prince, R. T. Sayre, Science
0.1 m TEOA 2011, 332, 805; c) P. D. Tran, L. H. Wong, J. Barber, J. S. C. Loo, Energ.
Au/CdTe/ Co@Ci 0.5 m KHCO3 0.85/NA CO ( & 80) [102] Environ. Sci. 2012, 5, 5902 – 5918.
ZnTe [4] R. L. Cook, R. C. MacDuff, A. F. Sammells, J. Electrochem. Soc. 1988, 135,
RuRe/NiO CoOx/ 50 mm NA/@0.3 CO (68) [103] 3069 – 3070.
TaON NaHCO3 [5] J. Qiao, Y. Liu, F. Hong, J. Zhang, Chem. Soc. Rev. 2014, 43, 631 – 675.
(pH 8.3) [6] a) X. Chang, T. Wang, J. Gong, Energ. Environ. Sci. 2016, 9, 2177 – 2196;
b) S. Xie, Q. Zhang, G. Liu, Y. Wang, Chem. Commun. 2016, 52, 35 – 59.
[a] RGO = reduced graphene oxide, NA = not available. [b] A = anode, C = [7] a) N. S. Spinner, J. A. Vega, W. E. Mustain, Catal. Sci. Technol. 2012, 2,
cathode. [c] MnP = fac-[MnBr(4,4’-bis(phosphonic acid)-2,2’-bipyridine)(- 19 – 28; b) D. Kim, K. K. Sakimoto, D. Hong, P. Yang, Angew. Chem. Int.
CO)3. Ed. 2015, 54, 3259 – 3266; Angew. Chem. 2015, 127, 3309 – 3316; c) H.
Zhang, G. Liu, L. Shi, H. Liu, T. Wang, J. Ye, Nano Energy 2016, 22, 149 –
168.
[8] M. Halmann, Nature 1978, 275, 115 – 116.
acterization techniques for a deeper understanding of catalysts [9] a) Y. Taniguchi, H. Yoneyama, H. Tamura, Bull. Chem. Soc. Jpn. 1982, 55,
2034 – 2039; b) B. Aurian-Blajeni, M. Halmann, J. Manassen, Sol. Energy
and CO2 reduction pathways. To acquire direct evidence, in
Mater. 1983, 8, 425 – 440; c) K. Ito, S. Ikeda, M. Yoshida, S. Ohta, T. Iida,
situ characterization methods, such as X-ray absorption spec- Bull. Chem. Soc. Jpn. 1984, 57, 583 – 584; d) S. Ikeda, M. Yoshida, K. Ito,
troscopy, attenuated total reflection IR spectroscopy, or diffuse Bull. Chem. Soc. Jpn. 1985, 58, 1353 – 1357; e) S. Ikeda, Y. Saito, M. Yosh-
reflectance IR Fourier transform spectroscopy, to investigate ida, H. Noda, M. Maeda, K. Ito, J. Electroanal. Chem. Interfacial Electro-
chem. 1989, 260, 335 – 345; f) H. Flaisher, R. Tenne, M. Halmann, J. Elec-
catalysts and intermediates are increasingly employed and ex-
troanal. Chem. 1996, 402, 97 – 105; g) E. E. Barton, D. M. Rampulla, A. B.
pected in future studies. 7) Extending the range of effective Bocarsly, J. Am. Chem. Soc. 2008, 130, 6342 – 6344.
catalysts for the nitrogen reduction reaction, which resembles [10] a) B. Aurian-Blajeni, I. Taniguchi, J. O. M. Bockris, J. Electroanal. Chem.
CO2 reduction, but is being investigated by fewer researchers. Interfacial Electrochem. 1983, 149, 291 – 293; b) M. Szklarczyk, J. Sob-
kowski, J. Pacocha, J. Electroanal. Chem. Interfacial Electrochem. 1986,
The reduction of dinitrogen also undergoes PT–ET processes
215, 307 – 316; c) R. Hinogami, T. Mori, S. Yae, Y. Nakato, Chem. Lett.
beginning with adsorption and activation of nonpolar N2 mole- 1994, 23, 1725 – 1728; d) R. Hinogami, Y. Nakamura, S. Yae, Y. Nakato,
cules and requires a sufficiently high CB to drive the reaction, Appl. Surf. Sci. 1997, 121, 301 – 304; e) R. Hinogami, Y. Nakamura, S.
which can be referred to photoelectrodes in CO2 reduction.[118] Yae, Y. Nakato, J. Phys. Chem. B 1998, 102, 974 – 980; f) Y. Nakamura, R.
Hinogami, S. Yae, Y. Nakato in Studies in Surface Science and Catalysis,
Briefly, CO2 conversion is significant and we are still far from
Vol. 114 (Eds.: T. Inui, M. Anpo, K. Izui, S. Yanagida, T. Yamaguchi), Elsev-
the overall goal of reducing its emission to net zero in artificial ier, Amsterdam, 1998, pp. 565 – 568; g) T. Cottineau, M. Morin, D. B8-
photosynthesis. More efforts should be put into this field to langer, ECS Trans. 2009, 19, 1 – 7.

Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org 140 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

[11] a) I. Taniguchi, B. Aurian-Blajeni, J. O. M. Bockris, Electrochim. Acta
1984, 29, 923 – 932; b) H. Yoneyama, K. Sugimura, S. Kuwabata, J. Elec-
troanal. Chem. Interfacial Electrochem. 1988, 249, 143 – 153.
[12] a) S. K. Choi, U. Kang, S. Lee, D. J. Ham, S. M. Ji, H. Park, Adv. Energy
Mater. 2014, 4, 1301614; b) Q. Kong, D. Kim, C. Liu, Y. Yu, Y. Su, Y. Li, P.
Yang, Nano Lett. 2016, 16, 5675 – 5680; c) S. Jun Tae, I. Takayuki, H.
Mutsuko, Jpn. J. Appl. Phys. 2015, 54, 04DR05; d) K. D. Yang, Y. Ha, U.
Sim, J. An, C. W. Lee, K. Jin, Y. Kim, J. Park, J. S. Hong, J. H. Lee, H.-E.
Lee, H.-Y. Jeong, H. Kim, K. T. Nam, Adv. Funct. Mater. 2016, 26, 233 –
242.
[13] a) X. Liu, S. Inagaki, J. Gong, Angew. Chem. Int. Ed. 2016, 55, 14924 –
14950; Angew. Chem. 2016, 128, 15146 – 15174; b) Y. Yamazaki, H.
Takeda, O. Ishitani, J. Photochem. Photobio. C 2015, 25, 106 – 137; c) B.
Kumar, M. Llorente, J. Froehlich, T. Dang, A. Sathrum, C. P. Kubiak,
Annu. Rev. Phys. Chem. 2012, 63, 541 – 569.
[14] a) D. D. Zhu, J. L. Liu, S. Z. Qiao, Adv. Mater. 2016, 28, 3423 – 3452;
b) Z.-L. Wang, C. Li, Y. Yamauchi, Nano Today 2016, 11, 373 – 391.
[15] J. L. White, M. F. Baruch, J. E. Pander Iii, Y. Hu, I. C. Fortmeyer, J. E. Park,
T. Zhang, K. Liao, J. Gu, Y. Yan, T. W. Shaw, E. Abelev, A. B. Bocarsly,
Chem. Rev. 2015, 115, 12888 – 12935.
[16] X. Zhou, R. Liu, K. Sun, Y. Chen, E. Verlage, S. A. Francis, N. S. Lewis, C.
Xiang, ACS Energy Lett. 2016, 1, 764 – 770.
[17] D. A. Vermaas, W. A. Smith, ACS Energy Lett. 2016, 1, 1143 – 1148.
[18] a) X. Ba, L.-L. Yan, S. Huang, J. Yu, X.-J. Xia, Y. Yu, J. Phys. Chem. C 2014,
118, 24467 – 24478; b) J. F. de Brito, A. R. Araujo, K. Rajeshwar, M. V. B.
Zanoni, Chem. Eng. J. 2015, 264, 302 – 309; c) G. Ghadimkhani, N. R. de
Tacconi, W. Chanmanee, C. Janaky, K. Rajeshwar, Chem. Commun.
2013, 49, 1297 – 1299; d) E. Kecsenovity, B. Endrodi, Z. Papa, K. Hernadi,
K. Rajeshwar, C. Janaky, J. Mater. Chem. A 2016, 4, 3139 – 3147; e) M.
Schreier, J. Luo, P. Gao, T. Moehl, M. T. Mayer, M. Gr-tzel, J. Am. Chem.
Soc. 2016, 138, 1938 – 1946; f) M. Schreier, P. Gao, M. T. Mayer, J. Luo, T.
Moehl, M. K. Nazeeruddin, S. D. Tilley, M. Gr-tzel, Energy Environ. Sci.
2015, 8, 855 – 861.
[19] a) J.-W. Jang, S. Cho, G. Magesh, Y. J. Jang, J. Y. Kim, W. Y. Kim, J. K. Seo,
S. Kim, K.-H. Lee, J. S. Lee, Angew. Chem. 2014, 126, 5962 – 5967;
b) D. H. Won, J. Chung, S. H. Park, E.-H. Kim, S. I. Woo, J. Mater. Chem. A
2015, 3, 1089 – 1095; c) Y. J. Jang, J.-W. Jang, J. Lee, J. H. Kim, H. Kuma-
gai, J. Lee, T. Minegishi, J. Kubota, K. Domen, J. S. Lee, Energy Environ.
Sci. 2015, 8, 3597 – 3604.
[20] T. Hisatomi, J. Kubota, K. Domen, Chem. Soc. Rev. 2014, 43, 7520 –
7535.
[21] a) I. Willner, D. Mandler, J. Am. Chem. Soc. 1989, 111, 1330 – 1336;
b) W. M. Latimer, The Oxidation States of the Elements and Their Poten-
tials in Aqueous Solutions, Prentice-Hall, New York, 1938.
[22] M. T. M. Koper, J. Electroanal. Chem. 2011, 660, 254 – 260.
[23] Y. Hori, H. Wakebe, T. Tsukamoto, O. Koga, Electrochim. Acta 1994, 39,
1833 – 1839.
[24] M. R. Singh, E. L. Clark, A. T. Bell, Phys. Chem. Chem. Phys. 2015, 17,
18924 – 18936.
[25] Y. Chen, N. S. Lewis, C. Xiang, ACS Energy Lett. 2016, 1, 273 – 280.
[26] G. Ertl, H. Knçzinger, F. Scheth, J. Weitkamp, Handbook of Heterogene-
ous Catalysis, Vol. 8, Wiley-VCH, Weinheim, 2008.
[27] M. T. M. Koper, Phys. Chem. Chem. Phys. 2013, 15, 1399 – 1407.
[28] a) M. T. M. Koper, Chem. Sci. 2013, 4, 2710; b) R. Kortlever, J. Shen,
K. J. P. Schouten, F. Calle-Vallejo, M. T. M. Koper, J. Phys. Chem. Lett.
2015, 6, 4073 – 4082.
[29] H. Tong, S. Ouyang, Y. Bi, N. Umezawa, M. Oshikiri, J. Ye, Adv. Mater.
2012, 24, 229 – 251.
[30] a) S. Kaneco, H. Katsumata, T. Suzuki, K. Ohta, Appl. Catal. B 2006, 64,
139 – 145; b) S. Kaneco, H. Katsumata, T. Suzuki, K. Ohta, Chem. Eng. J.
2006, 116, 227 – 231; c) K. Hirota, D. A. Tryk, K. Hashimoto, M. Okawa,
A. Fujishima in Studies in Surface Science and Catalysis, Vol. 114 (Eds.: T.
Inui, M. Anpo, K. Izui, S. Yanagida, T. Yamaguchi), Elsevier, Amsterdam,
1998, pp. 589 – 592.
[31] L. Junfu, C. Baozhu, J. Electroanal. Chem. 1992, 324, 191 – 200.
[32] A. B. MuÇoz-Garc&a, E. A. Carter, J. Am. Chem. Soc. 2012, 134, 13600 –
13603.
[33] J. A. Keith, A. B. MuÇoz-Garc&a, M. Lessio, E. A. Carter, Top. Catal. 2015,
58, 46 – 56.
[34] E. E. Barton, A. B. Bocarsly, ECS Meeting Abstracts 2008, MA2008-02, 18-
18.
Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org
Focus Review
[35] M. Zafrir, M. Ulman, Y. Zuckerman, M. Halmann, J. Electroanal. Chem. In-
terfacial Electrochem. 1983, 159, 373 – 389.
[36] G. Zeng, J. Qiu, B. Hou, H. Shi, Y. Lin, M. Hettick, A. Javey, S. B. Cronin,
Chem. Eur. J. 2015, 21, 13502 – 13507.
[37] J. Qiu, G. Zeng, M.-A. Ha, M. Ge, Y. Lin, M. Hettick, B. Hou, A. N. Alexan-
drova, A. Javey, S. B. Cronin, Nano Lett. 2015, 15, 6177 – 6181.
[38] P. Li, X. Sui, J. Xu, H. Jing, C. Wu, H. Peng, J. Lu, H. Yin, Chem. Eng. J.
2014, 247, 25 – 32.
[39] T. T. Guaraldo, J. F. D. Brito, D. Wood, M. V. B. Zanoni, Electrochim. Acta
2015, 185, 117 – 124.
[40] L. Zhang, D. Zhu, G. M. Nathanson, R. J. Hamers, Angew. Chem. 2014,
126, 9904 – 9908.
[41] W. Wei, Z. Yang, W. Song, F. Hu, B. Luan, P. Li, H. Yin, J. Colloid Interface
Sci. 2017, 496, 327 – 333.
[42] K. Rajeshwar, N. R. de Tacconi, G. Ghadimkhani, W. Chanmanee, C.
Jan#ky, ChemPhysChem 2013, 14, 2251 – 2259.
[43] X. Huang, T. Cao, M. Liu, G. Zhao, J. Phys. Chem. C 2013, 117, 26432 –
26440.
[44] Q. Shen, Z. Chen, X. Huang, M. Liu, G. Zhao, Environ. Sci. Technol. 2015,
49, 5828 – 5835.
[45] Z. Yang, H. Wang, W. Song, W. Wei, Q. Mu, B. Kong, P. Li, H. Yin, J. Col-
loid Interface Sci. 2017, 486, 232 – 240.
[46] J. Yuan, C. Hao, Sol. Energy Mater. Sol. Cells 2013, 108, 170 – 174.
[47] J. Yuan, P. Wang, C. Hao, G. Yu, Electrochim. Acta 2016, 193, 1 – 6.
[48] J. Gu, A. Wuttig, J. W. Krizan, Y. Hu, Z. M. Detweiler, R. J. Cava, A. B. Bo-
carsly, J. Phys. Chem. C 2013, 117, 12415 – 12422.
[49] U. Kang, S. K. Choi, D. J. Ham, S. M. Ji, W. Choi, D. S. Han, A. Abdel-
Wahab, H. Park, Energ. Environ. Sci. 2015, 8, 2638 – 2643.
[50] X. Yang, E. A. Fugate, Y. Mueanngern, L. R. Baker, ACS Catal. 2017, 7,
177 – 180.
[51] S. Kamimura, N. Murakami, T. Tsubota, T. Ohno, Appl. Catal. B 2015,
174 – 175, 471 – 476.
[52] N. Sagara, S. Kamimura, T. Tsubota, T. Ohno, Appl. Catal. B 2016, 192,
193 – 198.
[53] Y. Lin, R. Kapadia, J. Yang, M. Zheng, K. Chen, M. Hettick, X. Yin, C. Bat-
taglia, I. D. Sharp, J. W. Ager, A. Javey, J. Phys. Chem. C 2015, 119,
2308 – 2313.
[54] Y. Zhao, N. C. Anderson, K. Zhu, J. A. Aguiar, J. A. Seabold, J. V. D. Lage-
maat, H. M. Branz, N. R. Neale, J. Oh, Nano Lett. 2015, 15, 2517 – 2525.
[55] D. He, T. Jin, W. Li, S. Pantovich, D. Wang, G. Li, Chem. Eur. J. 2016, 22,
13064 – 13067.
[56] B. Kumar, J. P. Brian, V. Atla, S. Kumari, K. A. Bertram, R. T. White, J. M.
Spurgeon, ACS Catal. 2016, 6, 4739 – 4745.
[57] I. Taniguchi, B. Aurian-Blajeni, J. O. M. Bockris, J. Electroanal. Chem. In-
terfacial Electrochem. 1984, 161, 385 – 388.
[58] I. Sullivan, B. Zoellner, P. A. Maggard, Chem. Mater. 2016, 28, 5999 –
6016.
[59] X. Chang, T. Wang, P. Zhang, Y. Wei, J. Zhao, J. Gong, Angew. Chem. Int.
Ed. 2016, 55, 8840 – 8845; Angew. Chem. 2016, 128, 8986 – 8991.
[60] A. Kudo, Y. Miseki, Chem. Soc. Rev. 2009, 38, 253 – 278.
[61] A. Aljabour, D. H. Apaydin, H. Coskun, F. Ozel, M. Ersoz, P. Stadler, N. S.
Sariciftci, M. Kus, ACS Appl. Mater. Interfaces 2016, 8, 31695 – 31701.
[62] G. Liu, T. Wang, H. Zhang, X. Meng, D. Hao, K. Chang, P. Li, T. Kako, J.
Ye, Angew. Chem. Int. Ed. 2015, 54, 13561 – 13565; Angew. Chem. 2015,
127, 13765 – 13769.
[63] a) H. Shi, G. Chen, C. Zhang, Z. Zou, ACS Catal. 2014, 4, 3637 – 3643;
b) H. Li, S. Gan, H. Wang, D. Han, L. Niu, Adv. Mater. 2015, 27, 6906 –
6913.
[64] G. Gao, Y. Jiao, E. R. Waclawik, A. Du, J. Am. Chem. Soc. 2016, 138,
6292 – 6297.
[65] a) Y. Hori in Modern Aspects of Electrochemistry (Eds.: C. G. Vayenas,
R. E. White, M. E. Gamboa-Aldeco), Springer, Heidelberg, 2008, pp. 89 –
189; b) M. Azuma, K. Hashimoto, M. Hiramoto, M. Watanabe, T. Sakata,
J. Electrochem. Soc. 1990, 137, 1772 – 1778.
[66] A. Zakharyan, Elektrokhimiya 1977, 13, 1818.
[67] E. Andrews, M. Ren, F. Wang, Z. Zhang, P. Sprunger, R. Kurtz, J. Flake, J.
Electrochem. Soc. 2013, 160, H841 – H846.
[68] S. Chu, S. Fan, Y. Wang, D. Rossouw, Y. Wang, G. A. Botton, Z. Mi,
Angew. Chem. Int. Ed. 2016, 55, 14262 – 14266; Angew. Chem. 2016,
128, 14474 – 14478.
141 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

[69] Y. Wang, S. Fan, B. AlOtaibi, Y. Wang, L. Li, Z. Mi, Chem. Eur. J. 2016, 22,
8809 – 8813.
[70] J. T. Song, H. Ryoo, M. Cho, J. Kim, J.-G. Kim, S.-Y. Chung, J. Oh, Adv.
Energy Mater. 2016, 1601103.
[71] L. Liu, X. Zhang, L. Yang, L. Ren, D. Wang, J. Ye, Natl. Sci. Rev. 2017,
DOI: doi.org/10.1093/nsr/nwx019.
[72] R. Kostecki, J. Augustynski, J. Appl. Electrochem. 1993, 23, 567 – 572.
[73] a) A. Furube, L. Du, K. Hara, R. Katoh, M. Tachiya, J. Am. Chem. Soc.
2007, 129, 14852 – 14853; b) D. Kumar, A. Lee, T. Lee, M. Lim, D. K. Lim,
Nano Lett. 2016, 16, 1760 – 1767; c) P. Mulvaney in Nanoscale Materials
in Chemistry (Ed.: K. J. Klabunde), Wiley, Hoboken, 2001, pp. 121 – 167.
[74] B. Rezaei, S. Mallakpour, M. Taki, J. Power Sources 2009, 187, 605 – 612.
[75] G. Liu, S. Xie, Q. Zhang, Z. Tian, Y. Wang, Chem. Commun. 2015, 51,
13654 – 13657.
[76] D. Hurs#n, A. Kormanyos, K. Rajeshwar, C. Janaky, Chem. Commun.
2016, 52, 8858 – 8861.
[77] D. Guzm#n, M. Isaacs, I. Osorio-Rom#n, M. Garc&a, J. Astudillo, M. Ohl-
baum, ACS Appl. Mater. Interfaces 2015, 7, 19865 – 19869.
[78] a) T. Masuda, Y. Sun, H. Fukumitsu, H. Uehara, S. Takakusagi, W.-J.
Chun, T. Kondo, K. Asakura, K. Uosaki, J. Phys. Chem. C 2016, 120,
16200 – 16210; b) Y. Sun, T. Masuda, K. Uosaki, Chem. Lett. 2012, 41,
328 – 330.
[79] K. K. Sakimoto, A. B. Wong, P. Yang, Science 2016, 351, 74.
[80] C. Liu, B. C. Coljn, M. Ziesack, P. A. Silver, D. G. Nocera, Science 2016,
352, 1210.
[81] E. M. Nichols, J. J. Gallagher, C. Liu, Y. Su, J. Resasco, Y. Yu, Y. Sun, P.
Yang, M. C. Y. Chang, C. J. Chang, Proc. Natl. Acad. Sci. USA 2015, 112,
11461 – 11466.
[82] a) R. Liu, G. Yuan, C. L. Joe, T. E. Lightburn, K. L. Tan, D. Wang, Angew.
Chem. Int. Ed. 2012, 51, 6709 – 6712; Angew. Chem. 2012, 124, 6813 –
6816; b) R. Liu, C. Stephani, J. J. Han, K. L. Tan, D. Wang, Angew. Chem.
Int. Ed. 2013, 52, 4225 – 4228; Angew. Chem. 2013, 125, 4319 – 4322.
[83] B. Kumar, J. M. Smieja, C. P. Kubiak, J. Phys. Chem. C 2010, 114, 14220 –
14223.
[84] B. Kumar, J. M. Smieja, A. F. Sasayama, C. P. Kubiak, Chem. Commun.
2012, 48, 272 – 274.
[85] E. Torralba-PeÇalver, Y. Luo, J.-D. Compain, S. Chardon-Noblat, B. Fabre,
ACS Catal. 2015, 5, 6138 – 6147.
[86] T. Arai, S. Sato, K. Uemura, T. Morikawa, T. Kajino, T. Motohiro, Chem.
Commun. 2010, 46, 6944 – 6946.
[87] J. Cheng, M. Zhang, G. Wu, X. Wang, J. Zhou, K. Cen, Environ. Sci. Tech-
nol. 2014, 48, 7076 – 7084.
[88] T. Arai, S. Tajima, S. Sato, K. Uemura, T. Morikawa, T. Kajino, Chem.
Commun. 2011, 47, 12664 – 12666.
[89] G. Sahara, R. Abe, M. Higashi, T. Morikawa, K. Maeda, Y. Ueda, O. Ishita-
ni, Chem. Commun. 2015, 51, 10722 – 10725.
[90] T. E. Rosser, C. D. Windle, E. Reisner, Angew. Chem. 2016, 128, 7514 –
7518.
[91] H. Tian, ChemSusChem 2015, 8, 3746 – 3759.
[92] a) J. Hawecker, J.-M. Lehn, R. Ziessel, J. Chem. Soc. Chem. Commun.
1983, 536 – 538; b) J. Hawecker, J.-M. Lehn, R. Ziessel, J. Chem. Soc.
Chem. Commun. 1984, 328 – 330; c) D. H. Apaydin, E. Tordin, E. Porten-
kirchner, G. Aufischer, S. Schlager, M. Weichselbaumer, K. Oppelt, N. S.
Sariciftci, ChemistrySelect 2016, 1, 1156 – 1162.
[93] C. R. Cabrera, H. D. AbruÇa, J. Electroanal. Chem. Interfacial Electrochem.
1986, 209, 101 – 107.
[94] A. Nakada, K. Koike, T. Nakashima, T. Morimoto, O. Ishitani, Inorg.
Chem. 2015, 54, 1800 – 1807.
Chem. Asian J. 2018, 13, 127 – 142 www.chemasianj.org
Focus Review
[95] S. Lin, C. S. Diercks, Y.-B. Zhang, N. Kornienko, E. M. Nichols, Y. Zhao,
A. R. Paris, D. Kim, P. Yang, O. M. Yaghi, C. J. Chang, Science 2015, 349,
1208.
[96] K. Alenezi, S. K. Ibrahim, P. Li, C. J. Pickett, Chem. Eur. J. 2013, 19,
13522 – 13527.
[97] Y. Kou, S. Nakatani, G. Sunagawa, Y. Tachikawa, D. Masui, T. Shimada, S.
Takagi, D. A. Tryk, Y. Nabetani, H. Tachibana, H. Inoue, J. Catal. 2014,
310, 57 – 66.
[98] O. Khaselev, J. A. Turner, Science 1998, 280, 425.
[99] C. Liu, J. J. Gallagher, K. K. Sakimoto, E. M. Nichols, C. J. Chang, M. C.
Chang, P. Yang, Nano Lett. 2015, 15, 3634 – 3639.
[100] S. Sato, T. Arai, T. Morikawa, K. Uemura, T. M. Suzuki, H. Tanaka, T.
Kajino, J. Am. Chem. Soc. 2011, 133, 15240 – 15243.
[101] T. Arai, S. Sato, T. Kajino, T. Morikawa, Energ. Environ. Sci. 2013, 6,
1274 – 1282.
[102] Y. J. Jang, I. Jeong, J. Lee, J. Lee, M. J. Ko, J. S. Lee, ACS Nano 2016, 10,
6980 – 6987.
[103] G. Sahara, H. Kumagai, K. Maeda, N. Kaeffer, V. Artero, M. Higashi, R.
Abe, O. Ishitani, J. Am. Chem. Soc. 2016, 138, 14152 – 14158.
[104] S. Yotsuhashi, M. Deguchi, Y. Yamada, K. Ohkawa, AIP Adv. 2014, 4,
067135.
[105] M. Asadi, K. Kim, C. Liu, A. V. Addepalli, P. Abbasi, P. Yasaei, P. Phillips,
A. Behranginia, J. M. Cerrato, R. Haasch, P. Zapol, B. Kumar, R. F. Klie, J.
Abiade, L. A. Curtiss, A. Salehi-Khojin, Science 2016, 353, 467.
[106] a) M. Schreier, L. Curvat, F. Giordano, L. Steier, A. Abate, S. M. Zakeerud-
din, J. Luo, M. T. Mayer, M. Gr-tzel, Nat. Commun. 2015, 6, 7326; b) M.
Schreier, F. H8roguel, L. Steier, S. Ahmad, J. S. Luterbacher, M. T. Mayer,
J. Luo, M. Gr-tzel, Nat. Energy 2017, 2, 17087.
[107] M. Li, P. Li, K. Chang, H. Liu, X. Hai, H. Zhang, J. Ye, Chem. Commun.
2016, 52, 8235 – 8238.
[108] J. Cheng, M. Zhang, G. Wu, X. Wang, J. Zhou, K. Cen, Sol. Energy Mater.
Sol. Cells 2015, 132, 606 – 614.
[109] C. W. Li, J. Ciston, M. W. Kanan, Nature 2014, 508, 504 – 507.
[110] Y. Chen, C. W. Li, M. W. Kanan, J. Am. Chem. Soc. 2012, 134, 19969 –
19972.
[111] Y. Chen, M. W. Kanan, J. Am. Chem. Soc. 2012, 134, 1986 – 1989.
[112] H.-E. Lee, K. D. Yang, S. M. Yoon, H.-Y. Ahn, Y. Y. Lee, H. Chang, D. H.
Jeong, Y.-S. Lee, M. Y. Kim, K. T. Nam, ACS Nano 2015, 9, 8384 – 8393.
[113] M. Li, J. Wang, P. Li, K. Chang, C. Li, T. Wang, B. Jiang, H. Zhang, H. Liu,
Y. Yamauchi, N. Umezawa, J. Ye, J. Mater. Chem. A 2016, 4, 4776 – 4782.
[114] X. Meng, L. Liu, S. Ouyang, H. Xu, D. Wang, N. Zhao, J. Ye, Adv. Mater.
2016, 28, 6781 – 6803.
[115] Y. Shi, J. Wang, C. Wang, T.-T. Zhai, W.-J. Bao, J.-J. Xu, X.-H. Xia, H.-Y.
Chen, J. Am. Chem. Soc. 2015, 137, 7365 – 7370.
[116] G. Liu, P. Li, G. Zhao, X. Wang, J. Kong, H. Liu, H. Zhang, K. Chang, X.
Meng, T. Kako, J. Ye, J. Am. Chem. Soc. 2016, 138, 9128 – 9136.
[117] Z. Cao, D. Kim, D. Hong, Y. Yu, J. Xu, S. Lin, X. Wen, E. M. Nichols, K.
Jeong, J. A. Reimer, P. Yang, C. J. Chang, J. Am. Chem. Soc. 2016, 138,
8120 – 8125.
[118] a) S. Wang, X. Hai, X. Ding, K. Chang, Y. Xiang, X. Meng, Z. Yang, H.
Chen, J. Ye, Adv. Mater. 2017, 29, 1701774; b) C. J. M. van der Ham,
M. T. M. Koper, D. G. H. Hetterscheid, Chem. Soc. Rev. 2014, 43, 5183 –
5191.
Manuscript received: November 13, 2017
Accepted manuscript online: November 28, 2017
Version of record online: January 2, 2018
142 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim