Artificial Photosynthesis For High-Value-Added Chemicals Old Material, New Opportunity

Received: 14 June 2021 | Revised: 1 September 2021 | Accepted: 3 September 2021
DOI: 10.1002/cey2.159
REVIEW
Artificial photosynthesis for high‐value‐added chemicals:

Old material, new opportunity
Sungsoon Kim1 | Kwang Hee Kim1 | Cheoulwoo Oh1 | Kan Zhang2 |

Jong Hyeok Park1
1
Department of Chemical and
Biomolecular Engineering, Yonsei Abstract
University, Seoul, Republic of Korea Solar energy utilization has drawn attention due to ever‐increasing
2
Institute of Optoelectronics & environmental and energy issues. Photoelectrochemical (PEC) and
Nanomaterials, Nanjing University of
Science and Technology, Nanjing, China photocatalytic (PC) water splitting for hydrogen production, which is the
most popular and well‐established solar‐to‐chemical conversion process,
Correspondence
has been studied thoroughly to date but is now facing limitations related to
Kan Zhang, Institute of Optoelectronics &
Nanomaterials, MIIT Key Laboratory of low conversion efficiency. To resolve this issue, research in PEC cells or
Advanced Display Material and Devices, photocatalysts has recently aimed to produce alternative value‐added
School of Materials Science and
chemicals by modifying their redox reactions, which potentially enables
Engineering, Nanjing University of
Science and Technology, Nanjing 210094, high economic reward to compensate for the low efficiency. Here, various
China. kinds of redox reactions that decouple classic water splitting reactions to
Email: zhangkan@njust.edu.cn
produce value‐added chemicals via PEC and PC processes are introduced.
Jong Hyeok Park, Department of Successful coupling of CO2 reduction, O2 reduction and organic synthesis
Chemical and Biomolecular Engineering, with either water oxidation or water reduction is comprehensively
Yonsei University, Seoul 03722,
Republic of Korea. discussed from the perspective of basic fundamental and product selectivity
Email: lutts@yonsei.ac.kr in terms of the band structure of materials, cocatalyst design, and ther-
modynamics and kinetics of the reactions. Throughout the review, future
Funding information
challenges and opportunities are suggested with respect to the redesigned
National Natural Science Foundation of
China, Grant/Award Number: 51802157; artificial synthesis, which might be an alternative development for
National Research Foundation of Korea, the commercialization of PEC or PC value‐added chemical production
Grant/Award Numbers:
NRF‐2017M3A7B4041987,
technologies in the near future.
NRF‐2019R1A4A1029237,
NRF‐2021M3E6A1015823 KEYWORDS
artificial photosynthesis, photocatalysts, photoelectrochemical cells, redox reactions,
value‐added chemical production
1 | INTRODUCTION from CO2 and H2O to O2 and glucose in natural

photosynthesis, solar water splitting into H2 and O2 is
As interest in energy and environmental issues has in- regarded as the natural target transformation.1–5 The
creased worldwide, solar energy utilization has drawn conversion of photon energy into chemical energy in an
attention for a long time. Inspired by the transformation uphill reaction could be called artificial photosynthesis,
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2021 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.
Carbon Energy. 2022;4:21–44. wileyonlinelibrary.com/journal/cey2 | 21

26379368, 2022, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cey2.159 by Museu Paraense Emílio Goeldi, Wiley Online Library on [27/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
22 | KIM ET AL.
the conversion efficiency of which is generally expressed various valuable hydrocarbons in aqueous electro-
as lytes.36,40–42 On the water oxidation side, by converting O2 to
H2O2, the economic reward of water splitting can be in-
∆G×R creased by 20 times.35 However, the redesigned redox couple
η = ,
Psun × S requires a high selectivity to compete with water splitting,
and suitable band edge energetics to drive the reaction thus
where ∆G is the change in the Gibbs free energy in the needs to be considered in the system design and material
natural target transformation, R is the reaction rate, Psun choice. Nevertheless, decoupling two half‐reactions for both
is the power density of the solar light, and S is the value‐added products is the most promising approach for
irradiation area.6,7 As the economic viability is linked to eliminating our dependence on fossil fuels beyond the ef-
η, η is required to be 10% to achieve simple water split- forts to enhance the η value.
ting. Hence, the artificial photosynthesis market is Herein, we introduce an overview of recent progress in
striving to achieve a high R value with an invisible artificial photosynthesis for producing value‐added che-
indicator of ∆G being a constant of 237 kJ mol−1. micals. In this review article, the fundamentals of artificial
At present, photoelectrochemical (PEC) and photo- photosynthesis, including the basic concepts of develop-
catalytic (PC) water splitting processes have attracted con- ment strategies, which have been typically established on
siderable attention because they drive the direct conversion the basis of solar water splitting technology, are first de-
of photon energy to chemical energy without ohmic loss, scribed. Second, various redox reactions applied in artificial
enabling artificial photosynthesis at a lower cost. However, photosynthesis, including CO2 reduction, O2 reduction,
PEC and PC systems have difficulty in improving the R oxidizing reagent production, and organic synthesis are
value because of several limitations: light harvesting ability, summarized, and strategies to improve the efficiency or
charge separation, and sluggish reaction activity. Indeed, selectively of these reactions are introduced. Finally, some
the difficulty in achieving the desired η in the existing challenges and perspectives for future exploration of arti-
systems is due to the limitation of the materials, especially ficial photosynthesis of value‐added chemicals are dis-
for low‐cost natural materials. For example, titanium di- cussed. Because the half‐reaction is not entirely clear from
oxide (TiO2), which is the most well‐known PEC and PC the practical perspective (namely, high‐cost scavenger use)
material, has a short light absorption range within only the of attaining economic viability, we limit our scope to
UV region, making it impossible to harvest visible light.8–11 definite value‐added reactions.
Bismuth vanadate (BiVO4) and graphitic carbon nitride
(g‐C3N4) have poor water oxidation kinetics, while copper
(I) oxide (Cu2O) and cadmium sulphide (CdS) show very 2 | F UN D A M E N T A L S O F RE D OX
poor stability during operation, resulting in many draw- REACTION DESIGN
backs in reaching the theoretical maximum efficiency.12–19
The race for the desired η is mainly focused on the search In the typical solar water splitting reaction, the redox
for new materials, mainly including oxynitride,20,21 couple consists of the hydrogen evolution reaction (HER)
oxysulfide,22,23 heterojunction,24–26 doping,27,28 interface and the oxygen evolution reaction (OER), with a theoretical
engineering,29,30 nanoengineering,31 cocatalyst loading,32,33 redox potential of 1.23 V, whereas the minimum energy
and so forth, as alternatives or solutions to these required for the semiconductor should include the activa-
drawbacks; here, the concern is whether the additional tion overpotential and a few other minor losses and has
manufacturing cost disrupts the balance between the been proposed to be at least 2.3 eV under thermodynamic
economic reward and the target η value of 10%. conditions.43,44 In such foundational reactions, while the
More recently, motivated by the economic reward, economic product is H2, O2 from the OER which has little
artificial photosynthesis has progressed to decoupling two economic value restricts the overall economic value of the
half‐reactions of water to produce value‐added chemicals water splitting system. Therefore, designing new redox
from either the reduction or oxidation side by using pairs to produce more valuable products than H2 by sub-
established PEC and PC materials.34–39 This novel strategy to stituting the HER or to generate value‐added products in-
overcome current limitations is highlighted by artificial stead of O2 is more ideal from an economic point of view
photosynthesis because numerous kinds of valuable (Figure 1A). High‐value hydrocarbons, organic compounds
chemicals can be produced by simply modifying the PEC and H2O2 can be produced by the reduction of CO2, O2, and
and PC systems established to date, without requiring sub- so forth, while several organic compounds and oxidizing
stantial effort to discover new materials. For example, by reagents can be formed from low‐cost raw materials. These
applying common materials, such as TiO2, silicon, and redesigned redox systems with different redox potentials
Cu2O, CO2 can be photoelectrochemically reduced to are shown in Figure 1B. Basically, the reaction pathway is
KIM ET AL. | 23
that of other target reactions (e.g., reduction of CO2 to CH4

[∆Grxn = 818 kJ mol−1]).46,47 The lower activation energy of
the water molecule enables a high kinetic rate to compete
with the desired reduction or oxidation. However, when
the thermodynamic band structure favours several pro-
ducts simultaneously, the product selectivity with different
charge exchange numbers is strongly dependent on the
kinetics of each reaction. Thus, the charge transfer rate
constants and activation energies are crucial to all possible
interfacial charge transfer processes, ultimately determin-
ing the product selectivity.48,49 On the other hand, the
surface chemical structure is strongly related to the reac-
tion pathway because the PEC and PC reactions are het-
erogeneous catalysis processes.50 Thus, modulating the
surface chemical structure of the PEC and PC materials
can greatly improve the selectivity for the targeted value‐
added chemicals, as the quasi‐Fermi level formed at the
semiconductor/reactant interface is secured by the pre-
sence of the surface state, hence exerting less effect on the
F I G U R E 1 (A) Schematic of photoelectrochemical water
splitting for hydrogen production. (B) Schematic of various redox
activation energies and rate constants associated with in-
potentials of value‐added chemical production. (C) Schematic of terfacial charge transfer. Moreover, the semiconductor
the three fundamentals of energy band structure, thermodynamic surface has intrinsic adsorption property about proton or
activation energies, and kinetic rate constant hydroxide ion, which makes different pH conditions re-
lative to the bulk electrolyte.51 Thus, the surface chemical
determined by whether it is thermodynamically favourable structure of PEC and PC materials can determine the re-
or not so that every catalytic reaction should consider its action pathway or product selectivity of some pH‐
thermodynamic barrier to successfully produce the target dependent reactions. Employing a cocatalyst is another
product. To overcome the thermodynamic barrier, the en- good way to enhance both the reactivity and selectivity
ergy band gap of a semiconductor should exceed the sum of because most photoactive semiconductors have poor sur-
the theoretical redox potential and the activation over- face kinetics compared to metals or metal compounds.52
potential of the redesigned redox system.45 For photo- Thus, the deposition of certain cocatalysts on the surface is
catalysis, the energy band gap should strictly straddle the a good strategy to improve the product selectivity of value‐
sum of the theoretical redox potential and the over- added chemicals in a simple and facile way.
potentials when using a single semiconductor. Decoupling Most studies of artificial photosynthesis for value‐added
the redox process into two half‐reactions occurring in each chemicals are currently focused on several fundamentals in
of two different semiconductors offers a greater possibility terms of energy band structure, activation energy, and pro-
to design the artificial photosynthesis of value‐added che- duct selectivity (Figure 1C). Indeed, more factors re-
micals in the PC reaction. For the PEC reaction, the dif- main, such as stability, cost‐effectiveness, or environmental
ference between the band level of the photoelectrode and issue, while these issues are much close to commercializa-
the redox potential can be compensated by an additional tion while the current step of research on artificial photo-
external voltage without seriously considering the energy synthesis is still yet to be commercialized.53 Thus, controlling
band structure and redox potential. the three abovementioned factors to increase selectivity
In addition to the fundamental thermodynamic re- would lead to a high R value of the desired value‐added
quirements to induce target redox reactions, the selectivity chemical production to achieve future commercialization.
for value‐added chemical products is a key consideration
because the η value of artificial photosynthesis depends on
the R value. There are generally three strategies to improve 3 | V AL U E‐ AD DED CHEMIC AL S
the selectivity of the desired redox reaction: (1) control PRODUC ED BY REDUC TION
of the rate kinetics of the reaction, (2) modulation of the
surface chemical structure, and (3) deposition of a coca- 3.1 | CO2 reduction
talyst. In an aqueous solution, the water splitting products
of either H2 or O2 are hardly suppressed because activation CO2 is the main product of fossil fuel combustion, which
of the water molecule (∆Grxn = 237 kJ mol−1) is easier than is released into the atmosphere and exerts a greenhouse
24 | KIM ET AL.
effect. Converting CO2 into selective hydrocarbon‐based CO2RR. The optimal sample with 2 wt.% Cu loading
chemicals and fuels provides efficient CO2 recycling si- achieved a steady‐state 250 μmol g−1 after 20 h of irra-
milar to the carbon cycle in nature.36,54,55 Since CO2 has diation. Cheng et al. designed a PEC cell composed of a
the highest oxidation state of carbon, there are various Pt‐rGO counter electrode as a cocatalyst for CO2 reduc-
kinds of gaseous/liquid products that can be obtained tion to ethanol and a Pt‐TiO2 photoanode for water oxi-
through multiple electron transfer mechanisms. As dation.63 Compared to other photocathodes, Pt‐rGO
shown in Table 1, the reduction potentials for various showed a high CO2 conversion rate due to the rapid
CO2 reduction products are located near the H2O re- electron transfer and the provision of reactant adsorption
duction potential, and the materials used for solar water sites. In the PEC system, the production of ethanol could
splitting are also viable for simultaneous CO2 reduction be explained by the interaction between the produced
and O2 evolution. Nevertheless, CO2 is chemically stable methanol and the surface adsorbed methylene group
and inert due to its linear structure, thereby requiring (:CH2). Additionally, the selectivity of ethanol could be
high energy to cleave the C=O double bond (>750 kJ increased through the combination of Cu, which had
mol−1); thus, co‐catalysts are required for CO2 absorption remarkable selectivity for high‐order hydrocarbon
and activation. Since Halmann first reported the PEC production.
conversion of CO2 to methanol, formic acid, and for- Not only liquid products, such as formic acid, me-
maldehyde via a p‐GaP photocathode and carbon anode, thanol and ethanol, but also gaseous products, such as
many follow‐up studies have been devoted to increasing CH4 and CO, can be produced by CO2 reduction.64–69
the hydrocarbon product selectivity of CO2 reduction by Methane is a possible product of CO2 photoreduction,
developing cocatalysts.56–59 Yin et al. selectively reduced where the Gibbs free energy required for the CO2‐to‐
CO2 to formic acid using a Cu‐Zn alloy cocatalyst on methane conversion reaction is very high, with a value of
SrTiO3 (STO) nanoparticles.60 The CO2 reduction path- 818 kJ mol−1, with eight electron transfers.46,70 There-
way depends on the adsorption strength of the reduction fore, a complex multistep reaction mechanism involving
intermediates on the catalyst surface. The above authors multiple proton‐coupled electron transfer processes is a
found that the adsorption strength can be controlled by major challenge. Wang et al. obtained a methane yield of
optimization of the Cu‐to‐Zn ratio to enable selective 1361 μmol g−1 h−1 with high selectivity using a Pt‐TiO2
conversion of CO2 to formic acid. In addition, Lan's nanostructured film prepared by a versatile gas phase
group converted CO2 to HCOOH with 100% selectivity by deposition method.71 Efficient electron‐hole separation
using heterometallic Fe2M (M is Co, Ni or Zn) cluster‐ occurred due to the coating of a small Pt nanoparticle
based metal‐organic frameworks (MOFs).61 Density cocatalyst of 0.5–2 nm on a single‐crystal TiO2 film with a
functional theory (DFT) and time‐dependent DFT high surface area (Figure 2A). Additionally, the se-
(TDDFT) computations revealed that the low‐valent lectivity of CH4 production was improved by increasing
metal M and high‐valent Fe are electron and hole ac- the possibility of a multielectron reaction originating
ceptors, respectively, for the CO2 reduction reaction from electrons, trapping in Pt nanoparticles coated on
(CO2RR) and the OER reaction. In contrast to the for- the TiO2 surface. On the other hand, Neaţu et al. per-
mation of formic acid, CO2‐to‐methanol conversion over formed CO2‐to‐methane conversion using Au‐Cu alloy
Cu‐loaded TiO2 under UV irradiation at 254 nm was nanoparticle‐modified P25 TiO2.75 Due to the plasmonic
demonstrated by Tseng et al.62 It was found that Cu not effect of Au, reactivity in the visible region was improved,
only suppressed electron‐hole recombination by effective and Cu served as an activation site for CO2, thereby en-
electron trapping but also served as an active site for the hancing the selectivity of CH4 production. As a result, the
T A B L E 1 Standard reduction
Product Reaction E (V vs. SHE at pH 7)
potential of CO2 reduction reactions
Methanol CO2 + 6H+ + 6e− → CH3OH + H2O −0.38
−
Formic acid CO2 + 2H + 2e → HCOOH
+
−0.61
−
Formaldehyde CO2 + 4H + 4e → HCHO + H2O
+
−0.48
Ethanol 2CO2 + 12H+ + 12e− → C2H5OH + 3H2O 0.08
−
Methane CO2 + 8H + 8e → CH4 + 2H2O
+
−0.24
−
Carbon monoxide CO2 + 2H + 2e → CO + H2O
+
−0.52
−
Ethylene 2CO2 + 12H + 12e → C2H4 + 4H2O
+
0.06
KIM ET AL. | 25
F I G U R E 2 (A) Charge separation and band

energy level of Pt/TiO2 film in a CO2 conversion
system. Reproduced with permission: Copyright
2012, American Chemical Society.71
(B) Proposed mechanism for the activity and
selectivity of CO/CH4 generation according to
the Ag loading level. Reproduced with
permission: Copyright 2016, Elsevier.72
(C) CO/H2 ratios on a‐Si/TiO2/Au
photocathodes with various thicknesses of Au.
Reproduced with permission: Copyright 2019,
The Royal Society of Chemistry.73 (D) Schematic
illustration of the tandem photoelectrochemical
cell with an integrated enzyme‐cascade (TPIEC)
system. Reproduced with permission: Copyright
2017, Wiley74
Au‐Cu alloy nanoparticle‐modified P25 TiO2 showed a favoured with a CO production rate of 5.19 μmol g−1 h−1
methane production rate of 2.2 mmol g−1 h−1 and 97% and 100% selectivity under visible light illumination. In
selectivity. Since CO can be simultaneously produced addition, Bi et al. synthesized an Li2TiO3/TiO2 hetero-
with CH4 at the same surface of the catalyst, Li et al. structure and investigated CO2 photoreduction.77 The
investigated the effect of the crystal facet on the se- heterostructure considerably enhanced the adsorption
lectivity of the CO and CH4 products by loading Ag na- capacity of CO2 and suppressed electron trapping due to
noparticles onto brookite TiO2 nanocubes with four {210} the presence of increased Ti3+ ions. It also reduced the
and two {001} exposed facets.72 The Ag distribution on energy barrier of CO2‐to‐CO conversion by providing a
the exposed facet varied according to the amount of Ag reaction pathway, including a formate intermediate. As a
loading. An increased amount of Ag loaded on the {210} result, Li2TiO3/TiO2 achieved a CO production rate of
facet resulted in a CO‐selective reaction, while more Ag 1.7358 μmol g−1 h−1, which is three times higher than
loaded on the {001} facet resulted in a CH4‐selective re- that of pure TiO2. On the other hand, Zhao and cow-
action (Figure 2B). These results indicate that the activity orkers performed CO2‐to‐CO conversion using defect‐
and selectivity of PC can be controlled by adjusting the rich ZnAl‐layered double hydroxide (LDH) nanosheets.78
exposed surface crystal facet. In contrast to the crystal ZnAl‐LDH increased the oxygen vacancy defect density
facet‐dependent product selectivity, kinetically selective to form a Zn+ centre, which can act as an active site for
CO production by g‐C3N4/Bi2WO6 was investigated by Li electron transfer. Additionally, the oxygen vacancy‐Zn+
et al.76 The well‐arranged band energy level between the centre served as a trapping site for adsorption of CO2 and
two semiconductors formed a Z‐scheme structure to H2O to promote charge separation, thereby achieving
promote separation of the photogenerated carrier. Ad- high catalytic activity. Furthermore, direct production
ditionally, only CO production on g‐C3N4/Bi2WO6 was from C1 products to C2 + hydrocarbons through CO2
possible because the further reduction of CO2 to CH4, reduction have been studied.79–81 C2 + products have
which undergoes multiple electron transfer reactions by advantages of higher energy density and economic value
electron stacking, was suppressed by the fast consump- than C1 products. However, direct production of C2 +
tion of electrons into CO production. Thus, only CO products has many thermodynamic limitations, such
conversion occurred selectively, which is dynamically as C‐C coupling, which is a rate‐determining step.
26 | KIM ET AL.
F I G U R E 3 (A) Bare STO and (B) Rh/STO in an N2 atmosphere and (C) Rh/STO in an N2, CO2 or CH4/CO2 atmosphere under
illumination. (D) Overall schematic of photocatalytic DRM. Reproduced with permission: Copyright 2020, Springer Nature.85
(E) Proposed mechanism and schematic of PNC and Co@PNC. Reproduced with permission: Copyright 2020, The Royal Society of
Chemistry.86 Relative energy diagrams for (F) 1‐phenylethanol deprotonation over CdSe and CdS and (G) adsorption and dissociation
of CO2 to generate CO over CdSe and CdS. Reproduced with permission: Copyright 2019, Elsevier87
Sorcar et al. investigated C2H6 production by using in Au effectively stabilized the *COOH intermediate of
Pt‐sensitized graphene‐wrapped defect‐induced TiO2.81 the CO2 reduction reaction, which remarkably increased
They suggested that photogenerated holes migrate to the CO selectivity. Moreover, changing the grain
graphene and electrons accumulate on the surface Ti3+ boundary by adjusting the Au thickness enabled mod-
sites of defect‐induced TiO2, which generated ·CH3 ra- ulation of the CO/H2 production ratio from CO2 con-
dicals by the multielectron transfer process. Moreover, version (Figure 2C). Moreover, Kuk et al. designed a
·CH3 radicals can be stabilized by graphene, which leads tandem PEC cell with an integrated enzyme‐cascade
to C2H6 production by ·CH3 coupling. They achieved a (TPIEC) system (Figure 2D).74 Co‐Pi/α‐Fe2O3 was used
rate of 11 μmol g−1 h−1 and an apparent quantum yield of as a photoanode, which acted as an electron donor,
2.7% for C2H6 production. and BiFeO3 was used as a photocathode, which reduced
In addition to these successful designs of PC and PEC NAD+ to NADH to enable methanol synthesis through
redox systems, tandem PEC cells composed of both pho- the enzyme. Notably, PcFaldDH, one of the enzymes,
tocathodes and photoanodes probably enable higher solar‐ enhanced the formate reduction reaction, which is
to‐fuel efficiency due to efficient charge separation and known as the rate‐determining step in the conversion of
bias‐free conditions.82,83 Wang and coworkers integrated CO2 to methanol. As a result, the TPIEC system achieved
a TiO2/Ni photocathode and BiVO4 photoanode for si- a methanol production rate of 1280 μmol g−1 h−1, which
multaneous CO2 reduction and water oxidation, achieving is much higher than that of conventional PEC or
a methanol formation rate of 153 μmol h−1 cm−2.84 PC‐based systems.
Moreover, integration of the BiVO4 photoanode and ZnO The above cases coupled water oxidation with CO2
photocathode grown on Ni foam with an amine ligand reduction for the redesigned redox, which limited the
provided a favourable reaction pathway for C‐C coupling. added value of the reaction due to the negligible value of
The PEC system showed 100% selectivity of the C2 pro- the O2 product. It is necessary to design a more econom-
ducts, mainly ethanol and acetic acid, and a formation ical system that can yield additional high‐value products
rate of 12.5 μM h−1 cm−2. Gong and coworkers produced by using photo‐generated holes for organic oxidation in-
syngas with a tunable CO/H2 ratio using an a‐Si/TiO2/Au stead of water oxidation. Shoji et al. reported Rh‐loaded
photocathode and a BiVO4 photoanode.73 They used Au STO (Rh/STO) to simultaneously oxidize CH4 and reduce
as an electrocatalyst with high efficiency and selectivity CO2.85 By using electron spin resonance (ESR) analysis
for CO conversion, and adjustment of the grain boundary under illumination, they confirmed that trapped hole
KIM ET AL. | 27
peaks in the valence band (VB) of STO were observed in carbon nitride (C3N4/PDI) and boron nitride (BN) with
both Rh/STO and bare STO, whereas the trapped electron rGO to produce H2O2 under visible light.91 First, the
peaks in the conduction band (CB) disappeared in the case doping of PDI units positively shifts the VB level of
of Rh/STO (Figure 3A–C). Therefore, the electrons and g‐C3N4 to facilitate water oxidation, thus improving the
holes that accumulated at the Rh and STO surfaces, re- solar‐to‐chemical conversion (SCC) efficiency. Then, BN
spectively, promoted the CO product from both methane and rGO deposited on C3N4/PDI act as hole and electron
oxidation and CO2 reduction (Figure 3D). Furthermore, in acceptors, respectively, suppressing the recombination
addition to CH4 oxidation, the CO2 reduction system of charge carriers to carry out water oxidation and O2
combined with various organic oxidation reaction systems reduction. As a result, the SCC efficiency for H2O2 pro-
has also been studied.86–90 Dong et al. reported a redox duction on the hybrid catalyst is 0.27%. Zhu et al. re-
system combining CO2 reduction and methanol oxida- ported self‐supporting water oxidation and O2 reduction
tion,86 where a stable CsPbBr3 embedded in the Cs4PbBr6 for H2O2 production using carbon‐supported oxygen
matrix was employed. Co ions generated Co‐COOH in- vacancy‐rich Co3O4 (Figure 4A). The benefits of the
termediates to enable rapid adsorption of CO2, and the oxygen vacancies on Co3O4 include a reduced band gap,
reduction potential of Co/Co2+ provided sufficient driving an enhanced donor density, and improved charge
force for CO2 to CO reduction. CO2 can be reduced to CO separation and migration to promote O2 reduction. In
with a yield of 1835 μmol g−1 through Co doping, and addition to oxygen vacancies, carbon supporting Co3O4
methanol can be selectively oxidized to formic acid provides active sites for O2 reduction (Figure 4B,C). The
(Figure 3E). Additionally, Guo et al. reported a redox re- photocatalysts exhibit high activity, with an H2O2 pro-
action system by combining CO2 reduction and duction rate of 3.78 mmol g−1 h−1 under visible light ir-
1‐phenylethanol oxidation using CdSe/CdS quantum dots radiation (λ ≥ 420 nm), an apparent quantum efficiency
(QDs).87 Through optimization of the shell thickness of of 16.7% at 420 nm, an SCC of 0.4%, and stability for over
CdS for efficient charge separation, a CO production rate 720 h.92 Indeed, unlike CO2 reduction, highly efficient
of 27.64 mmol g−1 h−1 and a selectivity of 94% were O2‐based reduction of H2O2 not only is needed to sup-
achieved, while the pinacol product was generated at a press the HER but also is desired to inhibit H2O2 dis-
rate of 26.5 mmol g−1 h−1 via 1‐phenylethanol oxidation. proportionation by consuming holes. Therefore, the PEC
In this study, the S‐vacancy of CdS was considered an approach with a physically separated chamber for the
active site to reduce the energy barrier of CO2‐to‐CO re- redox system is more suitable. Mase et al. developed a
duction and 1‐phenylethanol‐to‐pinacol oxidation, thereby double reaction chamber to avoid possible H2O2 dis-
achieving a high selectivity and production rate (- proportionation, where a cobalt chloride complex coca-
Figure 3F,G). CO2 reduction combined with organic oxi- talyst was used as a cathode for O2‐based reduction of
dation yields a very high economic value, so it is expected H2O2 and WO3 or BiVO4 was used as a photoanode to
to open a new horizon in the conversion of solar energy to drive the redox reaction.93,94,106 Formation of protonated
value‐added product systems. A summary of CO2 reduc- CoII(Ch) by facile electron‐transfer reduction of
tion along with various oxidative products are shown in [CoIII(ChH)]2+ with O2 reduction is the rate‐determining
Table 2. step in the catalytic cycle. The potential of the one‐
electron reduction of [CoIII(ChH)]2+ was positively
shifted by adding HClO4, improving the kinetics of the
3.2 | O2 reduction rate‐determining step to enhance the overall catalytic
reaction. The highest solar energy conversion efficiency
In addition to the CO2RR to form various hydrocarbons, was determined to be 6.6% under simulated solar illu-
the reduction of O2 is also a promising candidate reaction mination. In addition to these reaction chamber en-
producing the value‐added product H2O2. In such a cou- gineering applications, it is also necessary to search for
pled redox system, O2 from water oxidation can be utilized high Faradaic efficiency (FE) for H2O2 evolution. Su et al.
as a reduction feedstock to form a self‐supporting redox directly introduced anthraquinone (AQ) into metal‐free
system. Because the redox potential is lower than the organic dye‐sensitized PEC cells, which achieved a pho-
water reduction potential, coupling O2 reduction with tocurrent density of 1.8 mA cm−2 with an FE of up to 95%
H2O oxidation can be performed by semiconductors with for H2O2 production under 1 sun condition.95 AQ, which
narrower band gaps, which potentially enables high solar acts as a redox mediator, can be reduced to anthrahy-
conversion efficiency. A summary of reports on O2 re- droquinone (H2AQ), followed by the generation of H2O2
duction to produce H2O2 by PEC and PC systems is pro- from O2 by auto‐oxidation of H2AQ. H2O2 generation
vided in Table 3. Kofuji et al. prepared a metal‐free hybrid occurs stably and selectively due to the high stability
photocatalyst composed of pyromellitic diimide‐doped of H2AQ without further reduction or decomposition.
28 | KIM ET AL.
TABLE 2 Summary of CO2 conversion to various products

Materials Light source Products Production rate Selectivity System References
−1 −1a
Cu‐Zn/SrTiO3 UV Formic acid 0.7 μmol g h – PC [60]
Hg‐Xe lamp O2
Cu/TiO2 UV (254 nm) Methanol 3.28 μmol g−1 h−1 – PC [62]
8 W Hg lamp O2
Ti‐containing silica UV Methane 7 μmol g−1 h−1a – PC [57]
−1 −1a
100 W Hg lamp Methanol 2 μmol g h
O2
Ru/C3N4 Vis (>420 nm) CO 4.78 μmol g−1 h−1 71.8% PC [65]
−1 −1
300 W Xe lamp Methane 0.78 μmol g h
O2
g‐C3N4/Bi2WO6 Vis (>420 nm) CO 5.19 μmol g−1 h−1 100% PC [76]
300 W Xe lamp O2
MgO/Pt/TiO2 UV, Vis Methane 11 μmol g−1 h−1 79% PC [70]
100 W Xe lamp O2
Pd‐Au/TiO2 UV (<420 nm) Methane 48.2 μmol g−1 h−1 91.4% PC [66]
300 W Xe lamp O2
Pt‐Cu/C3N4 Vis (>400 nm) Methane 7.46 μmol g−1 h−1 90.6% PC [67]
300 W Xe lamp O2
Pt/LaPO4 UV, Vis Methane 12.4 μmol g−1 h−1 100% PC [69]
125 W Hg lamp O2
Au‐Cu/TiO2 1 Sun Methane 2000 μmol g−1 h−1 97% PC [75]
1000 W Xe lamp O2
−2
Pd/NR2@TiO2 200 mW cm UV, Vis Methanol 106 μM h−1 cm−2 – PEC [82]
Xe lamp O2 (−0.6 V [solar cell])
−2
CHO/NH2/TiO2/Ni 200 mW cm UV, Vis Methanol 153 μM h−1 cm−2 – PEC [84]
Xe lamp O2 (−0.6 V vs. SCE)
ZnO/Ni foam 1 Sun Ethanol 12.5 μM h−1 cm−2 100% (C2 PEC [83]
product)
300 W Xe lamp Acetic acid (−0.6 V [solar cell])
O2
BiFeO3 Vis (>420 nm) Methanol 1280 μmol g−1 h−1 – PEC [74]
450 W Xe lamp O2 (1.0 V)
Pt‐rGO/Ni UV, Vis Ethanol 270 nmol h−1 cm−2a 48%a PEC [63]
300 W Xe lamp O2 (2.0 V)
Au/TiO2/a‐Si 1 Sun CO 4.7 mA cm−2a 48%a,b PEC [73]
300 W Xe lamp O2 (−1.0 V vs. RHE)
STO/Rh UV‐Vis CO 54,000 μmol g−1 h−1a – PC [85]
150 W Hg‐Xe lamp H2
Co@PNC (CsPbBr3/ UV, Vis CO 122.3 μmol g−1 h−1 – PC [86]
Cs4PbBr6) −1 −1
300 W Xe lamp Formic acid 55.81 μmol g h
KIM ET AL. | 29
TABLE 2 (Continued)
Materials Light source Products Production rate Selectivity System References

−1 −1
Ag/TiO2 UV Methanol 7.47 μmol g h – PC [88]
Hg lamp Benzaldehyde 91.7% conversion 98%
−1 −1
Cu/Cu2O Vis (>420 nm) Formic acid 2.5 μmol g h – PC [89]
−1 −1
300 W Xe lamp Benzyl acetate 116.7 μmol g h
Cu/TiO2 UV, Vis Methanol 96.14 μmol g−1 h−1 – PC [90]
Hg lamp Imine 88.7% conversion 98%
−1 −1
CdSe/CdS QDs Vis CO 27.63 mmol g h 94.7% PC [87]
450 nm LEDs
NNU‐31‐Zn Vis (>420 nm) Formic acid 26.3 μmol g−1 h−1 100% PC [61]
300 W Xe lamp O2
Abbreviations: PC, photocatalytic; PEC, photoelectrochemical; QDs, quantum dots.
a
Approximately calculated from data.
b
Faradaic efficiency.
Moreover, Fan et al. constructed a tandem PEC cell using might be difficult economically over the short term be-
an NiFeOx/BiVO4 photoanode and a polyterthiophene cause of the cost of deriving fuel or H2 from fossil energy
(pTTh) photocathode in a chamber separated by a Nafion as the competitor continues to be significantly cost‐
membrane.96 The pTTh has not only a narrow band gap effective.35,37 Modifying the scenario of water oxidation
of 2 eV but also an FE of nearly 100% for O2‐based re- in artificial photosynthesis is a more correct choice be-
duction of H2O2 at pH 13. In this system, the selectivity cause water oxidation is a crucial factor limiting the ef-
of pTTh was strongly dependent on the pH of the elec- ficiency of water reduction to H2, and its product, O2, is
trolyte. During the reaction cycle of pTTh, O‐O bond not valuable. Due to the positive position of VB for most
cleavage in the pTTh‐OOH state determines selectivity photoanode materials, oxidizing reagents, such as
towards the two‐electron process to generate H2O2 rather S2O82−, ClO−, and Ce4+ are readily produced by the high
than the four‐electron process to generate hydroxide oxidative potential of photogenerated holes. A summary
(Figure 4D). This is because the energy barrier of hy- of recent reports on PEC and PC reactions to produce
droxide formation increased when the concentration of oxidizing reagents is presented in Table 4.
hydroxide in the electrolyte was increased at high pH. In 1987, Vestro and Grätzel investigated the electro-
Then, based on the higher energy barrier of the four‐ chemical and PEC oxidation of Cl−, Br−, HSO4−, Fe2+,
electron pathway at high pH, the two‐electron pathway and Ce3+.107 They found that a steeper photocurrent was
was kinetically preferred, leading to high selectivity generated in the presence of the above ions than in SO42−
(Figure 4E,F). The tandem cell enabled the bias‐free and ClO4− solutions. As a result, Cl−, Br−, HSO4−, Fe2+,
light‐driven H2O2 production of concentration ∼90 mmol and Ce3+ were oxidized to Cl2, Br2, S2O82−, Fe3+, and
L−1 for several cycles without any noticeable decay. Ce4+, respectively. Based on investigations by Vestro and
Grätzel, many kinds of research have been conducted on
oxidizing reagent production. Nakajima and coworkers
4 | VALUE ‐ ADDED CHEMICALS reported S2O82− production by a WO3 nanosponge pho-
PRODUCED BY OXIDATION toanode in 1.0 M H2SO4.99 They observed that H2 and
S2O82− were produced with nearly 100% FE and that the
4.1 | Oxidizing reagent production absorbed photon‐to‐current efficiency reached 95.4% at a
wavelength of 410 nm. The photoanode produced a high
In contrast to water reduction, water oxidation has re- photocurrent density of 3.04 mA cm−2, which originated
ceived less attention over the last few decades because from interconnected WO3 nanoparticles with abundant
artificial photosynthesis is mainly focused on the water‐ nanopores. Moreover, Ahn et al. prepared WO3 nano-
based reduction to H2. Thus, the practical use of artificial flakes grown on a mesoporous WO3 interlayer and
photosynthesis exclusively as a producer of H2 and fuels measured S2O82− production.108 The WO3 photoanode
30 | KIM ET AL.
TABLE 3 Summary of materials for hydrogen peroxide production

Materials Light source Products Yield Efficiency System References
−2
g‐C3N4/PDI 43 W m H2O2 SCC 0.27% PC [91]
Vis (>420 nm) O2 ORR
Xe lamp
OVCo3O4/C Vis (>420 nm) H2O2 SCC 0.4% PC [92]

300 W Xe lamp AQE 16.7% ORR
BiVO4/FeO(OH) 100 mW cm−2 H2O2 61 mMH2O2 PEC [93]
CoII(Ch) 1 Sun O2 ORR
m‐WO3 100 mW cm−2 H2O2 48 mMH2O2 PEC [94]
CoII(Ch) 1 Sun O2 ORR
pTTh/NiO 100 mW cm−2 H2O2 1.8 mA cm−2 FE ~95% PEC [95]
1 Sun (−0.3 V vs. NHE) ORR
Xe lamp
NiFeOx/BiVO4 100 mW cm−2 H2O2 ~90 mmol H2O2 L−1 PEC [96]
PTTh/CP UV‐Vis O2 ORR
Xe lamp (bias free)
CoO/TS‐1 5W H2O2 1390 μmol H2O2 g CoO−1h−1 PC [97]
Vis (420–700 nm) H2 1460 μmol H2 g CoO−1h−1 WOR
Cu/TiO2 UV H2O2 75μmol H2O2 g−1h−1 PC [98]
300 W Xe lamp H2 140 μmol H2 g−1h−1 WOR
PI5.0‐NCN Vis (>420 nm) H2O2 3000 μmol H2O2 g−1h−1 QY 3.2% PC [114]
300 W Xe lamp WOR
CPN Vis (420–700 nm) H2O2 1968 μmol H2O2 g−1h−1 QE 1.57% PC [100]
WOR
Co@TiO2 Vis (400 nm) H2O2 1.71 mmol H2O2 dm−3 PC [101]
WOR
HTNT‐CD UV‐Vis (>365 nm) H2O2 3420 μmol H2O2 g−1h−1 PC [102]
350 W Xe lamp WOR
WO3/BiVO4 Vis (>420 nm) H2O2 Bias free FEanode ~50% PEC [103]
Au Xe lamp FEcathode ~90% WOR
P‐Mo‐BiVO4 100 mW cm−2 H2O2 Bias free FEanode 46% PEC [104]
AQ‐CNT/C 1 Sun FEcathode 100% WOR
BiVO4 1 Sun H2O2 0.48 μmol H2O2 min−1 cm−2 PEC [105]
C AM 1.5 G (bias free) WOR
SnO2‐x/BiVO4 100 mW cm−2 H2O2 FEanode 86% PEC [48]
UV‐Vis H2 FEcathode 100% WOR
300 W Xe lamp
Abbreviations: AQE, apparent quantum efficiency; FE, faradaic efficiency; ORR, oxygen reduction reaction; PEC, photoelectrochemical; QE, quantum
efficiency; QY, quantum yield; SCC, solar to chemical efficiency; WOR, water oxidation reaction.
a
FApproximately calculated from data.
showed a photocurrent density of 2.6 mA cm−2 with 95% et al. investigated the PC reaction for S2O82− production
and 100% FE during solar S2O82− and H2 production, by noble‐metal loaded WO3.109 Because WO3 cannot re-
respectively (Figure 5A,B). Due to the interfacial layer duce the water due to the positive position of the CB, the
between the WO3 nanoflake and FTO, interfacial re- PC reaction was performed under the flow of O2. As a
combination was reduced, which results in highly effi- result, Pt‐loaded WO3 showed a remarkably high S2O82−
cient PEC performance to produce an oxidizing reagent. production of 226 μmol g−1 h−1, while other noble me-
Different from the above reports on PEC systems, Huang tals, such as Pd, Au and Rh, showed poor performance.
KIM ET AL. | 31
F I G U R E 4 (A) XPS spectra of O 1s, (B) band structure diagram, and (C) EIS analysis for different annealing temperatures of oxygen
vacancy‐rich Co3O4. Reproduced with permission: Copyright 2019, American Chemical Society.92 (D) Energy profile diagram of possible
pathways to reduce oxygen on pTTh. (E) Free energy diagram of the 2e− (C‐O bond cleavage) and 4e− (O‐O bond cleavage) pathways for the
selectivity of oxygen reduction at pH 13. (F) Overall reaction scheme of reaction on pTTh. Reproduced with permission: Copyright 2020, The
Royal Society of Chemistry96
TABLE 4 Summary of materials for oxidizing reagent production

Faradaic
Materials Light source Electrolyte Product Yield efficiency (%) System References
2− −2
WO3 W‐halogen/ 3.0 M KHSO4 S2O8 0.6 mA cm 85 PEC [107]
Xe lamp H2 (0.8 V vs. SCE)
WO3 1 Sun 1.0 M H2SO4 S2O82− 3.04 mA cm−2 10 PEC [99]
150 W Xe lamp H2 (1.5 V vs. RHE)
WO3 1 Sun 1.0 M H2SO4 S2O82− 2.6 mA cm−2 95 PEC [108]
H2 (1.5 V vs. RHE)
Pt‐WO3 1 Sun 1.0 M NaHSO4 S2O82− 220 μmol gcat−1 h−1 – PC [109]
H2O2 2.7 μmol gcat−1 h−1
WO3 W‐halogen/ 1.0 M HCl HClO 0.6 mA cm−2 76 PEC [107]
Xe lamp H2 (0.6 V vs. SCE)
RhO2/Mo‐BiVO4 1 Sun Seawater HClO 2.16 mA cm−2 – PEC [110]
Xe lamp H2 (1.0 V vs. RHE)
WO3 1 Sun 0.5 M H2SO4 HClO 0.2 mA cm−2 30 PEC [111]
Xe lamp 0.5 M NaCl H2 (1.2 V vs. Ag/AgCl)
BiVO4/WO3/ 1 Sun 0.1 M NaCl HClO 0.325 mA cm−2 – PEC [112]
FTO H2 (0.22 V vs. CE)
Abbreviations: CE, counter electrode; PEC, photoelectrochemical.
32 | KIM ET AL.
F I G U R E 5 Gas evolution and FE of (A) S2O82− and (B) H2 by using a WO3 photoanode. Reproduced with permission: Copyright 2017,
Elsevier.108 (C) Schematic of S2O82− and H2O2 production by using Pt‐ or Pd‐loaded WO3 photocatalysts. Reproduced with permission:
Copyright 2019, The Royal Society of Chemistry109
Interestingly, Pt‐loaded WO3 was able to produce H2O2 photoanode.112 They found that the photocurrent den-
by an oxygen reduction reaction with S2O82− simulta- sity was proportionally enhanced by increasing the NaCl
neously when the additive was NaHSO4 (Figure 5C). concentration (Figure 6C). The chloride ion oxidation
Reactive chlorine species (Cl2, HClO, ClO−) are well‐ performance of the BiVO4/WO3 heterojunction photo-
known oxidizing reagents for various applications, such as anode showed 81.4% FE when the applied potential was
organic synthesis, wastewater treatment, and disinfection. 0.22 V versus the counter electrode. Moreover, 2000 s of
Chlorine is present in seawater at a concentration of PEC operation was sufficient to accumulate 600 μM
18.98 g mL−1, but ionic chlorines with alkali metal ions HClO, which can serve as water disinfection or bleaching
are almost useless. Thus, the transformation of chlorine reagent (Figure 6D).
species into the molecular chlorine or hydrochlorous form H2O2, an oxidizing reagent, can also be synthesized
is necessary, even though the standard reduction poten- by oxidizing water in addition to reducing O2. Water
tials of chlorine oxidation reactions are very positive. oxidation to form H2O2 is more cost‐effective than oxy-
From this point of view, PEC or PC systems are very gen reduction to form H2O2 because water oxidation is
suitable due to the highly oxidative holes generated by the being coupled with the reduction of H2 which is eco-
positive position of the VB, which are widely applicable to nomically more valuable than O2. However, water oxi-
most oxidation reactions. In 2011, Luo et al. reported PEC dation to form H2O2 faces the inevitable challenge of a
chlorine species generation by using a RhO2‐loaded Mo‐ thermodynamically unfavourable H2O2 evolution reac-
doped BiVO4 photoanode in seawater.110 They found that tion compared to the O2 evolution reaction and decom-
the high photocurrent density of the Mo‐doped BiVO4 position of the formed H2O2. Therefore, enhancing the
photoanode originates from the chloride oxidation reac- two‐electron transfer reaction by suppressing the four‐
tion coupled with H2 evolution when RhO2 is loaded as a electron transfer reaction while preserving the formed
cocatalyst (Figure 6A). During the reaction, gaseous H2O2 is a crucial point for H2O2 production.113 Zhu et al.
bubbles were not observed, which implies that the pho- utilized CoO nanodots stabilized by titanium silicalite to
tocurrent generated from the BiVO4 photoanode partici- split water into H2 and H2O2.97 CoO well dispersed on
pated in the chloride oxidation reaction rather than the titanium silicalite‐1 (TS‐1) has many exposed active sites
OER. They suggested that oxygen detected after a few without aggregation during the reaction. Due to TS‐1
hours without any bubbles was formed by photo- properties of high stability, specific area, and H2O2 ad-
decomposition of HClO, but not from the OER. Juodka- sorption ability, it can protect CoO nanodots from the
zytė et al. studied the oxidation of chloride ions coupled formed H2O2 and prevent decomposition of the formed
with H2 evolution by using a mesoporous WO3 H2O2. By combining two efficient materials, an H2O2
photoanode (Figure 6B).111 In the case of the chlorine production rate of 1460 μmol gCoO−1 h−1 and H2 pro-
oxidation reaction, 30% FE was achieved in a 0.5 M H2SO4 duction of 1390 μmol gCoO−1 h−1 were achieved. On the
and 0.5 M NaCl mixed electrolyte. They suggested that other hand, Wei et al. reported a function‐switchable Cu/
chlorine oxidation, which follows a two‐electron‐transfer TiO2 junction to selectively split water into H2 and H2O2,
mechanism, is much more kinetically favourable than where the accumulated holes at the surface of TiO2 are
the OER, especially under acidic conditions. Similarly, responsible for water oxidative H2O2 evolution under UV
Iguchi and coworkers investigated hydrochlorous illumination.98 On the other hand, under visible light,
acid and H2 coproduction by using a BiVO4‐based holes accumulated on Cu nanoparticles. By means of
KIM ET AL. | 33
F I G U R E 6 (A) J‐V curve of the RhO2‐deposited Mo‐BiVO4 photoanode for hydrochlorous acid formation. (B) H2, dissolved
Cl2/hypochlorite and O2 production graph using the RhO2− deposited Mo‐BiVO4 photoanode. Reproduced with permission: Copyright
2011, The Royal Society of Chemistry.110 (C) J‐V curve of the BiVO4/WO3 heterojunction photoanode in various molar concentrations of
NaCl. (D) Photograph of human hair before and after bleaching using HClO produced from a BiVO4/WO3 heterojunction photoanode.
Reproduced with permission: Copyright 2018, The Royal Society of Chemistry112
DFT calculations, the conversion of H2O adsorbed on the visible region. In addition, doped phosphorus offers
TiO2 (101) and Cu (111) surfaces to H2O2 and O2 was adsorption sites for oxygen, which promotes H2O2
compared. In the case of the TiO2 (101) surface, H2O2 evolution. Reduced band gaps with abundant active sites
formation is preferable. In contrast, H2O adsorbed on the could efficiently utilize solar energy to generate H2O2.
Cu (111) surface was favourable for oxidization to O2. Baran et al. proposed TiO2 modified with cobalt(II)
The holes accumulated at the surface of TiO2, therefore, 2‐ethylhexanoate for the generation of H2O2 under visible
selectively oxidized water to H2O2. Yang et al. con- light.101 Metal‐to‐metal charge transfer usually induces
structed a Z‐scheme heterojunction by assembling per- electron injection into the CB under illumination. Herein,
ylene imides (PIs) on g‐C3N4 nanosheets.114 Specifically, due to electron injection from the cobalt‐to‐titanium‐
photoexcited electrons in PI were transferred to the VB of charge transfer, H2O2 synthesis was achieved through
g‐C3N4, resulting in an enhancement of charge separa- both water oxidation and oxygen reduction with the sui-
tion and a larger number of electrons reducing O2 to table band position of the photocatalyst. In addition, Ma
H2O2. Furthermore, since the VB of PI was higher than et al. also utilized proton‐form titania nanotubes with
that of NCN, the hole can oxidize OH− to ·OH, producing carbon dots (HTNT‐CD) to generate H2O2, which was
H2O2 at the same time. Cao et al. reported that accelerated by solid acids.102 The proton on the HTNT‐CD
phosphorus‐doped porous g‐C3N4 was applied to a two‐ surface efficiently accelerates the oxygen reduction reac-
channel pathway towards H2O2, achieving an H2O2 tion and prevents the decomposition of the formed H2O2.
generation of 1968 μmol g−1 h−1 under visible light The pyridine‐adsorption FTIR spectrum of HTNT showed
without a cocatalyst or scavenger.100 Doping of phos- an additional peak corresponding to the Brønsted acid
phorus on g‐C3N4 reduces its band gap compared to that sites in its surface chemical structure compared to P25,
of pure C3N4, expanding the light absorption range in the leading to the high performance of H2O2 production.
34 | KIM ET AL.
Successful cases of water oxidation merely occurred the redox process of AQ/H2AQ. The combined system
on the surface of the semiconductor; to date, there has with the photoanode and cathode achieved 40%–50%
been no report of a well‐defined cocatalyst for selective anodic FE and ~100% cathodic FE without bias. Based on
suppression of the O2 evolution reaction. As a result, the bias‐free H2O2 evolution from water oxidation and O2
redesigned oxidation is more difficult than the rede- reduction, Shi et al. demonstrated a PEC H2O2 redox flow
signed reduction in artificial photosynthesis for H2O2 battery based on a BiVO4 anode and carbon cathode.105
production due to the lower energy barrier of water The light‐driven fuel cell with H2O2 as the main product
oxidation of O2 than other possible reactions. The com- at the two electrodes achieved a maximum power density
petition between water oxidation and other oxidation of 0.194 mW cm−2, an open‐circuit voltage of 0.61 V, and
reactions depends not only on thermodynamics but also a short‐circuit current density of 1.09 mA cm−2. Recently,
on kinetics. Regulating the selectivity and efficiency of Zhang et al. reported that two‐electron and four‐electron
water oxidation to produce H2O2 is elusive because of the competitive reactions can be transformed into single‐
complicated surface state of the semiconductor. Recently, electron and two‐electron competitive reactions by taking
an HCO3− containing electrolyte was proven to sig- advantage of the Fermi‐level pinning effect of the BiVO4
nificantly promote PEC water oxidation to produce photoanode, achieving 86% FE for H2O2 production and
H2O2.115–117 Fuku et al. combined a WO3/BiVO4 photo- nearly 100% FE for H2 production.60 As the VB of bare
anode and an Au cathode to generate H2O2 from both BiVO4, photoinduced holes favour O2 evolution instead
electrodes under illumination without applied bias of H2O2 generation. However, the SnO2‐x overlayer
(Figure 7A).103 Furthermore, this procedure was per- coated on BiVO4 reduces the band bending of bare
formed without a separation membrane in an HCO3− BiVO4. Thus, the hole migrating from BiVO4 to SnO2‐x
containing electrolyte, achieving 50% anodic FE and 90% kinetically prefers the water oxidation reaction due to the
cathodic FE. Jeon et al. reported a dual photoanode and pinned Fermi level at the electrode and reactant inter-
photocathode process towards H2O2 production in bias‐ face. In addition, SnO2‐x changes the competitive reaction
free conditions by using HCO3− containing electro- from two‐electron and four‐electron transfer to single‐
lytes.104 Here, Mo‐doped and phosphate‐treated BiVO4 electron and two‐electron transfer. One‐electron transfer,
was utilized as a photoanode to oxidize water to H2O2, which generates hydroxyl radicals, can mediate the for-
and anthraquinone anchored on carbon nanotubes (AQ‐ mation of H2O2, ultimately suppressing the decomposi-
CNTs) was used as the cathode to reduce oxygen to H2O2 tion of H2O2. This study introduced a possible strategy to
simultaneously. First, doping Mo into BiVO4 was in- suppress thermodynamically favourable water oxidation
vestigated. Since Mo6+ ions can substitute for V5+ sites in of O2 by kinetic control (Figure 7B). A summary of pre-
BiVO4, the donor density increases due to an additional viously reported H2O2 production by PEC and PC is
donor from Mo6+. This enhanced donor density results in shown in Table 3.
a high photocurrent of the anode. Nevertheless, the de-
composition of H2O2 on the surface was a problem trig-
gered by holes from the photoanode. To decrease the 4.2 | Organic synthesis
decomposition of the formed H2O2, the surface of Mo‐
doped BiVO4 was treated with phosphate to inhibit the Organic synthesis in the chemical industry has been es-
adsorption of H2O2 on the photoanode. Furthermore, tablished for a long time; however, manufacturing pro-
AQ‐CNT as a photoanode facilitated charge transfer due cesses have not undergone significant change even
to the role of the redox mediator as mentioned above for though the process requires harsh conditions, such as
F I G U R E 7 (A) Scheme of the photoelectrochemical system for generating H2O2 from both electrodes under illumination. Reproduced
with permission: Copyright 2017, Wiley.103 (B) SnO2‐x overlayer deposited on BiVO4 with reduced band bending, suppressing the OER.
Reproduced with permission: Copyright 2020, American Chemical Society48
KIM ET AL. | 35
high temperature and pressure. Thus, PEC and PC or- cocatalyst onto Zn2In2S5 remarkably increased its PC
ganic synthesis is highly favourable due to its mild op- performance, which achieved 90% selectivity and
erational conditions. Moreover, heterogeneous PEC and 18.9 mmol gcat−1 h−1 of ethylene glycol production with
PC semiconductors are very stable and regenerative H2 from methanol (Figure 8E). Moreover, C‐H activation
during the reaction, which makes them cost‐effective. of ethanol was also observed by using Zn2In2S5, which
Since PEC and PC semiconductors can generate highly ultimately produced 2,3‐butanediol by C‐C coupling of
reductive and oxidative electrons and holes from the CB ·CH(OH)CH3 species (Figure 8F). Not only hydrogen
and VB, respectively, they are applicable to various kinds generation by the reduction reaction but also the CO2
of organic syntheses. The difference between the band reduction reaction is possible with the counterpart of
positions and the redox reaction potential can be com- methanol oxidation. As mentioned in the previous
pensated by the applied electric field in the PEC reaction, chapter, Dong et al.86 reported CO2 reduction using ha-
and the PC approach has difficulties in controlling elec- lide perovskite with methanol oxidation. The addition of
tron and hole pathways in the reaction. To solve this methanol into the solution greatly improved PC perfor-
problem, many studies on PC organic synthesis have mance, while formic acid was produced by methanol
been conducted by using charge scavengers that elim- oxidation. The improved PC performance of either CO2
inate one electron or hole. However, charge scavengers, reduction or methanol oxidation originates from the sy-
such as silver ions, sulphite ions, and hydrogen peroxide nergetic effect of the electron and hole scavenging effects
are expensive, and one of the redox reactions is dis- of CO2 and methanol, respectively.
regarded, which remarkably reduces the value of the Along with the methanol oxidation reaction, aromatic
operation. Thus, the PC organic synthesis that produces compounds can be an excellent substrate for value‐added
both oxidative and reductive products would be the true chemical synthesis. Considering that aromatic rings are
meaning of solar‐driven value‐added chemical produc- very stable and nonpolar structures, cleavage of an aro-
tion. In this chapter, decoupled organic synthesis by PEC matic ring is generally impossible by PC or PEC reac-
and PC systems, including methanol, aromatic com- tions. Thus, recent studies on the PC and PEC reactions
pounds, and glycerol oxidation, with decoupled H2 pro- of aromatic compounds have focussed on modifying the
duction, will be discussed, and a summary is provided in functional groups attached to the aromatic rings. Hao
Table 5. et al. reported PC benzyl alcohol oxidation in an aqueous
Xie et al. reported C‐H activation of methanol to solution using ZnS‐NixSy composites (Figure 9A).120
produce ethylene glycol by using MoS2 loaded on CdS The loading of NixSy species onto ZnS improved either
(Figure 8A).118 Catalytic performances of various PC the H2 production or the benzyl alcohol oxidation.
semiconductors in methanol‐containing solutions were The conversion of benzyl alcohol into benzaldehyde
investigated in advance, and the results showed that occurred simultaneously, achieving 49.3% and 80.4%
most of the semiconductors produced formaldehyde and conversion and selectivity of benzaldehyde formation,
hydrogen as a major product, simultaneously. This im- with 3.658 mmol g−1 h−1 of H2 production (Figure 9B,C).
plied that most of the semiconductors favoured O‐H Similarly, Luo et al. investigated deoxybenzoin and
bond activation while the C‐H bond is hardly activated. H2 coproduction through tandem redox reactions.121
Different from most cases, CdS with or without MoS2 The benzyl alcohol can be first oxidized to hydrobenzoin
showed relatively higher selectivity of ethylene glycol by photo‐holes generated from ZnIn sulphide, followed
production, which can be produced by C‐H bond acti- by redox‐neutral dehydration of hydrobenzoin to form
vation only. Moreover, this unique property is re- deoxybenzoin (Figure 9D,E). Moreover, increasing the
markably reinforced by adding MoS2 foam on the CdS Zn/In ratio in ZnIn sulphide dominantly leads to the
rod surface, which achieved 90% selective ethylene glycol production of deoxybenzoin, while a decrease in the ratio
production with improved ethylene glycol and H2 for- results in the production of benzaldehyde. This is due to
mation rates (Figure 8B). It was suggested that highly the decrease in the CB bottom potential by increasing the
selective ethylene glycol formation via concerted proton‐ Zn/In ratio, which facilitates the reduction of the
electron transfer is mainly due to the weak adsorption of hydroxyl groups in hydrobenzoin to form deoxybenzoin.
CH3OH and ·CH2OH on the CdS surface (Figure 8C). In contrast to the use of benzyl alcohol, Huang et al.
After that, Zhang and coworkers further extended the reported the PC reaction of aromatic benzyl amines to
C‐H activation on methanol and ethanol to produce benzyl imines together with hydrogen evolution.122
ethylene glycol and 2,3‐butanediol, respectively, by using The decoration of nickel clusters onto CdS nanosheets
Zn2In2S5 (Figure 8D).119 It was found that the transfor- enhanced the dehydrogenation of the amines, which
mation of methanol to ethylene glycol is strongly related further improved the production of imines and molecular
to the Zn/In atomic ratio. The addition of a CoP hydrogen.
| 36
TABLE 5 Summary of materials for solar‐driven organic synthesis

Materials Light source Substrate Product Conversion (%) Yield (%) Selectivity (%) System References
−1 −1
MoS2 foam/CdS AM 1.5 G Methanol Ethylene glycol – 11 mmolEG gcat h 90 PC [118]
300 W Xe lamp H2
CoP/Zn2In2S5 AM 1.5 G Methanol Ethylene glycol – 18.9 mmolEG gcat−1 h−1 90 PC [119]
300 W Xe lamp Ethanol 2,3‐butanediol 3.2 mmolBD gcat−1 h−1 53
H2
Co1%@PNC 100 mW cm−2 Methanol Formic acid – 56.5 μmolFA gcat−1 h−1 – PC [86]
300 W Xe lamp CO2 CO
ZnS‐NixSy UV‐Vis (>200 nm) Benzyl alcohol Benzaldehyde 49.3 – 80.4 PC [120]
500 W Xe lamp H2
Zn0.6In2S3.6 UV (365 nm) Benzyl alcohol Deoxybenzoin >99 64 – PC [121]
6 W LED H2
Ni/CdS Vis (>420 nm) Benzyl amine N‐benzylidenebenzylamine – 99 >99 PC [122]
300 W Xe lamp H2
BiVO4 1 Sun Glycerol Dihydroxyacetone – 200 mmolDHA m−2·h−1 51 PEC [123]
300 W Xe lamp H2
TiSi2 1 SUN Glycerol Glyceric acid 97.6 – 100 PC [124]
300 W Xe lamp H2
Abbreviations: BD, 2,3‐butanediol; DHA, dihydroxyacetone; EG, ethylene glycol; FA, formic acid: PC, photocatalytic; PEC, photoelectrochemical.
KIM
ET AL.
KIM ET AL. | 37
F I G U R E 8 (A) Schematic of solar‐driven ethylene glycol synthesis decoupled with H2 generation by MoS2 foam on CdS nanorods.
(B) Yield and selectivity of ethylene glycol production by MoS2 foam on CdS nanorods. (C) Mechanistic study of methanol oxidation on CdS
and TiO2. Reproduced with permission: Copyright 2018, Springer Nature.118 (D) Schematic of methanol and ethanol oxidation on ZnIn
sulphide to produce ethylene glycol and 2,3‐butanediol, respectively. (E) Comparison graph of ethylene glycol formation with and without
CoP cocatalyst under visible and AM 1.5 G light irradiation. (F) Comparison graph of 2,3‐butanediol formation with different molar ratios of
Zn/In in ZnIn sulphide. Reproduced with permission: Copyright 2020, The Royal Society of Chemistry119
Glycerol, which is a C3 hydrocarbon material with achieved 3.7 mA cm−2 at 1.2 V versus RHE with 51%
three hydroxyl functional groups (‐OH), is a byproduct of DHA selectivity, which is equivalent to 200 mmol of
biodiesel manufacturing. The increasing number of bio- DHA production per m2. The mechanistic study of gly-
diesel manufacturing industries has allowed glycerol cerol oxidation on BiVO4 indicated that adsorbed glycerol
production to overcome its annual demands. Thus, gly- on the BiVO4 (112) surface undergoes an oxidation re-
cerol transformation into value‐added chemicals is ex- action with energetic holes, followed by hydration and
pected to be promising in the future. Owing to its dehydration (Figure 10B). Additionally, the intermediate
chemical structure, glycerol is highly miscible with water glycerol radical with tertiary radicals on the central car-
compared to simple hydrocarbons. Thus, glycerol can bon is much more stable than the radical at the terminal
possibly be applied in PEC or PC systems as a starting carbon, which explains the selective formation of DHA
material for value‐added chemical production decoupled on the BiVO4 surface. Mohapatra and coworkers in-
from hydrogen production. Liu et al. investigated the vestigated the PC oxidation of glycerol by using TiSi2.124
glycerol oxidation reaction on a BiVO4 photoelectrode Interestingly, TiSi2 can produce glyceric acid rather than
at different pH values and applied potentials other C3 materials with 97% conversion and 100% se-
(Figure 10A).123 Note that BiVO4 is a well‐known mate- lectivity after 12 h of reaction. The author proposed the
rial for PEC water oxidation due to its moderate band reaction mechanism by which glyceric acid is produced
position and visible light absorption ability. Because of its by glycerol adsorption, aldehyde formation, hydration
appropriate PEC properties, the BiVO4 photoanode and dehydration. Moreover, the basicity is a key factor
38 | KIM ET AL.
F I G U R E 9 (A) Schematic of benzyl alcohol oxidation to benzaldehyde on the surface of ZnS‐NixSy composites. (B) H2 production graph
of ZnS‐NixSy composites and (C) conversion and selectivity graph of benzyl alcohol oxidation by ZnS‐NixSy composites. Reproduced with
permission: Copyright 2019, American Chemical Society.120 (D) Schematic of deoxybenzoin production on ZnIn sulphide.
(E) Conversion and yield graph of various products, including H2, deoxybenzoin, benzyl alcohol, hydrobenzoin, and trimers.
Reproduced with permission: Copyright 2020, American Chemical Society121
F I G U R E 10 (A) Production graph of formic acid, glyceric acid, and 1,3‐dihydroxyacetone at different potentials and electrolyte pH
values using a BiVO4 photoanode. (B) Schematic of the glycerol oxidation mechanism on the BiVO4 surface. Reproduced with permission:
Copyright 2019, Springer Nature123
for initializing oxidation of adsorbed glycerol and deso- photosynthesis aims to decouple two half‐reactions,
rption of glyceric acid. utilizing either the reduction or oxidation side to produce
both oxidative and reductive products. Through previously
established PEC and PC materials, such as TiO2, WO3,
5 | CONCLUS ION AN D BiVO4, and CdS, various kinds of half‐reactions have been
OU TL OOKS investigated. For example, CO2 reduction, O2 reduction,
oxidizing reagent production, and organic synthesis with
Artificial photosynthesis is an ideal system for future gen- decoupled counterreactions driven by solar energy have
eration because of its economical, environmentally friend- been reported, which offer new opportunities for accel-
ly, and sustainable features. Recently, research on artificial erating and promoting the practicability of artificial
photosynthesis has progressed towards changing the redox photosynthesis.
reaction to produce value‐added chemicals. Moreover, due Recent studies on electrocatalytic or PC reactions are
to the economic advantages, state‐of‐the‐art artificial focused on not only achieving high efficiency but also
KIM ET AL. | 39
understanding the mechanism of target reaction because on‐site utilization of oxidizing reagents for environmental
the reaction mechanism determines the results of catalytic treatment or disinfection would be a simpler and more
reaction. In fact, the mechanistic study based on compu- convenient method. Through the combination of PEC and
tational calculation requires various information, such as PC redox reactions with separation and on‐site utilization
surface/interface structure, oxidation states or adsorption processes, solar‐driven value‐added chemicals are ex-
properties of catalyst materials.125–127 Thus, for a better pected to be commercialized in the near future and
understanding of catalyst materials, highly developed in- available to customers at low cost and high quality.
vestigation, such as X‐ray absorption fine structure, X‐ray
absorption near edge structure, and electron microscopies AC KNOW LEDGEM ENTS
are introduced to the materials characterization, and the Sungsoon Kim, Kwang Hee Kim and Cheoulwoo Oh
results are applied to the computational calculations.128,129 contributed equally as co‐first authors. Kan Zhang ac-
Moreover, in situ or in operando investigations on cata- knowledges the support from NSFC (51802157,
lytic reactions are frequently reported nowadays, where 21902104), the Natural Science Foundation of Jiangsu
these techniques provide very important information Province of China (BZ2020063) and Jong Hyeok Park
during each reaction steps in the mechanism.130,131 acknowledges the support from the National Research
However, the abovementioned analysis of the reaction Foundation (NRF) of Korea (2019R1A4A1029237,
mechanism so far has been mainly applied to the elec- 2021M3E6A1015823, 2017M3A7B4041987.
trochemical reactions and thermal reactions while the
PEC or PC reactions were hardly tried. Different from the C O NF L I C T O F I N T E R E S T
electrochemical and thermal reactions, PEC or PC pro- The authors declare no conflict of interest.
cesses are always facing many technical limitations on
their investigations due to the light‐required complex re- ORC ID
action. Even though PEC or PC processes have some Jong Hyeok Park https://orcid.org/0000-0002-
complexity, some researchers have applied these techni- 6629-3147
ques to PEC and PC processes and the results provide
significant information of the reaction.132–134 Thus, in the
REFER ENCES
near future, state‐of‐the‐art investigation techniques will 1. Lewis NS, Nocera DG. Powering the planet: chemical chal-
be well applied to PEC and PC processes so that artificial lenges in solar energy utilization. Proc Natl Acad Sci U S A.
photosynthesis will be further developed. 2006;103(43):15729‐15735.
Last, in line with the PEC and PC process, separation 2. Lewis NS. Research opportunities to advance solar energy
of the targeted product to moderate purity should be si- utilization. Science. 2016;351(6271):aad1920.
multaneously considered to satisfy the need of end‐users. 3. Kudo A, Miseki Y. Heterogeneous photocatalyst materials for
water splitting. Chem Soc Rev. 2009;38(1):253‐278.
In particular, the separation process should always be ta-
4. Osterloh FE. Inorganic nanostructures for photoelec-
ken into account in the case of liquid products since most
trochemical and photocatalytic water splitting. Chem Soc Rev.
PEC and PC processes are operated under a liquid en- 2013;42(6):2294‐2320.
vironment. The distillation process is one of the most 5. Maeda K, Domen K. Photocatalytic water splitting: recent
common separation processes for liquid‐liquid mixtures progress and future challenges. J Phys Chem Lett. 2010;1(18):
and is widely commercialized in industrial areas. How- 2655‐2661.
ever, the concentration of the liquid product by PEC and 6. Chen Z, Jaramillo TF, Deutsch TG, et al. Accelerating ma-
PC may not be high enough, which makes the separation terials development for photoelectrochemical hydrogen pro-
duction: standards for methods, definitions, and reporting
process much harder and more inefficient. Additionally,
protocols. J Mater Res. 2010;25(1):3‐16.
most of the C1 and C2 liquid products form an azeotropic 7. Zhang K, Ma M, Li P, Wang DH, Park JH. Water splitting
mixture with water, and the oxidizing reagents are not progress in tandem devices: moving photolysis beyond elec-
suitable for distillation due to their poor stability. There- trolysis. Adv Energy Mater. 2016;6(15):1600602.
fore, a more efficient and energy‐saving strategy is re- 8. Fujishima A, Honda K. Electrochemical photolysis of water
commended for the separation of solar‐driven value‐added at a semiconductor electrode. Nature. 1972;238(5358):37‐38.
chemicals. Selective permeation of the chemicals from the 9. Chen C, Shen S, Guo L, Mao SS. Semiconductor‐based photo-
electrolyte by using a membrane may enable high‐purity catalytic hydrogen generation. Chem Rev. 2010;110(11):
6503‐6570.
separation by solving the cost and energy problems. Ad-
10. Schneider J, Matsuoka M, Takeuchi M, et al. Understanding
ditionally, a salt‐assisted liquid‐liquid extraction strategy TiO2 photocatalysis: mechanisms and materials. Chem Rev.
can efficiently separate the target products from water, 2014;114(19):9919‐9986.
which may be a good choice for applying the separation 11. Kim S, Cho Y, Rhee R, Park JH. Black TiO2: what are exact
of organic liquid products. Among these liquid products, functions of disorder layer. Carbon Energy. 2020;2(1):44‐53.
40 | KIM ET AL.
12. Tan HL, Amal R, Ng YH. Alternative strategies in improving 30. Su T, Shao Q, Qin Z, Guo Z, Wu Z. Role of interfaces in two‐
the photocatalytic and photoelectrochemical activities of dimensional photocatalyst for water splitting. ACS Catal.
visible light‐driven BiVO4: a review. J Mater Chem A. 2017; 2018;8(3):2253‐2276.
5(32):16498‐16521. 31. Bai S, Jiang W, Li Z, Xiong Y. Surface and interface en-
13. Suarez CM, Hernández S, Russo N. BiVO4 as photocatalyst gineering in photocatalysis. ChemNanoMat. 2015;1(4):
for solar fuels production through water splitting: a short 223‐239.
review. Appl Catal A‐Gen. 2015;504:158‐170. 32. Ran J, Zhang J, Yu J, Jaroniec M, Qiao SZ. Earth‐abundant
14. Cao S, Low J, Yu J, Jaroniec M. Polymeric photocatalysts cocatalysts for semiconductor‐based photocatalytic water
based on graphitic carbon nitride. Adv Mater. 2015;27(13): splitting. Chem Soc Rev. 2014;43(22):7787‐7812.
2150‐2176. 33. Chang X, Wang T, Yang P, Zhang G, Gong J. The develop-
15. Zhao Z, Sun Y, Dong F. Graphitic carbon nitride based na- ment of cocatalysts for photoelectrochemical CO2 reduction.
nocomposites: a review. Nanoscale. 2015;7(1):15‐37. Adv Mater. 2019;31(31):1804710.
16. Wu L, Tsui L, Swami N, Zangari G. Photoelectrochemical 34. Parrino F, Bellardita M, García‐López EI, Marcì G, Loddo V,
stability of electrodeposited Cu2O films. J Phys Chem C. 2010; Palmisano L. Heterogeneous photocatalysis for selective
114(26):11551‐11556. formation of high‐value‐added molecules: some chemical
17. Cheng L, Xiang Q, Liao Y, Zhang H. CdS‐based photo- and engineering aspects. ACS Catal. 2018;8(12):11191‐11225.
catalysts. Energy Environ Sci. 2018;11(6):1362‐1391. 35. Liu J, Zou Y, Jin B, Zhang K, Park JH. Hydrogen peroxide
18. Yuan Y‐J, Chen D, Yu Z‐T, Zou Z‐G. Cadmium sulfide‐based production from solar water oxidation. ACS Energy Lett.
nanomaterials for photocatalytic hydrogen production. 2019;4(12):3018‐3027.
J Mater Chem A. 2018;6(25):11606‐11630. 36. Kumaravel V, Bartlett J, Pillai SC. Photoelectrochemical
19. Wang L, Si W, Tong Y, et al. Graphitic carbon nitride (g‐C3N4)‐ conversion of carbon dioxide (CO2) into fuels and value‐
based nanosized heteroarrays: promising materials for photo- added products. ACS Energy Lett. 2020;5(2):486‐519.
electrochemical water splitting. Carbon Energy. 2020;2(2): 37. Sayama K. Production of high‐value‐added chemicals on
223‐250. oxide semiconductor photoanodes under visible light for so-
20. Wu Y, Lazic P, Hautier G, Persson K, Ceder G. First princi- lar chemical‐conversion processes. ACS Energy Lett. 2018;
ples high throughput screening of oxynitrides for water‐ 3(5):1093‐1101.
splitting photocatalysts. Energy Environ Sci. 2013;6(1): 38. Tilley SD. Recent advances and emerging trends in photo‐
157‐168. electrochemical solar energy conversion. Adv Energy Mater.
21. Pan C, Takata T, Nakabayashi M, et al. A complex 2019;9(2):1802877.
perovskite‐type oxynitride: the first photocatalyst for water 39. Reid LM, Li T, Cao Y, Berlinguette CP. Organic chemistry at
splitting operable at up to 600 nm. Angew Chem Int Ed. 2015; anodes and photoanodes. Sustainable Energy Fuels. 2018;
54(10):2955‐2959. 2(9):1905‐1927.
22. Wang Q, Nakabayashi M, Hisatomi T, et al. Oxysulfide 40. Tu W, Zhou Y, Zou Z. Photoconversion: photocatalytic con-
photocatalyst for visible‐light‐driven overall water splitting. version of CO2 into renewable hydrocarbon fuels: state‐of‐
Nat Mater. 2019;18(8):827‐832. the‐art accomplishment, challenges, and prospects. Adv
23. Maeda K, Takata T, Domen K. (Oxy)nitrides and oxysulfides as Mater. 2014;26(27):4607‐4626.
visible‐light‐driven photocatalysts for overall water splitting. In: 41. Liu X, Inagaki S, Gong J. Heterogeneous molecular systems
Zang L, ed. Energy Efficiency and Renewable Energy Through for photocatalytic CO2 reduction with water oxidation.
Nanotechnology. Green Energy and Technology. Springer‐Verlag; Angew Chem Int Ed. 2016;55(48):14924‐14950.
2011:487. 42. Zeng S, Kar P, Thakur UK, Shankar K. A review on photo-
24. Moniz SJA, Shevlin SA, Martin DJ, Guo Z‐X, Tang J. Visible‐ catalytic CO2 reduction using perovskite oxide nanomater-
light driven heterojunction photocatalysts for water splitting— ials. Nanotechnology. 2018;29(5):052001.
a critical review. Energy Environ Sci. 2015;8(3):731‐759. 43. Ali A, Shen PK. Nonprecious metal's graphene‐supported
25. Low J, Yu J, Jaroniec M, Wageh S, Al‐Ghamdi AA. Hetero- electrocatalysts for hydrogen evolution reaction: funda-
junction photocatalysts. Adv Mater. 2017;29(20):1601694. mentals to applications. Carbon Energy. 2020;2(1):99‐121.
26. Guo Y, Li H, Ma W, Shi W, Zhu Y, Choi W. Photocatalytic 44. Bhatt MD, Lee JS. Recent theoretical progress in the devel-
activity enhanced via surface hybridization. Carbon Energy. opment of photoanode materials for solar water splitting
2020;2(3):308‐349. photoelectrochemical cells. J Mater Chem A. 2015;3(20):
27. Takata T, Domen K. Defect engineering of photocatalysts by 10632‐10659.
doping of aliovalent metal cations for efficient water splitting. 45. Li J, Wu N. Semiconductor‐based photocatalysts and photo-
J Phys Chem C. 2009;113(45):19386‐19388. electrochemical cells for solar fuel generation: a review.
28. Park JH, Kim S, Bard AJ. Novel carbon‐doped TiO2 nanotube Catal Sci Technol. 2015;5(3):1360‐1384.
arrays with high aspect ratios for efficient solar water split- 46. Ulmer U, Dingle T, Duchesne PN, et al. Fundamentals and
ting. Nano Lett. 2006;6(1):24‐28. applications of photocatalytic CO2 methanation. Nat
29. Kuang Y, Yamada T, Domen K. Surface and interface en- Commun. 2019;10:3169.
gineering for photoelectrochemical water oxidation. Joule. 47. Fang S, Hu YH. Recent progress in photocatalysts for overall
2017;1(2):290‐305. water splitting. Int J Energy Res. 2019;43(3):1082‐1098.
KIM ET AL. | 41
48. Zhang K, Liu J, Wang L, et al. Near‐complete suppression of 66. Cai H, Wang P, Xu Y, et al. Interface engineering on Janus
oxygen evolution for photoelectrochemical H2O oxidative Pd‐Au heterojunction co‐catalysts for selective photocatalytic
H2O2 synthesis. J Am Chem Soc. 2020;142(19):8641‐8648. reduction of CO2 to CH4. J Mater Chem A. 2019;7(10):
49. Beranek R. Selectivity of chemical conversions: do light‐ 5266‐5276.
driven photoelectrocatalytic processes hold special promise? 67. Lang Q, Yang Y, Zhu Y, et al. High‐index facet engineering of
Angew Chem Int Ed. 2019;131(47):16878‐16883. PtCu cocatalysts for superior photocatalytic reduction of CO2
50. Nie X, Luo W, Janik MJ, Asthagiri A. Reaction mechanisms to CH4. J Mater Chem A. 2017;5(14):6686‐6694.
of CO2 electrochemical reduction on Cu(111) determined 68. Pan B, Luo S, Su W, Wang X. Photocatalytic CO2 reduction
with density functional theory. J Catal. 2014;312:108‐122. with H2O over LaPO4 nanorods deposited with Pt cocatalyst.
51. Kim S, Ji S, Kim KH, et al. Revisiting surface chemistry in Appl Catal B‐Environ. 2015;168:458‐464.
TiO2: a critical role of ionic passivation for pH‐independent 69. Nguyen DLT, Kim Y, Hwang YJ, Won DH. Progress in de-
and anti‐corrosive photoelectrochemical water oxidation. velopment of electrocatalyst for CO2 conversion to selective
Chem Eng J. 2021;407:1269292. CO production. Carbon Energy. 2020;2(1):72‐98.
52. Ran J, Jaroniec M, Qiao SZ. Cocatalysts in semiconductor‐ 70. Xie S, Wang Y, Zhang Q, Deng W, Wang Y. MgO‐ and Pt‐
based photocatalytic CO2 reduction: achievements, chal- promoted TiO2 as an efficient photocatalyst for the pre-
lenges, and opportunities. Adv Mater. 2018;30(7):1704649. ferential reduction of carbon dioxide in the presence of wa-
53. Idriss H. Toward large‐scale hydrogen production from water: ter. ACS Catal. 2014;4(10):3644‐3653.
what have we learned and what are the main researchhurdles to 71. Wang WN, An WJ, Ramalingam B, et al. Sizer and structure
cross for commercialization? Energy Technol. 2021;9(2):2000843. matter: enhanced CO2 photoreduction efficiency by size‐
54. Masood ul Hasan I, Peng L, Mao J, et al. Carbon‐based metal‐ resolved ultrafine Pt nanoparticles on TiO2 single crystals.
free catalysts for electrochemical CO2 reduction: activity, J Am Chem Soc. 2012;134(27):11276‐11281.
selectivity, and stability. Carbon Energy. 2021;3(1):24‐49. 72. Li K, Peng T, Ying Z, Song S, Zhang J. Ag‐loading on brookite
55. Chang X, Wang T, Gong J. CO2 photo‐reduction: insights TiO2 quasi nanocubes with exposed {210} and {001} facets:
into CO2 activation and reaction on surfaces of photo- activity and selectivity of CO2 photoreduction to CO/CH4.
catalysts. Energy Environ Sci. 2016;9(7):2177‐2196. Appl Catal B‐Environ. 2016;180:130‐138.
56. Halmann M. Photoelectrochemical reduction of aqueous 73. Li C, Wang T, Liu B, et al. Photoelectrochemical CO2
carbon dioxide on p‐type gallium phosphide in liquid junc- reduction to adjustable syngas on grain‐boundary‐mediated
tion solar cells. Nature. 1978;275(5676):115‐116. a‐Si/TiO2/Au photocathodes with low onset potentials.
57. Shioya Y, Ikeue K, Ogawa M, Anpo M. Synthesis of trans- Energy Environ Sci. 2019;12(3):923‐928.
parent Ti‐containing mesoporous silica thin film materials 74. Kuk SK, Singh RK, Nam DH, Singh R, Lee JK, Park CB.
and their unique photocatalytic activity for the reduction of Photoelectrochemical reduction of carbon dioxide to me-
CO2 with H2O. Appl Catal A‐Gen. 2003;254(2):251‐259. thanol through a highly efficient enzyme cascade. Angew
58. Hasani A, Teklagne MA, Do HH, et al. Graphene‐based Chem Int Ed. 2017;56(14):3827‐3832.
catalysts for electrochemical carbon dioxide reduction. 75. Neaţu Ş, Agulló JAM, Concepción P, Garcia H. Gold‐copper
Carbon Energy. 2020;2(2):158‐175. nanoalloys supported on TiO2 as photocatalyst for CO2 re-
59. Chen D, Wang Y, Liu D, et al. Surface composition dom- duction by water. J Am Chem Soc. 136, 2014(45):15969‐15976.
inates the electrocatalytic reduction of CO2 on ultrafine CuPd 76. Li M, Zhang L, Fan X, Zhou Y, Wu M, Shi J. Highly selective
nanoalloys. Carbon Energy. 2020;2(3):443‐451. CO2 photoreduction to CO over g‐C3N4/Bi2WO6 composites
60. Yin G, Abe H, Kodiyath R, et al. Selective electro‐ or photo‐ under visible light. J Mater Chem A. 2015;3(9):5189‐5196.
reduction of carbon dioxide to formic acid using a Cu‐Zn 77. Bi W, Hu Y, Jiang N, et al. Ultra‐fast construction of plaque‐
alloy catalyst. J Mater Chem A. 2017;5(24):12113‐12119. like Li2TiO3/TiO2 heterostructure for efficient gas‐solid phase
61. Dong LZ, Zhang L, Liu J, et al. Stable heterometallic cluster‐ CO2 photoreduction. Appl Catal B‐Environ. 2020;269:118810.
based organic framework catalysts for artificial photosynth- 78. Zhao Y, Chen G, Bian T, et al. Defect‐rich ultrathin ZnAl‐
esis. Angew Chem Int Ed. 2020;59(7):2659‐2663. layered double hydroxide nanosheets for efficient photo-
62. Tseng IH, Chang WC, Wu JCS. Photoreduction of CO2 using reduction of CO2 to CO with water. Adv Mater. 2015;27(47):
sol‐gel derived titania and titania‐supported copper catalyst. 7824‐7831.
Appl Catal B‐Environ. 2002;37(1):37‐48. 79. Yu X, Ordomsky VV, Khodakov AY. Selective deposition of
63. Cheng J, Zhang M, Wu G, Wang X, Zhou J, Cen K. Photo- cobalt and copper oxides on BiVO4 facets for enhancement of
electrocatalytic reduction of CO2 into chemicals using Pt‐ CO2 photocatalytic reduction to hydrocarbons. ChemCatChem.
modified reduced graphene oxide combined with Pt‐modified 2020;12(3):740‐749.
TiO2 nanotubes. Environ Sci Technol. 2014;48(12):7076‐7084. 80. Zhang X, Han F, Shi B, Farsinezhad S, Dechaine GP,
64. Ou M, Tu W, Yin S, et al. Amino‐assisted anchoring of Shankar K. Photocatalytic conversion of diluted CO2 into
CsPbBr3 perovskite quantum dots on porous g‐C3N4 for en- light hydrocarbons using periodically modulated multiwalled
hanced photocatalytic CO2 reduction. Angew Chem Int Ed. nanotube arrays. Angew Chem Int Ed. 2012;51(51):
2018;130(41):13758‐13762. 12732‐12735.
65. Ye F, Wang F, Meng C, et al. Crystalline phase engineering 81. Sorcar S, Thompson J, Hwang Y, et al. High‐rate solar‐light
on cocatalysts: a promising approach to enhancement on photoconversion of CO2 to fuel: controllable transformation
photocatalytic conversion of carbon dioxide to fuels. Appl from C1 to C2 products. Energy Environ Sci. 2018;11(11):
Catal B‐Environ. 2018;230:145‐153. 3183‐3193.
42 | KIM ET AL.
82. Jia Y, Xu Y, Nie R, et al. Artificial photosynthesis of me- 97. Zhu M, Zhu C, Wu D, et al. Efficient photocatalytic water
thanol from carbon dioxide and water via a Nile red‐ splitting through titanium silicalite stabilized CoO nanodots.
embedded TiO2 photocathode. J Mater Chem A. 2017;5(11): Nanoscale. 2019;11(34):15984‐15990.
5495‐5501. 98. Wei D, Tan Y, Wang Y, Kong T, Shen S, Mao SS. Function‐
83. Wang J, Han B, Nie R, et al. Photoelectrocatalytic reduction switchable metal/semiconductor junction enables efficient
of CO2 to chemicals via ZnO@Nickel foam: controlling C‐C photocatalytic overall water splitting with selective water
coupling by ligand or morphology. Top Catal. 2018;61(15‐17): oxidation products. Sci Bull. 2020;65(16):1389‐1395.
1563‐1573. 99. Nakajima T, Hagino A, Nakamura T, Tsuchiya T, Sayama K.
84. Wang L, Jia Y, Nie R, et al. Ni‐foam‐supported and amine‐ WO3 nanosponge photoanodes with high applied bias photon‐
functionalized TiO2 photocathode improved photoelec- to‐current efficiency for solar hydrogen and peroxydisulfate
trocatalytic reduction of CO2 to methanol. J Catal. 2017;349: production. J Mater Chem A. 2016;4(45):17809‐17818.
1‐7. 100. Cao J, Wang H, Zhao Y, et al. Phosphorus‐doped porous
85. Shoji S, Peng X, Yamaguchi A, et al. Photocatalytic uphill carbon nitride for efficient sole production of hydrogen per-
conversion of natural gas beyond the limitation of thermal oxide via photocatalytic water splitting with a two‐channel
reaction systems. Nat Catal. 2020;3(2):148‐153. pathway. J Mater Chem A. 2020;8(7):3701‐3707.
86. Dong GX, Zhang W, Mu YF, Su K, Zhang M, Lu TB. A halide 101. Baran T, Wojtyła S, Minguzzi A, Rondinini S, Vertova A.
perovskite as a catalyst to simultaneously achieve efficient Achieving efficient H2O2 production by a visible‐light ab-
photocatalytic CO2 reduction and methanol oxidation. Chem sorbing, highly stable photosensitized TiO2. Appl Catal
Commun. 2020;56(34):4664‐4667. B‐Environ. 2019;244:303‐312.
87. Guo Q, Liang F, Li X‐B, et al. Efficient and selective CO2 102. Ma R, Wang L, Wang H, et al. Solid acids accelerate the
reduction integrated with organic synthesis by solar energy. photocatalytic hydrogen peroxide synthesis over a hybrid
Chem. 2019;5(10):2605‐2616. catalyst of titania nanotube with carbon dot. Appl Catal
88. Wang L, Zhang X, Yang L, Wang C, Wang H. Photocatalytic B‐Environ. 2019;244:594‐603.
reduction of CO2 coupled with selective alcohol oxidation 103. Fuku K, Miyase Y, Miseki Y, Funaki T, Gunji T, Sayama K.
under ambient conditions. Catal Sci Technol. 2015;5(10): Photoelectrochemical hydrogen peroxide production from
4800‐4805. water on a WO3/BiVO4 photoanode and from O2 on an Au
89. Chen Y, Wang M, Ma Y, Li Y, Cai J, Li Z. Coupling photocathode without external bias. Chem Asian J. 2017;12(10):
catalytic CO2 reduction with benzyl alcohol oxidation to 1111‐1119.
produce benzyl acetate over Cu2O/Cu. Catal Sci Technol. 104. Jeon T, Kim H, Kim HI, Choi W. Highly durable photo-
2018;8(8):2218‐2223. electrochemical H2O2 production via dual photoanode and
90. Yang T, Yu Q, Wang H. Photocatalytic reduction of CO2 to cathode processes under solar simulating and external bias‐
CH3OH coupling with the oxidation of amine to imine. Catal free conditions. Energy Environ Sci. 2020;13(6):1730‐1742.
Letters. 2018;148(8):2382‐2390. 105. Shi X, Zhang Y, Siahrostami S, Zheng X. Light‐driven Bi-
91. Kofuji Y, Isobe Y, Shiraishi Y, et al. Hydrogen peroxide VO4–C fuel cell with simultaneous production of H2O2. Adv
production on a carbon nitride‐boron nitride‐reduced gra- Energy Mater. 2018;8(23):1801158.
phene oxide hybride photocatalyst under visible light. 106. Mase K, Ohkubo K, Fukuzumi S. Efficient two‐electron re-
ChemCatChem. 2018;10(9):2070‐2077. duction of dioxygen to hydrogen peroxide with one‐electron
92. Zhu C, Zhu M, Sun Y, et al. Carbon‐supported oxygen reductants with a small overpotential catalyzed by a cobalt
vacancy‐rich Co 3O 4 for robust photocatalytic H 2O 2 chlorin complex. J Am Chem Soc. 2013;135(7):2800‐2808.
production via coupled water oxidation and oxygen 107. Desilvestro J, Grätzel M. Photoelectrochemistry of poly-
reduction reaction. ACS Appl Energy Mater. 2019;2(12): crystalline n‐WO3: electrochemical characterization and
8737‐8746. photoassisted oxidation processes. J Electroanal Chem. 1987;
93. Mase K, Yoneda M, Yamada Y, Fukuzumi S. Efficient 238(1‐2):129‐150.
photocatalytic production of hydrogen peroxide from 108. Ahn SH, Zhao J, Kim JH, Zheng X. Effect of interfacial
water and dioxygen with bismuth vanadate and a blocking layer morphology on the solar peroxydisulfate
cobalt(II) chlorin complex. ACS Energy Lett. 2016;1(5): production of WO3 nanoflakes. Electrochim Acta. 2017;244:
913‐919. 184‐191.
94. Mase K, Yoneda M, Yamada Y, Fukuzumi S. Seawater usable 109. Huang Z, Miseki Y, Sayama K. Solar‐light‐driven photo-
for production and consumption of hydrogen peroxide as a catalytic production of peroxydisulfate over noble‐metal
solar fuel. Nat Commun. 2016;7:11470. loaded WO3. Chem Commun. 2019;55(26):3813‐3816.
95. Sun J, Wu Y. Anthraquinone redox relay for dye‐sensitized 110. Luo W, Yang Z, Li Z. Solar hydrogen generation from sea-
photo‐electrochemical H2O2 production. Angew Chem Int Ed. water with a modified BiVO4 photoanode. Energy Environ
2020;59:10904‐11000. Sci. 2011;4(10):4046‐4051.
96. Fan W, Zhang B, Wang X. Efficient hydrogen peroxide 111. Juodkazytė J, Petrulevičienė M, Parvin M, et al. Activity of
synthesis by metal‐free polyterthiophene via photoelec- sol‐gel derived nanocrystalline WO3 films in photoelec-
trocatalytic dioxygen reduction. Energy Environ Sci. 2020; trochemical generation of reactive chlorine species.
132(27):238‐245. J Electroanal Chem. 2020;871:11427.
KIM ET AL. | 43
112. Iguchi S, Miseki Y, Sayama K. Efficient hypochlorous acid 127. Singh AK, Mathew K, Zhuang HL, Henning RG. Computa-
(HClO) production via photoelectrochemical solar energy tional screening of 2D materials for photocatalysis. J Phys
conversion using a BiVO4‐based photoanode. Sustainable Chem Lett. 2015;6(6):1087‐1098.
Energy Fuels. 2018;2(1):155‐162. 128. Luo J, Zhang S, Sun M, Yang L, Luo S, Crittenden JC. A
113. Park SY, Abroshan H, Shi X, Jung HS, Siahrostami S, Zheng X. critical review on energy conversion and environmental
CaSnO3: an electrocatalyst for two‐electron water oxidation remediation of photocatalysts with remodeling crystal
reaction to form H2O2. ACS Energy Lett. 2018;4(1):352‐357. lattice, surface, and interface. ACS Nano. 2019;13(9):
114. Yang L, Dong G, Jacobs DL, Wang Y, Zang L, Wang C. Two‐ 9811‐9840.
channel photocatalytic production of H2O2 over g‐C3N4 na- 129. Wang Y, Liu Y, Liu W, et al. Regulating the coordination
nosheets modified with perylene imides. J Catal. 2017;352: structure of metal single atoms for efficient electro-
274‐281. catalytic CO2 reduction. Energy Environ Sci. 2020;13(12):
115. Shi X, Siahrostami S, Li G‐L, et al. Understanding activity 4609‐4624.
trends in electrochemical water oxidation to form hydrogen 130. Handoko AD, Wei F, Jenndy, Yeo BS, Seh ZW. Under-
peroxide. Nat Commun. 2017;8:701. standing heterogeneous electrocatalytic carbon dioxide re-
116. Fuku K, Sayama K. Efficient oxidative hydrogen peroxide duction through operando techniques. Nat Catal. 2018;1(12):
production and accumulation in photoelectrochemical water 922‐934.
splitting using a tungsten trioxide/bismuth vanadate photo- 131. Zou Y, Wang S. An investigation of active sites for
anode. Chem Commun. 2016;52(31):5406‐5409. electrochemical CO 2 reduction reactions: from in situ
117. Fuku K, Miyase Y, Miseki Y, Gunji T, Sayama K. Enhanced characterization to rational design. Adv Sci. 2021;8(9):
oxidative hydrogen peroxide production on conducting glass 2003579.
anodes modified with metal oxides. ChemistrySelect. 2016; 132. Pawar AU, Kim CW, Nguyen‐Le M‐T, Kang YS. General
1(18):5721‐5726. review on the components and parameters of photoelec-
118. Xie S, Shen Z, Deng J, et al. Visible light‐driven C−H acti- trochemical system for CO2 reduction with in situ analysis.
vation and C–C coupling of methanol into ethylene glycol. ACS Sustainable Chem Eng. 2019;7(8):7431‐7455.
Nat Commun. 2018;9:1181.
133. Cen J, Wu Q, Liu M, Orlov A. Developing new understanding
119. Zhang H, Xie S, Hu J, et al. C–H activations of methanol
of photoelectrochemical water splitting via in‐situ techni-
and ethanol and C–C couplings into diols by zinc–
ques: a review on recent progress. Green Energy Environ.
indium–sulfide under visible light. Chem Commun. 2020;
2017;2(2):100‐111.
56(12):1776‐1779.
134. Cho Y, Park B, Padhi DK, et al. Disordered‐layer‐mediated
120. Hao H, Zhang L, Wang W, Qiao S, Liu X. Photocatalytic
reverse metal–oxide interactions for enhanced photocatalytic
hydrogen evolution coupled with efficient selective benzal-
water splitting. Nano Lett. 2021;21(12):5247‐5253.
dehyde production from benzyl alcohol aqueous solution
over ZnS‐NixSy composites. ACS Sustainable Chem Eng.
2019;7(12):10501‐10508. AU T HO R B I O G R A P HI E S
121. Luo N, Hou T, Liu S, et al. Photocatalytic coproduction of
deoxybenzoin and H2 through tandem redox reactions. ACS Sungsoon Kim is currently a PhD
Catal. 2020;10(1):762‐769. candidate under the supervision of Prof.
122. Huang Y, Liu C, Li M, et al. Photoimmobilized Ni clusters Jong Hyeok Park in the Department of
boost photodehydrogenative coupling of amines to imines via Chemical and Biomolecular Engineering
enhanced hydrogen evolution kinetics. ACS Catal. 2020;
at Yonsei University, Republic of Korea.
10(6):3904‐3910.
His research interests include the surface
123. Liu D, Liu JC, Cai W, et al. Selective photoelectrochemical
oxidation of glycerol to high value‐added dihydroxyacetone. and interface engineering of nanomaterials for
Nat Commun. 2019;10:1779. electrochemical and photoelectrochemical water
124. Kondamudi N, Misra M, Banerjee S, Mohapatra S, splitting.
Mohapatra S. Simultaneous production of glyceric acid and
hydrogen from the photooxidation of crude glycerol using
Kwang Hee Kim is currently an inte-
TiSi2. Appl Catal B‐Environ. 2012;126:180‐185.
125. Iyler A, Kearney K, Ertekin E. Computational approaches to
grated MS/PhD course student under the
photoelectrode design through molecular functionalization supervision of Prof. Jong Hyeok Park in
for enhanced photoelectrochemical water splitting. ChemSus the Department of Chemical and Biomo-
Chem. 2019;12(9):1858‐1871. lecular Engineering at Yonsei University,
126. Zhao Y, Zhang S, Shi R, Waterhouse GIN, Tang J, Zhang T. Republic of Korea. His research interests
Two‐dimensional photocatalyst design: a critical review of include the surface and interface engineering of
recent experimental and computational advances. Mater nanomaterials for electrochemical and photoelectro-
Today. 2020;34:78‐91.
chemical water splitting.
44 | KIM ET AL.
Cheoulwoo Oh is currently a PhD Jong Hyeok Park is a professor in the

candidate under the supervision of Prof. Department of Chemical and Biomolecu-
Jong Hyeok Park in the Department of lar Engineering at Yonsei University,
Chemical and Biomolecular Engineering Republic of Korea. He received his PhD
at Yonsei University, Republic of Korea. degree in Chemical Engineering from
His research interests include the surface KAIST, Republic of Korea, in August
and interface engineering of nanomaterials for 2004. Then, he joined the University of Texas at Austin,
electrochemical and photoelectrochemical water USA, as a postdoctoral researcher in 2004 (under Prof.
splitting and methane conversion. Allen J. Bard). From March 2007 to February 2008, he
worked at ETRI. He is an author and a coauthor of 297
Kan Zhang obtained his PhD degree at papers and 50 patents. His research focuses on solar‐to
the SKKU Advanced Institute of Nano‐ Li & Na ion batteries, Perovskite & organic solar cells,
technology (SAINT) from Sungkyunk- and solar‐to‐hydrogen conversion devices.
wan University, Korea. He is currently a
professor working at the College of
Chemistry, School of Materials Science How to cite this article: Kim S, Kim KH, Oh C,
and Engineering, Nanjing University of Science and Zhang K, Park JH. Artificial photosynthesis for
Technology, China. His research interests involve high‐value‐added chemicals: old material, new
photoelectrocatalytic synthesis of high‐value‐added opportunity. Carbon Energy. 2022;4:21‐44.
chemicals and photoelectrocatalytic systems in energy https://doi.org/10.1002/cey2.159
conversion and environmental treatment.

Artificial Photosynthesis For High-Value-Added Chemicals Old Material, New Opportunity

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Artificial Photosynthesis For High-Value-Added Chemicals Old Material, New Opportunity

Uploaded by

Copyright:

Available Formats

Received: 14 June 2021 | Revised: 1 September 2021 | Accepted: 3 September 2021

Artificial photosynthesis for high‐value‐added chemicals:

Sungsoon Kim1 | Kwang Hee Kim1 | Cheoulwoo Oh1 | Kan Zhang2 |

1 | INTRODUCTION from CO2 and H2O to O2 and glucose in natural

Carbon Energy. 2022;4:21–44. wileyonlinelibrary.com/journal/cey2 | 21

that of other target reactions (e.g., reduction of CO2 to CH4

F I G U R E 2 (A) Charge separation and band

TABLE 2 Summary of CO2 conversion to various products

Materials Light source Products Production rate Selectivity System References

TABLE 3 Summary of materials for hydrogen peroxide production

OVCo3O4/C Vis (>420 nm) H2O2 SCC 0.4% PC [92]

TABLE 4 Summary of materials for oxidizing reagent production

TABLE 5 Summary of materials for solar‐driven organic synthesis

Cheoulwoo Oh is currently a PhD Jong Hyeok Park is a professor in the

You might also like