Zhu 2017

Review
Photocatalysis www.advenergymat.de
Photocatalysis: Basic Principles, Diverse Forms of

Implementations and Emerging Scientific Opportunities
Shasha Zhu and Dunwei Wang*
development of the semiconductor theory
Photocatalysis promises a solution to challenges associated with the intermit and practice has greatly advanced this
tent nature of sunlight which is considered as renewable and ultimate energy branch of technology, and large-scale pro-
source to power activities on Earth. This review aims to provide a broad over duction of solar panels (mostly enabled by
crystalline Si) continue to dominate the
view of the field. Insight into natural photosynthesis is discussed first, which market, how to cost-effectively store the
provides a scientific basis for most efforts on photocatalysis. Afterwards, electricity remains a grand challenge.[6]
the details of four existing types of photocatalysis are presented, namely Another well-studied route of solar energy
photosynthesis by plants, photosynthesis by microalgae, photocatalysis by harvesting and storage concerns photo-
suspension and photoelectrocatalysis. Detailed analyses of simple photo chemical reactions.[7] The rationale is that
chemical bonds are convenient media for
catalysts and integrated photocatalytic systems are followed to shed light
energy storage. Indeed, if we consider the
on the different functionalities of different components in a working photo 21% of O2 in the atmosphere is mostly
catalyst. Special attention is given to the roles played by surface and interface biological O2 owing to natural photo-
chemical phenomena. Lastly, perspectives on artificial photosynthesis are synthesis, the scale of energy stored by
discussed briefly at the end. chemical reactions over billions of years
of evolution is enormous, far exceeding
what can be measured by known fossil
fuel reserves. The recognition of this fact
1. Introduction has inspired generations of scientists to learn from natural
photosynthesis and ultimately to develop technologies much
As the main energy source delivered from the extraterrestrial more efficient and less costly than natural photosynthesis
space, solar energy promises to surpass the annual global to meet our ever-growing energy needs.[8] Nevertheless, it is
energy demand by a large margin.[1] Given the long predicted important to note that the overarching research of photosyn-
lifetime of the Sun, solar energy is also considered the ulti- thesis has broader impacts beyond solar energy storage. How
mate renewable source that we can harvest on the planet of to use the energy delivered by photons instead of heat to enable
Earth.[2] The diurnal and intermittent nature of this energy and/or power chemical reactions is interesting in its own
source, nonetheless, presents significant challenges in terms right. This branch of research has been broadly referred to as
of harvesting, storage and utilization.[3] Presently, there are photocatalysis in the literature.[9] Our goal of writing this review
a number of technologies in place that may be used to meet article is to provide a broad overview of this field. We aim to
the challenges. For instance, solar energy can be directly col- offer a historical account of the development of photocatalysis,
lected, converted and stored in the form of heat, which can its current status, and possible future directions. Most impor-
either provide heat to residence or be further converted into tant of all, we hope to unify some often-confusing concepts sur-
electricity (as well as other forms of energy).[4] The most studied rounding the keyword of photocatalysis and provide the readers
technologies concerning solar photon harvesting may be on an opportunity to focus on the important common scientific
those by the photovoltaic effect, the discovery of which has been merits of seemingly different approaches. The article is organ-
credited to Edmond Becquerel dated back to 1839.[5] While the ized in the following ways. We start with basic principles that
govern photosynthesis and then move on to introduce the his-
torical view of photocatalysis. Existing variations of photocata-
S. Zhu, Prof. D. Wang lytic reactions are next summarized, followed by discussions
Department of Chemistry on integrated systems where components with distinct func-
Boston College tionalities are presented. Afterwards, the article examines the
Merkert Chemistry Center
2609 Beacon Street, Chestnut Hill, MA 02467, USA importance of interfaces between different components within
E-mail: [email protected] an integrated system. At the end of the review, we present our
S. Zhu perspectives on where the field is headed.
Department of Chemistry
Zhejiang University
Hangzhou 310027, P.R. China
The ORCID identification number(s) for the author(s) of this article 2. Lessons from the Nature
can be found under https://doi.org/10.1002/aenm.201700841.
Photosynthesis refers to the process by which green plants,
DOI: 10.1002/aenm.201700841 microalgae and some forms of bacteria harvest the energy from
Adv. Energy Mater. 2017, 7, 1700841 1700841 (1 of 24) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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www.advancedsciencenews.com www.advenergymat.de
the sunlight to power thermodynamically uphill reactions such

as the conversion of CO2 and H2O to carbohydrate.[10] While the Shasha Zhu received her
detailed thermodynamic discussions will be presented later in bachelor’s degree in 2013
this review (Section 3), it suffices here that these reactions are from Harbin Institute
thermodynamically uphill, meaning that providing energy to of Technology. She is a
power these reactions is critical. The detailed mechanisms of Ph.D. student in Zhejiang
photosyntheses by these different organisms indeed vary, but University. Currently, she
they share some common fundamental underlying principles. studies under supervision
We borrow the general form of oxygenic photosynthesis as of Prof. Dunwei Wang as a
shown in Figure 1 to facilitate our discussions.[11] Using this visiting student. Her research
mechanism, we discuss 3 important aspects of the process, interests focus on solar water
namely the energy flow, the electron flow, and the detailed splitting.
chemical reactions.
Dunwei Wang graduated

2.1. Energy Flow from Stanford University
with a Ph.D. in chemistry in
As is true in any photosynthetic system, the most important 2005. He has been at Boston
aspect is how the energy from light is harvested and transferred. College since 2007, where
Figure 1 includes two key components, photosystem I, or PSI, and he researches on materials
photosystem II, or PSII. Photons are absorbed by the pigments in for energy conversion and
these photosystems, where the energy is used to excite electrons. storage. He has been a Sloan
Collectively, these two photosystems harvest enough energy to Fellow and a JSPS Fellow.
power the reactions of H2O oxidation (on the site of PSII) and
the synthesis of NADPH (on PSI). In the meanwhile, protons
transfer across membrane coupled with electrons transfer (will be
discussed in Section 2.2). As such, a (significant) portion of the
harvested energy helps build a proton gradient (3–3.5 pH units,
corresponding to a proton-motive force of 200 mV) across the thy- the PSI site, a second excitation takes place, providing enough
lakoid membrane, which will be used to power the synthesis of energy for the electrons to enable the synthesis of NADPH. In
ATP.[12] Together, the ATP and NADPH are later used in the dark many ways, NADPH can be regarded as a temporary electron
reactions (Calvin cycle) for the CO2 fixation reactions. storage medium (in the form of reduced protons). These stored
electrons are ultimately transferred to CO2 during the dark
reactions to complete their journey from H2O to CO2.
2.2. Electron Flow
Excited electrons are the main vehicles in photosynthesis to 2.3. Main Chemical Processes in Oxygenic Photosynthesis
carry the energy flow. They are extracted from the negatively
charge O in H2O at the site of PSII during the light reactions. Figure 1 only shows one of the two important stages of natural
Once excited, they are quickly moved away from this site by a photosynthesis, the light reactions. Here the chlorophylls in
series of proteins as indicated by the green arrows in Figure 1, PSII absorb photons to enable charge separation for the crea-
losing some of their energies in the process. Once they reach tion of P680+—Pheo−.[13] The concerted activity of the oxygen
Figure 1. Schematic representation of natural photosynthesis. Reproduced with permission.[11] Copyright 2014, The Royal Society of Chemistry.
12H2O + 12NADP+ + 48hv → 6O2 + 12NADPH + 12H+ (1)
What are not represented in Figure 1 are the dark reactions:
6CO2 + 12NADPH + 18ATP + 12H+

→ C6 H12O6 + 12NADP+ + 18ADP + 18p i + 6H2O (2)
where pi is inorganic phosphate.[15] Of these chemical reac-

tions, we wish to particularly point out the details of water
oxidation (Equation (1a)). It is important because it is the first
step of natural photosynthesis which supplies electrons for
the subsequent reduction reactions. The electrons can be used
for CO2 fixation. They can also be used for direct H+ reduc-
tion which enables solar H2 synthesis. The reaction is also
important because its 4-electron, 4-proton nature renders it the
rate determining step (RDS) in many photosynthetic reactions.
The understanding of its chemical mechanisms holds the key
to a large number of processes that are currently being devel-
oped. For instance, the main limiting factor of solar hydrogen
production is the lack of suitable photoanodes for water oxida-
tion with good performance in terms of kinetics and stability
to match that of the photocathodes.[16] Studies of the OEC of
PSII reveal that it consists of one Ca atom and four Mn atoms
in a Mn4Ca2+ complex.[17] The complex can be oxidized by PSII
through a series of proton-coupled electron transfer (PCET)
processes in four steps, from S0 to S4 (Figure 2a). S4 can be
turned over to S0 by oxidizing H2O to liberate O2.[17,18]
To date, the design principles represented by Figure 1 are
the only ones demonstrating large-scale successes in operation.
Figure 2. a) Schematic illustration of the five stages of OEC. Reproduced As such, much can be learned from this model in developing
with permission.[17] Copyright 2013, The Royal Society of Chemistry. artificial photosynthesis systems. From the simplified discus-
b) Frost diagram for oxygen production half reactions at pH 6 vs NHE. sions presented above, we gain several important insights
Red line: OEC; blue long-dashed line: four-electron S4/S0 couple; blue into the design principles. First and foremost, the system is
short-dashed line: two electron couples, S4/S2 and S2/S0; blue solid line:
2H2O (0), H2O + OH· (1), H2O2 (2), O2−• (3), and O2 (4); green line:
an integrated complex system. Components of different, and
a single manganese ion; magenta line: a manganese tetramer hypoth- often well-defined, functionalities are needed. For instance,
esized without PCET. Slopes of each line indicate driving force for water the roles of the light absorbers and charge separation mecha-
oxidation. Green and magenta line: proposed catalyst for water oxida- nisms are distinct and easy to distinguish. Second, we see that
tion. Reproduced with permission.[20] Copyright 2006, The Royal Society the balance between stability and reactivity is critical. Consider
of Chemistry. the OEC as an example. As a RDS in the light reactions, the
activity of the catalytic centers is critically important. However,
evolving center (OEC, Mn4Ca-cluster) is critical to the func- these active centers are by definition also highly unstable. The
tionality of PSII. As will be seen in Figure 2a, P680+ oxidizes natural photosystems protect these centers with a large group
OEC stepwise, during which process H2O is oxidized by the of proteins and repair the OEC continuously.[17] Third, well-
activated OEC to molecular O2 and H+. Another area where controlled energy and electron flows are of fundamental impor-
rich chemistries take place is the PSI site, where light absorp- tance. In the natural photosystems, this is achieved through
tion induces the formation of the P700+—A0− charge pair.[14] Of precise arrangements of functional proteins buried in the thy-
them, P700+ can be reduced by electrons supplied by PSII and lakoid membrane. Similar arrangements of different functional
further excited by PSI. A0− will be used to reduce NADP+ to groups in an artificial system will likely be equally important.
NADPH. In parallel, the processes concentrate H+ on one side The remainder of the review is guided by these insights.
(the bottom side in Figure 1) of the thylakoid membrane to
build up a large concentration gradient, which is used by the
ATPase to power the ATP synthesis.[12] 2.4. Thermodynamic Analysis
The light-induced processes can be represented as:
An intriguing question to ask about the natural photosystems
2H2O + 4hv → O2 + 4H+ + 4e − (1a) is why two light absorbers are needed. Intuitively, we see the
needs arise from the reducing powers necessary to complete the
water splitting reactions. Let us take a look at Figure 1 again. At
2NADP+ + 2H+ + 4e − + 4hv → 2NADPH (1b)
neutral pH (pH ≈ 7), the dual photosystems provide a photo-
Together, the overall reaction may be written as: voltage to match the redox reaction (O2/H2O: 0.82 V vs NHE
and NADP+/NADPH: −0.32 V vs NHE, where NHE stands for

Normal Hydrogen Electrode as a reference).[13] The reactions
should be possible if we have a single photosystem that pro-
vides much greater energy than the natural PSI and PSII com-
bined, enough to power the overall reactions. Indeed, detailed
thermodynamic balance has been utilized to study the different
scenarios consisting of varying numbers of lighter absorbers,
including the single-absorber possibility.[19] It was found that
from an efficiency perspective, higher efficiencies are expected Figure 3. Thermodynamic illustration of photocatalysis. a) Uphill reac-
tions, b) downhill reactions. R: reactants, P: products.
when more light absorbers are involved. When one takes into
account that the system would be too complex to balance when
more light absorbers are involved, 2-absorber systems would system’s thermodynamics to permit the broad application of
almost be the ideal compromise. We see from this point the “photocatalysis” to describe such systems.[9,22] In parallel, there
ingenuity of the natural photosystems. In other words, when are a large number of chemical reactions that are spontaneous
regarded as an engineered system, the natural photosystems whose kinetics is hindered by the high activation energies
are optimized. Similar conclusions can be drawn when one (such as pollutant oxidation; Figure 3b).[23] Here the introduc-
looks at the detailed energy landscapes of the OEC of the PSII tion of light to enable the reaction falls in the canonical defini-
as shown in Figure 2b.[20] As a consecutive 4-electron, 4-proton tion of catalysis. As a result, photocatalysis would be an ideal
process, the relative energy levels of the intermediate states terminology to describe such reactions. Additionally, a less
(S0, S1, S2, S3 and S4) are shown in red solid dots connected by obvious class of reactions that also often borrow the keyword
the red solid line. Any deviations from this line present some photocatalysis are those require externally applied potentials.
forms of challenges. Consider the blue solid line as an example. They are variably referred to as photoelectrochemical or photo-
The driving force (as measured by the slope of the energy vs electrocatalytical reactions in the literature.[24] Our view is that
the oxidation number) of the first step would be so high that the fundamental processes involved in these reactions are the
it would promote the formation of hydroxide radical (OH·). same should it be photosynthesis or canonical photocatalysis.
Similarly, during the second step of the process outlined by the Consequently, they should be treated as the same group of reac-
solid-blue line, the formation of H2O2 would prevail, followed tions for the benefit of understanding and further development.
by O2−• formation during the third step. This possible route
presents at least two critical issues. First, greater energy would
be needed as the intermediates are of higher energies. Second, 3.1. History of Photocatalysis
highly reactive byproducts would be produced. Next, we can
look at the importance of PCET. If we follow the magenta line As early as 1901, chemist Giacomo Ciamician was one of the
in Figure 2b, we see that significantly greater energy would be first to conduct experiments to study whether “light and light
needed if electron transfer is not coupled by proton transfer. alone” would enable chemical reactions.[25] He carried out
Lastly, we also see the importance of the OEC complex by experiments with blue and red lights and found that a chemical
looking at the green lines, where much higher oxidation states effect took place only in blue light. He was careful enough to
of the Mn active center would be needed for the oxidation of exclude the possibility that these reactions were instead pow-
H2O. Taken as a whole, we come to appreciate the optimization ered by thermal heating induced by light. In 1911, the keyword
of the natural photosystems and further realize how important “photocatalysis” first appeared in scientific literatures.[26] Scien-
it is to learn from the successful example when designing arti- tists referred to Prussian blue bleaching by ZnO under illumi-
ficial systems. nation photocatalysis. This observation has inspired subsequent
experiments of using ZnO as a photocatalyst for other reac-
tions such as the reduction of Ag+ to Ag under irradiation in
3. Photocatalysis 1924.[27] It is noted that although photosensitive reactions had
been long discovered prior to these efforts, those processes did
In this section, our goal is to provide a broad definition of not involve a light-sensitive catalyst.[28] Later, TiO2 and Nb2O5
photocatalysis as it has been interchangeably used in the litera- were reported to drive photocatalytic reduction of AgNO3 to Ag
ture, creating considerable confusion when the terminology is and AuCl3 to Au in 1932.[29] Afterwards, TiO2 was investigated
not treated with care. As will be seen next, the development of in 1938 as a photosensitizer to bleach dyes in the presence of
photocatalysis was indeed inspired by natural photosynthesis. O2.[30] Nevertheless, interests in photocatalysis remained a
From this perspective, it should be fair to regard thermody- hobby due to the absence of mainstream practical applications.
namically uphill reactions powered by light as photocatalysis The situations changed in the early 1970s for two reasons. First,
(Figure 3a). However, a source of confusion may come from the “oil crisis” prompted scientists to seek alternative energy
the uphill thermodynamic nature itself. In catalysis, such supplies to fossil fuels.[31] Second, the concerns over environ-
reactions are not spontaneous.[21] Hence, the introduction mental impacts by large-scale industrial operations motivated
of a canonical “catalyst” is not expected to enable a nonspon- researchers to search for renewable energy sources.[9] Several
taneous reaction. To reconcile the discrepancies in the termi- seminal papers were published during this period of time. In
nology, it is not uncommon in the literature where authors 1968, scientists from the Bell Lab first reported O2 evolution on
regard light as a reactant, which would alter the view of the TiO2.[32] In 1972, Fujishima and Honda reported photo-assisted
H2O oxidation with H2 production using TiO2 electrodes under (II) separation of excited charges; (III) transfer of electrons and
UV light irradiation.[33] Photocatalytic water splitting without holes to the surface of photocatalysts; and (IV) utilization of
external energy input other than light yielding H2 and O2 under charges on the surface for redox reactions. For the third step, a
argon in stoichiometric ratio of 2:1 was reported in 1977.[34] large portion of electron-hole pairs recombine, either en route
Interestingly, this work found that O2 formed but H2 evolution to the surface or on the surface sites.[24c,42] The recombination
was inhibited in the presence of N2. The authors concluded dissipates the harvested energy in the form of heat (nonradia-
that N2 was reduced to NH3 and trace amount of N2H4 by TiO2. tive recombination) or light emission (radiative recombina-
During the same period of time, Frank and Bard first reported tion).[43] The long-lived photogenerated charges on the surface
the decomposition of CN− and SO32− by TiO2, ZnO, and CdS have the potential to promote different redox reactions, the
under light.[35] Later, Fujishima et al. reported studies on photo details of which depend on the donor or acceptor properties of
catalytic CO2 reduction using various inorganic semiconduc- the surface absorbed species.
tors as photocatalysts in 1979.[36] These early efforts extended As discussed above, what conforms to the canonical
the applications of photocatalysis, drawing significant research definition of “catalysis” would be photocatalysis of organic
attention in the 1980’s to similar reactions using, in particular, pollutant degradation, where the reaction would be spontaneous
TiO2 nanoparticles as the photocatalysts.[37] Since then, inves- from a thermodynamic perspective.[21] The introduction of a
tigations have been concentrated on understanding the fun- photocatalyst would alter the reaction route and thus improve
damental principles, enhancing the photocatalytic efficiencies, the kinetics. The topic has been studied extensively and has
searching for new photocatalysts, and expanding the scope of been reviewed previously.[44] In this review, we wish to put an
the reactions. For instance, photo-induced super-hydrophilicity emphasis on the photosynthetic reactions that are inherently
effect was discovered on TiO2 in 1997.[38] As a result, TiO2 with non-spontaneous without the energy input of light. The new
self-cleaning and anti-fogging functionalities has been applied round of research efforts over the past decade on this topic
to building materials.[39] In the development of new photocata- has been motivated by the rapidly growing need for large-scale
lysts, many candidates with higher photocatalytic activities than solar energy storage.[45] The Gibbs free energy changes of a few
TiO2 have been studied, most featuring wide bandgaps and only representative chemical reactions of interest in this category
active under UV lights.[40] For higher efficiencies, visible light are shown in Figure 5.[46] Due to the similarities of these reac-
absorbing photocatalysts have been pursued in parallel.[41] In tions to natural photosynthesis, these reactions are commonly
the meanwhile, researchers gradually learned more about the referred to as artificial photosynthesis in the literatures.[47] Note
principles that govern photocatalysis, which will be discussed that here we take a broad view of what photosynthesis means.
later in this review (Sections 5, 6, and 7). In some literature, it may be specifically tied to reactions
involving water splitting and CO2 reduction. Among the reac-
tions shown in Figure 5, water splitting produces hydrogen,
3.2. Broad Definition of Photocatalysis which is a posterchild of renewable (or clean) energy. It has
arguably received the most research attention.[48] The reaction
Photocatalysis, while varying in details in terms of reactions and is indeed fundamentally important because it is also the first
mechanisms, may be described by four important steps (shown step in natural photosynthesis (see Section 2.3) where electrons
in Figure 4): (I) light absorption to generate electron-hole pairs; are extracted from H2O for the subsequent reduction reactions.
The interest in CO2 reduction is self-evident given that CO2 is
the key culprit in today’s global warming discussions.[49] From
a chemistry standpoint, the reduction of CO2 is also tremen-
dously interesting because it can involve up to 8 electrons and
8 protons in a one-carbon pathway (in the formation of CH4,
for instance) and more than 8 electrons in two or three-carbon
pathways.[50] The complexity and the many different possibili-
ties in product formation provide a fertile field to test various
Figure 4. Steps in photocatalytic reaction process. R: chemicals in reduc-

tive reactions, O: chemicals in oxidative reactions. (I) light absorption
to generate electron-hole pairs; (II) separation of excited charges; (III)
transfer of electrons and holes to the surface of photocatalysts; (III′)
recombination of electrons and holes; (IV) utilization of charges on the Figure 5. Energy diagrams of representative thermodynamically uphill
surface for redox reactions. reactions.
separated by a reasonable distance (greater than a few hundred

nanometers).[54]
4.1. Photosynthesis by Plants
In plant photosynthesis, the energy delivered by sunlight is

absorbed by chlorophylls to power the conversion of CO2 and
H2O into carbohydrate, with the production of O2. It pro-
duces food (either directly or indirectly via animal products),
oxygen, and thermal energy for lives. The process is the ulti-
mate source of energy supply for most fossil fuels, coal, oil
and a large portion of natural gases. Plant photosynthesis also
represents a main mechanism by which atmospheric CO2 is
consumed and reduced, balancing the global warming effect.
While an incredible system in its own right, the natural photo-
synthesis system of plants is by no means optimized for effi-
ciency. As a matter of fact, when the broad solar spectrum is
considered, by only counting what portion of the energy is har-
vestable and useful, and by averaging over seasons and nights
and days, we rarely see plants that are >1% in converting and
storing solar energy.[55] The low overall efficiency leaves much
Figure 6. Types of photocatalytic reactions. a) Natural photosynthesis in
room for improvement. Such room has been the key motiva-
plants, b) photosynthesis by microalgae, c) nanoparticles photocatalysis, tion for artificial photosynthesis.[56] Additional considerations
d) photoelectrocatalysis. for not over-exploiting plant photosynthesis to quench our
thirst for energy include the competition of food production
chemical theories. The formation of valuable chemical prod- and the high cost associated with irrigation and soil depletion,
ucts such as NH3 and various alcohols represents a key issue among others.
in modern chemical industry. How to carry out these processes
with significantly reduced cost and/or energy input constitutes
a grand challenge that has enormous economic implications. 4.2. Photosynthesis by Microalgae
Different from plants, microalgae are single cell micro

4. Summary of Existing Photocatalysis organisms without roots, stems and leaves.[57] They present an
opportunity for system engineering with a focus on the prod-
Reaction Types
ucts without having to share the harvested solar energy with
In an effort to categorize existing approaches of photocatalysis, parasitic processes such as tissue formation. Moreover, micro-
we present in Figure 6 four classes of reactions. In the first cat- algae can be placed at locations on non-arable lands and/or in
egory (Figure 6a), we see the most successful photocatalysis, marine environments.[58] Saline and wastewater, but not nec-
natural photosynthesis. An ingenious result of billions of years essarily fresh water, can be directly fed to the system.[59] For
of evolution by Mother Nature, the process has been the main these advantages, microalgae-based photosynthesis is favored
source of our energy supply. Carbohydrates are the key prod- for further developments. The most investigated application
ucts of these reactions.[51] A variation of this reaction is shown of microalgae-based photosynthesis is to produce H2 from
in Figure 6b, where microalgae perform reactions similar to sunlight and H2O.[60] This is because many microalgae can be
those in plants but synthesize unique chemicals such as H2 or genetically engineered to promote hydrogen metabolism. Elec-
other valuable chemicals (e.g., ethanol, butanol, glycerol, and trons from PSII (as a result of water oxidation) are accepted by
isoprene).[51,52] When it comes to artificial photosynthesis sys- hydrogenase to directly reduce H+ for the production of H2.[51]
tems, a great number of variations exist. They may be grouped In fact, the ease of genetic engineering renders microalgae a
into two general types as summarized in Figure 6c and 6d. versatile platform for photosynthesis. For example, different
When the reduction and oxidation reactions are not intention- synthase genes can be expressed in microalgae through het-
ally separated (Figure 6c), a system with the benefit of inher- erologous transformation for the production of isoprene.[51]
ently low cost is obtained. Note that reactions involving both There, however, remains a long way to go before photo
heterogeneous and homogeneous catalysts can be included in synthetic microorganisms can enable large scale, economical
this category. A competing strategy is to physically separate biofuel production. The relatively narrow absorption within
the reduction and oxidation sites. A wired version of the last the solar spectrum represents one challenge that has yet to be
strategy is shown in Figure 6d. But the wire is not essential addressed.[61] Another challenge is the saturation effect, where
here. A back-to-back wireless configuration falls in the same cat- the conversion efficiency does not scale with the increasing
egory, as well.[53] A key distinguishing feature of Figure 6c and concentrations of microorganisms, limiting the overall effi-
6d is whether the reduction and oxidation sites are physically ciency of the system.[62]
4.3. Photocatalysis by Suspensions and/or Homogeneous the sizes of the photocatalyst have indeed been confirmed by
Photocatalysis prototypical studies on TiO2.[69]
A variation of particle-based photocatalysis is to immobi-
4.3.1. Heterogeneous Powdery Photocatalysis lize the photocatalysts on a support.[68b] The idea is to address
the issues connected to the removal/recovery of the nanoscale
One of the least complicated applications of photocatalysis is photocatalyst while maintaining the benefits. Such issues can be
to simply suspend photocatalysts in a solution and shine light significant where the removal of the photocatalyst is important
on it. Often, the photocatalysts are nanoscale particles. In such but too difficult or too expensive or both. In addition, light scat-
a system, each photocatalyst nanoparticle may be regarded as tering by photocatalyst particles near the light source limits light
an integrated system consisting of short-circuited photoanode penetration in the solution for a suspension system, leading to
and photocathode. Naturally, the ease of implementation offers insufficient photocatalyst utilization. In an immobilized pow-
the benefit of low cost. The simplicity, nevertheless, also intro- dery photocatalyst system, the substrate does not necessarily
duces significant challenges, the most critical of which is the have to participate in the photocatalytic reactions. It can merely
low efficiency.[63] Reasons for the low efficiency include severe serve as a support. The strategy not only facilitates photocatalysis
recombination.[42b] Because the reduction and oxidation sites at in liquid solution but also opens up the possibility of carrying
the nanoscale in such an integrated system are often not well out photocatalysis in the gas phase.[70] As shown in Figure 7,
defined, the charge separation mechanisms are consequently TiO2 photocatalyst was immobilized on β-SiC foam with a high
not optimized, thereby resulting in charge recombination open porosity structure, which benefited larger loading amount
within an individual photocatalyst or on the surface or both. of TiO2 and air flow during gas phase photocatalytic reaction.[71]
The close proximity of the reduction and oxidation sites pro-
vides ample opportunities for the reduction intermediates and/
or products to be oxidized, and vice versa. Additionally, having 4.3.2. Homogeneous Molecule Photocatalysis
a mixture of oxidizing and reducing products (e.g., O2 and H2)
raises concerns over safety.[64] The separation of the mixture As far as photocatalysis is concerned, the light absorbing and/
later incurs additional cost. or catalytic units can also be homogeneous molecules dissolved
Next, we focus on two aspects of the photocatalytic processes in H2O (or another medium).[72] Under light irradiation, a
to illustrate that it is beneficial to keep the photocatalyst sizes in molecular photocatalyst (Pcat) can be promoted to the excited
the nanoscale. Domen et al. calculated the relationship between state (Pcat*) (Figure 8).[73] The typical result is electrons excited
photon absorption and photocatalyst sizes by assuming photo- from the highest occupied molecular orbital (HOMO) to the
catalyst with a spherical shape.[65] Light intensity of AM 1.5G lowest unoccupied molecular orbital (LUMO), similar to how
for photons with wavelength ranging from 280 to 600 nm was electrons are excited from the valence band to the conduction
used for the estimate. As the diameter of the photocatalyst grew band in semiconducting solid photocatalysts. The excited state
larger, the number of photons striking the photocatalyst per Pcat* is both a strong reductant and a strong oxidant. Ideally, it
second was greater. Consequently, the time interval between can drive full redox reactions such as water splitting. In reality,
photon strikes was smaller. For instance, the
average time between photon strikes for a
50 nm particle would be 5.6 × 10−1 µs; that
for a 5 µm particle would be 5.6 × 10−5 µs.
Given that the time it takes for surface chem-
ical reactions to complete is typically longer
than µs, it should be beneficial to choose
photocatalyt sizes to allow for longer dura-
tions between photon strikes. In other words,
it is desired to keep the photocatalyst sizes
small.
Second, from the standpoint of reducing
bulk recombination, it is desired to keep the
photocatlyst small. The smaller the photo-
catalyst, the fewer grain/crystal boundaries
within the bulk of the particle and, hence, less
bulk recombination.[66] The benefits offered
by small photocatalyst sizes are counterbal-
anced by issues connected to the small sizes.
For example, smaller particles tend to aggre-
gate more easily, presenting issues of poor
suspension.[67] Higher surface areas inherent
to smaller particles also mean greater surface
recombination.[68] The expectations on how Figure 7. Optical and SEM images of bare β-SiC foam a,b) and TiO2/β-SiC foam c,d). Repro-
the photocatalytic activities would depend on duced with permission.[71] Copyright 2015, Elsevier.
system. While the oxidants and reductants may co-exist, as

is seen in many homogeneous and powdery heterogeneous
photocatalysis systems, or are well separated, as will be seen in
the next section, the complete reactions require both to func-
tion as desired. Otherwise, the overall reaction would not be
balanced and, hence, non-sustainable. Consider water splitting
as an example. In a simplified form, H2O is being oxidized and
reduced at the same time, producing reduced product of H2
and oxidized product of O2. In many photocatalysis systems,
particularly the nanoparticle-based ones, the oxidation and
reduction sites are often poorly understood. The lack of detailed
Figure 8. Photoredox catalysis by homogeneous photocatalyst. The oxi- information has been an important reason why full photocata-
dation steps are depicted on the right; the reduction steps are shown on lytic water splitting remains low efficiency. After all, it is exceed-
the left. Pcat: photocatalyst, Q: quencher, D: donor, A: acceptor. Repro- ingly difficult to balance both thermodynamics and kinetics of
duced with permission.[73] Copyright 2009, Wiley-VCH Verlag GmbH & two fundamentally different types of reactions at the same time.
Co. KGaA, Weinheim. In the literature, it is a common practice to introduce sacrificial
reagents that would either provide electrons or holes to facilitate
a sacrificial quencher (Q) is often necessary to yield a reduced the overall reactions. For example, alcohols are frequently used
species Pcat− and an oxidized species Q+ in the case of reduc- as a sacrificial reductant to donate electrons for photocatalytic
tive quenching, or a pair of Pcat+ and Q− in the case of oxidative H2 generation studies.[82] Such approach circumvents the chal-
quenching (Figure 8).[73] In the former case, the reduced com- lenges associated with OER. Likewise, electron scavengers such
pound Pcat− then interacts with the reactants. And in the latter as AgNO3 are often used to enable studies of OER without wor-
case, Pcat+ oxidizes the reactants to higher oxidation states. A rying about the HER reactions.[83] In canonical photochemistry
good example of such a system is found in polyoxometalates studies, chemical oxidants are also used to replace photosensi-
(POMs), which have been investigated as photocatalysts for tizers to enable the chemical processes without light, providing
water oxidation, degradation of organic pollutants, and removal convenience as well as chemical insights.[84] However, knowl-
of metal ions in water.[74] Another example of homogeneous edge generated by these substitutes is not always transferrable
photocatalyst is metal complexes such as Re(CO)3(bpy)+ -based to the real photochemical full reactions.[66b,85] It is critical to
complexes, which have been studied for photocatalytic CO2 note here that it has almost become a common practice to call
reduction.[75] Similarly, the [Ru(bpy)3]2+ family complexes have some of these substituted reactions as “solar hydrogen produc-
been investigated for water oxidation.[72b,76] Notwithstanding, at tion” in the literature. While it is strictly not wrong to do so, the
least three important challenges need to be addressed before practice can be misleading because the presence of sacrificial
homogeneous photocatalysts can be more widely used. First, reagents would make the overall performance artificially better
the solubility of the photocatalysts makes it difficult to sepa- than the real water splitting reaction. As a result, the practice
rate them from the solution after reaction either for reuse or would make it subsequently difficult to highlight results from
for the purification of products or both. Second, homogeneous efforts focused on solving key issues in the true water splitting
molecules with well-defined HOMO–LUMO separations often reactions, which is badly needed at the current stage.
absorb narrowly within the solar spectrum. For exmple, most
POMs only absorb 5% of the solar light due to the large separa-
tion between HOMO and LUMO.[77] Third, the photocatalytic 4.4. Photoelectrocatalysis
activity and stability of homogeneous photocatalysts are lim-
ited by the instability inherent to the molecular nature of their Photoelectrocatalysis is also variably referred to as photoelectro-
structures.[76b,78] In the tests, precipitation is indeed frequently chemistry (PEC) in the literature. The essence of this approach
observed due to the decomposition of the photocatalysts.[79] is to combine heterogeneous photoactive catalysts with elec-
Finding homogeneous photocatalysts that are stable and can trochemical apparatus. This approach offers several distinct
absorb broadly in the solar spectrum is of great importance.[80] advantages. First and foremost, by separating the reduction
In recent years, many efforts have been devoted to hetero- and oxidation sites, PEC greatly limits impacts by issues con-
genizing homogeneous photocatalysts onto solid substrate nected to product crossover. As a result, much higher efficien-
(e.g., TiO2, SiO2, and g-C3N4) by adsorption, grafting, and/or cies than simple powdery photocatalysis are expected. Second,
electrostatic interaction to achieve better performance.[8,81] In the quantitative measure of the number of charge (current) and
such an immobilization strategy, molecular photocatalysts act their relative energies (voltage or potential) provides insights
as additional light absorbers or co-catalyst with active centers into the principles underpinning the function of photocatalysts.
or both. This kind of integrated photocatalysis system will be From this perspective, PEC is not only an engineering design
discussed later in this review (Section 6). for practical photocatalysis, but also serves as a characterization
tool to understand the photocatalysts. Many advances made
4.3.3. Full Reactions and Half Reactions in electrochemistry can be readily borrowed to characterize
photocatalysts in a quantitative fashion. Rich thermodynamic
The majority of studied photocatalytic reactions are redox reac- and kinetic information has indeed been collected using PEC
tions, meaning that there are oxidants and reductants in the techniques.[86]
4.4.1. Performance Evaluation of PEC Redox Reactions
The basic experimental setup of a PEC experiment can take a

two-electrode or a three-electrode configuration. Of the elec-
trodes, at least one is photoactive. A key convenience by PEC
is the opportunity to separate the photoanode and the photo-
cathode by a membrane. As a result of the separation, the
photoelectrocatalyzed oxidation and reduction products can be
collected separately. The separation minimizes, if not elimi-
nates completely, the product crossover and hence greatly
improves the efficiency. The separation also offers an opportu-
nity to study the two half reactions separately. In practice, the
reactions are carried out in either a two-electrode or a three-
electrode configuration, depending on whether a reference
electrode is employed.[87] For the former, the potentials of the
anode would be measured against the cathode. Although this
configuration more closely mimics a realistic PEC device in real
applications, the inaccuracies of measuring the potential differ-
ence between the working and counter electrodes due to, for
example, electrolyte polarization, membrane polarization, con-
centration gradient, among other factors, presents significant
challenges in quantitative data analysis. The latter case elimi-
nates these complications with a calibrated reference electrode.
In data representations, the photocurrent density-potential
(J–E) curve is most frequently employed to describe a PEC
system. Two variables in a J–E curve, the photocurrent density
(Jph) and the onset potential (Eon) are of critical importance
(Figure 9a).[88] The photocurrent density measures the rate at
which the reactions take place, and the onset potential describes
the inherent driving force of the reaction. Using water splitting Figure 9. a) Overlaid J–E curves of photoanode (orange line) and photo-
as an example, we show in Figure 9a how these two variables cathode (blue line) in a PEC system. Illustration of energy requirements
in photocatalysis b) and photoelectrocatalysis c).
can be utilized to evaluate the performance of a PEC system.
Simply, the goal of any integrated PEC system is to obtain a
high photocurrent density at the point where the J–E curve of alternating current method to interrogate the system for infor-
the photoanode intercepts that of the photocathode (Jop).[88,89] In mation difficult to obtain by simple direct current methods. For
order for this to happen, we need the Eon of the photoanode as example, various electrochemical impedance spectroscopy (EIS)
negative as possible, and that of the photocathode as positive techniques have been developed to study the system, similar to
as possible. In the case where the Eon of the photocathode is how EIS was used to study other electrochemical systems.[91]
less positive than that of the photoanode, external bias would In particular, we wish to mention that photoelectrochemical
be needed for the overall reaction to take place. For the situa- impedance spectroscopy (PEIS) studies have been carried out
tion shown in Figure 9a, if we assume 100% Faradic efficiency by Peter, Bisquert and Hamann et al., separately, to understand
for both reactions, the solar-to-hydrogen (STH) conversion effi- the behaviors of the photoelectrode and the co-catalysts.[86g,92]
ciency (ηSTH) can be conveniently calculated as follows: More on this point will be discussed in the following sections.
Another useful technique was the intensity-modulated photo-
J op × (1.23V ) (3) current spectroscopy (IMPS) pioneered by Peter et al. to char-
ηSTH =
Pin acterize the kinetics of the photoelectrodes in a quantitative
fashion.[86e] Under ideal conditions, the rate constants of surface
where Pin is the power of overall photon input (W cm−2).[88] It is recombination, charge transfer can be obtained quantitatively.
noted that how to correctly calculate the efficiencies of an artifi-
cial photosynthesis system has been reviewed by other authors,
although no consensus has been reached regarding what is 4.5. Energy Requirements in Artificial Photosynthesis
acceptable and what is not.[90]
The utilization of the J–E curves to describe a PEC is so The representations of the J–E curves as shown in Figure 9a
convenient that it has been overwhelmingly borrowed by most provide a good platform to discuss the energy requirements in
studies aimed at understanding and improving the perfor- photocatalytic and/or PEC reactions. In a photocatalytic reac-
mance of the photoelectrodes. When treated as being gener- tion, to power the overall reactions, one would need a total
ated by an equivalent circuit of electronic components, the data energy (i.e., the difference between the hole energy level and
can be analyzed in a similar fashion to how one would analyze the electron energy level) no less than the sum of the standard
an electronic circuit. It thus opens up opportunities to use free energies of the reaction (ΔGΘ) and the activation energies
(Ea) of the oxidation and the reduction reactions (Figure 9b).

That is,
E ≥ ∆G Θ + E aR + E aO (4)
Similarly, in PEC, the total solar to chemical energy conver-

sion requires the photoelectrode energy (i.e., the difference
between the hole energy level in the photoanode and the elec-
tron energy level in the photocathode) no less than the sum of
ΔGΘ, the ohmic loss (EO), and the reaction activation energy
(Ea) in anode and cathode,[93] expressed as follows (Figure 9c),
E ≥ ∆G Θ + E aR + E aO + E OR + E OO (5)
The understanding leads us back to the discussions on the

optimum number of light absorbers (Section 2.4). For sim-
plicity, it would be beneficial to have a single light absorber Figure 10. Illustration showing surface of photocatalyst.
that provides the needed total energy (see, for instance,
Figure 9b). As far as water splitting is concerned, it means been extensively investigated on its water oxidation mecha-
that the bandgap of the light absorber needs to be >1.6 eV.[94] nisms.[96] To date, two water oxidation mechanisms on rutile
A more practical value would be 2.0 eV given that reasonable TiO2 have been discussed, namely the nucleophilic attack (NA)
reaction rates are needed, which would add additional kinetic mechanism and the redox photooxidation (RP) mechanism. In
overpotential requirements.[89b] Such a wide gap light absorber the NA mechanism, photogenerated holes are trapped by triply
is only capable of harvesting the UV portion of the solar spec- coordinated oxygen on the surface. Some of them diffuse to the
trum. Even with perfect quantum efficiency (100%), the overall bridging O at step, kink, or terrace sites. Water oxidation is con-
solar-to-chemical energy conversion efficiency would be low. sidered to initiate from NA by a water molecule (Lewis base) to
Because of this consideration, we see that having multiple light a surface trapped hole (Lewis acid) at the bridging O, followed
absorbers as shown in Figure 9c is more beneficial, where a by TiO bond breaking to form TiO·HOTi (Figure 11a).[96a]
narrow band gap light absorber can be combined with a rela- The RP mechanism is proposed to initiate water oxidation by
tively wide band gap one, to provide the overall energy needs interfacial transfer of photogenerated holes to H2Oads, resulting
while covering the solar spectrum more broadly than any single in the formation of OHads· radicals (Figure 11b).[96c] Although
light absorber can do. different at the molecular level, the two mechanisms share sev-
eral important common features. First, water oxidation is initi-
ated at the bridging oxygen site to form surface bound hydroxyl
5. Surface Chemistry of Photocatalysts species (TiOH·, or TiO·HOTi). Second, they both involve
the formation of surface-bound peroxide species. Third, proton
When photocatalysts in solution are illuminated, photogen- is coupled to electron transfer to play key roles in water oxi-
erated charges may transfer across the solid/electrolyte inter- dation, especially in pH < 13 conditions. More on this point
face to promote chemical reactions. They may also recombine will be discussed next. There is another phenomenon caused
within the body and/or on the surface of the photocatalysts. by this unique interaction of TiO2 with water under light irra-
As is true in most heterogeneous catalysis, the catalyst/reac- diation, the photoinduced hydrophilicity, which is most often
tant interface is of paramount importance.[95] The continuous attributed to the structural change of the TiO2 surface under
supply of reactants to the photocatalysts, the diffusion of the light.[97] Although it is proposed that the photoinduced hydro-
products away from the reaction sites, and the regeneration of philicity may be a consequence of photocatalytic decomposition
the photocatalysts are all important considerations to ensure the of surface contaminants, surface decomposition should not be
successful functionality of the system (shown in Figure 10). In the only cause of photoinduced hydrophilicity since complete
recognition of this aspect, we next examine the photocatalyst/ decomposition of contaminants has been reported to not nec-
electrolyte interface. Our goal is to understand the chemistry essarily lead to photoinduced hydrophilicity.[97a] Further sup-
nature of this interface and provide insight into how to opti- porting this conjecture is that photoinduced hydrophilicity can
mize the photocatalyst for more efficient photocatalysis. also be achieved when the surface contaminants are still pre-
sent.[98] From these discussions we see that researches on water
oxidation and photoinduced hydrophilicity should benefit from
5.1. Interactions with Water these previous surface studies of TiO2.
In parallel, the interactions between hematite (α-Fe2O3) and
To date most photocatalytic reactions are conducted in aqueous water have received significant attention. Peter et al. investi-
solutions. The interactions between the photocatalysts and gated PEC water oxidation by hematite.[99] It was revealed that
water play important roles in different photocatalytic reactions, surface holes accumulate in the form of oxidized surface state.
such as water splitting, pollutant degradation, and CO2 reduc- The oxidized surface state was later ascribed to high valence
tion. For instance, as the most studied photocatalyst, TiO2 has Fe = O species.[100] Zhao and co-workers investigated the key
Figure 11. a) Schematic representation of the NA mechanism. Reproduced with permission.[96a] Copyright 2014, American Chemical Society. b) Sche-
matic representation of the RP mechanism. Adapted with permission.[93b] Copyright 2011, Elsevier.
role of protons in water oxidation on hematite surface.[101] The mechanism during the interfacial hole transfer process. It
large H/D kinetic isotope effect (KIE) values suggested that was highlighted that the addition of buffer plays an important
electron transfer from water to the oxidized surface state was role in tuning the interfacial proton transfer to improve water
accompanied by proton transfer to solvent water along the splitting performance of hematite. Recently, Hamann group
hydrogen bond at pH < 12 (Figure 12). That is, water oxidation reported a detailed study by operando PEC infrared measure-
proceeded according to a concerted proton-electron transfer ments.[102] Their results showed direct evidence of the forma-
tion of FeIV = O intermediates produced from the first hole-
transfer reaction on hematite surface.
As discussed above, PCET plays important roles in water oxi-
dation in both natural photosynthesis and artificial photosyn-
thesis systems such as TiO2 and hematite surface. Moreover,
PCET is also crucial in other photocatalytic redox chemistries.
For example, in CO2 photoreduction, the negative potential of
the first electron transfer from CO2 to CO2− (E0 = −1.90 V vs
NHE) makes the reduction of CO2 thermodynamically unfa-
vorable.[103] The presence of protons together with CO2 on the
surface of photocatalyst was found to lead to multiple proton-
coupled electron transfer processes with significantly reduced
potential requirement to bypass the formation of CO2−. The role
of protons in CO2 photoreduction was investigated by experi-
ments and theoretical calculations.[104] As shown in Figure 13,
the initial stage was competitive electrons transfer from TiO2
to CO2 and protons. The process resulted in the breaking
of OCO bound and the attachment of a H atom to form
HCOO−. The overall process corresponded to a two-electron,
one-proton transfer process. The following consecutive elec-
Figure 12. KIE values of hematite photoanode in H2O and D2O at 1.2 V
tron/proton transfer led to the formation of methoxyl radicals,
(vs RHE) at various pH levels and electron-proton transfer mechanisms which were directly detected by EPR.[104] The PCET process at
for oxidation of (left) H2O and (right) OH−. Reproduced with permis- the initial stage further supports the critical role of protons in
sion.[101] Copyright 2016, American Chemical Society. CO2 photoreduction.
Figure 13. Mechanism of photoreduction of CO2 to methoxyl radical on TiO2 in the presence of water. Reproduced with permission.[104] Copyright
2011, American Chemical Society.
5.2. Interactions with Reactants oxidation by trapping photogenerated valence band holes, hence
the direct transfer (DT) mechanism. In contrast, chemisorption
For organic molecule/gas reactants related reactions, it is of of benzene on TiO2 surface in acetonitrile was not favored. Phy-
great importance to understand the reactant adsorption on sisorbed benzene on TiO2 was observed to be photooxidized
the surface of the photocatalyst. The surface interaction plays via an indirect transfer (IT) mechanism by the photogenerated
a crucial role in the photocatalysis mechanism. It was discov- terminal −Os− radicals (Figure 14b). For phenol, it could both
ered that different interactions of TiO2 with formic acid, ben- chemisorb and physisorb on TiO2 (Figure 14c,d). Its photooxi-
zene, and phenol resulted in different oxidation mechanisms dation mechanism was found to depend on the solvent used.
of these molecules.[105] For instance, formic acid strongly chem- When dissolved in water, phenol was photocatalytically oxidized
isorbed on TiO2 in water (Figure 14a), resulting in direct photo via a direct-indirect mechanism. The IT photocatalytic oxidation
mechanism led to reaction rates one order of magnitude higher
than that by the DT mechanism. The difference was due to the
competition between water and phenol in binding with TiO2
adsorption sites. When H2O was replaced by acetonitrile, the
reaction rates due to the IT mechanism remained unchanged.
The reaction rates due to the DT mechanism, on the other
hand, were increased by 2 orders of magnitude because the
interaction between the solvent (acetonitrile) and TiO2 was now
negligible.
In photocatalytic reactions involving gaseous reactants, it is
critical to adsorb the gas molecules onto the photocatalyst sur-
face to promote favorable redox reactions and to suppress the
competing ones. For instance, in photocatalytic CO2 reduction,
the difficulty to adsorb gaseous CO2 reactants to the photo-
catalysts and the thermodynamically unfavorable one-electron
reduction of CO2 result in a generally low yield of products. Liu
et al. proposed five adsorption modes to investigate the inter-
action between CO2 molecules and the surface of Zn2GeO4
using density functional theory (DFT).[106] It was found that dif-
ferent facets of the photocatalyst favor different CO2-adsorbed
structures, depending on the adsorption energy in each mode.
It was proposed that CO2 chemisorbed on catalysts with three
structures (Figure 14e): (1) oxygen coordination structure
with oxygen donating electrons to surface Lewis acid centers;
(2) Carbon coordination structure with carbon gaining electrons
from Lewis base centers; (3) Mixed coordination structure with
carbon gaining electrons and oxygen donating electrons.[107]
The chemisorption of CO2δ − changed CO2 geometry from
linear structure to a bent form, which featured a lower barrier
for accepting an electron since the LUMO level decreased as
the molecule bended.
Researchers have studied how to promote chemisorption of
Figure 14. a−d) Interaction modes of different reactants on TiO2: formic CO2 through surface active sites such as active metal Cu and
acid chemisorption (a), benzene physisorption (b), phenol chemisorp- oxygen vacancies.[108] It was reported that Cu acted as an active
tion (c), and phenol physisorption (d). Solid line: covalent bonding; site for CO2 adsorption, thus enhancing the photocatalytic
dashed line: weak interactions such as Van der Waals forces. Reproduced
CO2 reduction efficiency.[108a] In situ FTIR (Fourier transform
with permission.[105] Copyright 2014, American Chemical Society. e) The
three possible structures of partially charged CO2δ − adsorbed on cata- infrared spectroscopy) spectra of Cu-added MOF photocatalyst
lysts. Reproduced with permission.[107a] Copyright 2016, The Royal Society with asymmetric stretching vibration νas(OCO) of the “end-
of Chemistry. Reproduced with permission.[107b] Copyright 2006, Elsevier. on” and “C-coordination” coordination states supported the
chemisorption of CO2, whereas no CO2 signal was observed on active surfaces, which would mean less stability against photo-
MOF photocatalyst without Cu. CO2 adsorbed on the surface of corrosion. How to minimize charge and product recombination
SrTiO3 was also studied, where Ti4+ ions in SrTiO3 were sub- on the surface of the photocatalyst in contact with a solution is
stituted by other metal ions with smaller electronegativity.[109] not a trivial task either. These considerations underscore why
SrTiO3 doped with Co ions showed enhanced CO2 adsorption it has been exceedingly difficult to find a single material that
and photocatalytic CO2 reduction activity. At the same time, it can satisfy all the above-listed requirements at the same time.
was widely reported that surface states such as oxygen vacan- Realistically, most successful photocatalysts studied to date fea-
cies on the surface of photocatalysts might act as CO2 adsorp- ture wide bandgaps so they are inherently low efficiency.[114]
tion active sites, leading to enhanced photocatalytic activity for Many of them show fast charge recombination in the bulk and/
CO2 reduction.[108b] or on the surface. Combined with slow surface charge transfer
kinetics, these photocatalysts can only deliver a small portion of
the photogenerated charges for desired chemical conversion. In
5.3. Interactions with Photogenerated Species the meanwhile, poor long-term stability caused by self-degrada-
tion is another serious issue that limits further development of
In a typical photocatalytic reaction, the relative binding strength photocatalysts for large scale, long-term commercial implemen-
of the reactants, intermediates, and products to the photocata- tations.[115] To address these issues, researchers have exploited
lyst surface is of critical importance. For example, Guo et al. the idea of combining different components, each specifically
investigated the photocatalytic dissociation of partially deuter- designed to meet one or two aspects of the considerations,
ated methanol (CD3OH) and water on TiO2 (110).[110] It was for the achievement of the overall properties.[116] For example,
found that the dissociation of CD3OH began with O−H dis- additional light absorbers, co-catalysts, and/or protection layers
sociation first and then followed by C−D dissociation to finally have all been studied.[117] Increasingly, we see that the inte-
form CD2O. Two factors were important to the successful dis- grated system resembles that of the natural photo synthesis
sociation of CD3OH to CD2O. The first factor was the high bar- machinery (Figure 15).
rier for the D atom to jump back to the adsorbed CD2O. The
second factor was the easy desorption of CD2O product from
on TiO2 (110) surface. This body of research supports that facile 6.1. Forms and Effects of Integrated Systems
desorption of photocatalytic products helps promote forward
reactions. Another example concerns the study of WO3. It was 6.1.1. Combination with Additional Semiconductors
widely reported that bare WO3 exhibited poor PEC water oxi-
dation stability.[111] Lewis et al. revealed that the photocurrent While the materials for individual redox reactions, e.g., water
decrease of WO3 in HClO4 was due to the binding of pho- oxidation, water reduction, and CO2 reduction, are numerous,
togenerated ClO4· on WO3, which blocked the active site for those that can power the overall reactions involving both oxida-
water oxidation.[111b] More recently, graphitic-C3N4 (g-C3N4) tion and reduction are rare, let alone examples that are efficient
receives significant attention owing to its excellent water reduc- for the overall process under visible light illumination. The idea
tion activity for hydrogen evolution.[112] However, when used of combining two (or more) light absorbers offers an opportu-
for full water splitting, g-C3N4 exhibits poor activity due to the nity to break this barrier by offering high enough photovolt-
poisoning effect by photogenerated H2O2 on g-C3N4.[113] It was ages (Figure 9b,c) by absorbing complementary regions of the
found that when co-catalysts that can promote H2O2 decom- solar spectrum. The gradient of the internal potentials gener-
position are present, the performance of overall water split- ated by different absorbers create a driving force to guide the
ting by g-C3N4 is greatly improved.[113] These results highlight one-way charge flow within the integrated system, similar to
the importance of the interactions between photocatalyst and how charges are separated in the natural photosystem. Below,
adsorbates in photocatalysis. we examine various strategies falling in these considerations in
more details.
6. Integrated Photocatalyst System

In a simplistic view, a good photocatalyst
should meet at least three requirements
simultaneously, namely efficient light absorp-
tion (ideally in the visible range), high pho-
tocatalytic activity, and good stability against
photocorrosion. These considerations often
lead to complex, sometimes conflicting, prop-
erty expectations from the photocatalysts. For
instance, to drive redox reactions, we desire
large enough bandgaps. But the bandgap
should also be small enough so as to absorb Figure 15. Illustration showing natural photosynthesis system: a) and artificial integrated
broadly in the solar spectrum. Similarly, for photocatalyst system, b) light absorber combined with additional light absorber, co-catalyst,
high photocatalytic activities, we desire highly and passivation layer.
Figure 17. Energy band diagram of Cu2O a) and Cu2O/ZnS b). The band
edge positions of Cu2O are shown in pale blue solid line and the Fermi
level of Cu2O is in pale blue short-dashed line. Reproduced with permis-
Figure 16. Illustration of charge separation in a favored heterojunction. sion.[86] Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
R: chemicals in reductive reactions, O: chemicals in oxidative reactions.
Wider light absorption by multiple absorbers: The idea is to Separation of incompatible redox reactions: As shown in
couple a narrow bandgap semiconductor (or a visible-light Figure 16, a combined photocatalyst involving two separate
absorbing molecular photocatalyst) with a wide bandgap host light absorbers makes it possible to guide photogenerated holes
semiconductor. While it can be the other way around, more and electrons to different directions. This opens up opportuni-
often we see that a small bandgap light absorber is added to ties to separate incompatible redox reactions. By contrast, the
a wide bandgap photocatalyst. This way, photons in the short close vicinity of the reduction and oxidation sites on a nanoscale
wavelength region of the solar spectrum are absorbed by the photocatalyst increases the chances of product crossover and
main photocatalyst, and those of lower energies can be taken recombination. Consequently, the overall efficiency is reduced.
advantage of by the narrow bandgap co-absorbers. Examples of Such an issue can be circumvented by an integrated system as
this design can be found in TiO2-based systems, where small shown in Figure 16. In a way, the integrated photocatalyst can
bandgap materials such as CdSe (1.7 eV for bulk, 2.4 eV for be regarded as a micro-PEC cell with well separated photo oxi-
quantum dot) have been introduced for the absorption of vis- dative and photo reductive sites. A derivative of the design is to
ible light.[118] Another example is the combination of TiO2 with avoid direct contact of the two light absorbers, in which case a
PdS.[119] mediator would be needed to facilitate charge transfer between
Better charge separation: The direct contact between two the light absorbers. Importantly, the mediator can be a solid or
light absorbers results in the formation of a heterojunction. a redox couple in the solution.[122] Again, we wish to draw the
Using two-semiconductor photocatalysts as an example, we connections between the improved design with the Z-scheme
illustrate an optimized band diagram of such a heterojunc- in the natural photosystem.
tion in Figure 16. Electrons in the CB of semiconductor A
are driven to the CB of semiconductor B and holes from the
VB of semiconductor B to that of semiconductor A, driven by 6.1.2. Combination with Co-Catalyst
an internal built-in field. The net result is the separation of
photogenerated charge facilitated by the heterojunction.[120] Highly active electrocatalysts as co-catalysts have been popu-
Greater photovoltages: As discussed in Section 4.5, to drive the larly explored as a means to reduce overpotential requirement
overall reactions, the total input energy should be no less than so as to reduce the overall photovoltage requirements from the
the sum of the changes of the standard free energies and activa- light absorbers.[88] Another way to think about the benefit of co-
tion energies of both the oxidation and the reduction reactions. catalysts is that they facilitate forward charge transfer and thus
Consider PEC water splitting as an example. A single semicon- reduce charge recombination. Nevertheless, the integration of
ductor with a bandgap of 1.6–2.0 eV could in principle enable co-catalyst introduces new solid/solid interfaces between the
the overall reaction.[89b,94] However, due to the low photovoltage light absorber and the co-catalyst, resulting in complications
(as limited by the difference between the flatband potential of that only start to receive due attention.[123] Below, we sum-
the semiconductor and the electrochemical potential of the marize some of the key roles played by co-catalysts within the
desired reactions) and the less-than-ideal band edge positions, photocatalytic context.
a significant external bias potential is necessary.[121] Previous Lower activation energies: The primary motivation of inte-
research by us has shown that the situation can be greatly grating co-catalysts is to exploit their efficient catalytic proper-
improved by depositing a thin layer of an additional semi- ties in much the same way as how they are being used in elec-
conductor to form a buried junction.[86] We studied the effect trocatalysis. The presence of co-catalysts on a light absorber is
of a thin layer of n-type ZnS on p-type Cu2O and confirmed supposed to provide active sites with lower activation energies
the increase of band bending of Cu2O. The photovoltage was for surface reactions. For example, Pt is known for its relatively
increased correspondingly from 0.60 V to 0.72 V, as evidenced low activation energies for H2 evolution.[124] The integration
by the positive shift of the open circuit potential under light of a semiconducting light absorber with Pt has been shown to
irradiation (Figure 17). greatly facilitate photocatalytic hydrogen evolution.[125]
Better charge separation: Co-catalysts affect charge separation photocatalytic efficiency by the plasmonic effect. Briefly, a plas-
in the light absorber in several different ways. For example, monic metal harvests the photon energy through localized sur-
noble metals such as Ag,[126] Pt,[127] and Pd[128] have been studied face plasmon resonance oscillations.[133] The energy can then be
and shown to reduce the possibility of electron-hole recombina- transferred to the photocatalyst through at least three different
tion by serving as an electron sink. In other words, upon illu- mechanisms, direct electron transfer,[134] plasmon induced
mination, these metals provide favorable sites for electrons to resonant energy transfer,[135] and local electromagnetic field
concentrate, thereby better separating electrons from holes. enhancement.[136] Interested readers are suggested to read sev-
For another example, some metal oxides as water oxidation eral recent reviews on this topic.[137] We list this category here
catalysts can facilitate charge separation by decreasing charge because many of these plasmonic materials are also known
recombination when combined with light absorbers.[86b,129] In co-catalysts, such as metals including Au,[138] Ag,[139] Pd,[140]
the meanwhile, direct contact between co-catalysts and a light Cu,[141] Al,[142] and non-metals including Cu2−xSe,[143] Cu2−xS,[144]
absorber creates new interfaces. The nature of these inter- WO3−x[145] and each of them features unique resonant photon
faces plays an important role in defining the charge separation wavelengths. Importantly, the resonant photon wavelength
capability.[130] For instance, MoS2/CdS with intimate junctions of the plasmonic nanoparticles can be tuned by varying their
exhibited better photocatalytic hydrogen evolution performance sizes, shapes, and material compositions. It provides a versatile
than Pt/CdS, even though Pt was known to feature superior route to photocatalyst design for better utilization of the entire
catalytic activity toward electrocatalytic HER than MoS2.[131] solar spectrum.
Another example is the surface energetics change of hema-
tite/co-catalyst compared to bare hematite photoanode. Due
to Fermi level pinning caused by “surface states”, the degree 6.1.3. Combination with Surface Passivation Layer
of band bending did not change with the increase of applied
voltage, meaning that the increased voltage did not help to While in general stability is of paramount importance to catal-
achieve better charge separation.[86h] We deposited NiFeOx co- ysis, this is particularly true for photocatalysis because the inclu-
catalyst on hematite and carried out energetic measurements sion of light facilitates the formation of energetic intermediates
of hematite with and without NiFeOx co-catalyst.[86a–c] The exist- that can easily corrode the photocatalysts. As discussed above,
ence of NiFeOx on hematite could alter surface energetics by the degradation of photocatalytic performance is mainly due
removing surface states. These results indicated that with the to chemical corrosion by surface accumulated species such as
help of NiFeOx the band bending of hematite increased com- high concentration of OH− and self oxidation/reduction caused
pared with bare hematite, leading to better charge separation. by photogenerated holes/electrons. The idea of introducing sur-
The results highlighted the crucial effect of designing and con- face passivation layer is to isolate the light absorber from these
trolling the interface for optimized charge transport in an inte- reactive species, so as to avoid direct photocatalytic reactions on
grated photocatalyst system. the light absorber surfaces. In a way, this can be regarded as
Improved stability: In many cases, photocatalysts suffer from a brute force stabilization strategy, which has proven effective
activity degradation due to self-oxidation/reduction caused by for improving the stability of a large number of systems. Some
accumulated holes/electrons. The deposition of co-catalysts on added benefits of the passivation layer include reduced surface
the light absorber surface protects the photocatalyst from self- recombination by removing surface recombination centers.
decomposition by effectively removing holes/electrons from the Consequently, the overall charge separation within the photocat-
light absorber. As a result, photostability is effectively enhanced. alyst is also improved. For example, recent work by us revealed
Note that such a protection is fundamentally different from pas- that the surface oxidation of Ta3N5 during PEC water oxidation
sivation which relies on retarding surface chemical reactions. results in a thin layer of oxynitrdie (<3 nm).[146] Although thin,
More on this point will be discussed in the next section. A good this layer almost completely suppressed the photoactivity of
example of this effect can be found in a recent study by Li et al. Ta3N5. MgO was shown effective as a barrier to separate Ta3N5
where the authors developed ferrihydrite co-catalysts as “holes from H2O and, hence, reactive O species. Such a protection
storage layer”.[132] They reported that this layer suppressed layer led to significantly better stability as well as improved fill
hole-induced self-oxidation of Ta3N5 and improved the stability factors, supporting that better charge collection was enabled
of Ta3N5 by a large margin. Another mechanism by which by reduced surface recombination. In another investigation,
photocurrents can decay is the accumulation of products/ researchers quantitatively evaluated the surface recombination
by-products/intermediates on the surface of the photocatalyst, of ZnO and ZnO/TiO2 via in situ spectroscopic methods.[147] It
blocking the active sites for continuous reactions. Co-catalysts was revealed that 37% of the IPCE (incident photon-to-current
that can help decompose these species will improve the stability efficiency) was lost through bulk and surface recombination in
effectively. In this category, carbon nanodots have been recently ZnO. A thin layer TiO2 on ZnO reduced the surface recombina-
shown to enhance the g-C3N4 photocatalytic water splitting sta- tion by 14% and enhanced the photocatalytic efficiency.
bility by decomposing hydrogen peroxide, which is the oxida-
tion product of water by g-C3N4.[113] The surface accumulation
of H2O2 is recognized as the key reason for the quick decay of 6.2. Challenges Presented by Integrated Photocatalyst Systems
g-C3N4’s performance in overall water splitting.[113]
Broader light absorption: Apart from the above mentioned There remain challenges towards efficient enough photo
advantages, another unique positive consequence of the inte- activity in the integrated systems. Some of the issues are listed
grated light absorber/co-catalyst system is to enhance the below.
6.2.1. Blocking Active Site processes, particularly those concerning charge transfer, is still
lacking. Such knowledge is important because it holds the key
When a light absorber is combined with an additional semi- to further improvement. In this section, we aim to provide a
conductor/co-catalyst/passivation layer, some of the inherently general account on recent studies designed to fill in this knowl-
active sites on the light absorber would be blocked by the guest edge gap. Two key electrochemical techniques, IMPS and PEIS,
materials. This is particularly true when the coverage of the are at the heart of our discussions. The goals of these studies
guest materials is excessive. For example, Bai et al. designed are to collect quantitative information on the kinetics of the
two different phases of MoS2: MoS2(1T) and MoS2(2H) to inte- photocatalytic reactions. Of them, the theory behind IMPS
grate with TiO2.[148] TiO2-MoS2(1T) showed enhanced photo- considers the kinetics of two main competing processes, for-
catalytic properties, whereas TiO2-MoS2(2H) exhibited lower ward charge transfer and backword charge recombination, their
photocatalytic performance than bare TiO2. The difference was rate constants denoted as kt and kr, respectively (Figure 18).[157]
attributed to the blocking of active sites on the surface of TiO2 The net charge transfer efficiency is then defined as kt/(kt + kr).
by MoS2(2H) that are not active. In another example, Ag/BiVO4 PEIS considers each part of the photocatalytic process as an
with 4 wt% Ag loading showed decreased photocatalytic activity electronic element in a combined circuit.[92a] For example, the
than those with lower Ag loading.[149] resistance of charge transfer can be described as a resistor
and the capacitive behaviors of an interface may be modeled
as a capacitor. Thus, the electronic behavior of the overall reac-
6.2.2. Shielding Light Absorption tion can be mathematically modeled by an equivalent circuit,
the details of which can be probed by alternating current (AC)
The second challenge of integrated photocatalyst is decreased techniques developed for the understanding of electronics.
light absorption due to the shielding effect caused by the guest The parameters of each electronic element yield quantitative
materials. Many experimental studies demonstrated that when information of the corresponding process(es). A third tech-
combined with materials such as carbon nanotubes,[150] gra- nique, transient absorption spectroscopy (TAS), has also been
phene,[151] and NiSx,[152] the composite materials showed lower employed to study the charge dynamics on time scales between
light absorbance. In recent years, researchers have started a few picoseconds to milliseconds.[158] For the ease of discus-
to develop optically transparent guest materials, in the hope sions and to keep in sync with the rest contents of this review,
to minimize undesired light shielding. A number of opti- we focus our attention to the semiconducting photocatalyst and
cally transparent co-catalysts have been reported, including co-catalyst combinations.
Co(OH)2/Co3O4,[86g] NiOx,[153] and NiFeOx.[154] These optically
transparent materials have proven promising guest materials
for photocatalysis. 7.1. Kinetics of Photogenerated Electrons
For efficient utilization of photogenerated electrons, noble

6.2.3. Mismatch Between Light Absorbers and Guest Materials metals are popularly studied as co-catalysts or plasmonic deco-
rations or both. For instance, it was reported that Au nanoparti-
As is true in most junctions, the introduction of additional cles on TiO2 expanded the light absorption through plasmonic
material components increases the chances of recombination effect.[159] Transient absorption kinetic analysis and PEC studies
for a number of reasons. Aside from structural defects, the revealed that hot electrons generated by the plasmonic effect
energetics of the interface need to be carefully engineered to
minimize mismatches, which could set up charge traps for
significant recombination. For instance, when Fe2O3 was com-
bined with TiO2, the conduction band minimum and valence
band maximum of the latter straddle those of Fe2O3, meaning
that photogenerated electrons and holes promptly transfer to
Fe2O3 from TiO2.[155] The net result is that little benefit was
gained by having TiO2 in this system. In another work, it was
revealed that photoactive Cu2O octahedras became inactive
after the deposition of ZnO.[156] The result was explained by
unfavorable band alignment at the interface between ZnO (101)
and Cu2O (111).
7. Kinetic Information of Photocatalyst/

Co-Catalyst Systems
Figure 18. Scheme showing competition between charge transfer and
Recent works in designing composite photocatalysts showed
surface recombination. jh: hole flux into the surface; kt: first order rate
enhanced photocatalysis performance. However, most of the constant of charge transfer; kr: first order rate constant of surface recom-
photocatalysis studies focused on the overall photo-to-chemical bination. Reproduced with permission.[157] Copyright 2011, The Royal
conversion efficiency. A clear understanding of the detailed Society of Chemistry.
transfer from Au directly to the conduction band of TiO2. The typically require multiple oxidation/reduction steps to enable
lifetimes of these electrons were shown 1–2 orders of mag- the desired photocatalytic reactions. In such a system, the elec-
nitude longer than those of the conduction band electrons in tron transfer from semiconductor to co-catalyst can be more
TiO2. Nevertheless, the true role of noble metal nanoparticles complicated. For instance, a cobaloxime H2 evolution catalyst
in such systems remains the subject of debates.[160] For one (CoP) covalently attached to TiO2 was revealed to undergo
reason, the reported enhancements due to the plasmonic effect double reduction of CoP from CoIII to CoI in order to drive the
were limited. Furthermore, how the introduction of metal to proton reduction to hydrogen.[161] Transient absorption results
a semiconducting light absorber influences the nature of the suggested that the reduction from CoIII to CoII and CoII to CoI
metal-semiconductor junction can be complicated. In a study were very different. The first reduction step of the co-catalyst
focused on the TiO2/Ag interface, Kamat et al. investigated the by electrons from the semiconducting light absorber could pro-
electron behaviors across and found that Ag enhanced the pho- ceed quickly, but the second reduction, which was desired for
toelectrochemical performance TiO2 by capturing and storing hydrogen evolution, appeared to be 105 times slower. In other
photogenerated electrons with an apparent negative shift of the words, the molecular co-catalyst was efficient in extracting pho-
Fermi level (Figure 19a).[160] togenerated electrons from the light absorber to complete the
Along this line, these authors also investigated charge first step of reduction, but faced a RDS of the second electron
transfer behaviors in CdSe/Pt and CdSe/Pt/MV2+ systems transfer.
(Figure 19b).[158a] Transient absorption spectra revealed that
the rate of electron transfer from CdSe to Pt nanoparticles
was 1.22 ± 0.19 × 109 s−1. In the CdSe/Pt/MV2+ system, both 7.2. Kinetics of Photogenerated Holes
MV2+ and Pt were good electron acceptors but they worked in
different ways. The electron transfer rate constant from CdSe Compared with proton reduction, water oxidation is far more
to MV2+ was 1.7 ± 0.11 × 1010 s−1, which was faster than elec- difficult due to its 4-electron, 4-proton nature. It is regarded as
trons transfer to Pt. But the electrons transferred to the sur- the limiting factor in solar water splitting research. As such, the
face bounded MV2+ were quickly scavenged by Pt as the low- detailed understanding of the kinetics of photogenerated hole
lying Fermi level of Pt made it a good electron acceptor. These transfer in water oxidation reactions is of critical importance. It
results suggest that Pt in this system acts as an electron sink to has indeed received significant attention.
enhance charge separation.
In addition to metal co-catalysts, molecular co-catalysts have
been studied in photocatalyst systems. Different from bare 7.2.1. Enhanced Charge Transfer
photocatalysts and inorganic co-catalysts, molecular co-catalysts
Despite the obvious reason to introduce water oxidation co-cat-
alysts for faster reaction kinetics, direct evidence that supports
mechanisms aligned with this motive is few in the literature.
As a rare example that does support this mechanism, hema-
tite photoanode was coated with a thin layer of cobalt oxide
catalyst.[86g] The PEC water oxidation performance was signifi-
cantly enhanced as evidenced by the 100–200 mV cathodic shift
of the onset potentials. The authors employed PEIS to investi-
gate the role of the catalyst. Two key features can be seen from
the data shown in Figure 20. First, the deposition of cobalt
oxide catalyst reduced the magnitude of the peak capacitance
connected to the surface catalytic reactions. It supported that
better charge transfer decreased the need for high surface hole
concentration. Second, the potential at which the surface capac-
itance peaks was cathodically reduced by 100 mV, suggesting
that a lower overpotential was obtained. Together, these results
prompted the authors to conclude that the cobalt oxide catalyst
functioned as a true catalyst by facilitating charge transfer.
7.2.2. Reduced Charge Recombination

Figure 19. a) Scheme showing equilibration between TiO2 and Ag: under
UV irradiation (left) and in the dark (right). Reproduced with permis- In a somewhat interesting twist, there are more reports support
sion.[160] Copyright 2011, American Chemical Society. b) Scheme showing that the role of the water oxidation co-catalysts actually improve
reactions in the CdSe/Pt/MV2+ system. Dashed line: electrostatic interac- the performance of the overall reaction by reducing recombi-
tions; red arrow: charge transfer between MV+ and MV2+; blue arrow:
charge transfer between MV2+ and Pt; green arrow: oxidation of Ptn− by
nation. Peter et al. pioneered kinetic and mechanistic studies
holes from CdSe; yellow arrow: direct photogenerated electron transfer on PEC water oxidation by hematite. They suggested that the
to Pt; black arrow: oxidation of MV+ radicals by holes from CdSe. Repro- apparent “catalytic” effect by surface treatments with Co(II) was
duced with permission.[158a] Copyright 2010, American Chemical Society. in fact owing to the suppression of surface recombination but
conclusions were drawn on other photoelec-

trode materials such as TiO2 as well.[86a] The
understanding was further cemented by
quantitative kinetic measurements by IMPS,
where the kt was shown to remain slow with
the introduction of NiFeOx, but the kr was sig-
nificantly reduced (>10 times).[86b]
7.2.3. Both Reduced Charge Recombination and

Enhanced Charge Transfer
The works by Hamann et al. on the Co-Pi/

hematite system provided further insights
Figure 20. a) Equivalent circuit of water oxidation on photoelectrodes. b) Representative Css
for a bare hematite photoanode (black dot symbols) and a hematite deposited with 1 ALD into the detailed mechanism.[86j] They con-
cycle Co(II)/Co3O4 (blue square symbols). Reproduced with permission. [86g]
Copyright 2013, firmed that Co in the Co-Pi co-catalyst indeed
American Chemical Society. underwent oxidation from Co(III) to Co(IV),
acting as a true catalyst, even though this
not to the acceleration of charge transfer.[86e] Li et al. reported may not necessarily lead to an increase in the charge transfer
that Ni(OH)2 “hole storage layer” captured the photogenerated kinetics. Through careful PEIS studies they were able to verify
holes from hematite to reduce electron-hole recombination at that water oxidation predominantly take place on the surface
the interface of hematite and IrOx catalyst.[86d] In particular, of Co-Pi but not on hematite. Consistent with later works by
cobalt phosphate (Co-Pi) as water oxidation co-catalyst has Gamelin et al. as discussed above, their results suggested the
received significant attention. Correspondingly, there have been thickness of the Co-Pi catalyst was of importance to the roles
a large number of studies on their mechanisms when combined the catalyst plays. From a different angle, Gamelin et al. varied
with photocatalysts. Gamelin et al. were the first to report that the morphology of the hematite substrate and found that water
the addition of Co-Pi significantly enhanced the performance of oxidation could either take place on Co-Pi or directly on hema-
hematite.[162] But it was not until recently did the authors show tite, depending on the applied potentials.[86k] These studies
the PEC water-oxidation kinetics actually slowed upon addition together highlight the complexities of the light absorber/co-
of Co-Pi to the α-Fe2O3 surface.[163] What improved the overall catalyst interfaces. They serve as an important basis for future
performance is the greater suppression of surface electron-hole studies of similar systems. Recently, we studied effects of two Ir-
recombination as compared to charge transfer. As a result, the based water-oxidation co-catalysts on a hematite photoelectrode
overall charge transfer efficiency was improved (Figure 21). systematically.[86f ] It was found that heterogenized molecular Ir
As far as the mechanism of CoPi on hematite is con- co-catalyst could speed up the hole transfer rate but recombina-
cerned, the works by Barroso et al. are especially notable. They tion rate remained unchanged (as shown in Figure 22). For het-
studied the kinetics using transient absorption spectroscopy in erogeneous IrOx co-catalyst, it not only enhanced charge transfer
the micro to millisecond range.[164] No evidence of faster hole but also reduced surface recombination by replacing hematite/
transfer, as expected from shorter hole lifetimes, was observed. electrolyte interface. These results focusing on kinetics at the
Instead, they observed longer lived holes, which the authors semiconductor/electrolyte interface, clear understanding of the
attributed to direct evidence of reduced recombination. In other role of co-catalyst provides a basis for further improvement.
words, the main role of the Co-Pi co-catalyst was to “passivate”
the surface of hematite for reduced recombination but not to
8. Conclusions and Perspectives
“catalysze” the surface for faster charge transfer. Later, the same
group extended similar studies to a variety of different surface 8.1. Conclusions
modifications, including CoOx and Ga2O3 overlayers.[158b] The
last example is particularly worth noting because Ga2O3 is not Photocatalysis is different from conventional catalysis in the
known as an active water oxidation catalyst, and yet it improved function of light, which provides energy to meet the activation
the performance of water oxidation by hematite, supporting the needs in a large number of chemical reactions. It enables pro-
authors’ conjecture as stated above. cesses that are either difficult (such as pollutant oxidation) or
On a parallel system, we have embarked on a study of NiFeOx impossible (such as thermodynamaically uphill reactions like
as a water oxidation co-catalyst. It enabled one of the most CO2 reduction) under normal conditions. The inspirations
notable cathodic shifts in hematite PEC water oxidation perfor photocatalysis can be traced back to the understanding of
formance, up to 400 mV.[86c] To study the true reasons for the natural photosynthesis. Within this context, a summary of
dramatic performance improvement, we carried out a series of popularly studied photocatalytic systems is presented. The
systematic studies focused on probing the thermodynamic equi- examples summarized here include particulate photocatalysts
librium potentials and found that the cathodic shift can be fully and complex integrated systems. The variations in their forms
accounted for by the shifts of the Fermi levels. That is, the per- and complexities notwithstanding, the fundamental governing
formance improvement was entirely due to better charge separa- principles are shared. Further understanding and optimization
tion as a direct result of reduced surface recombination. Similar of these existing photocatalysts are likely to benefit from the
Figure 21. Schemes showing the charge transfer and charge recombination pathways of α-Fe2O3 photoanodes a) and α-Fe2O3 deposited with a thin
(optimized) b), and a thick c) Co-Pi layer on their surfaces. Reproduced with permission.[163] Copyright 2016, The Royal Society of Chemistry.
summary. In describing the varying systems, we paid particular absorbing materials will likely to play a critical role in future
attention to how the functional components in a photocatalyst research on photocatalysis. Indeed, past efforts have identified
affect each other. For instance, we discussed how the introduc- a large number of inorganic materials, including TiO2, ZnO,
tion of co-catalyst may change the charge separation capabilities SrTiO3, Si, WO3, Fe2O3, and Ta3N5.[24c,87b] Similar to efforts in
of the light absorber, and whether the co-catalyst truly acts as a the past, while the most important considerations will still be
catalyst in a conventional sense. Despite the over 4 decades of the bandgap, which defines the ultimate efficiency of these
intense efforts, photocatalysis research still in its infancy in its light absorbers, factors such as stability will receive increasing
development. Much is still needed for photocatalysis to make attention. In addition to composition, more attention should
impacts to the real world. Below, we present our perspectives be paid to the nanoscale features as charge behaviors in rele-
on how the field may benefit in the years to come. vant length scales have been recognized as important factors,
as well.[165] Though highly robust, a major challenge faced by
8.2. Perspectives crystalline inorganic semiconductors is that their properties
are difficult to tune at wish.[166] As far as property tenability
8.2.1. New Light Absorbing Materials is concerned, organic semiconductors seem more intriguing
but are less explored for photocatalysis. Among those that
The first step of photocatalysis is light absorption. For this have been studied within the context of photocatalysis, g-C3N4
reason, we believe the search for high-performance light with a two-dimensional porous structure may be the most
Figure 22. Schemes showing the kinetic models for bare hematite a), hematite with het-WOC (heterogenized molecular Ir catalyst) b), and hematite
with IrOx c). d–f) IMPS data of bare hematite, hematite with het-WOC, and hematite with IrOx. Charge transfer rate constants (ktrans) are shown in (d),
charge recombination rate constants (krec) shown in (e), and charge transfer efficiencies are shown in (f).
investigated.[112c,167] Despite its promises, however, monolayer enable the development of new reaction routes. In addition,
g-C3N4 remains far less active than what is theoretically pre- investigations into the photocatalytic pathways are important.
dicted.[167] In addition, its low-cost, large-scale preparation has They are expected to reveal the fundamental mechanisms and
yet to be optimized. Another organic semiconductor that has to guide further performance improvement. Efforts focused on
piqued research interests for photocatalysis is hexagonal boron understanding the mechanisms will be especially critical when
nitride (BN). Although an inherent insulator itself (Eg>5 eV), studying photocatalysis involving multi-electron processes
BN has been predicted by DFT calculations to feature desired (such as CO2 reduction), where kinetics and product selectivity
electronic band structures for photocatalysis when doped with are highly dependent on the reaction pathways. Furthermore,
C.[168] Indeed, experimental results demonstrated that ternary studies focused on understanding the reaction mechanisms
BCN compounds exhibited catalytic activity toward H2 evolu- are expected to shed light on the identification of catalytically
tion and CO2 reduction under visible light irradiation better active sites on photocatalysts. Such understanding is particu-
than TiO2 (P25) and g-C3N4.[168b] Preliminary results like these larly important to organic semiconductors, whose active sites
on g-C3N4 and BCN are encouraging as they open doors to are poorly understood to date.[169] For instance, the surface
researches on light (and earth-abundant) elements. In addition, terminations and defects sites on organic semiconductors are
polymeric semiconductors such as linear polymers (e.g., poly- considered active toward photocatalysis, but critical details are
p-phenylene) and conjugated porous polymers show promising missing. The lack of information makes it exceedingly diffi-
photocatalytic activities.[166,169] A key advantage offered by these cult to further optimize these emerging photocatalysts. Toward
organic semiconductors is the opportunity to guide experi- this end, collaborations between experimentalists focused on
mental efforts in tuning their properties by theoretical and/or understanding the mechanisms by techniques such as oper-
computational calculations. Of course, how to achieve high car- ando spectroscopic tools and theorists skilled with calculations
rier mobility and adequate stability under photocatalytic condi- are expected to yield new and exciting insights that will serve
tions will be challenges that future research has to address. as guidelines for materials scientists to design and synthesize
new, better materials.
8.2.2. Multi-functional Layer

8.2.4. Understanding the Interface of Different
As we have learned from natural photosystems, the require- Material Components
ments for photocatalysts are indeed incredibly complex. The
chances of satisfying all these considerations on a single mate- Similar to the above mentioned understanding on the surface
rial are little. As such, we anticipate material design to play a of the photocatalysts, mechanistic understanding at the inter-
critical role in future photocatalysis research. In particular, faces of different components, including the light absorber,
we expect the introduction of multifunctional layers, for the co-catalyst, passivation layers, will be critical. This is because
purpose of improving the catalytic activities and also for the increasingly we realize that the complex requirements for the
purpose of stabilizing the otherwise quickly decaying photo- photocatalytic functionality are most likely realized on complex,
catalysts, will become more and more common. For instance, integrated systems. How these different components influ-
the introduction of thin transition metal on top of Si has proven ence each other will become more and more important. For
effective in enhancing the PEC stability and activity of Si.[170] instance, it is not clear whether and/or how the energy is sup-
In this approach, the metal layer provides protection and the plied (through heat or light) changes how a catalyst functions.
surface metal oxide serves as a co-catalyst (toward water oxida- In addition to the energetics at the interface of different mate-
tion). Approaches like this, however, also introduce issues such rial components, how the various other parameters influence
as late Eon due to the relatively low work function of the transi- the photocatalytic performance is understudied when com-
tion metal. Future investigations are expected to keep searching pared with similar influences at the surfaces. For example, the
for materials that can provide the desired functionalities while details of the interfaces at the molecular level are poorly under-
addressing the related issues. stood for most systems. The electronic states introduced by
chemical impurities and lattice mismatches need to be mapped
out in greater detail in order to further optimize the interfaces.
8.2.3. Catalysis Understanding How dynamic changes to the components, which is often the
case for co-catalysts during chemical reactions, may change
Photocatalysis, despite its uniqueness, is first and foremost the nature of the interface is yet another important scenario to
heterogeneous catalysis. Mechanistic understanding, espe- consider.
cially that at the molecular and atomic levels, is key to further In conclusion, we see that photocatalysis is by no means a
developments. Whether and how the reactions proceed with new field. It draws inspirations from natural photosynthesis
and without light on the surface of the photocatalyst remain and promises a direct route to photo-to-chemical energy conver-
poorly understood. Advances in this direction will likely propel sion and pollutant removal. At the present stage, the challenges
efforts to optimize photocatalysts at the molecular levels. Spec- that limit its development are by and large issues connected to
troscopic and computational studies will likely play increasingly materials. These issues are complex and difficult because they
more important roles in this direction as tools to understand simultaneously concern two distant fields of optoelectronics
the system at this scale remain limited. Insights generated by and catalysis. The challenges nonetheless also provide a fer-
these studies will be critical to further development and may tile field for research, to test different hypotheses and material
design principles. What has been discussed in this article only [16] a) S. Hu, M. R. Shaner, J. A. Beardslee, M. Lichterman,
represents a general overview of the vast field, with a focus on B. S. Brunschwig, N. S. Lewis, Science 2014, 344, 1005; b) Y. Li,
inorganic photocatalysts. It is, nevertheless, important to note L. Zhang, A. T. Pardo, J. M. G. Calbet, Y. Ma, P. Oleynikov,
that we believe the underlying principles discussed are generic O. Terasaki, S. Asahina, M. Shima, D. Cha, L. Zhao, K. Takanabe,
J. Kubota, K. Domen, Nat. Commun. 2013, 4, 2566.
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Review

Photocatalysis: Basic Principles, Diverse Forms of

the sunlight to power thermodynamically uphill reactions such

Dunwei Wang graduated

12H2O + 12NADP+ + 48hv → 6O2 + 12NADPH + 12H+ (1)

What are not represented in Figure 1 are the dark reactions:

6CO2 + 12NADPH + 18ATP + 12H+

where pi is inorganic phosphate.[15] Of these chemical reac-

and NADP+/NADPH: −0.32 V vs NHE, where NHE stands for

Figure 4. Steps in photocatalytic reaction process. R: chemicals in reduc-

separated by a reasonable distance (greater than a few hundred

4.1. Photosynthesis by Plants

In plant photosynthesis, the energy delivered by sunlight is

Different from plants, microalgae are single cell micro­

system. While the oxidants and reductants may co-exist, as

4.4.1. Performance Evaluation of PEC Redox Reactions

The basic experimental setup of a PEC experiment can take a

(Ea) of the oxidation and the reduction reactions (Figure 9b).

Similarly, in PEC, the total solar to chemical energy conver-

The understanding leads us back to the discussions on the

6. Integrated Photocatalyst System

For efficient utilization of photogenerated electrons, noble

7. Kinetic Information of Photocatalyst/

7.2.2. Reduced Charge Recombination

conclusions were drawn on other photoelec-

7.2.3. Both Reduced Charge Recombination and

The works by Hamann et al. on the Co-Pi/

8.2.2. Multi-functional Layer

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Different from plants, microalgae are single cell micro