Review

Cite This: ACS Nano 2019, 13, 9811−9840 www.acsnano.org

A Critical Review on Energy Conversion and

Environmental Remediation of Photocatalysts
with Remodeling Crystal Lattice, Surface, and
Interface
Jinming Luo,† Shuqu Zhang,*,‡ Meng Sun,§ Lixia Yang,‡ Shenglian Luo,‡ and John C. Crittenden*,†
†
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Brook Byers Institute for Sustainable Systems and School of Civil and Environmental Engineering, Georgia Institute of Technology,
828 West Peachtree Street, Atlanta, Georgia 30332, United States
‡
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University,
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Nanchang 330063, Jiangxi Province, People’s Republic of China

§
Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520-8286, United States

ABSTRACT: Solar energy is a renewable resource that can

supply our energy needs in the long term. A semiconductor
photocatalysis that is capable of utilizing solar energy has
appealed to considerable interests for recent decades, owing to
the ability to aim at environmental problems and produce
renewal energy. Much effort has been put into the synthesis of a
highly efficient semiconductor photocatalyst to promote its real
application potential. Hence, we reviewed the most advanced
methods and strategies in terms of (i) broadening the light
absorption wavelengths, (ii) design of active reaction sites, and
(iii) control of the electron−hole (e−-h+) recombination, while
these three processes could be influenced by remodeling the
crystal lattice, surface, and interface. Additionally, we individ-
ually examined their current applications in energy conversion
(i.e., hydrogen evolution, CO2 reduction, nitrogen fixation, and oriented synthesis) and environmental remediation (i.e.,
air purification and wastewater treatment). Overall, in this review, we particularly focused on advanced photocatalytic
activity with simultaneous wastewater decontamination and energy conversion and further enriched the mechanism by
proposing the electron flow and substance conversion. Finally, this review offers the prospects of semiconductor
photocatalysts in the following three vital (distinct) aspects: (i) the large-scale preparation of highly efficient
photocatalysts, (ii) the development of sustainable photocatalysis systems, and (iii) the optimization of the photocatalytic
process for practical application.
KEYWORDS: semiconductor photocatalyst, solar energy, energy conversion, environmental remediation, photocatalytic activity,
large-scale preparation, sustainable, practical application

S ustainable development requires the growth of practical

and clean energy to avoid subsequent environmental
problems.1 Solar energy is a clean energy and is generally
accepted as an abundant, endless, and renewable source that
meets the current and future energy needs of humans.2,3 The
semiconductor photocatalyst is an ideal candidate in solar
energy applications, as it can efficiently utilize solar energy with
simultaneous energy conversion and environmental remedia-
tion. The energy conversion aspect mainly includes hydrogen
evolution, CO2 reduction, nitrogen fixation, and oriented
synthesis to fulfill the sustainable strategy. Additionally, its
environmental remediation applications are more likely to focus
on air purification (i.e., NOx and volatile organic compound
(VOC) conversion) and wastewater decontamination (i.e.,
organic pollutant degradation), which has been reported by
recent studies.7,12 Hence, the development of efficient artificial
photocatalysts is highly desirable, and it is deemed to be “Holey
Grail of Chemistry”.4,5
However, ever since the Fujishima−Honda effect of the TiO2
photoelectrode was first reported in 1972,6 none of the
photocatalysts developed have completely satisfied all the
practical requirements. The ideal photocatalysts need to fulfill
Received: May 11, 2019
Accepted: July 31, 2019
Published: July 31, 2019

© 2019 American Chemical Society 9811 DOI: 10.1021/acsnano.9b03649

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Figure 1. State-of-the-art methods and strategies for improved photocatalytic energy conversion and environmental remediation.
several key factors, such as (i) photogenerated charges with long
lifetimes, (ii) an appropriate band gap, (iii) full range of sunlight
utilization, and (iv) low cost, high efficiency, and stability.7−9
The previous strategies have mainly focused on morphologies
and structural feature regulation, which cannot fully satisfy the
current demand of designing efficient and stable photocatalysts.
By constructing abundant active sites and tuning the electron
structure, the photocatalytic performance can be enhanced and
stabilized.10 Meanwhile, it is accepted that the photocatalytic
activity is governed by thermodynamics and kinetics of
reaction.11 Hence, a comprehensive analysis of light harvesting,
active sites, and carrier generation/separation should be further
explored, combined with thermodynamics and kinetics to design
an efficient and stable photocatalyst that can realize the practical
application requirements.
Overall, we have detailed the state-of-the-art methods and
strategies that have enhanced the photocatalytic performance
and the photocatalytic application achievements in two aspects:
energy conversion and environmental remediation (Figure 1).
Finally, suggestions are provided on how to promote the
practical application of the solar-driven photocatalyst.
STRATEGIES TO IMPROVE PHOTOCATALYTIC
PERFORMANCE
Photons can excite the photocatalyst when incident solar energy
is great than or equal to the photocatalyst band gap (Eg). As a
result, electrons can be excited from the valence band (VB) to
the conduction band (CB), and holes are left on the VB.
Generally, the photocatalytic reactions involve the following
four major steps: (i) light harvesting and absorption, (ii)
photogenerated carrier (e−-h+ pairs) generation, (iii) separation
and migration of carriers, and (iv) electron or hole utilization for
reduction or oxidation. In recent decades, researchers have
devoted tremendous efforts to exploiting photocatalysts with a
broader absorption spectrum of solar energy (step i), increasing
the quantity and quality of active sites (step ii), and separating
the charge efficiently in the bulk and interface of the
photocatalyst system (step iii) by a series of designs,
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constructions, and modifications.12,13 Hence, enhancing light
absorption, development of active sites, and the building of a
tunnel for efficient charge separation need to be simultaneously
fulfilled to maximally utilize solar energy.
Enhance and Broaden Light Absorption. For efficient
utilization of solar energy, it is still a great challenge to explore
semiconductor photocatalysts, which can capture a wide
spectrum, from ultraviolet (UV) to visible light and even the
near-infrared (NIR) region, to enhance and broaden light
absorption.14−17 The Lambert−Beer law and the absorption
coefficient determine the ability to absorb light for photo-
catalysts. The light to be trapped will be lost because light can
reflect directly from a smooth and flat surface. However, a rough
surface can improve light scattering. Surface modifying or
alteration and structure design of photocatalysts can optimize
light utilization since it can enhance the distribution degree of
incident light via light scattering.18 This compels researchers to
devote themselves to nanotechnology and even single atoms.
Surface Reconstruction. Surface Hybridization. Because
surface modification can largely optimize light utilization, the
combination of one semiconductor with other semiconductors
or cocatalysts was always the first choice by most researchers. As
a result, the light absorption ability has been strengthened
accompanied with better longevity for the composite photo-
catalysts. TiO2 was the first photocatalyst to be reported back in
1972, and it has been well studied and applied in some areas;
therefore here we take TiO2 as an example. In the case of TiO2,
many methods were implemented to enhance the photocatalytic
activity of TiO2 by broadening its light absorption ability. Still
today, researchers usually combine metal oxides with a series of
photocatalysts, such as C3N4,19−21 CdS,22,23 Bi2MoO6,24
BiVO4,25 ZnIn2S4,26,27 graphene,28,29 and MoS2.30,31 Surface
reconstruction can be achieved by hybridizing the metal oxides,
which can broaden and enhance photon absorption abilities.
Specifically, we thought that a new band gap was formed by the
introduction of other semiconductors, which was responsive to
longer wavelengths in order to improve its light-scattering
ability.
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Meanwhile, surface plasmons during the hybridization
process are another common technique that has been widely
used to enhance photocatalytic absorption. The resonance in the
absorption takes place at the plasmon frequency when the
dielectric function approaches zero. Intense electric fields at the
surface of metal nanoparticles will be generated when light
irradiates metal nanoparticles at the plasmon frequency.32
Different materials have different resonance frequencies, which
can be tuned by modifying the sizes and morphologies of the
materials.33−36 The plasmon resonance can be moved into the
visible range from the UV range by tuning the nanoparticles’ size
to nanosize or to a single atom.37 Analogously, plasmon
resonance can be shifted from the visible to the infrared
wavelength by further minimizing the size. Meanwhile,
assembling the metallic nanoparticles (i.e., Au, Ag, Pt, Pd, or
alloys) on the semiconductor’s surface can largely enhance and
broaden the light absorption using the surface plasmon
resonance (SPR) effect of the metallic nanoparticles.38−42 It
was accepted traditionally that SPR was only induced by metallic
nanoparticles, while Yang et al. reported that MoS2/TiO2
heterostructures can act as nonmetal plasmonic photocatalysts
by regional growth of MoS2 inside TiO2 nanotubes for efficient
photocatalytic hydrogen evolution.17 This research greatly
enriched the field of SPR. Therefore, controlling the confined
growth of semiconductors is a good way to produce the SPR
effect.
Surface Hydrogenation. It should be noted that the poor
light absorption ability is due to the unacceptably wide band gap.
Adjusting the band gap to improve photoadsorption could be
achieved by bandgap engineering. In recent years, it was
reported that the band gap could be narrowed by hydrogenation
on the surface of the semiconductor to enhance the light
absorption capability.43−48 For example, Mao et al. increased the
light absorption with black hydrogenated TiO2 nanocrystals.43
Huang et al. focused on black titania with an amorphous shell/
crystalline core structure (TiO2−xHx@TiO2) assisted by hydro-
gen plasma, which revealed intense light absorption abilities in
the visible and infrared range.44 Furthermore, the absorption
edge and intensity of hydrogenated ZnO,45 γ-TaON,46
Cu2WS4,47 In2O3,48 etc., were broadened and enhanced
immensely as well after hydrogenation. Hydrogenation could
give rise to disorder of surface atoms to improve light scattering,
enhancing and broadening the light absorption.
Structure Design. To achieve an efficient light absorption
ability, constructing a photocatalyst with an on-limits nano-
structure to increase the illumination area can take full advantage
of reflection and refraction. A hierarchical assembly of the
nanomaterials with different dimensions is a crucial way to
fabricate an on-limits nanostructure that can exhibit superior
performance.49,50 Researchers have built the structure vertically,
hierarchically, omnidirectionally, and architecturally in reason-
able space configurations of components and meticulous
designs.11,51−56 For example, Xu et al. hierarchically decorated
zero-dimensional (0D) CdS nanoparticles on the hybrids of
one-dimensional (1D) ZnO nanorods (NRs) grown vertically
on two-dimensional (2D) graphene to enhance its overall
photocatalytic performance.57 Hierarchical nanostructures
include ternary components of 0D, 1D, and 2D. Additionally,
graphene oxide acts as a flexible substrate for the formation of
ZnO NR arrays (Figure 2a); meanwhile, it is reduced in the
process of ZnO growth. Furthermore, CdS nanoparticles were
clearly doped on 1D ZnO NRs (Figure 2b and c), which is a
typical hierarchical structure that exists vertically. This
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Review
Figure 2. (a) Schematic illustration of hierarchical nanostructures of
binary CdS nanostars@ZnO NRs and ternary CdS@ZnO NRs@
RGO. (b and c) SEM images of ternary CdS@ZnO NRs@RGO-5%
(RGO: 5 wt %). Reprinted with permission from ref 57. Copyright
2014 Wiley-VCH.
nanostructure showed an excellent optical light absorption
property, which is mainly due to this structure having an
excellent performance regarding reflection, refraction, and
scattering of photons.
Developing Active Sites. It is accepted that the catalysis
occurs on the active sites generally, while the active sites exist in
the edges, unsaturated steps, terraces, kinks, and/or corner
atoms. Meanwhile, the quantity of carriers is directly determined
by the quantity and quality of the active sites.58 The exploration
of methods to develop active sites is unceasing. From
conventional viewpoints, a larger surface area was usually
regarded as having rich active sites. In fact, we believe that the
design of an efficient photocatalyst system needs to develop the
active sites more adequately and completely by basal engineer-
ing and quantum size engineering from lengthwise and
breadthwise, respectively (Figure 3).
Basal Engineering. On one hand, the 2D catalyst with atomic
thickness has attracted extensive attention and has become the
optimum foundation of next-generation materials due to its
novel photochemical properties, etc.59 Lengthwise, the bulk
catalyst can be peeled into few-layer or monolayer nanosheets to
increase the ratio of exposed surface atoms to develop active
sites.
The general principle of exfoliating layered catalysts is by
weakening interlayer forces, either through an enlargement of
the interlayer distance by intercalation or slippage of the layer
along the in-plane direction by assistance of an external force.60
Currently, many strategies have been well set up to exfoliate
various layered photocatalysts, such as (i) mechanical
exfoliation,61,62 (ii) intercalated expansion and exfoliation,63,64
and (iii) etched exfoliation.65 Regarding (i) mechanical
exfoliation, Wang et al. reported that graphitic carbon nitride
(g-C3N4) nanosheets with 2 nm thickness were obtained via
simple sonicated exfoliation from bulk g-C3N4.66 Ball milling is
another mechanical means to exfoliate bulk photocatalysts, and
it can produce layered catalysts in large scale, which is one of the
most notable advantages.67,68 Regarding (ii) intercalated
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Figure 3. Strategies to develop active sites by basal engineering and quantum size effect.

expansion and exfoliation, the interlayer spacing and van der

Waals force of a layered catalyst is enlarged and broken by means
of an intercalator, such as tetrabutylammonium and propylam-
monium hydroxide63 and n-butyllithium (n-BuLi).64 Regarding
(iii) etched exfoliation, MXenes, with chemical formula Mn+1Xn
(n = 1, 2, 3), are a type of 2D transition-metal carbides and
nitrides, where M represents a transition metal (Ti, Ta, Nb, V,
Mo) and the X can be C and/or N.65 Thin MXenes are typically
obtained by chemical etching from bulk MAX phases,69 which
cannot be assisted by general exfoliating means due to strong
covalent bonds among of the ions and layers. It was reported that
isolated 2D Ti3C2 could be obtained through hydrofluoric acid
(HF) to etch aluminum layers in Ti3AlC2 bulk materials and
intercalation of organic molecules by Naguibet et al. in 2011.65
However, the HF-etched process is not environmentally friendly
and decreases the material performance, especially the
capacitance owing to the inert F terminals.70,71 Recently,
Zhang et al. reported on a high-purity fluorine-free Ti3C2Tx
(T = OH, O) that can be synthesized under alkali conditions,
which is considered to be an innovative method to synthesize
functional MXenes.72 Figure 4. (a) Schematic diagram of a Ni−Al LDH atomic structure.
On the other hand, pores mainly include two types, i.e., (b) After etching by NaOH hydrothermal conditions. (c) β-
stacked pores and in-phase pores. The stacked pores are crucial Ni(OH)2 nanomeshes with uniform in-phase nanopores after the
to preserve a hierarchical and firm construction, which can Ostwald ripening process. (d) Values of the Gibbs free energy
largely enhance the cycling stability of the photocatalyst.73 The variation by DFT calculation of the ΔG of vacancy formation with
different nanopore sizes. (e−h) HRTEM (high-resolution TEM)
in-phase pores give rise to the formation of low-coordinated
images of the morphology evolution of Ni−Al LDH. Scale bars: 5
atoms, edges, terraces, kinks, and corners where the active sites nm ((g) is the β-Ni(OH)2 ultrathin nanomesh). Reprinted with
locate. Previous studies have proved that the construction of in- permission from ref 78. Copyright 2017 Wiley-VCH.
phase pores on ultrathin 2D nanosheets showed enhanced
photocatalytic performance due to more active sites induced by 4d). The larger the vacancy was, the higher the energy required
more in-phase pores, such as ultrathin In2O3 porous sheets,74 in order to form a vacancy-free nanomesh equally. Thermody-
uniform 2D Co3O4 porous sheets,75,76 and BN porous sheets.77 namically, larger pores were more unstable than smaller ones. As
Furthermore, it was an effective strategy to solve the exposure of a result, under the coexistence of larger and smaller pores, the
active sites by constructing ultrathin nanosheets with abundant larger pores tended to shrink and the smaller pores continued to
in-phase nanopores. Xie et al. reported on an etching- be compressed. Finally, nanomeshes with uniform in-phase
intralayered Ostwald ripening process to achieve porous β- nanopore distributions could be produced (Figure 4e−h).
Ni(OH)2 ultrathin nanomeshes to manufacture more active Quantum Size Engineering. Active sites are generally
sites in the basal phase (Figure 4).78 After etching under NaOH situated on low-coordinated edges.58 Hence, reducing the size
hydrothermal conditions, the Al atoms and some Ni atoms to expose and increase the edges can increase the quantity of
surrounded with Al atoms were eliminated from the basal plane, active sites. The bulk catalysts can turn into nanoparticles,
resulting in porous β-Ni(OH)2 nanosheets with different pore quantum dots (QDs), sub-nanoclusters, trimers, dimers, and
sizes (Figure 4b). Last, β-Ni(OH)2 ultrathin nanomeshes with single metal atoms by quantum size engineering (Figure 3).
uniform in-phase nanopores were fabricated (Figure 4c). The Nanoparticles, QDs, and sub-nanoclusters contain multiple
Gibbs energy (ΔG) of vacancy formation with different active centers, but their catalytic activity cannot be ideally
nanopore sizes was calculated by density function theory achieved. Herein, it is necessary to search for well-defined single
(DFT) to demonstrate the Ostwald ripening process (Figure active sites for photocatalysts to improve their performance and
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understand the catalytic mechanisms.79 Accordingly, increasing
the atom-utilization efficiency is the most effective and
reasonable way to use metal resources and facilitate atomic
economy. The ultimate goal of fine dispersion is single-atom
catalysts by downsizing the metal nanostructures, which can be
well distributed on metal active centers. However, the surface
tension of particles markedly increases with size decreases,
which can largely promote their aggregation.59 Inspired by
nanoparticles and QDs anchored on different 2D photocatalysts,
it was necessary to search for an adaptive template to catch single
atoms controllably and efficiently.80−83
Zhang et al. first reported the practical platinum (Pt) single
atom catalyst supported on iron oxide (FeOx), named Pt1/
FeOx.84 Xie et al. reported that the independent single Pt atoms
as an efficient cocatalyst were highly dispersed on g-C3N4 (Pt-
CN) successfully (Figure 5a and b).85 Extended X-ray
Figure 5. (a) HAADF-STEM image of Pt-C3N4. The inset shows the
size statistics of the Pt single atom. (b) Schematic diagram of Pt-
C3N4. (c) Fourier transforms of the Pt L3-edge EXAFS oscillations
over Pt-C3N4, K2PtCl6, and Pt foil. (d) FT-EXAFS curves of
experimental data and fit of the Pt-C3N4. Reprinted with permission
from ref 85. Copyright 2016 Wiley-VCH.
absorption fine structure (EXAFS) spectroscopy confirmed
that isolated Pt atoms were anchored on the g-C3N4 network
(Figure 5c and d). When single-atom Pt was present as the
cocatalyst, Pt-CN showed an excellent photocatalytic H2
generation, which showed 50 times higher pristine g-C3N4.
Furthermore, single Cu atoms acting as a cocatalyst could be
deposited on polymeric carbon nitride (p-CN), which was first
reported recently by Xie et al.86 Meanwhile, in 2016, for the first
time, Du et al. unraveled the path and mechanism of CO2
reduction using single palladium (Pd) and Pt atoms anchored on
g-C3N4 photocatalysts by DFT.87 The individual metal atoms
(i.e., Pd and Pt) functioned as the active sites. In addition,
depositing single-atom catalysts on g-C3N4 can markedly
enhance the light absorption in the visible range. Xiong et al.
also reported a heterogeneous single-atom catalyst for visible-
light-driven high-turnover CO2 reduction.88 Ye et al. successfully
decorated isolated single Pt atoms onto the surface of CdS
nanowires (Pt/CdS), and its structure has been confirmed by
EXAFS spectroscopy and HAADF-STEM images (Figure 6b−
f).89 The DFT results verified that the Pt/CdS structure could
enhance the excited carrier density (Figure 6f−i). The single-
atom cocatalyst with high stability can maximize atom utilization
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Figure 6. (a) Schematic diagram of Pt/CdS atomic structure. (b)
Fourier transform magnitudes of the experimental Pt L3-edge
EXAFS spectra over four samples. (c) TEM images and (e) HAADF-
STEM image of Pt/CdS. (d) Cd, S, and Pt mapping images of Pt/
CdS. (f) Calculated density of states (DOS) and (g−i) the charge
density distribution of the conduction band edge over Pt/CdS, Pt-
NP-CdS, and CdS, respectively. Reprinted with permission from ref
89. Copyright 2018 Elsevier.
and can obviously boost the separation efficiency of e−-h+.
Hence, the overall photocatalytic hydrogen evolution perform-
ance has been greatly enhanced, which is 63.77 times that of bare
nanowires. Li et al. recently reported that bulk copper could
transform to a Cu single atom via directly emitting atoms. This
simple method can be used at industrial levels.90 Hence, it is
reasonable to believe that the trimers and dimers of semi-
conductor photocatalysts could become the next generation of
photocatalysts.
By basal engineering and quantum size engineering from
lengthwise and breadthwise, more edges, unsaturated steps,
terraces, kinks, and/or corner atoms are formed. Increasing the
external atom utilization efficiency is an effective and reasonable
way to use metal resources and facilitate atomic economy.
Finally, the quantity and quality of the active sites can be
improved tremendously.
Separating Charges Efficiently. Semiconductor photo-
catalysts absorb photons to induce photogenerated carriers,
which separate or recombine in the process to reach surface
reaction sites. The efficiency of charge separation determines the
conversion efficiency. In the photocatalytic process, e−-h+ pairs
are generated within several femtoseconds (fs); the time span
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from bulk to reactive sites is hundreds of picoseconds (ps). from the splitting of the Co 3d states (Figure 7a−d). Thus, the
However, the catalytic reaction time between carriers and the photoinduced electrons could easily arise via the d → d internal
adsorbed reactants changes from nanoseconds (ns) to micro-
seconds (μs).91,92 In contrast, photogenerated carriers recom-
bine in the range of ps to ns.93 Particularly, the e−-h+
recombination requires several ps, which is much more rapid
than charge migration and carrier utilization.94 Therefore,
separation of photogenerated carriers that are more effective is
highly desirable.95−98 Hereinafter, the charge separation will be
discussed in the following six different categories: (i) loading
cocatalyst, (ii) doping engineering, (iii) vacancy engineering,
(iv) crystal engineering, (v) interface engineering, and (vi) the
Z-scheme photocatalyst system.
Loading Cocatalyst. The cocatalyst can afford trapping sites
for the photogenerated carriers and promote carrier separation
to improve the performance of the semiconductor photocatalyst,
thus enhancing the quantum efficiency.10 Most importantly, the
cocatalysts deposited on the surface of the semiconductor
photocatalyst accelerate the reactions through lowering the
activation energy.2,3 Many reported studies have confirmed that
the photocatalytic activities can be significantly enhanced by
composing suitable cocatalysts on the semiconductor photo-
catalysts. The cocatalysts mainly include the oxidation
cocatalysts (RuO2,99 RhOx,100 IrO2,101 MnOx,102 CoOx,103
etc.) and reduction cocatalysts (Ru,104 Rh,105 Pd,106 Pt,107,108
Au,109 graphene,110,101 etc.). Two-dimensional cocatalysts are
interesting for researchers to explore and modify.111−115
Furthermore, the transition-metal dichalcogenides (TMDs),
such as MoS2 and MoSe2, representing inexpensive, earth-
abundant, and functional cocatalysts, have been extensively
investigated in recent years. Typically, TMDs were loaded with Figure 7. Calculated DOS of (a) Co-doped In2S3 atomic layer and
graphene with better conductivity,116 and they have shown great (c) bare In2S3. (b) Distribution of charge density of (b) Co-doped
performance. Moreover, owing to the interesting structures of In2S3 and (d) bare In2S3. (e) UV−vis diffuse reflectance spectra and
(f) IPCE over Co-doped In2S3 atomic layer, In2S3 atomic layer, and
TMDs (the existence of a semiconducting phase (2H) and a
bulk In2S3. Reprinted with permission from ref 127. Copyright 2015
metallic phase (1T)), efforts are still being made regarding the Wiley-VCH.
exfoliation of exposed active edges,117 oxygen incorporation,118
construction of S vacancies,119 and phase engineering.120,121
What is more, it is interesting to research if the deposition sites converting of Co atoms, which would allow the possibility of
of cocatalysts can be precise and controllable. achieving higher photoconversion efficiency. Meanwhile, the
Doping Engineering. Heterogeneous doping in the crystal light absorption ability of the Co-doped In2S3-based photo-
lattice is one of the most valid methods to regulate the electronic electrode was definitely improved with observed values from
structure, separating the charges efficiently.122,123 However, the 600 to 2000 nm (Figure 7e). Notably, the incident photon-to-
effect that dopants have on the photocatalyst remains electron conversion efficiency (IPCE) of the Co-doped In2S3-
controversial. Dopants act as the recombination centers for based photoelectrode can reach as high as 46% at 450 nm, which
the photoexcited carriers, which can impede photocatalytic is 2 and 9 times higher than that of the bare In2S3 atomic layer
reaction.124,125 Moreover, the dopant’s type, content, and and bulk In2S3, respectively. What is more, the Co-doped In2S3
distribution also significantly influence the host semiconductor’s atomic layer exhibits an obvious increase in IPCE in wavelength
properties. Consequently, it is of great concern to figure out the ranges between 750−900 and 1500−1750 nm, demonstrating
latent mechanism of dopants and how it can influence the their remarkably improved light conversion efficiency in the
photocatalytic performance. visible range.
Metal Doping. The generation of the impurity levels can be Nonmetal Doping. In addition to metal doping, efficient
achieved by incorporating metal ions into the crystal lattice, charge separation can also be achieved by nonmetal doping.128
which can largely benefit the carrier separation.126−128 It has Oxygen-doped ZnIn2S4 (O-doped ZIS) nanosheets with five S−
been reported that the bulk/surface dopants could result in Zn−S−In−S−In−S layers were prepared by Xie et al. A highly
regulation sites for the separation of e−-h+ pairs and enhance the distorted structure was formed by replacing sulfur atoms with
photocatalytic activities.126 Atomic layers confined with dopant oxygen atoms.129 Due to the adjustment of pristine atomic
are beneficial for determining the role of the dopant on structures by replacing the S atom with the O atom, the
photocatalysis at the atomic level. Co-doped In2S3 atomic layers electronic structure was evidently changed. Based on the DFT
with good dispersity were controllably prepared by Xie et al., calculation, O doping can enhance the density of states (DOS)
which can implement the strategy of lamellar hybrid at the VB maximum (VBM) compared to bare ZnIn2S4,
intermediates.127 Furthermore, the DFT calculations demon- indicating the generation of an enhanced charge density around
strated that the introduction of Co atoms can increase the charge the VBM (Figure 8a−d). Apart from the effect of electronic
density at the CB minimum (CBM), which might be observed structure, O doping can also impact the atomic assignment, and
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Figure 8. Calculated DOS of (a) O-doped ZIS nanosheet and (b) the bare ZnIn2S4. The corresponding charge density distributions on the VBM
of (c) the O-doped ZnIn2S4 nanosheet and (d) the bare ZnIn2S4. (e) K-edge EXAFS oscillation function and (f) the corresponding Fourier
transforms around Zn of the O-doped ZnIn2S4 nanosheets, bare ZnIn2S4, and ZnO. Ultrafast transient absorption spectroscopy (UTAS) of (g)
bare ZnIn2S4 nanosheets and (h) O-doped ZnIn2S4 nanosheets. Reprinted with permission from ref 129. Copyright 2016 Wiley-VCH.
the structure distortion of atoms could be distinguished from the
transmission electron microscopy (TEM) images and further
confirmed by X-ray absorption fine structure spectroscopy
(XAFS) (Figure 8e and f). Furthermore, the average lifetime of
photogenerated electrons in O-doped ZnIn2S4 was increased by
1.53 times compared to bare ZnIn2S4 nanosheets, which was
verified by ultrafast transient absorption spectroscopy (UTAS)
(Figure 8g and h). This phenomenon can further confirm that O
doping can regulate the band gap by atomic arrangement to
separate charges to increase the lifetime of electrons.
Vacancy Engineering. Under ideal conditions, vacancies
confined in lattices have tremendous potential for operating the
electron properties without destroying the pristine lattices and
exposing a high proportion of surface atoms. The electron
properties are generated by modulating the mutual effect
between the intracell and the movement of outer valence
electrons, while the band gap structure, concentration, density of
carrier, and so on are related to the electron properties.64
Therefore, the development of a vacancy-confined semi-
conductor photocatalyst could be the future direction to
regulate the band gap and the migration of photogenerated
carriers, optimizing the overall photocatalytic performance of
photocatalysts.130−132
Anion Vacancy. As one of the anion vacancies, sulfur
vacancies (VS) have been extensively researched since they can
tune the electronic structure to guide the carrier flow.133−137
The role of the anion vacancy was more than that. New
photocatalyst systems could be constructed by induction of an
anion vacancy. For example, MoS2 QDs were induced by VS to
grow on a ZnIn2S4 monolayer (VS-M-ZnIn2S4) selectively to
construct an atomic-level heterostructure that was applied in
hydrogen evolution by our group.138 The VS-M-ZnIn2S4
nanosheets were produced by exfoliating bulk ZnIn2S4 through
n-butyllithium intercalation (Figure 9a). The monolayer
property of VS-M-ZnIn2S4 was measured by atomic force
microscopy (AFM) with a thickness of approximately 1.0 nm
(Figure 9b). The HRTEM image of VS-M-ZnIn2S4 confirmed
that atoms were absent and pores were formed (Figure 9c). The
HRTEM image indicated that MoS2 QDs were located on the VS
area (S vacancy-rich area) of VS-M-ZnIn2S4, which was proven
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by the existence of the {100} facet of MoS2 (Figure 9d).
Moreover, VS-M-ZnIn2S4 showed a strong S electron spin
resonance (ESR) response compared to bulk ZnIn2S4, which
suggested that VS-M-ZnIn2S4 had many S vacancies (Figure 9e).
By analyzing In 3d and Zn 2p of VS-M-ZnIn2S4 and ZnIn2S4, it
further suggested that the S vacancies were around the Zn atoms
not the In atoms (Figure 9f and g). The regional charge density
calculations demonstrated that the charge density of the Zn
atom without S atoms was more positive than the other Zn
atoms (Figure 9h). The VS on the Zn facet served as electron
traps and regulated the electron cloud.139−141 Under illumina-
tion, the VS on the Zn facet served as electron traps, which can
enrich the e− on the Zn facet to restrict vertical migration of e− to
recombine with h+. Last, separation of photogenerated charge
carriers was efficient because of e− transferring by means of the
Zn−S intimate interface. On the other hand, the h+ was left on
VS-M-ZnIn2S4 (Figure 9i). Hence, VS can not only efficiently
achieve spatial photogenerated charge separation but also act on
constructing smart photocatalytic hydrogen reaction systems.
Cation Vacancy. Besides anion vacancies, cation vacancies
are another effective way to build attractive electronic
nanostructures due to their diverse electron configuration and
orbit.142 For the first time, the freestanding orthorhombic-
BiVO4 (o-BiVO4) atomic layers with vanadium vacancies (VV)
were successfully synthesized via Xie et al.143 A V-defective
orthorhombic-BiVO4 atomic layer and a perfect o-BiVO4 atomic
layer along the {001} orientation are shown in Figure 10b and d.
The introduction of VV generated a defect level and induced a
higher hole concentration near the Fermi level, revealed by DFT
calculation; the result is that the e− can be easily transited into
the CB under solar irradiation. Moreover, the higher DOS at the
VB edge was due to the engineering-modified VV (Figure 10a
and c). Positron annihilation spectrometry (PAS) was
performed to investigate the species and amounts of defects in
o-BiVO4 (Figure 10e). The higher lifetime of the positron
suggested that a higher concentration of VV existed. It is
precisely because of the existence of VV that the carriers’ lifetime
was increased from 74.5 ns to 143.6 ns, as demonstrated by time-
resolved fluorescence emission decay spectra (Figure 10f). The
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Figure 9. (a) Scheme of the preparation of MoS2QDs@VS-M-ZnIn2S4. (b) AFM image of VS-M-ZnIn2S4 (the inset shows the height profiles of
lines 1 and 2). (c) False-color image of the HRTEM image. (d) HRTEM image of MoS2QDs@VS-M-ZnIn2S4. (e) ESR spectra of prepared
samples. High-resolution XPS spectra of (f) In 3d and (f) Zn 2p in MoS2QDs@VS-M-ZnIn2S4, VS-M-ZnIn2S4, and bulk ZnIn2S4. (h) Charge
density distributions of the side view structural model of VS-M-ZnIn2S4 (the inset shows the corresponding distribution of the charge density at
the edge of the conduction). (i) Schematic illustration of the hydrogen generation over MoS2QDs@VS-M-ZnIn2S4. Reprinted with permission
from ref 138. Copyright 2018 American Chemical Society.

theoretical and experimental data demonstrated that VV could
separate carriers efficiently.
Crystal Engineering. Facet Engineering. The active sites of
reduction and oxidation reaction are probably situated close to
each other on the photocatalyst surface. Under the circum-
stances, recombination of photogenerated carriers may occur
before they migrate to active sites of reduction and oxidation
reaction. It has been reported that different crystal facets of
semiconductor photocatalysts with low symmetry can separate
photogenerated carriers.144
Monoclinic BiVO4 showed increased light absorbance, benign
photocatalytic performance, and nontoxic properties. Thus, it
was chosen as a typical photocatalyst to figure out the facet
functionality regarding the reduction and oxidation catalytic
sites by tailoring the deposition methods (Figure 11).145,146 As
9818
shown in Figure 11a, BiVO4 is a polyhedron. Under irradiation,
the photogenerated electrons are abundant on the {010} facets
to participate in the reduction reaction. Reduction cocatalysts
(Au, Pt, Ag, etc.) were easily and individually anchored on the
{010} facets by photodeposition. The holes are abundant on the
{110} facets to participate in the oxidation reaction. Oxidation
cocatalysts (Co3O4, MnOx, PbO2, etc.) tended to be deposited
on the {110} facets selectively. The photodeposition of metals
proceeded with water as a hole scavenger. The photodeposition
of MnOx or PbO2 on BiVO4 was performed by using IO3− as the
electron acceptor (Figure 11b−d). All these results clearly
revealed that the photogenerated e− and h+ tended to migrate on
the {010} and {110} facets of BiVO4, respectively. This could
lead to reduction and oxidation reactions occurring on the {010}
and {110} facets, respectively. Facet engineering can steer
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Figure 10. Calculated DOS of (a) the V-defective orthorhombic-
BiVO4 atomic layers and (c) the perfect orthorhombic-BiVO4
atomic layers along the {001} orientation. Atomic structure of (b)
the V-defective orthorhombic-BiVO4 atomic layer and (d) the
perfect orthorhombic-BiVO4 atomic layer. Defect characterization
for the orthorhombic-BiVO4 atomic layers with rich and poor Vv. (e)
Positron lifetime spectrum. (f) Time-resolved fluorescence
emission decay spectra. Reprinted with permission from ref 143.
Copyright 2017 American Chemical Society.
Figure 11. (a) Schematic diagram of selective anchoring of the reduction and oxidation cocatalysts on the {010} and {110} facets of BiVO4. (b)
Photodeposition of noble metals on the {010} facet, (c) photodeposition of metal oxides on the {110} facet, and (d) co-instantaneous
photodeposition of metal and metal oxides on the different facets. Reprinted with permission from ref 145, copyright 2014 Royal Society of
Chemistry, and ref 146, copyright 2013 Springer Nature.
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photogenerated carriers orderly, anisotropically, and spatially by
separating catalytic sites of reduction and oxidation reaction.
Meanwhile, facet engineering can also help to control nucleation
and selectively grow the activated sites.
In fact, the facets of a semiconductor that can accumulate
charges would change photocatalytic reaction because they can
change the surface state of the semiconductor. Recently, Chen et
al. have reported photoexcited charge transport and accumu-
lation in anatase TiO2.147 They have indicated that anatase TiO2
can be further developed if the directions of charge separation
can be clearly understood. Specifically, the reduction and
oxidation reactions were favored on the crystal facets where
charge accumulation was preferred. They gained comprehensive
knowledge of the charge transport and preferred facets of charge
accumulations by analyzing electronic band structure calcu-
lations of various facets in the k space of anatase TiO2 (Figure
12A). The calculation showed that the order of the preferred
facet for oxidation reaction is as follows: {110} > {445} > {001}
> {100} > other facets (including {101}) and {000} > {001} >
{110} > {112} > {101} > other facets for reduction reaction.
Meanwhile, the results of surface electronic structure gained
from surface energy were different from the results based on
calculation. The oxidation facet preferred the following order:
{110} > {445} > {001} > {100} > other facets (including {101}
facet). The reduction facet tended to the order {001} > {110} >
{112} > {011} > {101} > other facets. This showed the
comparisons of charge aggregation trends for the bulk/surface
calculations with experimental observations (Figure 12B).
Figure 12B(a) illustrates that the accumulated trend of holes
and electrons was {110} > {445} > {001} and {001} > {110} >
{112}, respectively, which was based on the assumption that all
the related facets were exposed on the surface of the anatase
TiO2 in the bulk calculation. The {001} and {101} were
favorable for holes and electrons, respectively, according to the
experimental observation (Figure 12B(b)), which differed from
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Figure 12. (A) Calculated electronic structure of anatase TiO2 (on the CB, points 1−6 represent G {000}, Z {001}, {110}, {112}, R {011}, and
M {101}, respectively. On the VB, points 1−6 represent {110}, M {110}, G {000}, {445}, Z {001}, and {100}, respectively). (B) Schematic
diagram of the photoexcited charge accumulation on various facets of the (a, c, d) bulk and (e) surface calculations and (b, e) experimental
observations of anatase TiO2. Reprinted with permission from ref 147. Copyright 2018 American Chemical Society.

Figure 13. (a) HRTEM image of the nanotwin structure in a crystal; the insets show the FFT pattern. (b) Schematic illustration of the nanotwin
boundary in a zinc blende (ZB) nanocrystal to shape a ZB−WZ−ZB homojunction. (c) Mechanism for separation of photogenerated carriers
over Cd0.5Zn0.5S with a malposed crystal lattice. (d) Schematic diagram of the parallel homojunctions in Cd0.5Zn0.5S; black arrows and pink
squares represent the fragments of the ZB and WZ. Reprinted with permission from ref 148, copyright 2011 Royal Society of Chemistry, and ref
149, copyright 2013 Springer Nature.

the results of surface calculation. On the basis of the bulk
calculation, Figure 12B(c) displays the ending facets on the
surface for charge aggregation, and the electrons and holes were
9820
preferred on the {001} and {110} facets, respectively. However,
if the surface ended with {001} and {101} facets, both electrons
and holes could be aggregated on (001) (Figure 12B(d)), while
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in experimental observations, if the surface ended with {001}
and {101} facets, holes were favored on the {001} facet and
electrons on the {101} facet, consistent with the results of
surface calculations (Figure 12B(e)).
Therefore, photoexcited charges might tend to transport
following the order of the bulk electronic structures by
considering their thermodynamic energy. Nevertheless, the
direction of charge transport and the exposure of ultimate facets
are responsible for the charge accumulation and would result in
the surface energy alteration. An insightful understanding of the
charge transport and accumulation properties of a semi-
conductor can benefit the probing of the photocorrosion
phenomenon. This could benefit the synthetic procedure for
preparing highly active and stable photocatalysts to enhance the
photocatalytic performance, which was highly desirable.
Phase Engineering. A crystal facet can steer the e− and h+
flow in a macrostructure. Moreover, on a microstructure, the
management of crystal phase is crucial to the flow of
photogenerated carriers.148
For example, a twin crystal refers to a mirror-symmetric
orientation relationship (or a specific orientation relationship)
that is formed along a common plane between two crystals (or
two parts of a crystal); these two crystals are known as the
“twins”, and this common plane is known as the twin plane.
Some reports have stated that the twin structure could
regionalize the distribution of photogenerated charges.149
Typically, nanotwins Cd1−xZnxS with strip-like lattice structures
(Figure 13a) have a tunnel for free charge transport, and it can
also prevent the recombination of carriers.148 The photo-
generated carriers could be efficiently separated due to the
formation of a bending band edge and the “‘back to back”’
barrier potential (Figure 13b). Further research revealed that a
malposed crystal lattice was formed between the zinc-blende
(ZB) and wurtzite (WZ) segments, generating the enormous
homojunctions in a specific orientation (Figure 13c).149 A
similar type-II malposed crystal lattice was acquired in
Cd0.5Zn0.5S through linear estimation (Figure 13d). The upshift
of both CB and VB of the WZ segment can result in the efficient
separation of both photoexcited e− and h+ compared to the ZB
segments. The phase engineering with the “twin structure” could
regionalize and vectorize the charge transfer to enhance the
photocatalytic performance.150,151
Interface Engineering. The photocatalytic performance does
not solely depend on the properties of the photocatalysts; the
electron transfer on the interface is another key factor that needs
to be considered. Therefore, it is momentous to form an
intimate interface by spatial integration of the photocatalyst
systems.152 Generally, a large contact surface on the interface
can furnish abundant channels for transfer and separation of
photoinduced carriers.153 To realize optimal contact, research
on how to improve the construction of low contact resistance at
the appropriate contact region is needed.154 The interfacial
energy level is generally relevant to the electron migration
among components, which can lead to electronic redistribution
and modulation.155,156 Accordingly, due to the different types of
contact sites of two semiconductors, two representative
interfaces exist, a homojunction and heterojunction interface,
respectively.
For a homojunction, it could be constructed by phase
engineering in one semiconductor, like the above twin lattice,149
to regionalize the distribution of photogenerated charges. Ye et
al. reported that cyano terminal CN groups endowed the
defect-modified g-C3N4 with both n- and p-type conductivities,
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which could generate p−n homojunctions.157 Enhanced
photocatalytic activity demonstrated that this homojunction
structure was highly efficient in charge transfer and separation.
Moreover, Chen et al. indicated that anatase/rutile TiO2
composites displayed enhanced photocatalytic performance,
attributed to a synergistic effect between these two phases.158
However, this effect and the interfacial structure have not been
confirmed. It was surprising to reveal the influence of interfacial
structures and properties on reactivity and performance. They
found distinct differences in the thermal properties of anatase
and rutile by using Raman spectroscopy, and it was confirmed
that anatase has become more thermally dynamic than rutile
under laser irradiation. They also analyzed the atomic structure
and electronic properties to elucidate the process of directional
heat diffusion at the interface level by using first-principles
calculations. This asymmetric heat diffusion across the interface
could be the reason that facilitated phase transition of anatase to
rutile after nucleation, which was attributed to the distinctly
different elastic properties of two interfacial phases. This
research could be useful for the development of a two-phase,
even a multiphase, semiconductor with enhanced performance
at the homojunction interface level.
For a heterojunction, there are two interfaces (including the
basal interface and lateral interface) according to the contact site
of the two semiconductors. The heterointerface constructed by
epitaxial growth, where charge carriers can be subsequently
vectorially transferred, can favor the existence of long-lived e−-h+
pairs.159,160 Details are given in the following sections.
Basal Interface. There is a great quantity of active sites on the
interarea of 2D layered photocatalysts. For a semiconductor
with a different contact type, the “face to face” 2D−2D stack
exhibits greater stability, a larger contact area, and more flux to
allow higher charge transfers on the interface.161,162 Overall, the
2D−2D-structured basal interface can largely improve the
photocatalyst’s performance.
Zhang et al. prepared MoS2 monolayers constructed with
single-layered Bi12O17Cl2 accompanied by interarea oxygen
vacancies (VO) assisted by lithium intercalation.64 The internal
electric field, which was generated by the polarization of the
nonuniform distribution of charges among the different layers,
could enable efficient e−-h+ separation.163 In this system,
electrons were driven by the internal electric field and
transferred to the MoS2 monolayer via internal Bi−S bonds.
Moreover, 2D−2D stacking of the basal interface between the
cocatalyst and photocatalyst was reported by numerous studies,
such as MoS2/TiO2,164 MoS2/CdS or WS2/CdS,165 MoS2/
C3N4,166 and MoSe2/ZnIn2S4.167 A van der Waals (vdW)
heterostructure, which is a basal interface, has been put forward
to alter the properties of 2D materials.168,169 Strong band linking
maintains the basal stability of the 2D structure and the vdW
interaction can maintain the stacked structure. More impor-
tantly, the vdW heterostructure brings advancements in
photoelectric properties by building monolayers together to
construct the basal interface.170 In the future, it is quite desirable
to strengthen the interfacial acting force to trigger charge
separation by building an intimate basal interface.
Lateral Interface. Lateral heterostructures with lateral-
oriented attachment lead to unparalleled architectures and
tunable properties.171 Experimental and theoretical studies
revealed that active lateral sides or edges have the ability to lead
to nucleation with heterogeneous components and multiple
functions.172−174 The steerable selective nucleation of a catalytic
site in the lateral direction of the 2D photocatalyst is sorely
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Figure 14. (a) TEM and (b) HAADF STEM image of the lateral Bi2Se3−CdS NHS. (c) HRTEM image, scale bar 2 nm, and (d) schematic
diagram of interface between the Bi2Se3−CdS, along the {001} direction. (e and f) Scheme of the charge transfer in lateral Bi2Se3−CdS NHS,
HOMO−LUMO, and the band structure of Bi2Se3 and CdS based on DFT calculations. Reprinted with permission from ref 175. Copyright
2015 American Chemical Society.
needed but formidable. Wang et al. investigated the reaction
kinetics by ingenious construction of the site selectivity between
a 2D photocatalyst and other nanoparticles at the atomic
level.175 Specifically, CdS nanoparticles (NPs) can controllably
and basal selectively grow on 2D Bi2Se3 nanosheets through
solution phase reactions. S-related precursors are prone to
inactivate sodium diethyldithiocarbamate and react with
thiourea, which can benefit the lateral phase of Se-rich Bi2Se3
nanosheets being modified with CdS NPs (Figure 14a and b).
The HRTEM images showed the lattice orientation of CdS and
Bi2Se3 from basal and lateral nano-heterostructures (NHS) and
the crystal structures were both hexagonal (Figure 14c). This
signified the faultless match of these two components (Figure
14d). Based on the DFT calculations, the lateral phase of Se-rich
Bi2Se3 nanosheets was the most common and functional facet
(Figure 14e). The DFT calculation indicated that electron
coupling was present in the vicinity of the CBM between these
two components in the NHS, which was strong proof of electron
migration from CdS to Bi2Se3 (Figure 14f). The injected
electrons from CdS NPs can promptly shift away from the
interface due to the special surface states of Bi2Se3 nanosheets
that fell into the bulk energy gap.176 Finally, the existence of an
intimate and efficient lateral heterojunction yielded a moderate
improvement in the photocatalytic performance.
Z-Scheme System. The Z-scheme was driven by a two-part
photoexcitation in a photocatalytic system, which was first
introduced in 1979.177 Strong reductive electrons and oxidative
holes can simultaneously exist, which is the most notable
phenomenon in Z-scheme photosystems (Figure 15).178 This is
mainly because photosystems I (PS I) and II (PS II) are
connected by using a mediator. The holes from PS I and the
electrons from PS II can be guided directionally. In recent
decades, the Z-scheme system has been extensively studied and
applied in the photocatalytic field.179−184 Two main questions
still remain unclear and need to be resolved for indirect Z-
scheme systems. (i) First, the plasma resonance effect has been
overlooked. Those elements exhibiting a plasma resonance
effect have been used as mediators (i.e., Au, Ag), and it exists
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Figure 15. Schematic diagram of the electron migration in the Z-
scheme.
widely in the Z-scheme system. The electrons generated from
the mediator will inject into the PS I and PS II because of the
SPR. (ii) Second, the recombination site of the holes from PS I
and the electrons from PS II is still unclear. Some studies declare
that the electrons transfer to recombine with the holes on the
mediator or on the VB of PS I through the mediator.180,185,186 If
the recombination site occurs on the mediator, the deposited
site of the mediator must be located at a region that can affect
both the values of highest occupied molecular orbital (HOMO)
of PS I and the lowest unoccupied molecular orbital (LUMO) of
PS II. Systematic studies are needed to prove this concept. The
intrinsic property and externality of PS I, PS II, and the mediator
can affect the migration rate and the recombination site. For
direct Z-scheme systems, it is reported that the electrons would
recombine with the holes on the VB of PS I or on the
interface.27,187−189 PS I needs to be more stable in case the
recombination sites are located on the VB of PS I. Other crucial
factors need to be taken into consideration as well (such as the
thickness, interfacial acting force, and compactness of the
interface) if the recombination sites are located on the interface.
Strategy Association. The individual strategies can effec-
tively, directionally, vectorially, anisotropically, and spatially
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Figure 16. (a) Schematic diagram of the pathway of e− and h+ over mesoporous ZCS with a complex of Cu+ and VS. The charge density of the
electronic states of the VBM and CBM on {110}: (b) ZCS with VS, (c) Cu+-doped ZCS. Reprinted with permission from ref 126. Copyright 2016
Elsevier.
separate photogenerated carriers. Furthermore, combining the
individual strategies can achieve great photocatalytic synergy.
Pan et al. enabled high-activity photocatalytic H2 generation
under visible-light illumination through vacancies associated
with doping engineering in Zn0.5Cd0.5S (ZCS) nanocrystals
(Figure 16a).126 The complex of Cu+ and VS confined into
mesoporous ZCS would be locations of active sites, which could
improve the photocatalytic activities for H2 evolution. Once a VS
occurred, it affected the distribution of electrons (CBM states)
(Figure 16b). On the other side, Cu+-dopant influenced the
allocation of holes that were located on the {110} and {111}
facets (Figure 16c). Hence, as we can see, the oriented
separation of photoexcited carriers can largely benefit the
photocatalytic activities.
ENERGY CONVERSION
Photocatalytic Hydrogen Evolution. H2 has been
deemed to an ideal fuel due to its high energy capacity and
environmentally friendly nature. Meanwhile, solar energy is
currently identified as an abundant, endless, and renewable
resource that could meet human energy requirements.11
Photocatalytic hydrogen generation has been a broad prospect
to convert solar energy into H2.
In recent years, researchers have been devoted to constructing
an ideal photocatalyst system to improve H2 production. Janus
bilayer junctions via steering charge flow at the atomic level were
newly reported by Zhang et al., which have a superior hydrogen
evolution ability with a hydrogen production rate of 33 mmol
h−1 g−1, and the quantum yield was approximated to be 36% at
420 nm.64 Asymmetric VO-rich Bi12O17Cl2 (BOC) monolayer
nanosheets could make full use of the internal electric field to
channel holes to the [Cl2] and electrons to the [Bi12O17−x] end
faces, respectively.190 It was reported that VO had the intriguing
capability to entice the metals depositing on VO sites
selectively.191 MoS2 monolayers were selectively assembled on
[Bi12O17−x] facets to prompt electron migration, which was
driven by the internal electric field precisely (Figure 17a−h).
Moreover, VO can adjust the coordination of exposed Bi atoms
around the VO to bond with the S atoms on the MoS2 surface.
The coordination of Bi−S bonds can act as an efficient highway
on the interface between MoS2 and Bi12O17Cl2 with VS (Figure
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Review
Figure 17. (a and b) AFM images. (c) Side view of the HAADF-
STEM images and (d−h) the respective elemental maps. (i)
Schematic diagram of the photocatalytic behavior over BOC-MS.
(j) Charge-flow processes between Janus bilayers. Reprinted with
permission from ref 64 under a Creative Commons CC-BY License.
Copyright 2016 Springer Nature.
17i and j). Overall, the ingenious basal design enabled atomic-
level control for efficient charge migration. Furthermore, other
investigated photocatalytic systems for H2 production are listed
in Table 1. Modifying and reassembling photocatalysts to obtain
efficient photocatalyst systems are used to improve hydrogen
production.
Photocatalytic CO2 Reduction. Solar-driven CO2 reduc-
tion can produce carbon fuels with a simultaneous reduction in
the greenhouse effect.206 Under solar light illumination, CO2
molecules could be reduced into various reduction products by
the photoexcited electrons (i.e., CO, CH4, CH3OH, HCHO,
and HCOOH) at a certain potential, as shown in Table 2.
Developing an efficient photocatalyst is needed to enhance the
performance of CO2 photoreduction for practical implementa-
tion.
Numerous efforts have been done to improve the conversion
efficiency of CO2 photoreduction using efficient strategies to
construct photocatalysts in recent years (Figure 18). (i) Efficient
and metal-free cocatalysts. Ran et al. reviewed CO2 reduction
cocatalysts in recent years and advocated finding cheap and
efficient cocatalysts to enhance the activity of photocatalysts on
CO2 reduction.207 Pt,208 Ag,209 Pd,210,211 Ru,212 Rh,213 and
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Table 1. List of Photocatalytic H2 Production Systems to Date

performance (mmol h−1 g−1) and
photocatalyst reaction condition (light source, sacrificial agent, concentration of photocatalyst) AQE ref
MoS3@CdSe/CdS Hg/Xe 50−500 W dc arc lamp (λ > 450 nm), 0.1 M triethanolamine 100 192
CuO/TiO2 400 W high pressure Hg lamp, 10 vol % methanol, 1 g/L 71.6 193
graphene-Cu@TiO2 500 W Xe lamp (λ > 400 nm), water:methanol (v/v = 2:1) 20 mg/30 mL 63.750 194
Pd/C3N4 300 W Xe lamp (λ > 400 nm), 0.1 M formic acid, 20 mg/10 mL 53.4 195
MoS2/Bi12O17Cl2 300 W Xe arc lamp, 0.3 M ascorbic acid, 10 g/80 mL 33 36% at 420 nm 64
Co-Ni/CdS-NR 750 W xenon lamp (λ > 420 nm, 100 mW cm−2) 32.6 196
FA (containing NaHCO2) (1.04 mM = 150 μg mL−1)
Ni@La0.02Na0.98TaO3 400 W high-pressure Hg lamp (λ > 250 nm), 10% vol of methanol 29.2 197
500 mg/1500 mL
ZnO-MoS2-RGO 0.1 M Na2S and 0.1 M Na2SO3, 5 mg/45 mL 28.616 198
CdStitanate NiOx 300 W Xe arc lamp (λ > 420 nm), 20% vol of ethanol 26.940 199
Ni 100 mg/500 mL 11.038
AuPd/TiO2 AM 1.5 sunlight, 2.7 M formic acid, 5 mg/10 mL 17.7 28.1% at 420 nm 200
Fe-g-CN white-light LED (λ =400−750 nm), TEA (10% v/v) and EY (4.0 × 10−4 M), 0.025 g/L 16.2 0.8% 201
Cu(OH)2@TiO2 400 W high pressure Hg lamp as UV-light source 14.940 202
10 vol % methanol, 150 mg/500 mL
Pt@Cu1.94S−ZnxCd1−xS 0.1 M Na2S and 0.1 M Na2SO3, 20 mg/50 mL 13.533 26.4% at 420 nm 203
Cu/TiO2 300 W Xe lamp, 10 vol % methanol, 40 mg/40 mL 12.779 204
Pt@O-g-C3N4 300 W Xe lamp (λ > 400 nm), 10 vol % triethanolamine 8.875 13.7% at 420 nm 205
50 mg/100 mL
MoS2QDs@VS- 300 W Xe lamp (λ > 420 nm), 10 vol % lactic acid 6.884 138
MZnIn2S4 50 mg/80 mL
MoSe2/ZnIn2S4 300 W Xe lamp (λ > 400 nm), 10 vol % lactic acid, 5 mg/10 mL 6.454 167
MoS2/Cu−ZnIn2S4 λ = 420 nm, 0.1 M ascorbic acid, 50 mg/250 mL 5.463 153

Table 2. Standard Redox Potentials for the Mentioned

Reactions in This Article
E0 (V) vs NHE (pH =
reaction 0)
2H+ + 2e− → H2(g) 0
2H2O(aq) + 4h+ → O2(g) + 4H+ 1.230
2CO2(g) + 2H+ + 2e− → HOOCCOOH(aq) −0.481
CO2(g) + 2H+ + 2e− → HCOOH(aq) −0.199
CO2(g) + 2H+ + 2e− → CO(g) + H2O −0.117
CO2(g) + 4H+ + 4e− → HCHO(aq) + 2H2O −0.07
CO2(g) + 8H+ + 8e− → CH4(g) + 2H2O 0.169
CO2(g) + 6H+ + 6e− → CH3OH(aq) + H2O 0.03
2CO2(g) + 8H+ + 12e− → C2H4(g) + 12OH− 0.07
2CO2(g) + 9H2O + 12e− → C2H5OH(aq) + 12OH− 0.08
3CO2(g) + 13H2O + 18e− → C3H7OH(aq) + 0.09
18OH−
N2 + e− → N2− −4.16
N2 + H+ + e− → N2H −3.2 Figure 18. Related strategies for photocatalytic CO2 conversion.
N2 + 2H+ + 2e− → N2H2 −1.32
N2 + 4H+ + 4e− → N2H4 −0.36
N2 + 5H+ + 4e− → N2H5+ −0.23 conversion. Various cocatalysts include cheap and earth-
N2 + 6H+ + 6e− → 2NH3 −0.137 plentiful elements, such as Co(II) species,215,216 graphene,217
NO2(g) + 2H2O + 3h+ → NO3− + 4H+ 0.957 MoS2,218 and MXene.219 (ii) Vacancy engineering. Zhang et al.
NO2(g) + H2O + h+ → NO3− + 2H+ 0.80 employed defect engineering of a 2D nanolayer to enhance the
NH3 + H2O → NH3·H2O ⇋ NH4+ + OH− photocatalytic performance, such as defective BiVO4,143
O2 + e− → •O2− −0.284 BiOBr,220 ZnAl-layered double hydroxides (ZnAl-LDH),221
O2 + e− + H+ → HO2• −0.046 and BiOCl.222 (iii) Adding a dopant to adjust band gaps and
HO2• + e− + H+ → H2O2 1.44 charge-carrier separation kinetics, for instance, partially oxidized
OH− + h+ → •OH 2.403 SnS2 atomic layers,223 phosphorus-doped g-C3N4,224 and Ce-
doped ZnFe2O4.225 (iv) Core/shell hierarchical heterostruc-
tures. Lou et al. rationally designed ZnIn2S4−In2O3,226 In2S3−
Au214 have generally acted as highly suitable and active CdIn2S4,227 N-doped carbon@NiCo2O4,228 and hierarchical
cocatalysts for CO2 photoreduction. However, the rarity and heterostructures. (v) Z-scheme systems. Zhu et al. and some
high cost of the above-mentioned cocatalysts of noble metals other researchers adopted Z-scheme photocatalysts for CO2
have significantly hindered their large-scale adaptation for solar photoreduction, such as ZnIn2S4/TiO2,27 Ag3PO4/g-C3N4,183
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Figure 19. (a) TEM image and (b) HAADF-STEM image of MoS2 foam/CdS. (c) Schematic diagram of photocatalytic synthesis and H2
evolution over MoS2 foam/CdS. (d) EXAFS spectra of photocatalyst samples. (e) TRPL spectra of different photocatalyst samples. (f) Energy
barrier profiles of reaction via different free radicals. (g) Reaction mode with EG separation. (h) Performance of EG generation over MoS2
foam/CdS photocatalyst. Reprinted with permission from ref 245 under a Creative Commons CC-BY License. Copyright 2018 Springer Nature.

α-Fe2O3/g-C3N4,229 α-Fe2O3/Cu2O,230 BiOI/g-C3N4,231 and
metal sulfide-RGO-CoOx/BiVO4.232 (vi) Construction of
interfacial heterojunctions, such as MXene/Bi2WO6,219 g-
C3N4/NiAl-LDH,233 and P25@CoAl LDH.234
CO2 photoreduction indicates a potential pathway to convert
it into hydrocarbon fuels by harvesting eco-friendly solar energy.
Currently, the efficiency of CO2 photoreduction is still lower
than the demands for practical application. Moreover, it is still a
challenge to obtain the pure and single product of CO2
photoreduction, which needs further exploration in the future.
Photocatalytic Nitrogen Fixation. NH3 is one of the most
highly produced inorganic chemicals in the world, due to its
large demand in pharmaceutical, fertilizer, and many other
industries.235,236 The Haber−Bosch process is applied to
nitrogen fixation in industrial production; however, this process
needs to expend a lot of energy because of the rigorous reaction
conditions required (i.e., 673−873 K and 15−25 MPa).237,238
Moreover, over 1% of CO2 is generated and emitted to the
atmosphere from this industrial process, which promotes global
warming.239,240 Therefore, it is highly desirable to seek an
environmentally friendly and sustainable technology to fix the
nitrogen with low energy consumption and no CO2 emissions.
Semiconductor photocatalysis has attracted widespread interest
because of its potential to capture solar energy and drive
thermodynamically unfavorable chemical reactions. However,
two points need to be considered when designing photocatalysts
9825
for N2 fixation, which are as follows: (i) active adsorption sites
for N2 and (ii) NN activation by photoexcited electrons.
Zhang and co-workers found that engineering VO into BiOBr
nanosheets could adsorb the N2 molecule effectively and
prolong NN to active N2 to simultaneously promote the
nitrogen fixation reaction.199 It has been proven that a vacancy
can efficiently guide and trap the electrons. The electrons
around the VO can efficiently migrate to the adsorbed N2, which
can be activated. Ye et al. and Zhang et al. constructed Bi5O7Br
nanotubes and CuCr-LDH nanosheets with rich VO, which also
showed satisfactory performance for nitrogen fixation.241,242
Dong et al. reported that the N vacancy (VN) in C3N4 could also
relax the bond length of NN from 1.117 Å to 1.214 Å.243
Photocatalytic N2 fixation provides an environmentally
friendly and cost-efficient method to produce NH3.244 The
mechanisms of N2 reduction and the fundamental parameters
for efficient catalytic systems need to be further explored. It is
desirable to optimize the performance of photocatalytic N2
fixation by developing active sites for N2 adsorption and NN
activation under ambient conditions.
Photocatalytic Synthesis. Converting low value-added
products (i.e., methanol) into high value-added products (i.e.,
ethylene glycol) using “green technology” is highly preferable,
and it can meet the requirements of sustainable development.
However, the chemical transformation cannot occur via
conventional thermocatalytic conversion and needs rigorous
conditions to operate. Thus, a solar-light-driven photocatalysis
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Figure 20. (a) Energy barrier evolution of NO by •O2− over BiOCl {001}. (b) Nitrate conversion from peroxynitrite. The charge density and
DOS of the BiOCl {001} surface with (c) O2 and (d) nitrate. (e) Photocatalytic NO elimination over BiOCl. (f) Schematic illustration of
photocatalytic NO removal on VO-BiOCl. Reprinted with permission from ref 255. Copyright 2018 American Chemical Society.

reaction is a very attractive approach to meet this requirement.
Recently, photocatalysts displayed great potential in terms of
selective chemical transformation and directional synthe-
sis.245,246
Methanol is chosen to be the sacrificial compound in the
process of photocatalytic H2 generation; however, the oxidation
reaction of methanol and the products oxidized by h+ have
always been overlooked. For the first time, Wang et al.
emphasized this typical question.245 They studied the visible-
light-driven dehydrogenation coupled with the transformation
of methanol into ethylene glycol using a MoS2 foam/CdS
nanorod photocatalyst. The HRTEM and HAADF-STEM
images indicated that MoS2 nanosheets anchored on the CdS
nanorod could reveal more active sites. Meanwhile, MoS2 foam
can form a closer contact with CdS compared to MoS2 sheets
(Figure 19a−c). The EXAFS data indicated that the MoS2 foam
on CdS had less Mo−Mo bonds compared to the bare MoS2,
which suggested that more edge sites exist (Figure 19d). Time-
resolved PL spectroscopy (TRPL) confirmed that the charge
separation and photogenerated excitations have been enhanced
in the presence of MoS2 foam (Figure 19e). Systematic research
revealed a prior excitation of the C−H bond rather than the O−
H bond of methanol by photoexcited holes from CdS. This was
9826
mainly due to the formation of a hydroxymethyl radical
(•CH2OH), which could easily desorb from photocatalyst
surfaces for further reactions (Figure 19f). On separating EG,
the MoS2 foam/CdS photocatalyst could be easily recovered
without apparent inactivation (Figure 19g). Additionally, in a
conventional reactor, many byproducts were detected, such as
HCHO, HCOOH, and oxalic acid. However, relatively pure
products can be achieved by adding EG in this system. (Figure
19h). Moreover, Hu et al. reported the evolution of C−H
amination and arylation driven by the photocatalytic process.246
It showed high efficiency of conversion and selectivity by cerium
salt photocatalysts. Photocatalytic synthesis provided a unique
strategy to activate C−H to obtain a specific product with
excellent conversion and selectivity by photocatalysis.
ENVIRONMENTAL REMEDIATION
Photocatalytic Air Purification. Typical air pollutants
both outdoor and indoor are generating increasing environ-
mental concern.247,248 NOx, including nitric oxide and nitrogen
dioxide, are blamed for atmospheric pollution, such as ozone
depletion, acid rain, and photochemical smog, even in an
infinitesimal concentration (i.e., g/L). For NOx generated from
industrial processes, conventional strategies (i.e., adsorption,
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selective catalytic reduction, and thermocatalysis) have been removal was examined in both a reactor and an air cleaner
widely applied and show great performance at relatively higher (Figure 21a). The 001-TNT presented a better photocatalytic
concentrations (i.e., mg/L). Unfortunately, these techniques are
not economical for NOx removal at a low concentration level
(i.e., g/L).249−252 However, semiconductor photocatalysis can
utilize real sunlight or man-made light sources to eliminate air
pollutants even at low concentrations under mild environmental
conditions.
Dong et al. reported a g-C3N4/Al2O3 composite photocatalyst
that could effectively remove 77.1% of NO (initial concentration
was 600 g/L).253 The reaction mechanism was proposed as
follows:
g‐C3N4 + hν → e− + h+

e− + O2 → •O2−

•O2− + 2H+ + e− → H 2O2

H 2O2 + e− → •OH + OH−
NO + •O2− → NO3−
2•OH + NO → NO2 + H 2O

NO2 + •OH → NO3− + H+

To further improve the performance of NO removal, in 2015,
Dong et al. newly prepared an advanced Bi/g-C3N4 photo-
catalyst.254 The Bi/g-C3N4 composite photocatalyst presented
excellent high performance with excellent stability for NO
removal due to SPR endowed with Bi metal.
Avoiding NO2 emission is the key challenge during the
oxidation process from NO to nitrate. It has been proven that
•
O2− could directly oxidize NO to NO3−; however, •OH is not
capable of doing this.253,254 Zhang et al. reported that a well-
designed BiOCl with VO (VO-BiOCl) on the prototypical {001}
surface can efficiently generate •O2−. This is mainly because the
electron enrichment around VO can obviously enhance the
surface activity of BiOCl.255 As a result, it facilitated the
generation of •O2−. As shown in Figure 20a, surface-bridged
•
O2− could convert NO into monodentate nitrate directly in
route II, which was more thermodynamic than pathway I. The
oxidation of NO through route I or II was self-directed (Figure
20b). The deduction based on the DFT calculation explained
the mechanism of •O2− for the thorough oxidation of NO
without NO2 release. After O2 was captured on the VO of BiOCl
{001}, the electron enrichment around the VO was depleted on
the two Bi atoms (Figure 20c). Along with nitrate formation, it
was found that the •O2− interacted rigorously with the NO
formed (Figure 20d). The concentration of NO was evidently
decreased within 5 min and gradually reached a 70% removal
efficiency after 15 min (Figure 20e). Sure enough, just 4 μg/L
NO2 was detected, which is much lower than the specified
standard of indoor NO2 (0.24 mg/L). Overall, NO was oxidized
to NO3− directly with near-perfect selectivity. A schematic
diagram of photocatalytic NO elimination over VO-BiOCl is
shown in Figure 20f.
The existence of volatile organic compounds in the air is
harmful to the health of humans. Photocatalysis presents
potential among various technologies for air purification. It
can mineralize VOCs into CO2 and H2O completely under
ambient conditions.256,257 Choi et al. synthesized TiO2 nano-
tubes with a {001} facet exposed (001-TNT) by electrochemical
anodization.258 The performance of 001-TNT on the VOC
9827
Figure 21. (a) Schematic diagram of a TiO2 nanotube filter with a
{001} facet exposed to remove VOCs. (b) Toluene degradation over
TNT and 001-TNT under UV illumination. (c) Stability of toluene
degradation over TNT and 001-TNT. (d) Acetaldehyde and (e)
formaldehyde degradation over TNT and 001-TNT under visible
light illumination. Reprinted with permission from ref 258.
Copyright 2018 American Chemical Society.
performance than the TNT for toluene degradation under the
same conditions (Figure 21b). The 001-TNT kept its better
activity after five continuous operations without any deactiva-
tions (Figure 21c). Moreover, the 001-TNT can also degrade
acetaldehyde and formaldehyde, which was affirmed by the
generation of CO2. However, this phenomenon was not
observed using TNT (Figure 21d and e). The 001-TNT filters
equipped in the air cleaner reached a 72% efficiency for VOC
removal on average within a 30 min operation time in an 8 m3
test chamber.
Wastewater Decontamination. Process and Achieve-
ments of Water Decontamination. With economic develop-
ment and accelerated industrialization, water contamination has
raised public concern due to its negative impact on human
health. Currently, photocatalysis technology is applied to
alleviate water contamination. In terms of mechanism, e− is
activated, migrates from VB to CB, and forms e−-h+ pairs (Figure
22) under illumination. The generated h+ can directly oxidize/
mineralize organic contaminants to CO2 and H2O or create
•
OH to indirectly oxidize/mineralize organic contaminants. If
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Figure 22. Process and achievements and several key issues in the applicability of water decontamination.

photocatalytic degradation is performed in an aerobic environ- (Figure 23a), the C1 and C1′, C4 and C4′, and C6 and C6′ of
ment, e− can be trapped by O2 to generate •O2− and other BPA with positive and high f 0 values were the reactive sites for
reactive species, which can also oxidize organic pollutants. In
application, water contaminants, such as dyes,259 pesticides,260
herbicides,261 antibiotics,262 detergents,263 pathogens,264,265
viruses,266 coliforms,267 and spores,268 can be effectively
removed by using the photocatalytic process. Hence, photo-
catalysis based on a semiconductor has been determined to be a
promising method to eliminate water contamination.184,269−279
Furthermore, many byproducts are formed during the
mineralization process using photocatalysis approaches, which
is a particularly important aspect that needs to be considered
owing to the toxicity of byproducts generated from the
recalcitrant organics. Hence, it is worthwhile to seriously
consider the oxidation potential of contaminants, the adsorption
manner matched by electron clouds, and the attacked sites of
free radicals. (I) The oxidation potential of the contaminant.
The degree of oxidation byproducts has risen gradually. It is
critical to determine if the free radicals can also oxidize these
byproducts. (II) Adsorption manner matched by electron
clouds. The adsorption manner of contaminants on photo-
catalysts can also be determined by electron clouds. The optimal
adsorption mode can perfectly match electron clouds, which
makes the entire process much more efficient. (III) The attacked Figure 23. (a) NPA charge distribution and Fukui index; (b)
sites of free radicals. For the target contaminant, it is better to chemical structure of BPA. Reprinted with permission from ref 280.
know the mineralized pathway in order to comprehensively Copyright 2018 Elsevier.
evaluate the toxicity of the byproducts. Whether there are loop
openings or not is related to the attacked sites of free radicals, radical attacks, whereas C4, C4′, C6, and C6′ were determined
which influences the degree of mineralization. The Fukui to be the most reactive sites because C1 and C1′ were occupied
function describing the electron density in a frontier orbital in by O and not further attacked (Figure 23b). These studies can
computational chemistry has been determined to be an essential largely benefit the highly active photocatalytic system design and
tool to further understand organic contaminant degradation screening of nucleophilic and electrophilic free radicals to realize
behaviors, as it can represent the electrophilic (f −), nucleophilic hypersalinity of contaminants.
(f +), and radical attack (f 0) and has been widely used to Several Key Issues in the Applicability for Water
evaluate the reactive sites of organic contaminants.280 Recently, Decontamination. (I) Operation costs. Operation costs
Liang et al. and Liu et al. have researched attacked C atoms of depend on the actual water quality, technological processes
different organic contaminants (such as rhodamine B (RhB), (i.e., reactor, performance period, and desired effect), and
bisphenol A (BPA), and diclofenac (DCF)) by using the natural photocatalyst (performance, large-scale preparation, and life-
population analysis (NPA) charge distribution and the Fukui time). (II) The turbidity, substrate concentration, pH, temper-
index in order to fully determine the degradation pathways.281 ature, and metal ions in the real environment should be taken
For example, according to the calculated f 0 of the atoms in BPA into account, especially for insoluble particulate matter (i.e.,
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Figure 24. Organic wastewater recycling process driven by solar energy based on a semiconductor photocatalyst (enclosed and anaerobic
conditions).
mud, silt, fine organic matter, inorganic matter, plankton, other
suspended matter, and colloidal matter) that can interfere with
the penetration of solar energy. As reported by previous studies,
the degradation efficiency would be significantly reduced when
organic contaminants with high concentration were present in
the aqueous solution.282 The pH of the solution not only
changes the surface properties of the photocatalysts but also
influences the band gap of the semiconductor. Therefore, it is
necessary to design photocatalysts with great photocatalytic
performance in a wide pH range.283,284 Meanwhile, the
photocatalytic degradation can proceed at normal temperatures
and pressure, which is beneficial for water treatment to save
energy. (III) Technological process. The photocatalytic process
acts either as a forepart of technology or an individual system.282
As a forepart, the hydraulic retention time and the quantity of
the sludge could be obviously reduced from the biological
treatment.282 As an individual system, the requirement of the
retention time might be drawn out because of microbiology
inactivation or mineralization.285,286 Moreover, the photo-
catalytic reactor system needs to be fabricated scientifically
and systematically to utilize solar energy efficiently to reduce
electricity costs. (IV) Photocatalyst. The scalable technology of
the photocatalyst should be explored, as well as its activity and
lifetime. Meanwhile, the stability of the photocatalyst is another
key factor that should be taken into consideration; it is highly
related to the continual performance and can also cause the
photocatalyst to have a leakage problem. (V) Recovery method.
The immobilization strategy of the photocatalyst can provide a
separating strategy for solids and liquids with low cost and high
efficiency.
CAPTURING ENERGY FROM WASTEWATER
DECONTAMINATION
Wastewater treatment techniques are currently only focused on
water purification or decontamination. However, to some
extent, wastewater can be defined as a renewable resource.
This is mainly because we can simultaneously obtain clean water
and energy (hydrogen, methane, methanol, ethanol, etc.) using
photocatalytic approaches.287,288 Panagiotis Lianos first showed
that electricity and hydrogen can be produced by photocatalytic
degradation of organic waste in a photoelectrochemical cell in
2011.289 The viewpoint was aroused that this whole process was
very attractive on both ending points with electricity and
hydrogen production and organic waste degradation, and it
should be a re-emerging research field. However, some aspects
of this research area need to be further studied. First, the choice
9829
Review
of electrocatalysts for the cathode electrode was rather limited
and needs tremendous efforts to improve its overall performance
and energy efficiency. Second, the final products generated from
the organic wastes (i.e., higher polyols and sugars) may arouse
great interest in the next research step. Third, more attention
needs to be paid regarding the byproducts generated during the
photodegradation process.
Choi et al. introduced an ideal mineralization process (eq 1)
that can capture energy in the process of wastewater
decontamination.290 In fact, the organic molecules in wastewater
can be completely mineralized to CO2 and H2O, and the
generated CO2 can be further reduced to methane, methanol,
and ethanol by accepting electrons.291 The electrons in this
process are mainly from the following two pathways: (i)
oxidation of organic pollutants and (ii) photoinduced
generation. Furthermore, the electrons could be injected into
the CB of the semiconductor photocatalyst to reduce the
absorbed H+ to H2. Herein, the co-occurrence of wastewater and
solar-driven semiconductor photocatalysts can not only miner-
alize organic pollutants to purify wastewater but also generate
energy substances (i.e., H2, CH4, CH3OH, and C2H5OH) from
wastewater (eq 2). This process was further described in Figure
24.
Cx HyOz + (2x − z)H 2O → xCO2 + (2x + 0.5y − z)H 2
(1)
solar energy
Cx HyOz + H 2O ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ H 2 + CH4 + CH3OH
photocatalyst
+ C2H5OH+ (2)
Solar energy driven reactions (eq 2) coupled with photo-
catalysis can realize the purpose of wastewater decontamination
synergistically with energy conversion, which can largely reduce
the overall cost of wastewater treatment. The hydrogen
production efficiency of photocatalytic water splitting is mainly
limited to the four-electron kinetics process of the O2 evolution.
The four-electron process of producing the O2 evolution
converting into the two-electron processes of H2O2/•OH can
further improve the kinetic rate,292 while the H2O2/•OH
generated by the two electronic mechanisms is the active species
for pollutant degradation. Specifically, organic pollutants, as
electron donors, can promote the hydrogen production of water
splitting, and the active species (i.e., •OH) with a strong
oxidizing ability can oxidize/mineralize the organic pollutants to
CO2.293 In 2006, Patsoura et al. reported Pt/TiO2 suspensions
that can degrade azo-dyes with simultaneous hydrogen
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Figure 25. (a) Schematic illustration of the migration of electrons and holes over TiO2/CuO heterojunctions. (b) Photocatalytic H2 generation
with increasing irradiation time of 3 h over photocatalyst samples and (c) comparison of H2 rate over photocatalyst samples. (d) Removal of
AO7 under UV−visible illumination. (e) Recycling of photocatalytic H2 generation over the TiO2/CuO photocatalyst composite. Reprinted
with permission from ref 301. Copyright 2013 Elsevier.

production.294 Since then, Pt/CdS/TiO2,295 F- and P-TiO2/
Pt,290,296,297 and Pt/C3N4 nanotubes293 have been prepared to
fulfill this goal. Although photocatalyst deposition with Pt is
efficient for hydrogen evolution reactions, Pt is easily poisoned
when it is surrounded by organic substances.298−300 By further
considering the overall efficiency, both the proton reduction
reaction and pollutant destruction reaction should be taken into
consideration.
TiO2/CuO photocatalyst composites were structured using
the electrospinning method by Liu et al. and were used for
efficient photocatalytic dye degradation with simultaneous H2
generation. The mechanism is detailed in Figure 25a.301
Furthermore, as shown in Figure 25b, the H2 generation over
the TiO2/CuO photocatalyst composite was significantly better
than with pristine TiO2. Moreover, as shown in Figure 25c, the
H2 evolution rate was measured to be 62.7 μmol h−1 using TiO2/
CuO composite nanofibers, which was about 5 times higher than
pristine TiO2. The removal of acid orange II (AO7) was
significantly improved over TiO2/CuO photocatalyst (Figure
25d). Complete AO7 removal was observed within 20 min. AO7
degradation was due to the destruction of the azo-bond into
smaller molecules by the h+ and •OH. Figure 25e shows the
9830
stable photocatalytic activity of H2 generation within 3 cycles,
which indicated that the TiO2/CuO photocatalyst composite
had excellent stability and reutilization.
Zou et al. prepared the one-pot conversion of methylene blue
(MB) into useful fuels over GQDs/V-TiO2 using photo-
generated CO2 as the carbon source (Figure 26).302 The e−
was excited from the VB to the CB of vanadium-doped TiO2 (V-
TiO2) and subsequently migrated to graphene QDs (GQDs).
The holes in the VB reacted with the MB to form CO2 and H2O.
Meanwhile, the photoinduced e− on GQDs was responsible for
the CO2 reduction, which could lead to the generation of
CH3OH, C2H5OH, and CH4. Ion chromatography detected the
existence of CO32−, which was from the mineralization of MB
(Figure 25a and b). CH3OH, C2H5OH, and CH4 were produced
due to CO2 photoreduction in the system (Figure 25c). The
proposed process of the one-pot conversion of MB to useful
fuels using GQDs/V-TiO2 is shown in Figure 25d. It was a novel
project to harvest and convert solar energy to generate reusable
liquid fuels with simultaneous organic wastewater purification.
Zhang et al. enriched the area of photocatalytic organic
degradation and simultaneous H2 production over a MoS2 QD-
decorated hybrid of ZnIn2S4 assembled on RGO.303 The
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Figure 26. (a) Ion types in the process of MB degradation over 5%GQDs/V-TiO2. (b) Accumulation of CO32− in the MB solution with
increasing irradiation time. (c) Comparison of CH3OH, C2H5OH, and CH4 generation rate. (d) Proposed mechanism of conversion of MB into
useful fuels over 5%GQDs/V-TiO2. Reprinted with permission from ref 302. Copyright 2016 American Chemical Society.

Figure 27. (a) LUMO and HOMO of pollutants: RhB (rhodamine B), EY (eosin Y), MB (methylene blue) and PNP (p-nitrophenol). (b) Band
gap diagram of photocatalysts: ZnIn2S4, MoS2 QDs, and RGO, pollutants: RhB, EY, and MB, (c) TRPL spectra of photocatalyst samples and (d)
schematic diagram of pollutant conversion and energy flow. Reprinted with permission from ref 303. Copyright 2017 Elsevier.

LUMO and HOMO of different organic pollutants were
investigated by DFT calculations (Figure 27a). The band
matching mechanism was first proposed to take the organic
compound structure into consideration to determine the
degradation rate and amount of H2 production. In terms of
reaction kinetics. TRPL was also applied to further indicate the
lifetime and migrating behavior of photogenerated carriers
(Figure 27b). The emission lifetime for 5MoS2QDs@ZnIn2S4@
RGO1 decreases to 12.05 ns, which is 6.27 times shorter than
that of ZnIn2S4 (75.57 ns), thus indicating a faster interfacial
charge transfer (Figure 27c). A schematic illustration of
pollutant conversion and energy flow is shown in Figure 27d.
9831
CONCLUSION AND PERSPECTIVES
Benefiting from the advancements with various characterization
tools and the growing demands for both environment and
energy sustainability, the evolution of photocatalysts has
dramatically increased in the past decades. Herein, we
summarized the state-of-the-art methodologies and strategies
comprehensively and systematically to improve photocatalytic
performance in the following aspects: (i) how to enhance and
broaden light absorption, (ii) how to develop active sites, and
(iii) how to separate charges efficiently. The photocatalytic
application achievements in energy conversion, environmental
remediation, and capturing energy in wastewater decontamina-
tion by photocatalysis were also discussed. Although great
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achievements have been obtained in this intriguing field, studies
still must be further developed, and at least the following aspects
should be considered:
(1) The relationship among the photocatalytic performance,
the reaction mechanism, and structure−property needs to
be deepened, especially at the molecular level. Moreover,
in situ characterization techniques are urgently needed to
reveal the photocatalysis reaction process.
(2) Compatible architecture is required to achieve high
efficiency and great stability. The active sites must be
located, defined, and maximized. The focus on the active
sites needs to be deepened into the basal plane
microscopically and not just on the macrolevel. The
photoelectric conversion efficiency needs further im-
provement due to unavoidable e−-h+ recombination. It is
necessary to regulate the charge flow microscopically
especially at the atomic level, and achieve charge
separation directionally, vectored, anisotropically, and
spatially. The photocatalytic aspects of energy conversion
and environmental remediation were studied, while the
long-term stability and durability need to be further
tested. It is possible to improve the durability in practical
experiments by coating and wrapping the surface of the
photocatalyst with a porous inert layer.
(3) Scale production. The large-scale and high-yield
production of photocatalysts is another important
prerequisite for practical applications. The unceasing
development of science and technology will infuse fresh
energy into photocatalysis, for example, by means of 3D
printing and femtosecond lasers to prepare photo-
catalysts.
(4) Practical application is needed. Cost is another key factor
when considering practical application after satisfying the
high efficiency, stability, and large-scale preparation
requirements. Overall, this comprehensive and systematic
review can benefit the future studies on the application of
solar-driven photocatalysts in energy conversion and
environmental remediation.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zhangshuqu2013@126.com.
*E-mail: john.crittenden@ce.gatech.edu.
ORCID
Jinming Luo: 0000-0001-8698-7624
Meng Sun: 0000-0002-8188-9264
John C. Crittenden: 0000-0002-9048-7208
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (51868051, 51662031, 51720105001).
The views and ideas expressed herein are solely those of the
authors and do not represent the ideas of the funding agencies in
any form. We appreciate Dr. Shuqu Zhang from Nanchang
Hangkong University especially for his provided ideas, thoughts,
and the support. Additionally, we thank ChemWorx for the
English editing.
9832
Review
DEFINITIONS
photocatalysis, the acceleration of a photoreaction in the
presence of a catalyst; electron hole, often simply called a hole,
is the lack of an electron at a position where one could exist in an
atom or atomic lattice; energy conversion, the process of
changing energy from one form to another; environmental
remediation, a way to deal with the removal of pollution or
contaminants from environmental media such as soil, ground-
water, sediment, or surface water; crystal structure, a
description of the ordered arrangement of atoms, ions, or
molecules in a crystalline material
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DOI: 10.1021/acsnano.9b03649
ACS Nano 2019, 13, 9811−9840