Materials Today Chemistry 11 (2019) 197e216

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Materials Today Chemistry

journal homepage: www.journals.elsevier.com/materials-today-chemistry/

Photocatalyst design based on two-dimensional materials

Y. Li a, b, c, C. Gao a, c, R. Long d, **, Y. Xiong a, b, c, *
a
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, PR China
b
Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China, Hefei, Anhui 230026, PR China
c
School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, PR China
d
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Benefiting from large specific area and excellent charge transfer performance, two-dimensional (2D)
Received 15 October 2018 materials exhibit inspiring performance in photocatalytic H2 evolution, CO2 conversion, N2 fixation, and
Received in revised form other applications. Aiming to illustrate how to seek and modify 2D materials toward specific applications,
7 November 2018
here we present a review on photocatalyst design based on 2D materials. This review article starts with a
Accepted 9 November 2018
brief introduction to the strength and weakness of regular 2D materialebased photocatalysts, followed
by a summary on the 2D materials commonly used in photocatalysis and their synthetic approaches. As
the central part of this review, multifarious strategies for maneuvering the performance of 2D material
Keywords:
Photocatalysis
ebased photocatalysts are then outlined. Finally, we discuss the challenges and opportunities for further
Two-dimensional material development on 2D materialebased photocatalysts toward energy and environmental applications based
Synthetic strategy on the recent progress from the angle of surface science and coordination chemistry.
Materials design © 2018 Elsevier Ltd. All rights reserved.
Solar energy

1. Introduction
Solar energydthe radiant light and heat from the Sundcan be
harnessed by a range of ever-evolving technologies such as pho-
tovoltaics, artificial photosynthesis, solar heating, and molten salt
power plants. The increasing energy demand gradually turns the
highly efficient use of solar energy into a significant project. Among
various solar technologies, photocatalysis, which utilizes semi-
conductor materials to harvest solar energy, generate and separate
photoexcited electron-hole pairs, and transfer the charge carriers to
catalytic sites for reduction and oxidation reactions, can convert
solar energy into chemical energy and serve as a very different
approach to solar energy utilization.
Although a variety of photocatalysts have been explored in
recent decades, some conspicuous limitations in present photo-
catalytic systems bring down their overall performance in photo-
catalysis. For instance, the recombination of electron-hole pairs
takes place during the process of charge transport due to the low
mobility of photo-induced charge carriers in semiconductor and/or
becomes more severe when the charge carriers cannot be timely
* Corresponding author.
** Corresponding author.
E-mail addresses: longran@ustc.edu.cn (R. Long), yjxiong@ustc.edu.cn
(Y. Xiong).
consumed by surface reactions due to the low activity and limited
number of catalytic sites on semiconductor surface. The severe
charge recombination largely limits the quantum efficiency of
overall photocatalysis. Among the photocatalysts with different
morphologies, the photocatalysts based on two-dimensional (2D)
materials have been attracting increasing research interests due to
their remarkable chemical and physical properties [1e3]. The
planar structure of 2D materials endows them with abundant
surface atoms and certainly provides sufficient space for integra-
tion with co-catalysts. This feature boosts the number of active sites
for catalytic reactions and more importantly offers the flexibility of
enhancing catalytic activity by creating new active sites. Another
key structural characteristic to 2D materials is the substantially
reduced thickness. As the thickness is shrunk to nanoscale and even
atomic level, the photo-induced charge carriers can transport from
bulk to surface by traveling an extremely short distance. This
decrease in traveling length dramatically suppress the electron-
hole recombination during charge transport and preserve more
charge carriers for surface reactions.
Despite the fascinating properties of 2D semiconductors in
photocatalysis, numerous improvements are still required to
enhance catalytic activity, durability, and selectivity. In many cases,
the large specific surface area of 2D materials does not guarantee a
high density of active sites. Previous research has revealed that
catalytic activity usually originates from coordinatively unsaturated

https://doi.org/10.1016/j.mtchem.2018.11.002
2468-5194/© 2018 Elsevier Ltd. All rights reserved.
198 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216
atoms, for which edge atoms are expected to play a predominant
role in catalysis when 2D semiconductors have a perfect
surface structure without defects [4]. Moreover, pristine 2D semi-
conductors can barely achieve highly selective photocatalysis, as
high selectivity typically requires specific catalytic environment
around surface active sites. In addition to the issue of active sites, it
seems an irreconcilable conflict between satisfactory solar har-
vesting and sufficient reductive/oxidative ability. Strong reductive/
oxidative ability requires relatively negative conduction band
minimum (CBM) and positive valence band maximum (VBM),
leading to a wide band gap (Eg). Given this situation, only short-
wavelength light can be absorbed to excite electrons from valence
band (VB) to conduction band (CB). For instance, the light absorp-
tion by the most famous photocatalytic semiconductor, TiO2
(Eg ¼ 3.2 eV for anatase or 3.0 eV for rutile), is restricted in the range
of ultraviolet spectrum, which occupies only 4% in solar energy. For
this reason, the research community has developed a series of
methods for modifying 2D materials for photocatalysis, including
morphology and structure control [5], vacancy engineering,
elemental doping [6], and integration with other semiconductors or
metals [7].
In this review, we will first give a clear outline on the categories
of 2D materials commonly used for photocatalysis and their feature
structures, followed by a brief introduction to the synthetic stra-
tegies for 2D materials toward photocatalytic applications. As the
key content of this review, the strategies for designing 2D materi-
alebased photocatalysts with remarkable performance are
comprehensively summarized and discussed to reveal the corre-
lations of performance with design. Finally, a conclusion and
outlook is given to suggest potential directions for future works. We
hope that this review, with a specific focus on 2D materials and a
broad vision on various photocatalytic applications, would help
readers gain a clear understanding on the critical parameters to the
design of 2D materialebased photocatalysts and in turn stimulate
further investigations.
2. 2D materials used for photocatalysis
A variety of 2D materials have been successfully prepared for
photocatalysis owing to the rapidly developing structural cognition
and synthetic techniques. Basically, the origin of 2D structures can
be classified into layered and non-layered materials. As the name
suggests, the layered materials are formed by stacking layers with
weak interlayer interaction. As a result, they can be readily exfoli-
ated to generate 2D nanosheets through top-down methods.
Graphitic carbon nitride, transition metal dichalcogenides (TMDs),
some transition metal oxides, transition metal carbides/nitrides
(MXenes), and black phosphorus (BP) fall into this category.
Differently, the bulk materials formed with their atomic arrange-
ment isotropically in three dimensions, such as some metal oxides
and metal chalcogenides, are of non-layered structures. Neverthe-
less, “2D photocatalysts” here refer to the 2D materials with pho-
tocatalytic activities or can be served as co-catalysts in the photo-
related reactions. In this section, we will elaborate on the 2D
materialebased photocatalysts with various compositions and
structures.
2.1. Graphitic carbon nitride
Polymeric graphitic carbon nitride (namely, g-C3N4) is a special
allotrope of covalent carbon nitride. g-C3N4 has a stacking layered
structure, in which each planar layer is formed by tri-s-triazine
units bridged by amino groups. Considering the aromatic units, it is
expected to form a large graphite-like p-conjugated planar struc-
ture which carries out remarkable electron conductivity across the
layer [8]. Relying on the highly condensed and conjugated struc-
ture, g-C3N4 exhibits great tolerance to not only neutral but also
strongly acidic or alkaline environment and possesses a promising
band structure with proper CB, VB, and a band gap of 2.7 eV for
photocatalytic hydrogen generation [9,10]. Owing to the weak van
der Waals force between layers, it is accessible to transform bulk g-
C3N4 into g-C3N4 nanosheets, leading to an elevating performance
in photocatalytic water splitting [8,11]. In addition to the increasing
specific surface area, the band gap of g-C3N4 is widened by reducing
the thickness with the CB and VB shifting to more negative and
positive levels, which also contributes to the excellent performance
in water splitting. Another appealing feature for g-C3N4 is the
presence of abundant defects formed among tri-s-triazine units.
The defects in g-C3N4 are the key species to modulate band struc-
ture as well as the ideal sites for coordination with metal atoms or
metal complexes. Such a coordination strategy provides opportu-
nities for modifying g-C3N4 with various active sites to obtain
functionalized photocatalysts.
2.2. Black phosphorus
Since 2D BP monolayer was prepared by a scotch-tape me-
chanical cleavage technique toward field-effect transistors [12],
enormous efforts have been made to utilize BP in electronic and
optoelectronic devices because of its fascinating properties
[12e15]. In addition to the high specific surface area and carrier
mobility [16], 2D BP has an appealing band structure. The band gap
of BP can be tuned between 0.3 and 2 eV, achieved by peeling bulk
BP into monolayer BP [17]. This band gap range corresponding to
visible and infrared light makes 2D BP a promising photo-
responsive material. Although theoretical studies have predicted
the potential photocatalytic activity of 2D BP [17,18], little experi-
mental evidence was provided to demonstrate the photocatalysis
by BP alone until a recent work reported by Zhu et al. [19] By ball-
milling with LiOH, 2D BP alone exhibited a hydrogen evolution rate
of 512 mmol g1 h1 under visible light, which outperformed that of
g-C3N4. Inspired by this investigation, various photocatalytic ap-
plications based on BP are expected to emerge in the future.
2.3. Metal oxides
Many metal oxides possess wide band gaps so as to offer
favorable energy levels to carry out reduction or oxidation re-
actions; however, they often exhibit relatively low electron con-
ductivity, lowering photocatalytic rates. As it is a grand challenge to
accelerate the migration of photo-induced electrons in pristine
metal oxides, it seems a more effective way to improve photo-
catalysis by cutting down the migration path. Toward this goal, one
can reduce the scale of the third dimension while expanding the
other two to form a thin structure with high surface fraction. Such a
2D structure not only achieves a short distance for the electron
migration from bulk to surface active sites but also retains high
specific surface area [20]. As most metal oxides are not in the form
of layered structures, only a limited number of 2D metal oxides
were originally reported for photocatalysis. As new synthetic sys-
tems and techniques emerged, more 2D nanostructures of metal
oxides such as TiO2, Co3O4, and ZnO have been developed [20e27].
It is worth mentioning that perovskite oxides are a class of
conventional materials which have been reviving in recent years for
its emerging performance in photocatalysis and photovoltaic ap-
plications [28e32]. Perovskites have a general chemical formula in
the form of ABO3, where B is coordinated with six oxygen atoms to
form an octahedron while A is located in the center of a cubic unit
cell constructed by eight BO6 octahedrons. For many stratiform
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216
perovskites, their layered perovskite nanosheets can be produced
simply through exfoliation.
Bismuth oxyhalides are a class of layered transition metal oxy-
halides with remarkable photocatalytic activity, generally in the
formula of BiOX (X ¼ Cl, Br, I). Each layer of BiOX is constructed by
X-O-Bi-O-X, and the layers are interacted by van der Waals force. As
such, the BiOX layers can be readily exfoliated into nanosheets,
which enlarges atomic radius and reduces the electronegativity of
halogens. As a result, the band gaps for BiOCl, BiOBr, and BiOI are
reduced from 3.4 eV, 2.8 eV, and 1.8 eV, respectively, forming
satisfactory band structures for photocatalysis [33].
2.4. Metal chalcogenides, carbides, and nitrides
It has been proven that 2D metal chalcogenides have the po-
tential in photocatalytic reactions [34e37]. Peng et al. synthesized a
flower-like catalyst consisting of ultrathin CdSe nanosheets
through a solvothermal method [36]. The nanosheet assembly
outperformed the well-studied CdSe quantum dots in photo-
catalytic hydrogen evolution, owing to the optimized band struc-
ture and abundant surface sites.
Among metal chalcogenides, 2D transition metal dichalcoge-
nides (namely, 2D TMDs) are a branch of particular concern that
exhibits inspiring potential in photocatalysis. Unlike the metal ox-
ides with relatively low electron migration rates, 2D TMDs usually
exhibit remarkable electron conductivity. On the other hand, the
relatively weaker electronegativity for chalcogens results in a
smaller band gap. As a result, bulk TMDs are incapable of under-
going photocatalytic reactions as their insufficient band gaps cause
poor light-harvesting capacity and reduction/oxidation ability.
Utilizing quantum confinement effect, the band gaps of TMDs can
be enlarged to meet the requirement for photocatalytic reactions by
thinning them into ultrathin nanosheets [38]. Nevertheless, only a
few cases have been reported for photocatalytic applications based
on pristine TMD nanosheets because of their frustrating overall
performance in photocatalysis. In contrast, a number of works have
employed TMD nanosheets as co-catalysts, which turned out to
show appealing photocatalytic efficiency.
Most recently, a surge of research that utilizes 2D MXenes in
photocatalysis has emerged along with the development of new
MXenes materials. Although MXenes are incapable of harvesting
light, they can play a promising role as co-catalysts in photo-
catalysis owing to their layered structure, metallic conductivity,
abundant hydrophilic surface sites, and stable functionalized ability
[39e42].
3. Synthetic approaches to 2D materials for photocatalysis
The development of efficient synthetic strategies for 2D mate-
rials with desired composition and controllable morphology is the
foundation for investigating their physical and chemical properties
as well as further applications. In general, the synthetic approaches
to 2D materials for photocatalysis can be divided into two cate-
gories: top-down and bottom-up methods. The top-down
Table 1
The comparison of different synthetic approaches to 2D materials.
Strategy Controllability Scalable production
Mechanical techniques Low High
Liquid-phase exfoliation High Low
Solvothermal synthesis High High
2D-templated synthetic strategy Medium Low
TMD, transition metal dichalcogenide; MOF, metal organic framework; COF, covalent organic framework; LDH, layered double hydroxide.
199
strategies including mechanical cleavage and liquid-phase exfoli-
ation are only applicable to the materials with layered structures,
thereby limiting the development of 2D photocatalysts. To
circumvent this situation, bottom-up strategies have been explored
for preparing 2D materials from both layered and non-layered
structures. Chemical vapor deposition and wet-chemical synthe-
sis are the two major bottom-up methods. Together with top-down
approaches, the bottom-up methods have generated a wide range
of 2D materials toward photocatalysis with splendid performance
(Table 1). In this section, the well-developed synthetic strategies for
2D materials toward photocatalysis are concisely summarized.
3.1. Mechanical techniques
As a simple and straightforward method, scotch tape exfoliation
has become famous in the generation of 2D materials since the first
cleavage of high-quality graphene [43]. After 10 years, a new family
of 2D materialsdBPdemerged by employing the same approach
(Fig. 1a) [12]. This technique takes the advantage that the van der
Waals interaction between the planes of layered materials is
weaker than the adhesive force between the scotch tape and the
materials, so as to peel off ultrathin nanosheets. Until now, many
layered materials such as TMDs, BP, and h-BN have been success-
fully exfoliated by this method [1]. The ultrathin nanosheets ob-
tained through scotch tape exfoliation usually possess clean
surfaces and relatively large planar scales. Unfortunately, some
drawbacks, which include the low controllability in the number of
layers, wide distribution of lateral size, and frustrating yield, limit
its utilization in the production of photocatalysts. Another wide-
spread mechanical techniquedball millingdexhibits a higher
production rate. As a result, ball milling has been successfully
employed in the synthesis of ultrathin carbon nanosheets (Fig. 1b)
[44,45]. Triggered by mechanical milling, the planes in layered
structures slide to form ultrathin nanosheets.
3.2. Liquid-phase exfoliation
Liquid-phase exfoliation is developing rapidly in recent
years and has been enriched by many newly explored techniques.
Investigations have revealed that the solvents with suitable cohe-
sive energy to layered materials are the most desirable media for
such exfoliation. Although the exfoliation of various layered ma-
terials (e.g. MoS2, WS2, MoSe2, MoTe2, TaSe2, NbSe2, NiTe2, BN, and
Bi2Te3) has been achieved in pure common solvents [46], the de-
mand for exfoliation with high efficiency and high production rate
is not satisfied yet. Given this situation, many improvements have
been made to fulfill the requirements for liquid-phase exfoliation
method:
(1) Original liquid-phase exfoliation. The layered materials can
be easily exfoliated through ultrasonic treatment. For
instance, Wang et al. have successfully synthesized aza-CMP
with a layered structure and exfoliated it into 2D photo-
catalyst [47,48]. Another class of materials that have received
Cost Example
Low TMDs [1], carbon [44,45]
High Layered MOFs [49], COFs [47,48], TMD [51], LDHs [55e57], metal
sulfide such as MoS2, WS2 [46]
Medium metal oxide such as TiO2 [59,60], BiVO4 [61], BiOCl [62]
High In2O3 [63], CuSe [64]
200 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216

Fig. 1. (a) Atomic force microscope (AFM) images of black phosphorus thin flake. Reproduced with permission [12]. Copyright 2014, Nature Publishing Group. (b) Schematic
illustration for the physical cracking and edge carboxylation of graphite by ball milling. Reproduced with permission [44]. Copyright 2012, National Academy of Sciences. (c)
Schematic illustration for the partial lithiation of MX2 (M ¼ group IVB-VIB, X ¼ S, Se) single crystals to LixMX2 crystals that can be rapidly exfoliated into single-layer nanosheets by
only manual shaking. Reproduced with permission [51]. Copyright 2017, American Chemical Society. (d) Schematic illustration for the electrochemical lithiation process for
fabricating 2D nanosheets from layered bulk material. Reproduced with permission [54]. Copyright 2011, Wiley-VCH Verlag GmbH & Co. (e) Schematic illustration for the formation
of LDH monolayers through ion-exchange exfoliation. Reproduced with permission [58]. Copyright 2014, Nature Publishing Group. LDH, layered double hydroxide.

increased attentiondmetal organic frameworks (MOFs)d
with a layered structure could also be exfoliated into ultra-
thin 2D nanosheets [49]. It is worth noting that additional
transition metal cations should be excluded from the exfo-
liation system during the exfoliation of layered materials
(e.g. covalent organic frameworks, COFs). The additional
metal atoms may be bonded to the widely existing coor-
dinatively unsaturated sites in the layered COFs. Moreover,
this simple liquid-phase exfoliation motivated by sonication
usually need a long time that energy is mostly wasted. More
importantly, the exfoliated 2D materials can only be
dispersed at a low concentration, which requires a large
volume of solvents in the storage and usage. To overcome
this obstacle, various modifications have been made on
liquid-phase exfoliation.
(2) Ion intercalation-assisted liquid-phase exfoliation. Metal
ions with small radius (e.g. Liþ and Naþ) are capable of
intercalating the interlayer spacing of layered materials. The
intercalation enlarges the interlayer distance as well as
brings down the van der Waals force, which contributes to
the improved exfoliation efficiency [50e53]. Recently, Peng
et al. have synthesized high-quality monolayer TMD
nanosheets by exfoliating TMD single crystals with Liþ
interaction and without sonication, demonstrating a prom-
ising energy-saving approach (Fig. 1c) [51]. Unlike tradi-
tional chemical Liþ intercalation method, Zheng et al.
replaced thermal process by electricity, which developed a
highly efficient electrochemical lithiation approach. This
approach involves an electrochemical system consisting of a
lithium anode and a TMD cathode so as to realize high-
speed lithium insertion, followed by sonication and centri-
fugation (Fig. 1d) [54].
(3) Ion exchange-assisted liquid-phase exfoliation. Differently
from ion intercalation strategy, ion exchange-assisted exfo-
liation usually causes changes in product compositions.
Instead of inserting ions into interlayer spacing, the ions with
relatively large radius can take the place of the original ions
with small radius located at the layer surface. This process
expands the interlayer distance and weakens the van der
Waals interactions. This strategy is commonly used to exfo-
liate metal oxides (particularly perovskite metal oxides) or
layered double hydroxides (LDHs) with layered structures
[55e57]. For instance, LDHs are stacked by hydroxide layers
between which some extra anions exist to keep charge
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216 201

balance as shown in Fig. 1e. These anions are not strongly
fixed in the crystal lattice, so they can be exchanged by other
anions with large radius such as oxyacid anions and organic
anions [58].
3.3. Solvothermal synthesis
interaction, atomically thin structures could be generated through a
self-assembly process driven by the hydrophobic tail of organic
anions [31,32,35,63]. Sun et al. applied block copolymer (Pluronic
P123) and ethylene glycol to form inverse lamellar micelles, which
realized the self-assembly synthesis for a wide range of ultrathin 2D
metal oxides (Fig. 2a) [23].

Extreme condition often facilitates the anisotropic growth of
materials. Based on this mechanism, the synthesis of 2D materials
toward photocatalysis can be achieved by solvothermal methods
owing to high temperature and pressure conditions. For example, it
has been proven that the TiO2 {001} facets with high surface energy
are expected to possess excellent photocatalytic activity [59,60].
However, high surface energy also represents low stability, leading
to the difficulty in synthesis. Theoretical calculation has predicted
that the surface energy of {001} facets becomes lower than that of
{101} when the surface of anatase TiO2 is covered by F atoms [26].
Consequently, TiO2 nanosheets with up to 89% surface coverage of
{001} facets were successfully synthesized through a hydrothermal
method [21]. The 2D structures with certain surface facets were
also obtained on BiVO4 and BiOCl. The 2D structures not only
exhibited remarkable photocatalytic activity but also provided a
platform for investigating the correlation between surface facets
and photocatalytic performance [61,62].
In addition to the relatively thick nanostructures mentioned
above, atomically thin nanosheets have also been produced by
implementing this strategy. In particular, organic ligands have been
employed to assist the synthesis of ultrathin nanosheets. The in-
vestigations by Liang et al. revealed that by coordinating metal
cations with organic anions (e.g. oleate ions) via electrostatic
3.4. 2D-templated synthetic strategy
2D-templated synthetic strategy can efficiently produce 2D
materials with layered and non-layered structures. Basically, pre-
cursor atoms can be adsorbed onto the rationally selected 2D
templates. By optimizing reaction conditions, the crystal lattice will
expand along the planar face of the template to form a new com-
pound so that the template actually serves as a sacrificial agent
(Fig. 2b) [24].
In the 2D-templated synthetic strategy, another approach is to
transform 2D precursor into a desired phase so as to achieve the
synthesis of ultrathin 2D photocatalyst [64]. As mentioned above,
ultrathin transition metal hydroxide nanosheets can be synthesized
in a relatively convenient way than metal oxide nanosheets.
Therefore, it is a promising strategy for the development of 2D
metal oxide photocatalysts to calcinate ultrathin hydroxide nano-
sheets. For instance, as shown in Fig. 2c, In(OH)2 ultrathin nano-
sheets were first synthesized via a hydrothermal method with the
assistant of oleate and then calcined at 400 C in air to produce
oxygen vacancy-rich In2O3 nanosheets [63]. The In2O3 nanosheets
exhibited the promoted water splitting performance under visible
light. It is worth pointing out that metal oxide nanosheets obtained
via this approach often possess abundant porous structures [63,65].

Fig. 2. (a) Schematic illustration for the self-assembly of 2D metal oxide nanosheets. Reproduced with permission [23]. Copyright 2014, Nature Publishing Group. (b) Schematic
illustration for the synthesis of large-size ultrathin 2D metal oxide nanosheets using 2D graphene oxides as sacrifice templates. Reproduced with permission [24]. Copyright 2017,
Wiley-VCH Verlag GmbH & Co. (c) Schematic illustration for the formation of atomically thin In2O3 porous sheets. Reproduced with permission [63]. Copyright 2014, American
Chemical Society.
202 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216

Fig. 3. Electronic energy levels for various semiconductors and the redox potentials of different compounds involved in N2 fixation and CO2 reduction at pH ¼ 7, while a normal
hydrogen electrode (NHE) served as the reference electrode.

4. Current design of photocatalysts based on 2D materials
Pristine 2D materials often exhibit undesired performance in
photocatalysis because of their intrinsic properties. As shown in
Fig. 3, suitable band position and band gap are not both achieved
for a single semiconductor in many cases. Moreover, some reactions
such as N2 fixation and CO2 reduction require higher energy levels
than that the semiconductors can afford. To meet the demand for
improved performance, a number of ingenious thoughts have been
put on the design of ideal 2D materialebased photocatalysts,
including morphology/structure tuning [66,67], defect engineering
[63,68e71], elemental doping [35,72], and composite formation
[40,42,52,73e78]. These strategies are specifically developed to
improve the efficiency of each step during a photocatalytic process:
(1) proper band gaps to absorb incident light in a broad spectrum;
(2) reduced recombination of photo-induced carriers to ensure that
they can reach active sites; (3) competent energy levels of photo-
induced carriers to reduce/oxidize reactants; (4) abundant active
sites with high activity to adsorb and activate reactants; and (5)
efficient mass transfer in the entire reaction process. In this section,
while summarizing various strategies for designing optimal 2D
materialebased photocatalysts, we intend to analyze and discuss
how each strategy rationally works for the improvement of one or
more steps during photocatalysis.

Fig. 4. (a) Crystal structures of A5B4O15. (b) Density of states (DOS) of A5B4O15 materials (A ¼ Ca, Sr, Ba; B¼V, Nb, and Ta). Fermi levels are set to zero and denoted with dashed lines.
(c) VBM and CBM positions of various nanosheets. Redox potentials of Hþ/H2 and O2/H2O are represented by orange dash lines. Reproduced with permission [30]. CBM, conduction
band minimum; VBM, valence band maximum. Copyright 2016, Elsevier.
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216 203

4.1. Structure and morphology tuning strategy
Crystal structures are closely related to band structures of
semiconductors. Recently, Wu et al. investigated the behavior of
A5B4O15-type perovskite 2D materials (Fig. 4a) in photocatalytic
hydrogen generation through systematic calculations [30]. The
CBM of A5B4O15 is formed by d-orbitals of B and p-orbitals of O. By
varying the electronegativity of B, the band gap can be modified.
Although A cation is not responsible for the band gap, it plays an
important role in adjusting work function. Specifically, the lattice
constants are increased by the presence of A ions with larger radius.
This lattice expansion leads to the decrease in work function, cor-
responding to the elevation of band edge (Fig. 4b and Table 2).
Based on the theoretical findings, 2D Ca5V4O15 nanosheets with a
desired band gap of 2.24 eV were designed to harvest visible light.
The moderate band edge positions straddle the levels for Hþ/H2 and
O2/H2O so that the 2D Ca5V4O15 nanosheets are capable of trig-
gering hydrogen and oxygen generation (Fig. 4c).
Given a certain crystal structure, the crystal facet exposed to
reaction environments is a key parameter to the photocatalytic
performance of nanostructured materials [77,78]. Various crystal
facets offer different surface structures including lattice constants,
exposed atoms, and coordination numbers, as well as varied surface
energy, providing a knob for tuning catalytic activity. Yu et al.
achieved optimized performance in photocatalytic CO2 reduction
by manipulating the ratio of {001} to {101} facets on anatase TiO2
nanosheets with different hydrogen fluoride (HF) amounts [67]. As
revealed by density functional theory (DFT) calculations (Fig. 5), the
band edge positions of {001} facet shift up due to its larger TieOeTi
Table 2
Formation energies, lattice constants, and band gaps of A5B4O15 nanosheets.
bond angle, while the band edge positions of {101} remain un-
changed. This results in a surface heterojunction formed by co-
exposed {001} and {101} facets. On such a surface heterojunction,
the photo-induced electrons prefer to migrate toward {101} facet
while {001} is the favorable location for hole accumulation, sup-
pressing charge recombination. In addition to the suppression of
charge recombination, the ratio of exposed facets on this surface
heterojunction should be further taken into account. With a mod-
erate ratio of {001} to {101}, the consumption rates of electrons and
holes can be matched to avoid the accumulation of excessive
electrons on {101}. The presence of excessive electrons on surface
would hinder the migration of electrons from bulk to surface,
limiting the overall photocatalytic performance.
4.2. Vacancy engineering strategy
Active sites are indispensable to catalysis given their function of
adsorbing and activating reaction molecules. This important func-
tion is often accomplished by the coordinatively unsaturated sur-
face atoms with dangling bonds. In most cases, defects are
undesirable in bulk photocatalysts as photo-induced carriers will
recombine at these locations. However, the situation is quite
different in 2D materialebased photocatalysts. The large surface-
to-volume ratio for 2D materials ensures that the defects are
almost located at the surface, which provides abundant coor-
dinatively unsaturated sites. In addition, the defects can also in-
fluence the band structures of 2D photocatalysts to achieve optimal
light harvesting and energy transfer. The defect engineering stra-
tegies for 2D materialebased photocatalysts commonly include the
designs through the creation of anion vacancies, cation vacancies,
or both (i.e. coexisting vacancies).

Nanosheet Lattice Formation Band (1) Anion vacancy strategy. 2D metal oxides are a class of
constant (Å) energy (eV) gap (eV) important and widely used photocatalysts, for which oxygen
Ca5V4O15 5.305 1.80 1.14 vacancy has attracted tremendous attention [63,68,71,79].
Ca5Nb4O15 5.623 3.14 2.40 Recently, our group has developed defect-rich WO3 nano-
Ca5Ta4O15 5.593 3.38 2.85
sheets for efficient photocatalytic aerobic couplings of
Sr5V4O15 5.454 1.54 1.25
Sr5Nb4O15 5.740 2.62 2.46 amines to corresponding imines under visible-near-infrared
Sr5Ta4O15 5.684 1.92 2.83 illumination, which could be hardly achieved by defect-free
Ba5V4O15 5.651 1.11 1.31 WO3 [79]. Leveraging multiple characterization techniques,
Ba5Nb4O15 5.890 1.93 2.54 it was affirmed that the abundant defects located on surface
Ba5Ta4O15 5.855 2.00 2.89
not only contributed to the optimal band structures of

Fig. 5. (a) Schematic illustration for the spatial separation of redox sites on the HF0, HF4.5, and HF9 samples. (b) Comparison of the photocatalytic CH4-production activity of P25
and the TiO2 samples prepared by varying HF amount. (c) DOS plots for {101} and {001} surface of anatase TiO2. (d) Schematic diagram for {001} and {101} surface heterojunction.
Reproduced with permission [67]. Copyright 2014, American Chemical Society. DOS, density of states; CB, conduction band; VB, valence band.
204 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216

Fig. 6. (a) Atomic-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images of defect-rich WO3 (R-WO3) nanosheets. The lattice
disorder induced by defects is marked by blue arrows. (b) Room-temperature electron spin-resonance (ESR) spectra. (c) Schematic illustrating the locations of oxygen vacancies in
WO3 lattice. (d) Simulated charge density for the O2 chemisorbed at a coordinatively unsaturated W site of defective WO3. (e) ESR detection of superoxide radicals using a 5,5-
Dimethyl-1-pyrroline N-oxide (DMPO) spin-trapping agent. (f) Performance of various catalysts in aerobic coupling of benzylamine under irradiation of l > 400 nm with ther-
mostatic control at 298 K, in comparison with that by thermal process in the dark. Reaction time: 2 h. (g) Schematics illustrating the electronic band structures. (h) Performance of
R-WO3 and D-WO3 in catalytic aerobic coupling of benzylamine under various light irradiation at 298 K. Reaction time: 2 h. (i) Simulated differential charge density for the O2
chemisorbed at a coordinatively unsaturated W site of defective WO3 upon charging an electron to the WO3. Purple and olive colors represent increase and decrease in electron
density, respectively. VB, valence band; CB, conduction band. Reproduced with permission [79]. Copyright 2016, American Chemical Society.

defect-rich WO3 but also generated coordinatively unsatu-
rated W atoms to enable O2 chemisorption (Fig. 6). Further
investigations suggested that the adsorbed O2 can receive
photoexcited electrons from the coordinatively unsaturated
W atom, which would produce superoxide radicals to trigger
the aerobic couplings of amines. This work strongly dem-
onstrates that oxygen vacancy engineering can serve as a
versatile approach to develop low-cost photocatalysts.
Indeed, the oxygen vacancy can serve as the active site for
various reactions. For instance, N2 fixation is an important step in
the Earth's nitrogen cycle and plays key roles in the production of
fertilizer. Given the strong triple bond and non-polar feature of N2
molecule, the spontaneous conversion of N2 can be hardly achieved
although this process is thermodynamically favored [78,80]. The
industrial Haber-Bosch process is widely used with iron-based
catalysts but requires high power consumption. For this reason,
the photocatalytic conversion of N2 has been explored through
various designs [81e85]. Most recently, Li et al. developed the
BiOBr nanosheets with oxygen vacancies for efficient visible-light
nitrogen fixation [86]. The oxygen vacancies acted as active sites
for N2 adsorption and NeN bond activation. Meanwhile, the
vacancies could capture the photo-induced electrons, which
reduced charge recombination of carriers and transported the
trapped electrons to the adsorbed N2.
(2) Cation vacancy strategy. As compared with anion vacancies,
it is dramatically more challenging to create cation vacancies
(particularly metal cation vacancies in 2D inorganic photo-
catalysts) due to the large formation energy. Nevertheless,
the important role that metal cation vacancies can play has
largely motivated their investigations. Benefitting from the
tunable electron states in d-orbits for transition metals,
metal cation vacancies may introduce more complicated
changes than anion vacancies. This feature thus enables
multifarious manipulation on the band structures and sur-
face features of 2D photocatalysts. In a typical case, ZnIn2S4
atomic layers with different zinc vacancy concentrations
were successfully prepared by Jiao et al., which exhibited
distinguishable CO2 photoreduction performance (Fig. 7aec)
[70]. The zinc vacancies would introduce higher charge
density at the nearby sulfur atoms according to DFT calcu-
lations (Fig. 7fei), suggesting the promoted photoexcitation
and reduced electron-hole separation. Moreover, the zinc
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216 205

Fig. 7. (a) HAADF-STEM images of VZn-rich ZnIn2S4 (ZIS). (b) Intensity profile corresponding to the dark cyan arrow in a, demonstrating abundant zinc vacancies in the atomic layer.
(c) Room-temperature ESR spectra. Ultrafast transient absorption spectroscopy of (d) VZn-rich one-unit-cell ZIS layers and (e) VZn-poor one-unit-cell ZIS layers. Distribution of partial
charge density near the edge of conduction band for (f) VZn-rich one-unit-cell ZIS layers slab and (g) VZn-poor one-unit-cell ZIS layers slab along the [001] orientation. The cor-
responding unit cell structure of (h) VZn-rich one-unit-cell ZIS layers slab and (i) VZn-poor one-unit-cell ZIS layers slab along the [001] orientation. Reproduced with permission [70].
Copyright 2017, American Chemical Society.

vacancies could act as the sites for capturing photoexcited
electrons and suppressing charge recombination (Fig. 7d and
e). As a matter of fact, zinc vacancies contributed to a number
of factors, including the promoted light absorption, the
enhanced CO2 adsorption, and the excellent hydrophilicity to
host sufficient protons. All these features facilitated the
photocatalytic CO2 reduction activity by VZn-rich ZnIn2S4
ultrathin sheets. Similar results have been also observed for
VV-rich BiVO4 atomic layers, which can efficiently photo-
catalyze CO2 into methanol [32].
(3) Coexisting vacancy strategy. In certain situations, both anion
and cation vacancies can exist together in 2D photocatalysts.
Unlike the case of single-type vacancies, it is substantially
more complicated to predict the functions of coexisting va-
cancies [69,87,88]. The coexisting vacancies of different types
may have interplay effects on or work separately in photo-
catalysis. Specifically, for photocatalysis, the synergetic effect
by two vacancies attracts more interests as it may create new
opportunities for tuning molecule adsorptions and maneu-
vering carrier behavior. Guan et al. have synthesized BiOCl
nanoplates with surface Bi vacancies. As the thickness is
reduced to atomic level (Fig. 8a), both Bi and O vacancies
appeared, which exhibited strongly coupling behaviors [69].
As compared with single Bi vacancies, BieOeBi vacancies in
ultrathin BiOCl nanosheets could generate negatively charged
surface to facilitate the adsorption of cationic dye molecules
(Fig. 8b and c). Meanwhile, the associated vacancies altered
the band structure of BiOCl. The VBM and CBM of BiOCl
nanosheets are both up-shifted to produce more reductive
electrons upon photoexcitation, while the band gap is nar-
rowed to expand the range of light harvesting (Fig. 8d).
4.3. Elemental doping strategy
Although many efforts have been made to enhance the perfor-
mance of pristine 2D photocatalysts, it still remains a grand chal-
lenge to achieve highly active and selective 2D photocatalysts as the
properties of their active sites are largely restricted by intrinsic
compositions. Elemental doping offers an effective way to develop
outstanding 2D photocatalysts by optimizing band structures and
introducing new active sites [35,89,90].
Among various 2D materials, g-C3N4 is an ideal framework for
hosting heteroatoms owing to its abundant pores and nearby
coordinatively unsaturated atoms, which can be prepared by a va-
riety of synthetic methods including both bottom-up and top-down
strategies. To date, exciting progress has been made on the incor-
poration of various elements including metal and non-metal atoms
into g-C3N4, creating a variety of new materials with superb pho-
tocatalytic performance [91e95]. In terms of non-metal atoms,
(e.g. S and P), elemental doping usually takes place in two for-
msdsubstitutional doping and interstitial doping, which depends
on the atomic radii and negativities of elements. Specifically, S atoms
usually substitute N sites [96], while P atoms are often located at C
sites (Fig. 9a) [97]. The dopant sulfur introduces extra energy levels
into the VB of g-C3N4, leading to a broadened VB and an extended
light absorption (Fig. 10b). In addition to the promoted light har-
vesting, P-doped C3N4 shows enhanced electric conductivity, which
can be ascribed to the formation of carrier migration pathway
CeNePeNeC, where N atoms in two neighboring tri-s-triazine units
are linked by interstitial P atoms (Fig. 9cee). Similarly, the O-doped
ZnIn2S4 atomic layers that were successfully synthesized by Yang
et al. exhibited outperforming H2 evolution efficiency than pristine
ZnIn2S4 [72]. Dopant O enabled the increased DOS at VBM, indi-
cating more charge carriers in photocatalysis. Moreover, the exis-
tence of lattice oxygen created new defect states that could act as the
centers for trapping photo-induced electrons, thereby promoting
electron-hole separation and promising longer carrier lifetimes.
In parallel, metal atoms have been also incorporated into 2D
materials for enhanced photocatalysis. The doping of highly active
catalytic elements (e.g. Pd and Pt) into g-C3N4 is an effective
approach to develop efficient photocatalysts from the angle of
single-atom catalysis. Owing to the relatively large radii of metal
atoms, they prefer to locate at the pore structures. It is worth
pointing out that the function of incorporated metal elements
heavily relies on their valence states. By doping Pt2þ ions into g-
C3N4, our group has implemented metal-to-ligand charge transfer
(MLCT) effect to achieve improved photocatalytic hydrogen
206 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216

Fig. 8. (a) AFM image of ultrathin BiOCl nanosheets with an average thickness of 2.7 nm. (b) Schematic illustration for the trapped positrons of VBi000 V 000
O VBi vacancy associates. (c)
Schematic illustration for the photosensitization process under visible-light irradiation. (d) Schematic illustration for the band structure of ultrathin BiOCl nanosheets and BiOCl
nanoplates, in which the upshifting of valence band maximum and conduction band minimum effectively separates the photo-induced electron-hole pairs in ultrathin BiOCl
nanosheets. Reproduced with permission [69]. Copyright 2013, American Chemical Society.

generation performance (Fig. 10aec) [98]. As Pt2þ was coordinated
with N atoms, the d-orbits of Pt2þ could be hybridized with the
HOMO of nearby aromatic unit, which introduced a new hybrid
state located 1.2 eV above the HOMO of g-C3N4. Meanwhile, the
LUMO of g-C3N4-Pt2þ was shifted up by 0.3 eV, which resulted a
smaller band gap of 1.8 eV corresponding to an absorption of
visible-near-infrared light (Fig. 10d). As illustrated in Fig. 10e, the
MLCT process was achieved by the transfer of photoexcited elec-
trons from the Pt2þ-induced hybrid HOMO state below Fermi level
to the LUMO of g-C3N4-Pt2þ above Fermi level.
4.4. Composite photocatalyst strategy
The systems of composite photocatalysts cover a wide range of
heterostructures in efforts to enhance overall photocatalytic per-
formance. This strategy provides diverse opportunities for tuning
band structures, promoting carrier transfer, improving activity and
selectivity, and maneuvering other factors to achieve excellent
photocatalytic performance. Furthermore, the hybrid structures
also offer ideal models for deep investigations on the interfacial
effects that are of great importance to catalysis. The reported
composite configurations include 2D/0D (previously discussed in
Section 4.2 and 4.3) [98], 2D/1D [99e102], 2D/2D [103e107], and
2D/3D [108e113] composites.
(1) 2D/1D composite photocatalysts. 2D/1D composites have not
been widely explored given their shortcomings accompanied
with 1D materials. The 1D materials possess the relatively
low density of active sites as compared with 0D
materials and do not offer the contact area as high as 2D
materials. Nevertheless, 1D materials can play a role as sub-
strates to offer discrete sites for the distribution of 2D ma-
terials, thereby avoiding the agglomeration of 2D materials.
In a typical case, TiO2 nanorod arrays were adopted as a
substrate to in-situ grow ZnIn2S4 nanosheets, forming 3D
hybrid structures. The 3D hybrid structures possessed high-
quality interfacial contact and an increased number of
active sites for improved photoelectrochemical water split-
ting [106]. Other 1D materials such as carbon fibers were also
employed as excellent substrates to facilitate charge transfer
for promoted photocatalytic performance [102].
(2) 2D/2D composite photocatalyst. Taking advantage of large
specific area, the contact area in 2D/2D composite structures
is increased to enable strong interaction and efficient inter-
facial charge transfer. From this point of view, 2D/2D com-
posite structures have great potentials to realize
outperforming photocatalytic behaviors [40,41]. Graphene,
1T MoS2, and MXenes with metallic electronic behaviors can
serve as electron collectors, just like metals, to facilitate the
charge transfer from 2D semiconductors. Here we take n-
type semiconductor as an example. When a metal or
conductive material (e.g. graphene) with the relative low
Fermi level is in close contact with an n-type semiconductor,
the electrons in the semiconductor will flow to the metal or
conductive material. As a consequence, the surface of the
metal becomes to possess negative charges while positive
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216 207

Fig. 9. (a) Atomic structure models for a perfect graphitic C3N4 sheet consisting of melem units and two melem units with a substitutional nitrogen atom at different periodic sites
by sulfur atom. (b) Total DOSs of C3N4 (black line) and C3N4xSx (red line). Reproduced with permission [96]. Copyright 2010, American Chemical Society. (c) 31P solid-state magic
angle spinning nuclear magnetic resonance (MAS-NMR) spectra of P-doped g-C3N4. The asterisks mark spinning sidebands. The inset shows the building unit of C3N4 with P doping
at the corner-carbon site (C, gray; N, blue; P, orange). (d) UVevis spectra and (e) electrical conductivity of P-doped and pristine g-C3N4. (f) Current-potential curve of P-doped and
pristine g-C3N4 photoelectrodes. DOS, density of states. Reproduced with permission [97]. Copyright 2010, American Chemical Society.

charges are accumulated on the semiconductor. This lowers
the potential of the metal and lifts the potential of the
semiconductor, respectively. The confinement of free charge
density in semiconductor makes the positive charge
distribute in quite a range of the surface section, building an
electric field pointing from body to surface. As a result, the
energy level of the electrons in the semiconductor is
increased to bend the energy band upward, forming a surface
energy barrier. The Schottky barrier (namely, q4ms) can be
calculated by the equation: q4ms ¼ Wm  Ws þ EC  EFs,
where the Wm and Ws refer to the work functions of metal
and semiconductor, respectively. The Schottky barrier can
trap the electrons that have been transferred from semi-
conductor to metal, suppressing the recombination of the
photo-induced electron-hole pairs. In particular, graphene is
a splendid platform for construction of 2D/2D composite
photocatalysts. In addition to high electron conductivity, the
abundant surface functional groups of graphene allow its
facile integration with 2D semiconductor. The compact
interaction endows the composite with fast charge transfer
from 2D semiconductor to graphene, promoting the photo-
catalytic process [106,114,115].
208 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216

Fig. 10. (a) Structural illustration for the coordination of g-C3N4 with Pt2þ. (b) Fourier-transform IR spectra of g-C3N4-Pt2þ (0.18 wt%) in reference to bare g-C3N4. (c) Photocatalytic
H2 production rates with g-C3N4-Pt2þ (0.18 wt%) as a catalyst under irradiation of 400 nm < l < 470 nm and l > 470 nm in comparison with l > 400 nm. The power density of
l > 400 nm (200 mW cm2) is equivalent to the sum of 400 nm < l < 470 nm (30 mW cm2) and l > 470 nm (170 mW cm2). (d) Energy-band alignment diagrams for g-C3N4 and g-
C3N4-Pt2þ. (e) Photoexcited charge density transition from the Pt2þ-induced hybrid HOMO states (in the range of 0e1 eV below the Fermi level) to the LUMO of g-C3N4-Pt2þ (in the
range of 2e3 eV above the Fermi level), indicating the MLCT process. The yellow bubble represents electron population. MLCT, metal-to-ligand charge transfer. Reproduce with
permission [127]. Copyright 2016, Wiley-VCH Verlag GmbH & Co.

Fig. 11. (a) Side-view atomic-resolution HAADF-STEM image of 1L-BiOCl-MoS2 (BOC-MS). (b) Electron-hole separation within 1L-BOC. (c) Interfacial electron transfer from 1L-BOC
to 1L-MS along the Bi-S bonds. (d) Band alignments in 1L-BOC and 1L-MS. (e) Electrostatic potential viewed from the {110} facet of Bi12O17Cl2. Comparison of the electrostatic
potentials of (Cl2)-(Bi12O17)-(MoS2) (f) without and (g) with Bi-S bonds. VB, valence band; CB, conduction band. Reproduced with permission [52]. Copyright 2016, Nature Publishing
Group.

Similarly, the Janus bilayer junction consisting of single-layer
BiOCl and 1T MoS2 has been fabricated, which exhibited
improved visible-light hydrogen evolution activity (Fig. 11) [52].
The monolayer Bi12O17Cl2 has two asymmetric end-facesd[Bi12O17]
and [Cl2]; however, the integration with 1T MoS2 monolayer can
only take place at the [Bi12O17] side as the rich oxygen vacancies
sites favor the coupling with metals. In this unique structure, the
huge electrostatic potential difference between [Bi12O17] and [Cl2]
sides (Fig. 11b) forms a vertical internal electric field from the
former to the latter. This internal electric field can promote the
transfer of photo-induced electrons and holes to [Bi12O17] and [Cl2]
sides, respectively (Fig. 11c). As such, the electrons would transfer
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216
to the MoS2 monolayer through BieS bonds, achieving photo-
catalytic hydrogen evolution (Fig. 11d). MXenes such as Ti3C2 can
work as a co-catalyst in a similar way [39,41,42].
Certainly, the 2D/2D composite structures are not exclusively
based on the integration of 2D semiconductor with 2D electron
collector. Many hybrid photocatalysts consisting of two 2D semi-
conductors have been explored for enhanced photocatalytic per-
formance. As shown in Fig. 12, the composite semiconductors can
be classified into three typesdType I, Type II, and Z scheme. In the
Type-I configuration, the VBM and CBM of semiconductor B are
located within the band gap of semiconductor A. As such, both the
photo-induced electrons and holes tend to travel from A to B. In
most cases, semiconductor A is mainly responsible for harvesting
light, while semiconductor B enhances the adsorption and activa-
tion of molecules or promotes the charge transfer between cata-
lysts and molecules. In comparison, Type-II composite structures
consist of two semiconductors with a staggered energy band
alignment. In the photocatalytic process, the potential difference
drives the photo-induced electrons to flow from B to A, while the
holes in A are transferred to B. Such a structure is usually designed
when semiconductor A favors the reduction of molecules and
semiconductor B prefers to oxidize molecules. The energy levels of
photo-induced electrons and holes in both Type I and Type II are
lowered upon the charge flow between the two semiconductors,
which reduces the capabilities of reduction and oxidation half re-
actions. Enlightened by the working mechanism of photosynthesis
in green plants, researchers have developed a kind of
semiconductor-semiconductor heterostructures called Z-scheme
photocatalysts. The Z-scheme system cannot only enhance light
absorption but also suppress the recombination of electrons and
holes. To establish a Z-scheme system, the energy band positions of
two semiconductors should meet a certain requirement, similarly
to the situation in Type-II semiconductor. For one selected semi-
conductor (semiconductor B) with an ideal CBM position for
reduction reactions, the auxiliary semiconductor (semiconductor
A) should possess a CBM slightly higher than the VBM of semi-
conductor B. As such, the photogenerated electrons from semi-
conductor A would recombine with the holes from semiconductor
B, which leaves the photogenerated electrons in the CB of semi-
conductor B and the holes in the VB of semiconductor A for
reduction and oxidation reactions, respectively. To achieve broad-
band solar utilization, another requirement for the two semi-
conductors is that they should possess complementary band gaps.
She et al. have developed an efficient 2D a-Fe2O3/g-C3N4 catalyst
for photocatalytic water splitting [74]. As shown in Fig. 13, the
electrons in the CB of a-Fe2O3 could easily jump to the VB of g-C3N4
owing to their solid interface and recombine with the photo-
induced holes in the VB of g-C3N4. As a consequence, the
Fig. 12. Schematic diagrams of three types of the hybrid semiconductors. VB, valence band; CB, conduction band.
209
excitation of electrons in g-C3N4 became more efficient, and the
recombination of the photo-induced electrons in g-C3N4 was
strongly suppressed. Another geC3N4ebased 2D/2D composite
photocatalyst eBP/g-C3N4 was fabricated by Zhu et al. [116]
Different from 2D a-Fe2O3/g-C3N4, this hybrid structure formed a
Type-I heterojunction (Fig. 14). Under visible light, the excited
electrons in g-C3N4 moved to the CB of BP, which then merged with
the electrons generated in BP by absorbing NIR light. The electrons
together were trapped in the P-N coordinate bond formed at the
interface of BP and g-C3N4, thereby prolonging the lifetime of
electrons (Table 3).
(3) 2D/3D composite photocatalysts. One of the motivations for
developing composite photocatalysts is to broaden the range
of light absorption in a single semiconductor. For this reason,
2D semiconductor materials are often integrated with the
materials covering a different photo-response range, such as
semiconductor particles, quantum dots, and plasmonic
metals. In particular, the light-harvesting region for plas-
monic metals such as Au and Ag can be conveniently
manipulated by controlling their nanostructures. Benefiting
from the precise control over the morphology of Au nano-
particles, our research group has expanded the light ab-
sorption range to visible and near-infrared spectra by
integrating TiO2 sheets with Au nanocubes
(l ¼ 500e600 nm) and Au nanocages (l ¼ 600e1000 nm). To
promote charge separation, the resulted composite was
further combined with Pd nanocubes as a co-catalyst. The
synergetic effects of plasmonic light absorption and co-
catalyst efficiently promoted photocatalytic H2 evolution
(Fig. 15aed) [117].
Indeed, another motivation for developing composite photo-
catalysts is the introduction of co-catalysts into photocatalysts. The
metal co-catalysts play a dual role in photocatalysis. The Schottky
junction formed between semiconductor and metal co-catalyst can
efficiently trap photoexcited electrons and spatially promote
charge separation, while the co-catalyst provides active sites for
reduction reactions. As a matter of fact, transition metal alloy
nanoparticles commonly act as co-catalysts to enhance the pho-
tocatalytic performance of 2D semiconductors, whose composi-
tions offer a versatile knob for tuning the activity and selectivity of
reduction reactions. For example, bare TiO2 nanosheets only
exhibited a limited activity in photocatalytic CO2 conversion [67].
By optimizing the metal ratio of CuPd alloy co-catalysts loaded on
TiO2 nanosheets (Fig. 15e and f), our research group has achieved
the enhanced activity and selectivity (up to 96%) in the photo-
catalytic conversion of CO2 to CH4 [118].
210 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216

Fig. 13. (a) Schematic illustration for the proposed synthetic route to produce the a-Fe2O3/2D g-C3N4 hybrids. (b) Energy band diagram of Z-scheme mechanism in a-Fe2O3/2D g-
C3N4 hybrids at pH ¼ 0. (c) Turnover frequency by different materials. Reproduced with permission [74]. Copyright 2017, Wiley-VCH Verlag GmbH & Co.

Fig. 14. (a) Proposed schematic diagram for the visible- and NIR-light activated photocatalytic H2 evolution using BP/CN in the presence of methanol. (b) Photocatalytic H2 evolution
from water containing methanol (20 vol %) on different catalysts under visible-light (>420 nm) irradiation. BP, black phosphorus; VB, valence bond; CB, conduction band.
Reproduced with permission [116]. Copyright 2017, American Chemical Society.

4.5. Key parameters to 2D materials-based photocatalysts
Given the improved performance of 2D photocatalysis, it be-
comes imperative to decode the mechanisms behind the perfor-
mance and formulate the rules for further designing their
structures. The design strategies for efficient 2D photocatalysts
reported by previous articles are summarized in Fig. 16. It should be
noted that in many cases, more than one parameter are tuned for
each strategy and/or similar effects play key roles in different
strategies as listed in Table 4 [119e121]. To clarify the key points
and working mechanisms, here we would summarize the param-
eters and principles in each strategy.
(1) Solar absorption directly modulates the overall perfor-
mance for photocatalysts. In view of the energy distribu-
tion in the solar spectrum, 2D photocatalysts with an
energy band covering visible to near-infrared regions
should be in favor of fully utilizing solar energy toward
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216 211

Table 3 quantum confinement effect, vacancy control can readily

Lifetimes of charge carriers acquired from the time-resolved diffuse reflectance modulate band position by altering the electron density of
spectroscopic decays of CN, BP, and BP/CN under 400 nm and 780 nm irradiation,
respectively.
the atoms around vacancies. Meanwhile, new energy state
usually emerges when heteroatoms are doped into 2D
Sample t (ps) semiconductor, which in turn alters band position and
400 nm 780 nm band gap.
CN 101 (2) Another key parameter directly associated with the band
BP 0.8 0.8 structure is the reduction and oxidation ability of photo-
BP/CN 73 44 excited charge carriers. Hindered by the intrinsic band
BP, black phosphorus. feature, some 2D semiconductors are lack of sufficient
reduction or oxidation ability. One effective way is to build
chemical reactions. Three types of strategies are mainly hybrid band structures such as the Z-scheme system as
employed to optimize the band structures of photo- demonstrated above, which can enhance reduction/oxida-
catalystsdband shift, creation of new electronic state, and tion ability and maintain excellent light absorption
hybridization of band structures. In addition to the simultaneously.

Fig. 15. (a) Photograph of suspensions and (b) UVeviseNIR diffuse reflectance spectra of bare TiO2, Au cube-TiO2, Au cage-TiO2, Au cube/cage-TiO2, TiO2-Pd cube, as well as Au cube/
cage-TiO2-Pd cube hybrid structures. (c) Transmission electron microscopy (TEM) images of Au cube/cage-TiO2-Pd cube hybrid structure. (d) Photocatalytic average rates of
hydrogen production under light irradiation with l > 400 nm. Reproduced with permission [117]. Copyright 2016, Wiley-VCH Verlag GmbH & Co. (e) TEM images of Pd7Cu1eTiO2
hybrid structures. (f) Cycling production of CH4 and CO in photocatalytic CO2 reduction with H2O by Pd7Cu1-TiO2. Reproduced with permission [128]. Copyright 2017, American
Chemical Society.
212 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216

Fig. 16. Schematics illustrating the current design strategies and critical parameters for efficient 2D materialebased photocatalysts as well as the promising ones for future
development. MOF, metal organic framework.

Table 4
Design strategies and corresponding principles for 2D material-based photocatalysts.

Reactions Strategies Parameters Photocatalysts References

CO2 reduction Crystal structure and morphology Carrier lifetime TiO2 nanosheet [67]
Morphology Carrier mobility and separation Bi2WO6 nanoplate [119]
Zinc vacancies Carrier lifetime, active site, light harvesting ZnIn2S4 atomic layer [70]
2D/2D composite Light harvesting, carrier lifetime and mobility TiO2/Graphene [129]
2D/3D composite Active site PdCu alloy/TiO2 nanosheet [128]
N2 fixation Oxygen vacancies Carrier lifetime, active site BiOBr nanosheet [86]
Nitrogen vacancies Active site, carrier mobility and separation g-C3N4 [85]
Crystal facet Energy band position, carrier separation Bi5O7I nanosheet [120]
H2 evolution Crystal structure, morphology Light harvesting, energy band position Metal oxide [30]
Oxygen doping Energy band position, light harvesting, charge ZnIn2S4 [72]
density, and lifetime
Pt2þ doping Light harvesting g-C3N4-Pt2þ [127]
2D/2D composite Carrier separation, lifetime, and mobility 1L BiOCl/MoS2 [52]
2D/2D composite Energy band position, carrier lifetime a-Fe2O3/g-C3N4 [74]
2D/2D composite Light harvesting, carrier lifetime Black phosphorus/g-C3N4 [116]
2D/3D composite Light harvesting Au cube/cageeTiO2 sheetePd cube [117]
Oxidation Oxygen vacancies Energy band position, active site WO3 nanosheet [130]
reaction Oxygen vacancies Carrier lifetime, active site BiOCl/Au [121]
Bi-O-Bi coupling vacancies Active site, energy band position, light harvesting BiOCl atomic layer [69]
2D/1D composite Carrier mobility TiO2 sheet/carbon fiber [108]
 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216
(3) The lifetime and mobility of photo-induced carriers are also
critical parameters to photocatalysis. Facet engineering can
promote charge separation by guiding the migration of
electrons and holes toward different surface facets. In par-
allel, vacancy engineering (e.g. the creation of oxygen va-
cancies) may produce the sites of positive charges to trap
electrons, thereby reducing the recombination of electrons
and holes. Certainly, the hybrid band structures mentioned
above also provide an approach to prolong the lifetimes of
remaining electrons and holes. In the composite photo-
catalysts, the built-in electric field originating from hetero-
junctions is an indispensable factor for facilitating charge
separation and transfer as well.
(4) Upon absorbing solar photons and producing photoexcited
carriers, the photocatalytic reactions still rely on the in-
teractions between catalyst surface and reaction molecules,
accompanied with the charge transfer from photocatalyst to
reaction sites and then to reaction molecules [122]. Distin-
guished from regular surface sites, special active sites created
at coordinatively unsaturated atoms or heteroatoms can
provide very different activity for molecule adsorption and
activation. The coordinatively unsaturated atoms and het-
eroatoms are typically generated by vacancy creation and
elemental doping, respectively.
5. Promising design strategies for 2D photocatalysts
A series of emerging strategies have been developed in non-2D
material systems based on surface science and coordination
chemistry. For instance, interfacial electronic effect and hydrophilic
effect have been demonstrated for ethylenediamine (EDA)-coated
Pt nanowires and hydroxylated SiC quantum dots, respectively
[123e126]. Toward the further development of 2D photocatalysts,
these surface modification strategies could be borrowed from other
materials. Here, we would like to elaborate on a few promising
design strategies (Fig. 17).
(1) Organic modification: the surface modification of catalytic
materials with molecules is supposed to be a powerful
method, which may introduce Lewis acid sites to promote
Fig. 17. Adsorption modes (a) monodentated adsorption, (b) bent adsorption, (c) bidentated adsorption and (d) linear adsorption for heterogeneous CO2 photocatalytic reduction.
213
the adsorption of reaction molecules or reconstruct the
charge distribution over the modified surface [123]. For
instance, the ultrathin Pt nanowires with EDA chelated on
their surface have been synthesized by Chen et al., which
exhibit excellent selectivity in the hydrogenation of nitro-
benzene. DFT calculations show that EDA donates electrons
to surface Pt atoms owing to the lone-pair electrons in N. As a
result, the electron-rich environment can promote the se-
lective hydrogenation process. It is anticipated that the sur-
face ligands on 2D photocatalysts should also hold the
promise for tuning their performance.
(2) Hydroxyl modification: as catalytic reactions rely on the
transport of reaction species from solution to catalyst sur-
face, the hydrophilicity of catalyst surface is a key parameter
to heterogeneous catalysis. The surface modification with
hydrophilic or hydrophobic groups is capable of altering the
intrinsic characters of catalyst surface. These ligands not only
influence the mass transport but also participate in reactions
in many cases, resulting different activity and selectivity. An
investigation by Peng et al. has revealed that the surface
hydroxyl species on SiC quantum dots can provide H atoms in
the formation of HCOO* intermediate [124]. This unique re-
action path reduces the activation energy in the hydroge-
nation of CO2 into methanol. Thus, the hydrophilicity should
be a key factor taken into account during the surface modi-
fication of 2D photocatalysts.
(3) Ion exchange: ion exchange is a method commonly used for
the construction of heterojunctions with immiscible do-
mains for inorganic materials such as chalcogenides [125].
The carrier loss at the interface of heterojunctions can be
largely suppressed by forming this high-quality interface.
Leveraging this strategy, ultrathin 2D heterojunctions with
fine interface would be fabricated through ion exchange,
which are the ideal photocatalyst structures with extremely
short charge traveling lengths and abundant active sites on
flat surface.
(4) Space confinement effect: the building blocks that are
formed with different modifiers over the surface of catalysts
can modulate the selectivity of reactions (particularly for
those involving large reaction molecules) through space
214 Y. Li et al. / Materials Today Chemistry 11 (2019) 197e216
confinement. Among various building blocks, the MOFs with
tunable pore sizes have been widely used as efficient shells to
encapsule catalytic metal nanoparticles and to improve their
selectivity by shielding large-size molecules [126]. Appar-
ently, this strategy can be implemented in the photocatalysts
based on 2D materials to promote their selectivity in the
conversion of molecules with large sizes.
6. Conclusion and outlook
Ignited by the explosive development in material synthetic
strategies and characterization techniques, numerous 2D photo-
catalysts have been elaborately designed and emerging to meet
different demands. Many well-investigated 2D materials, such as
graphene, g-C3N4, and metal oxides nanosheets, are still active in
the cutting-edge research of photocatalysts. Meanwhile, BP,
MXenes, and organic/inorganic perovskites are attracting growing
attention. To be a promising 2D photocatalyst, one or more of the
following features are requireddproper band structure, long car-
rier lifetime, high carrier mobility, high physical and chemical
stability, and abundant surface-active sites. These requirements
well-define the main principles for designing efficient 2D photo-
catalysts. Toward these goals, structure manipulation, vacancy en-
gineering, elemental doping, and composite strategy are put into
use individually or simultaneously. In addition to the improved
performance, the insightful investigations on the kinetics in pho-
tocatalytic processes, with the help from powerful characterization
techniques and theoretical simulation methods have also provided
useful information for photocatalyst development.
Despite the great advances in photocatalyst development, some
problems still impede the invention of outstanding 2D photo-
catalysts. (1) In the view of practical applications, it is still a great
challenge to synthesize 2D materials of various kinds with
controllable structure and morphology in large quantities. Novel
synthetic strategies including chemical and physical processes are
to be developed along this line. (2) Another obstacle is the
agglomeration of 2D materials. To reserve the superiority of enor-
mous surface area, ultrathin 2D photocatalysts are usually
dispersed in solvent at low concentrations or spread on substrate to
form thin layers for photocatalytic reactions. These strategies
require a large volume of solvent or a large area of substrate to
realize high turnover number, which are not desirable in industry.
One available method is to assemble 2D photocatalysts into 3D
macroscale devices, through self-assembly or in-situ integration
with substrates. Although the substrates to this end such as carbon
fibers and semiconductor nanorod arrays have been fabricated,
further investigations on the involved physical processes and pa-
rameters are very deficient. Hence, developing functional sub-
strates may provide a new direction for fabricating ideal
photocatalysts. (3) In addition, active sites of different kinds and
forms should be taken into consideration to enable various activity
and selectivity. While vacancy engineering and integration with
transition metals are commonly used, coupling molecular catalysts
with 2D materials is an alluring way to combine the advantages of
homogenous and heterogeneous photocatalysts, in which the co-
ordination chemistry plays a key role in fulfilling the performance
request. (4) There still exists a huge lack of direct and accurate
techniques for unfolding the intrinsic feature and the real pathway
during photocatalytic reactions. The characterizations along this
direction can provide strong guidance for designing outstanding
photocatalysts. In-situ Raman spectroscopy, diffuse reflectance
infrared Fourier-transform spectroscopy and X-ray absorption fine
structure spectroscopy have appeared in many works, providing
the local information for reaction species and their intermediates.
While these techniques are limited by the working conditions,
operando and time-resolved characterization techniques are
strongly demanded by future developments.
Overall, 2D photocatalysts are essential in solving energy and
environmental problems. The fundamental design strategies based
on surface science and coordination chemistry have shown a po-
tential in the future development of 2D photocatalysts. The design
of novel efficient 2D photocatalysts requires deep understanding on
the mechanisms and parameters behind. In addition to developing
new 2D photocatalysts, there is plenty of room for exploring the
existing 2D materials for potential photocatalytic applications. The
key features of 2D photocatalysts, including surface electron states,
exposed atoms, and energy bands matching other materials, should
be systematically taken into account. Toward the ultimate goal of
identifying ideal 2D photocatalysts, both in-depth experimental
and theoretical research would be required and combined to pro-
vide the time-resolved information at the electronic and molecular
levels.
Acknowledgments
This work was financially supported in part by National Key R&D
Program of China (2017YFA0207301), NSFC (21471141, U1532135,
21601173, U1832156), CAS Key Research Program of Frontier Sci-
ences (QYZDB-SSW-SLH018), CAS Interdisciplinary Innovation
Team, Innovative Program of Development Foundation of Hefei
Center for Physical Science and Technology (2016FXCX003), Anhui
Provincial Natural Science Foundation (1608085QB24), and Chinese
Universities Scientific Fund (WK2310000067).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.mtchem.2018.11.002.
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[114] Y. Zhang, Z.-R. Tang, X. Fu, Y.-J. Xu, ACS Nano 5 (2011) 7426e7435. Ran Long was born in Anhui, China, in 1987. She received
[115] Y.T. Liang, B.K. Vijayan, O. Lyandres, K.A. Gray, M.C. Hersam, J. Phys. Chem. her B.S. in chemistry in 2009 and Ph.D. in inorganic
Lett. 3 (2012) 1760e1765. chemistry under the tutelage of Professor Yujie Xiong in
[116] M. Zhu, S. Kim, L. Mao, M. Fujitsuka, J. Zhang, X. Wang, T. Majima, J. Am. 2014, both from the University of Science and Technology
Chem. Soc. 139 (2017) 13234e13242. of China (USTC). After postdoctoral training with Pro-
[117] W. Jiang, S. Bai, L. Wang, X. Wang, L. Yang, Y. Li, D. Liu, X. Wang, Z. Li, J. Jiang, fessors Yujie Xiong and Li Song, she is currently an asso-
Y. Xiong, Small 12 (2016) 1640e1648. ciate professor working at the USTC. Her research interests
[118] H. Wang, S. Jiang, W. Shao, X. Zhang, S. Chen, X. Sun, Q. Zhang, Y. Luo, Y. Xie, focus on controlled synthesis and catalytic applications of
J. Am. Chem. Soc. 140 (2018) 3474e3480. metal nanocrystals.
[119] Y. Zhou, Z. Tian, Z. Zhao, Q. Liu, J. Kou, X. Chen, J. Gao, S. Yan, Z. Zou, ACS Appl.
Mater. Interfaces 3 (2011) 3594e3601.
[120] Y. Bai, L. Ye, T. Chen, L. Wang, X. Shi, X. Zhang, D. Chen, ACS Appl. Mater.
Interfaces 8 (2016) 27661e27668.
[121] H. Li, F. Qin, Z. Yang, X. Cui, J. Wang, L. Zhang, J. Am. Chem. Soc. 139 (2017)
3513e3521.
[122] T. Su, Q. Shao, Z. Qin, Z. Guo, Z. Wu, ACS Catal. 8 (2018) 2253e2276.
[123] G. Chen, C. Xu, X. Huang, J. Ye, L. Gu, G. Li, Z. Tang, B. Wu, H. Yang, Z. Zhao,
Z. Zhou, G. Fu, N. Zheng, Nat. Mater. 15 (2016) 564e569.
[124] Y. Peng, L. Wang, Q. Luo, Y. Cao, Y. Dai, Z. Li, H. Li, X. Zheng, W. Yan, J. Yang, Yujie Xiong received his B.S. in chemical physics in 2000
Inside Chem. 4 (2018) 613e625. and Ph.D. in inorganic chemistry in 2004, both from the
[125] Q. Yuan, D. Liu, N. Zhang, W. Ye, H. Ju, L. Shi, R. Long, J. Zhu, Y. Xiong, Angew. University of Science and Technology of China (USTC).
Chem. 129 (2017) 4270e4274. After 4-year postdoctoral training at the University of
[126] Q. Yang, Q. Xu, S.H. Yu, H.L. Jiang, Angew. Chem. 128 (2016) 3749e3753. Washington in Seattle and the University of Illinois at
[127] Y. Li, Z. Wang, T. Xia, H. Ju, K. Zhang, R. Long, Q. Xu, C. Wang, L. Song, J. Zhu, Urbana-Champaign, he joined the NSF-NNIN at Washing-
J. Jiang, Y. Xiong, Adv. Mater. 28 (2016) 6959e6965. ton University in St. Louis as the Principal Scientist. Start-
[128] R. Long, Y. Li, Y. Liu, S. Chen, X. Zheng, C. Gao, C. He, N. Chen, Z. Qi, L. Song, ing from 2011, he is a Professor of Chemistry at the USTC.
J. Jiang, J. Zhu, Y. Xiong, J. Am. Chem. Soc. 139 (2017) 4486e4492. He has published 160 papers with over 16,000 citations
[129] S. Bai, X. Li, Q. Kong, R. Long, C. Wang, J. Jiang, Y. Xiong, Adv. Mater. 27 (2015) (H-index 61). His research interests include synthesis,
3444e3452. fabrication, and assembly of inorganic materials for energy
[130] N. Zhang, X. Li, H. Ye, S. Chen, H. Ju, D. Liu, Y. Lin, W. Ye, C. Wang, Q. Xu, and environmental applications.
J. Zhu, L. Song, J. Jiang, Y. Xiong, J. Am. Chem. Soc. 138 (2016) 8928e8935.