Advanced Design and Synthesis of Composite Photocatalysts for the Remediation of Wastewater: A Review

Abstract

Serious water pollution and the exhausting of fossil resources have become worldwide urgent issues yet to be solved. Solar energy driving photocatalysis processes based on semiconductor catalysts is considered to be the most promising technique for the remediation of wastewater. However, the relatively low photocatalytic efficiency remains a critical limitation for the practical use of the photocatalysts. To solve this problem, numerous strategies have been developed for the preparation of advanced photocatalysts. Particularly, incorporating a semiconductor with various functional components from atoms to individual semiconductors or metals to form a composite catalyst have become a facile approach for the design of high-efficiency catalysts. Herein, the recent progress in the development of novel photocatalysts for wastewater treatment via various methods in the sight of composite techniques are systematically discussed. Moreover, a brief summary of the current challenges and an outlook for the development of composite photocatalysts in the area of wastewater treatment are provided.

Full text

catalysts
Review
Advanced Design and Synthesis of Composite
Photocatalysts for the Remediation of Wastewater:
A Review
Jianlong Ge, Yifan Zhang, Young-Jung Heo and Soo-Jin Park *
Department of Chemistry and Chemical Engineering, Inha University, 100 Inharo, Incheon 22212, Korea;
gejianlong1121@126.com (J.G.); zyf910626@inhaian.net (Y.Z.); heoyj1211@inhaian.net (Y.-J.H.)
*Correspondence: sjpark@inha.ac.kr; Tel.: +82-32-860-7234; Fax: +82-32-860-5604
Received: 29 December 2018; Accepted: 28 January 2019; Published: 30 January 2019


Abstract:
Serious water pollution and the exhausting of fossil resources have become worldwide
urgent issues yet to be solved. Solar energy driving photocatalysis processes based on semiconductor
catalysts is considered to be the most promising technique for the remediation of wastewater.
However, the relatively low photocatalytic efficiency remains a critical limitation for the practical
use of the photocatalysts. To solve this problem, numerous strategies have been developed for the
preparation of advanced photocatalysts. Particularly, incorporating a semiconductor with various
functional components from atoms to individual semiconductors or metals to form a composite
catalyst have become a facile approach for the design of high-efficiency catalysts. Herein, the recent
progress in the development of novel photocatalysts for wastewater treatment via various methods
in the sight of composite techniques are systematically discussed. Moreover, a brief summary of the
current challenges and an outlook for the development of composite photocatalysts in the area of
wastewater treatment are provided.
Keywords:
Composite catalysts; photocatalysis; synergy effect; solar energy; wastewater remediation
1. Introduction
In the past several decades, with the booming of industry, the ever-increasing consumption of
natural resources, especially fresh water and fossil resources, have caused alarming damage to the
environment and seriously threaten the sustainability of human society [
1
–
3
]. As a worldwide concern,
freshwater pollution drives people to seek for an effective approach to repair the polluted water
environment. In general, the contaminants in water are mainly derived from the sewage effluent
of industries (e.g., textile industry, paper industry, the pharmaceutical industry, etc.), and domestic
contaminants (e.g., pharmaceuticals, pesticide, detergent, etc.) [
4
]. Until now, numerous contaminants
have been detected and are classified as inorganic ions, organic chemicals, and pathogens; most
of those contaminants are toxic to organisms [
4
–
7
]. Up to now, a variety of strategies including
chemical or physical coagulation [
8
], sedimentation [
9
], adsorption [
10
], membrane filtration [
11
],
and biological degradation method [
12
] have been invented to treat wastewater. However, due to the
complex compositions and different physico-chemical properties of the contaminants, there are still
several limitations of these traditional techniques, such as the low efficiency, high energy consumption,
and the risk of secondary pollution [
13
–
15
]. Consequently, a promoted technique with high efficiency,
low energy consumption, and being environmentally friendly is highly desired for the remediation
of wastewater.
Nowadays, the advanced oxidation processes (AOPs) have been extensively explored to remove
the non-biodegradable and highly stable compounds in water [
16
,
17
]. In fact, the AOPs are chemical
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Catalysts 2019,9, 122 2 of 32
processes that can generate highly reactive hydroxyl radicals (
·
OH) in situ. The
·
OH in water exhibits
an extremely strong oxidizing property with a high oxidation potential of 2.80 V/SHE (
·
OH/H
2
O),
such that it can non-selectively oxidize the contaminants and finally convert them to CO
2
, H
2
O, or small
inorganic ions in a short time [
17
,
18
]. In most cases, the
·
OH could be produced with the presence
of one or more primary oxidants, and/or energy sources or catalysts. Therefore, the typical AOPs
could be classified as Fenton reactions, the electrochemical advanced oxidation processes, and the
heterogeneous photocatalysis [
17
]. Compared with the traditional water remediation techniques,
the AOPs exhibit many advantages, which include: (1) the contaminants are directly destroyed or
reduced in the water body, rather than simply coagulated or filtrated from the water, thus the secondary
pollution could be avoided; (2) the AOPs are suitable for a wide range of contaminants including some
inorganics and pathogens because of their robust non-selectively oxidizability; and (3) no hazardous
byproducts will be generated due to the final reduction products of the AOPs being just CO
2
, H
2
O,
or small inorganic ions. With the abovementioned merits, the AOPs have attracted significant attention
from both scientific research and industrial processing [19].
Solar energy is a green, costless, and inexhaustible energy resource. Effective utilization of
solar energy is of vital importance for enhancing the sustainability of industry, reducing pollution,
and retarding global warming. Consequently, solar energy has been widely used in a range of
applications, such as solar heating, photovoltaics, solar thermal energy, solar architecture, artificial
photosynthesis, photocatalysis, etc. [
20
] Among which, photocatalysis is one of the most effective
strategies for the AOPs, which just rely on the light radiation on the photocatalysts to drive the
oxidization reaction at the ambient condition, and during the whole reaction process, no additional
energy is needed and no toxic byproduct will be generated; therefore, it is a green chemical
technique [
21
,
22
]. Actually, the core of photocatalytic AOPs are photocatalysts; semiconductors as the
most employed heterogeneous photocatalysis for the AOPs have attained considerable development
since Fujishima et al. [
23
] carried out the first photo-catalyzed AOP based on the titanium-oxide
(TiO
2
) in 1972. Up to now, a myriad of photocatalytic AOPs have been designed for water treatment
based on various semiconductors. In general, semiconductors are light-sensitive because of their
unique electronic structure with a filled valence band (VB) and an empty conduction band (CB) [
18
,
21
].
Figure 1and Equations (1)–(6) demonstrate the basic reaction process of a semiconductor to generate the
photocatalytic radicals, which could be decomposed in the following steps: (i) photons with a certain
energy are absorbed by the semiconductor; (ii) the absorbed photons with energy greater than the band
gap energy (E
b
) of semiconductors lead to the formation of electrons in the CB and corresponding holes
in the VB; and (iii) the generated electron–hole pairs will migrate to the surface of semiconductors for
redox reactions, and fast recombination in nanoseconds will happen at the same time (it should be
mentioned that this process is negative for the AOPs, which shall be suppressed [21,22]).
Catalysts 2018, 8, x FOR PEER REVIEW 2 of 32
Nowadays, the advanced oxidation processes (AOPs) have been extensively explored to remove
the non-biodegradable and highly stable compounds in water [16,17]. In fact, the AOPs are chemical
processes that can generate highly reactive hydroxyl radicals (·OH) in situ. The ·OH in water exhibits
an extremely strong oxidizing property with a high oxidation potential of 2.80 V/SHE (·OH/H
2
O),
such that it can non-selectively oxidize the contaminants and finally convert them to CO
2
, H
2
O, or
small inorganic ions in a short time [17,18]. In most cases, the ·OH could be produced with the
presence of one or more primary oxidants, and/or energy sources or catalysts. Therefore, the typical
AOPs could be classified as Fenton reactions, the electrochemical advanced oxidation processes, and
the heterogeneous photocatalysis [17]. Compared with the traditional water remediation techniques,
the AOPs exhibit many advantages, which include: (1) the contaminants are directly destroyed or
reduced in the water body, rather than simply coagulated or filtrated from the water, thus the
secondary pollution could be avoided; (2) the AOPs are suitable for a wide range of contaminants
including some inorganics and pathogens because of their robust non-selectively oxidizability; and
(3) no hazardous byproducts will be generated due to the final reduction products of the AOPs being
just CO
2
, H
2
O, or small inorganic ions. With the abovementioned merits, the AOPs have attracted
significant attention from both scientific research and industrial processing [19].
Solar energy is a green, costless, and inexhaustible energy resource. Effective utilization of solar
energy is of vital importance for enhancing the sustainability of industry, reducing pollution, and
retarding global warming. Consequently, solar energy has been widely used in a range of
applications, such as solar heating, photovoltaics, solar thermal energy, solar architecture, artificial
photosynthesis, photocatalysis, etc. [20] Among which, photocatalysis is one of the most effective
strategies for the AOPs, which just rely on the light radiation on the photocatalysts to drive the
oxidization reaction at the ambient condition, and during the whole reaction process, no additional
energy is needed and no toxic byproduct will be generated; therefore, it is a green chemical technique
[21,22]. Actually, the core of photocatalytic AOPs are photocatalysts; semiconductors as the most
employed heterogeneous photocatalysis for the AOPs have attained considerable development since
Fujishima et al. [23] carried out the first photo-catalyzed AOP based on the titanium-oxide (TiO
2
)
in
1972. Up to now, a myriad of photocatalytic AOPs have been designed for water treatment based on
various semiconductors. In general, semiconductors are light-sensitive because of their unique
electronic structure with a filled valence band (VB) and an empty conduction band (CB) [18,21].
Figure 1 and Equations (1)–(6) demonstrate the basic reaction process of a semiconductor to generate
the photocatalytic radicals, which could be decomposed in the following steps: i) photons with a
certain energy are absorbed by the semiconductor; ii) the absorbed photons with energy greater than
the band gap energy (E
b
) of semiconductors lead to the formation of electrons in the CB and
corresponding holes in the VB; and iii) the generated electron–hole pairs will migrate to the surface
of semiconductors for redox reactions, and fast recombination in nanoseconds will happen at the
same time (it should be mentioned that this process is negative for the AOPs, which shall be
suppressed [21,22]).
Figure 1.
Schematic illustration of the photocatalytic reaction process of a semiconductor. Adapted with
permission from Reference [18]. Copyright (2012) Elsevier.

Catalysts 2019,9, 122 3 of 32
Excitation: Photon (hv) + Semiconductor →e−CB + h+VB (1)
Recombination: e−+ h+→energy (2)
Oxidation of H2O: H2O+h+VB → •OH + H+(3)
Reduction of adsorbed O2: O2+ e−→O2•−(4)
Reaction with H+: O2•−+ H+→ •OOH (5)
Electrochemical reduction: •OOH + •OOH →H2O2+ O2(6)
However, it remains a significant challenge to fabricate a high-efficiency visible light photocatalyst
solely based on an individual semiconductor photocatalyst. For example, the TiO
2
, as the most used
photocatalyst, possesses various advantages with excellent chemical stability, large surface area, non-toxicity,
and low cost [
24
]; however, its wide energy band gap (3.0–3.2 eV) means it can only be excited by the
UV light (
λ
< 400 nm), such that less than 5% of the irradiated solar energy can be effectively used [
25
].
Moreover, the fast recombination speed of electron–hole pairs seriously limits the further improvement of
its photocatalytic activity [
18
,
22
]. On the other hand, although the recently developed visible light response
semiconductors have a lower energy band gap (<3 eV), such as BiOX (X = I or Br) [
26
], they still suffer
from serious photo-corrosion problems in aqueous media via redox reactions and the fast recombination of
electron–hole pairs during the reaction process. Therefore, it is highly urgent to find an effect strategy to
further improve the performance of semiconductor photocatalysts.
From ancient times, people have recognized that the incorporation of two or more constituent
materials could obtain various composite materials with intriguing properties superior to the individual
components. Nowadays, a myriad of functional composite materials have been developed for different
applications [27,28]. Actually, the enhanced performance of a composite material is mainly attributed to
the synergistic effect of its individual constituent materials; meanwhile, this principle is also appropriate
to the design of semiconductor photocatalysts. Up to now, there have been numerous pioneering studies
reporting the design and fabrication of composite semiconductor photocatalysts via various methods,
such as doping heteroatoms or constructing heterojunctions via directly compositing with individual
semiconductors or carbonaceous nanomaterials, among others. Therefore, as shown in Scheme 1, in this
review, we aim to provide a systematic appraisal of the recent development in the design and fabrication
of various composite photocatalysts for the application of wastewater treatment. Meanwhile, some
representative photocatalysts with composite structures and morphologies from the atomic scale to
macroscopic scale are reviewed. Finally, the current developing status, challenges, and evolution trend of
the composite semiconductor photocatalysts for wastewater remediation are briefly proposed.
Catalysts 2018, 8, x FOR PEER REVIEW 3 of 32
Figure 1. Schematic illustration of the photocatalytic reaction process of a semiconductor. Adapted
with permission from Reference [18]. Copyright (2012) Elsevier.
Excitation: Photon (hv) + Semiconductor → e
−CB
+ h
+VB
(1)
Recombination: e
−
+ h
+
→ energy (2)
Oxidation of H
2
O: H
2
O + h
+VB
→ •OH + H
+
(3)
Reduction of adsorbed O
2
: O
2
+ e
−
→ O
2
•
−
(4)
Reaction with H
+
: O
2
•
−
+ H
+
→ •OOH (5)
Electrochemical reduction: •OOH + •OOH → H
2
O
2
+ O
2
(6)
However, it remains a significant challenge to fabricate a high-efficiency visible light
photocatalyst solely based on an individual semiconductor photocatalyst. For example, the TiO
2
, as
the most used photocatalyst, possesses various advantages with excellent chemical stability, large
surface area, non-toxicity, and low cost [24]; however, its wide energy band gap (3.0–3.2 eV) means
it can only be excited by the UV light (λ < 400 nm), such that less than 5% of the irradiated solar
energy can be effectively used [25]. Moreover, the fast recombination speed of electron–hole pairs
seriously limits the further improvement of its photocatalytic activity [18,22]. On the other hand,
although the recently developed visible light response semiconductors have a lower energy band gap
(<3 eV), such as BiOX (X = I or Br) [26], they still suffer from serious photo-corrosion problems in
aqueous media via redox reactions and the fast recombination of electron–hole pairs during the
reaction process. Therefore, it is highly urgent to find an effect strategy to further improve the
performance of semiconductor photocatalysts.
From ancient times, people have recognized that the incorporation of two or more constituent
materials could obtain various composite materials with intriguing properties superior to the
individual components. Nowadays, a myriad of functional composite materials have been developed
for different applications [27,28]. Actually, the enhanced performance of a composite material is
mainly attributed to the synergistic effect of its individual constituent materials; meanwhile, this
principle is also appropriate to the design of semiconductor photocatalysts. Up to now, there have
been numerous pioneering studies reporting the design and fabrication of composite semiconductor
photocatalysts via various methods, such as doping heteroatoms or constructing heterojunctions via
directly compositing with individual semiconductors or carbonaceous nanomaterials, among others.
Therefore, as shown in Scheme 1, in this review, we aim to provide a systematic appraisal of the
recent development in the design and fabrication of various composite photocatalysts for the
application of wastewater treatment. Meanwhile, some representative photocatalysts with composite
structures and morphologies from the atomic scale to macroscopic scale are reviewed. Finally, the
current developing status, challenges, and evolution trend of the composite semiconductor
photocatalysts for wastewater remediation are briefly proposed.
Scheme 1.
The schematic illustration demonstrating the design and synthesis strategies for
composite photocatalysts.

Catalysts 2019,9, 122 4 of 32
2. Principle of the Semiconductor Photocatalysts for Wastewater Remediation
As mentioned above, the trace contaminants (e.g., phenol, chlorophenol, oxalic acid) derived
from the dyeing industry, petrochemical industry, and the agricultural chemicals are quite difficult to
remove from the water due to the low concentration and complex compositions [
4
]. A photocatalytic
degradation method is considered as the most promising strategy to deal with this problem.
According to the previous studies [
18
,
29
,
30
], as shown in Figure 2, the basic mechanism of the
photocatalytic degradation process of a contaminant could be characterized as the following steps:
(i) the target contaminants transfer from the water body to the surface of the photocatalysts, in which
the migration rate of corresponding contaminants may be influenced by the morphology and surface
properties of the catalysts (e.g., surface area, porosity, and surface charges); (ii) the contaminants
are adsorbed on the surface of catalysts with photon excited reaction sites, therefore a high surface
area of the catalysts can provide more active sites for the reaction; (iii) the redox reactions of the
photon activated sites with the adsorbed contaminants and the degraded intermediates are produced,
which are finally degraded to CO
2
and H
2
O; (iv) part of the generated intermediates and the resultant
mineralization products (CO
2
and H
2
O) desorb from the surface of catalysts to expose the active sites
for the subsequent reactions; and (v) the desorbed intermediates transfer from the interface of catalysts
and water to the bulk liquid, and part of the intermediates will repeat the procedure i–v until they are
completely degraded to CO
2
and H
2
O. Based on the abovementioned principles of the semiconductor
photocatalysts for water contaminants degradation, five main criteria for the design of an effective
photocatalyst could be proposed as follow: (1) a semiconductor with a lower E
g
is preferred so that the
electron–hole pair could be excited easier; (2) the photon absorption capacity of the catalysts shall be
as high as possible to generate more electron–hole pairs; (3) the recombination process of electron–hole
pairs must be prevented as much as possible to enhance the quantum efficiency of the photo-generated
electron–hole pairs; (4) the surface area of the catalysts shall be large to provide more reaction sites;
and (5) the chemical and physical structures of photocatalysts must be stable and be beneficial for the
mass transfer in water. To meet the abovementioned requirements, a variety of strategies have been
developed for the design, some of the most-used strategies will be summarized in this review.
Catalysts 2018, 8, x FOR PEER REVIEW 4 of 32
Scheme 1. The schematic illustration demonstrating the design and synthesis strategies for composite
photocatalysts.
2. Principle of the Semiconductor Photocatalysts for Wastewater Remediation
As mentioned above, the trace contaminants (e.g., phenol, chlorophenol, oxalic acid) derived
from the dyeing industry, petrochemical industry, and the agricultural chemicals are quite difficult
to remove from the water due to the low concentration and complex compositions [4]. A
photocatalytic degradation method is considered as the most promising strategy to deal with this
problem. According to the previous studies [18,29,30], as shown in Figure 2, the basic mechanism of
the photocatalytic degradation process of a contaminant could be characterized as the following steps:
i) the target contaminants transfer from the water body to the surface of the photocatalysts, in which
the migration rate of corresponding contaminants may be influenced by the morphology and surface
properties of the catalysts (e.g., surface area, porosity, and surface charges); ii) the contaminants are
adsorbed on the surface of catalysts with photon excited reaction sites, therefore a high surface area
of the catalysts can provide more active sites for the reaction; iii) the redox reactions of the photon
activated sites with the adsorbed contaminants and the degraded intermediates are produced, which
are finally degraded to CO
2
and H
2
O; iv) part of the generated intermediates and the resultant
mineralization products (CO
2
and H
2
O) desorb from the surface of catalysts to expose the active sites
for the subsequent reactions; and v) the desorbed intermediates transfer from the interface of catalysts
and water to the bulk liquid, and part of the intermediates will repeat the procedure i–v until they
are completely degraded to CO
2
and H
2
O. Based on the abovementioned principles of the
semiconductor photocatalysts for water contaminants degradation, five main criteria for the design
of an effective photocatalyst could be proposed as follow: 1) a semiconductor with a lower E
g
is
preferred so that the electron–hole pair could be excited easier; 2) the photon absorption capacity of
the catalysts shall be as high as possible to generate more electron–hole pairs; 3) the recombination
process of electron–hole pairs must be prevented as much as possible to enhance the quantum
efficiency of the photo-generated electron–hole pairs; 4) the surface area of the catalysts shall be large
to provide more reaction sites; and 5) the chemical and physical structures of photocatalysts must be
stable and be beneficial for the mass transfer in water. To meet the abovementioned requirements, a
variety of strategies have been developed for the design, some of the most-used strategies will be
summarized in this review.
Figure 2. Schematic diagram demonstrating the removal of contaminants in water with the presence
of photocatalysts [18,29,30].
Figure 2.
Schematic diagram demonstrating the removal of contaminants in water with the presence of
photocatalysts [18,29,30].

Catalysts 2019,9, 122 5 of 32
3. Heteroatoms Doping
Recently, the strategy of introducing heteroatoms into the lattice of corresponding semiconductors
has been widely employed to regulate the band gap of the semiconductor photocatalysts so as to
improve their absorption capacity for visible lights, which takes up almost 45% in the solar light
spectrum [
31
]. In general, the most commonly used dopants in semiconductors (e.g., TiO
2
) could be
classified as the metal cations and the non-metallic elements [32,33].
3.1. Metal Cations Doping
The most-used metal cation dopants for semiconductors mainly involve transition metal ions, such
as Fe
3+
, Co
3+
, Mo
5+
, Ru
3+
, Ag
+
, Cu
2+
, Rb
+
, Cr
3+
, V
4+
, etc. [
32
,
34
–
37
]. In most cases, the redox energy
states of those employed metal cations lie within the band gap states of corresponding semiconductors
(e.g., TiO
2
); therefore, the introduction of those metal ions will result in an intraband state near
the CB or VB edge of a semiconductor. Consequently, the red shift in band gap absorption of a
metal-cation-doped semiconductor is mainly contributed by the charge migration between the d
electrons of the doped cations and the CB (or VB) of the corresponding semiconductors. In addition,
the doped metal cations could act as an electron–hole trap, regulating the charge carrier equilibrium
concentration [
38
–
40
]. Although some transition metal cations could provide new energy levels
as electron donors or acceptors, and virtually improved the visible light absorption capacity of
corresponding semiconductors, this approach is also known to suffer from many disadvantages,
such as bad thermal stability, significant increase in the carrier-recombination centers, and the high
cost for an expensive facility, which are critical limitations for the generalization of this strategy.
3.2. Non-Metallic Anions Doping
Alternatively, doping the semiconductors with appropriate non-metallic anions has been
proven to be a facile way to regulate the intrinsic electronic structure of semiconductors and could
construct various heteroatomic surface structures such that the resultant non-metallic-anion-doped
semiconductors exhibit improved photocatalytic performances under solar light irradiation [
33
,
41
].
In general, the chemical states and locations are key factors for the regulation of the electronic state of
the dopant and the corresponding heteroatomic surface structures of the composite semiconductor
catalysts. According to a previous study [
18
], three requirements needed to be satisfied for the doping
of a semiconductor: (i) the doping process should construct states in the band gap of corresponding
semiconductors with an enhanced visible light absorption capacity, (ii) the CB minimum including
the doped states should be equal to that of the semiconductor’s or higher than that of the H
2
/H
2
O
level such that the photoreduction can be conducted, and (iii) the states in the gap should sufficiently
overlap with the band states of semiconductors to ensure that the photoexcited carriers could migrate
to the surface of catalysts within their lifetime. Based on the abovementioned principles, various
elements, including C, N, F, P, and S, were employed to substitute for the O in TiO
2
[
42
], and the results
showed that N was the most effective dopant for the improvement of visible-light photocatalysis of
TiO
2
because the pstates of N can narrow the band gap of N-doped TiO
2
via mixing with the O 2p
states [
43
]. Moreover, owing to the comparable atomic size with oxygen, small ionization energy,
and high stability, the nitrogen has been one of the most promising elements for promoting the
photocatalysis performance of the semiconductors. In general, the doped N in the TiO
2
could be
classified as the substitutional type and interstitial type (Figure 3), the substitutional type N-doped
TiO2is attributed to the oxygen replacement, while the interstitial type is attributed to the additional
N element in the lattice of TiO
2
[
41
]. Up to now, the N-doping of semiconductors can be realized via
several strategies, and the most-used techniques with certain industrial application prospects could be
mentioned as the magnetron sputtering, ion implantation, chemical vapor deposition, atomic layer
deposition, and sol-gel and combustion method, which will be discussed as follows.

Catalysts 2019,9, 122 6 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 6 of 32
Figure 3. Schematic diagram demonstrating the N doping in the lattice of TiO
2
.
Adapted with
permission from Reference [41]. Copyright (2011) Royal Society of Chemistry.
3.2.1. Magnetron Sputtering Method
The magnetron sputtering method is widely used for the preparation of various hybrid
semiconductors. For example, Kitano et al. [44] fabricated nitrogen-substituted TiO
2
thin films by
using a radio frequency magnetron sputtering (RF-MS) method. The N
2
/Ar gas mixtures with
different concentration of N
2
was used as the sputtering gas. They systematically investigated the
influence of nitrogen content on the properties of the obtained N-TiO
2
thin films via regulating the
concentration of N
2
in the sputtering gases. Meanwhile, they proved that the extent of substitution of
oxygen positions with N in the lattice of TiO
2
as well as the surface morphologies of TiO
2
could be
controlled well. As a result, the visible light absorption capacity of the obtained N-TiO
2
was obviously
enhanced with bands up to 550 nm, and it was found that the band red shift extent was closely related
to the content of the substituted N element in the TiO
2
lattice. Moreover, they found that the as-
prepared N-TiO
2
photocatalyst exhibited an optimized photocatalysis reactivity with the N content
of 6%. This result was because of the excessive substituted N, which causes the formation of
undesirable Ti
3+
species and acts as the recombination centers to decrease the photocatalytic activity
[44]. Apart from the TiO
2
, some other N-doped semiconductors could also be prepared based on the
RF-MS method. Recently, Salah et al. [45] fabricated a series of N-doped ZnO nanoparticles films by
employing the RF-MS method. As shown in Figure 4, the obtained N-doped ZnO films exhibited an
improved response to the visible light, and possessed significantly enhanced
degradation/mineralization performance for 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), and 2,4-
dichlorophenoxyaceticacid (2,4-D) solely under the drive of natural sunlight.
Figure 3.
Schematic diagram demonstrating the N doping in the lattice of TiO
2
. Adapted with
permission from Reference [41]. Copyright (2011) Royal Society of Chemistry.
3.2.1. Magnetron Sputtering Method
The magnetron sputtering method is widely used for the preparation of various hybrid
semiconductors. For example, Kitano et al. [
44
] fabricated nitrogen-substituted TiO
2
thin films by using
a radio frequency magnetron sputtering (RF-MS) method. The N
2
/Ar gas mixtures with different
concentration of N
2
was used as the sputtering gas. They systematically investigated the influence of
nitrogen content on the properties of the obtained N-TiO
2
thin films via regulating the concentration of
N
2
in the sputtering gases. Meanwhile, they proved that the extent of substitution of oxygen positions
with N in the lattice of TiO
2
as well as the surface morphologies of TiO
2
could be controlled well.
As a result, the visible light absorption capacity of the obtained N-TiO
2
was obviously enhanced with
bands up to 550 nm, and it was found that the band red shift extent was closely related to the content
of the substituted N element in the TiO
2
lattice. Moreover, they found that the as-prepared N-TiO
2
photocatalyst exhibited an optimized photocatalysis reactivity with the N content of 6%. This result
was because of the excessive substituted N, which causes the formation of undesirable Ti
3+
species
and acts as the recombination centers to decrease the photocatalytic activity [
44
]. Apart from the TiO
2
,
some other N-doped semiconductors could also be prepared based on the RF-MS method. Recently,
Salah et al. [
45
] fabricated a series of N-doped ZnO nanoparticles films by employing the RF-MS
method. As shown in Figure 4, the obtained N-doped ZnO films exhibited an improved response to
the visible light, and possessed significantly enhanced degradation/mineralization performance for
2-chlorophenol (2-CP), 4-chlorophenol (4-CP), and 2,4-dichlorophenoxyaceticacid (2,4-D) solely under
the drive of natural sunlight.

Catalysts 2019,9, 122 7 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 7 of 32
Figure 4. (a) The degradation and (b) mineralization of N-doped ZnO films for 2-CP, 4-CP, and 2,4-
D. (c) The stability of pristine ZnO and N-doped ZnO film. (d) The stability and reusability of an N-
doped ZnO film for the degradation of 2-CP. Adapted with permission from Reference [45].
Copyright (2016) Elsevier.
3.2.2. Ion Implantation Method
The ion implantation method as a typical materials engineering strategy that can effectively
regulate the physical, chemical, and electronic properties of semiconductors, and the operation
process does not involve any other elements except the selected element, which ensures the purity of
the dopant [46]. Moreover, owing to the controllable parameters of ion beam implantation, such as
ion element, ion energy, ion density, uniformity of ion beam, and the doping efficiency, ion beam
implantation is a powerful approach for the heteroatom doping of semiconductors. For example,
Tang et al. [47] fabricated an N-doped TiO
2
layer with macrospores on a titanium substrate by using
the plasma-based ion implantation method. The fabrication process involves four steps: i) a helium
plasma was employed to generate He bubbles in the substrate, ii) an oxygen plasma treatment and a
followed annealing in air were used to obtain rutile and anatase phases of TiO
2
, iii) an Ar ion
sputtering method was used to exposure the He bubbles on the surface; and iv) the pre-treated
samples were doped by nitrogen though the nitrogen beam ion implantation method. Moreover, co-
doping of two or more non-metallic anions into a semiconductor photocatalyst (e.g., TiO
2
) could also
be realized using the ion implantation method. For example, Song et al. [48] prepared C/N-implanted
single-crystalline rutile TiO
2
nanowire arrays by using carbon and nitrogen ions beam to treat the as-
prepared TiO
2
nanowire arrays. After an annealing treatment, the obtained C/N-doped TiO
2
nanowire arrays exhibited a superior visible light response activity, which was attributed to the
synergistic effect between the doped C and N atoms. Their work proved that the co-doped C and N
in the lattice of TiO
2
not only greatly improves the visible light absorption capability, but also
enhances the separating and transferring property of photo-generated electron–hole pairs (Figure 5).
Figure 4.
(
a
) The degradation and (
b
) mineralization of N-doped ZnO films for 2-CP, 4-CP, and 2,4-D.
(
c
) The stability of pristine ZnO and N-doped ZnO film. (
d
) The stability and reusability of an
N-doped ZnO film for the degradation of 2-CP. Adapted with permission from Reference [
45
].
Copyright (2016) Elsevier.
3.2.2. Ion Implantation Method
The ion implantation method as a typical materials engineering strategy that can effectively
regulate the physical, chemical, and electronic properties of semiconductors, and the operation process
does not involve any other elements except the selected element, which ensures the purity of the
dopant [
46
]. Moreover, owing to the controllable parameters of ion beam implantation, such as
ion element, ion energy, ion density, uniformity of ion beam, and the doping efficiency, ion beam
implantation is a powerful approach for the heteroatom doping of semiconductors. For example,
Tang et al. [47]
fabricated an N-doped TiO
2
layer with macrospores on a titanium substrate by using the
plasma-based ion implantation method. The fabrication process involves four steps: (i) a helium plasma
was employed to generate He bubbles in the substrate, (ii) an oxygen plasma treatment and a followed
annealing in air were used to obtain rutile and anatase phases of TiO
2
, (iii) an Ar ion sputtering method
was used to exposure the He bubbles on the surface; and (iv) the pre-treated samples were doped by
nitrogen though the nitrogen beam ion implantation method. Moreover, co-doping of two or more
non-metallic anions into a semiconductor photocatalyst (e.g., TiO
2
) could also be realized using the ion
implantation method. For example, Song et al. [48] prepared C/N-implanted single-crystalline rutile
TiO
2
nanowire arrays by using carbon and nitrogen ions beam to treat the as-prepared TiO
2
nanowire
arrays. After an annealing treatment, the obtained C/N-doped TiO
2
nanowire arrays exhibited a
superior visible light response activity, which was attributed to the synergistic effect between the doped
C and N atoms. Their work proved that the co-doped C and N in the lattice of TiO
2
not only greatly
improves the visible light absorption capability, but also enhances the separating and transferring
property of photo-generated electron–hole pairs (Figure 5).

Catalysts 2019,9, 122 8 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 8 of 32
Figure 5. (a) UV–vis absorption spectra of TiO2 and various doped TiO2. (b) Linear sweep
voltammograms of C/N-TiO2 and TiO2. (c) Photo-response of TiO2 and the various doped TiO2
samples under visible light. (d) Incident photon-to-current conversion efficiency spectra of TiO2 and
various doped TiO2. Adapted with permission from Reference [48]. Copyright (2018) Wiley.
3.2.3. Chemical Vapor Deposition Method
Chemical vapor deposition (CVD) is a low-cost and scalable technique, which can directly grow
a solid-phase material from a gas phase containing specific precursors. The CVD method has been
widely used for the fabrication of semiconductors and the corresponding composite of oxides,
sulfides, nitrides, and other mixed anion materials [49]. For example, Lee et al. [50] prepared TiO2
composite materials doped by C (TiOC) and N (TiON) with the titanium tetraisopropoxide (TTIP),
oxygen, and NH3 as the precursors via combing the CVD method with a fluidized bed. The results
demonstrated that the visible light photocatalysis performance of the composite TiO2 (e.g., TiON)
was significantly improved compared to the commercial TiO2 catalyst (P25, Degussa). Similarly,
Kafizas et al. [51] employed a combinatorial atmospheric pressure chemical vapor deposition
(cAPCVD) method to prepare an anatase TiO2 film with a gradating N content. The obtained TiO2
film exhibited a gradating substitutional (Ns) and interstitial (Ni) nitrogen concentration, and the
transition process from predominantly Ns-doped TiO2 to Ns/Ni mixtures, and finally to purely Ni-
doped TiO2 was precisely characterized. In addition, the UV and visible light photocatalytic activities
of the obtained N-doped TiO2 were evaluated. As a result, this work demonstrated that Ni-doped
anatase TiO2 results in a better visible light photocatalytic activity than that of predominantly Ns-
doping. They proved that the different influences of substitutional and interstitial nitrogen doping
on the photocatalytic activity of TiO2 were due to that the greater stability of electron–holes in Ni-
doped TiO2 compare with that of Ns-doped TiO2, while the propensity of the Ns-doped TiO2 for
recombination is greater. This result indicated that the doped structures is well-deigned to improve
the photocatalytic activity of a semiconductor. Additionally, the CVD could also be combined with
other materials synthesis strategy; for example, as shown in Figure 6, Youssef et al. [52] prepared the
Figure 5.
(
a
) UV–vis absorption spectra of TiO
2
and various doped TiO
2
. (
b
) Linear sweep
voltammograms of C/N-TiO
2
and TiO
2
. (
c
) Photo-response of TiO
2
and the various doped TiO
2
samples under visible light. (
d
) Incident photon-to-current conversion efficiency spectra of TiO
2
and
various doped TiO2. Adapted with permission from Reference [48]. Copyright (2018) Wiley.
3.2.3. Chemical Vapor Deposition Method
Chemical vapor deposition (CVD) is a low-cost and scalable technique, which can directly
grow a solid-phase material from a gas phase containing specific precursors. The CVD method
has been widely used for the fabrication of semiconductors and the corresponding composite of
oxides, sulfides, nitrides, and other mixed anion materials [
49
]. For example, Lee et al. [
50
] prepared
TiO
2
composite materials doped by C (TiOC) and N (TiON) with the titanium tetraisopropoxide
(TTIP), oxygen, and NH
3
as the precursors via combing the CVD method with a fluidized bed.
The results demonstrated that the visible light photocatalysis performance of the composite TiO
2
(e.g., TiON) was significantly improved compared to the commercial TiO
2
catalyst (P25, Degussa).
Similarly, Kafizas et al. [
51
] employed a combinatorial atmospheric pressure chemical vapor deposition
(cAPCVD) method to prepare an anatase TiO
2
film with a gradating N content. The obtained TiO
2
film
exhibited a gradating substitutional (N
s
) and interstitial (N
i
) nitrogen concentration, and the transition
process from predominantly N
s
-doped TiO
2
to N
s
/N
i
mixtures, and finally to purely N
i
-doped TiO
2
was precisely characterized. In addition, the UV and visible light photocatalytic activities of the
obtained N-doped TiO
2
were evaluated. As a result, this work demonstrated that N
i
-doped anatase
TiO
2
results in a better visible light photocatalytic activity than that of predominantly N
s
-doping.
They proved that the different influences of substitutional and interstitial nitrogen doping on the
photocatalytic activity of TiO
2
were due to that the greater stability of electron–holes in N
i
-doped TiO
2
compare with that of N
s
-doped TiO
2
, while the propensity of the N
s
-doped TiO
2
for recombination is
greater. This result indicated that the doped structures is well-deigned to improve the photocatalytic
activity of a semiconductor. Additionally, the CVD could also be combined with other materials

Catalysts 2019,9, 122 9 of 32
synthesis strategy; for example, as shown in Figure 6, Youssef et al. [
52
] prepared the N-doped
anatase films via a one-step low-frequency plasma enhanced chemical vapor deposition (PECVD)
process. Furthermore, they demonstrated that this method did not need the subsequential annealing
step or post-incorporation of the doping agent, and the as–prepared N-TiO
2
film exhibited good
visible-light-induced photocatalytic performance.
Catalysts 2018, 8, x FOR PEER REVIEW 9 of 32
N-doped anatase films via a one-step low-frequency plasma enhanced chemical vapor deposition
(PECVD) process. Furthermore, they demonstrated that this method did not need the subsequential
annealing step or post-incorporation of the doping agent, and the as–prepared N-TiO
2
film exhibited
good visible-light-induced photocatalytic performance.
Figure 6. Schematic view of the capacitively-coupled low frequency PECVD reactor. Adapted with
permission from Reference [52]. Copyright (2017) Elsevier.
3.2.4. Atomic Layer Deposition
The atomic layer deposition (ALD) method is a recently developed and facile strategy for the
element doping of semiconductors. Actually, ALD is a gas-phase deposition process based on
alternate surface reactions of the substrates, and the ALD method possesses several advantages, such
as good reproducibility, considerable conformality, and excellent uniformity [53]. Consequently, the
ALD method is considered as a promising strategy for the preparation of doped and composite
photocatalysts [54]. For example, Pore et al. [55] prepared a series of N-TiO
2
films via employing the
ALD processes. In this study, TiCl
4
was used as the titanium precursor and there were two ALD
cycles during the fabrication process: i) a thin layer of TiN was grown from the TiCl
4
and NH
3
; and
ii) TiO
2
was deposited on the surface of TiN layer from TiCl
4
and H
2
O, meanwhile the as-prepared
TiN layer was part-oxidized to TiO
2
, thus resulting in the TiO
2−x
N
x
. Moreover, the nitrogen
concentration of the obtained TiO
2−x
N
x
could be well controlled via changing the ratio of TiN and
TiO
2
deposition cycles. Similarly, Lee et al. [56] reported a facile and effective vapor-phase synthesis
strategy to prepare a conformal N-TiO
2
thin film based on the ALD process. As shown in Figure 7,
the fabrication process of the corresponding N-TiO
2
film involved four main steps: (i) pulse the TiCl
4
vapor on the surfaces of a substrate to produce a monolayer of chemisorbed TiCl
x
species; (ii) remove
the remaining unreacted TiCl
4
and corresponding HCl byproducts using nitrogen gas; (iii) NH
4
OH
as the nitrogen source was subsequently pulsed to generate a mixture of gaseous H
2
O and NH
3
,
which react with the as-prepared TiCl
x
species to obtain the N-TiO
2
; and (iv) remove the unreacted
precursors and HCl byproducts again. This cycle could be repeated to achieve the N-TiO
2
film with
the desired thickness. The as-prepared N-TiO
2
exhibited significantly enhanced photocatalytic
degradation performance for organic pollutants solely driven by the solar irradiation.
Figure 6.
Schematic view of the capacitively-coupled low frequency PECVD reactor. Adapted with
permission from Reference [52]. Copyright (2017) Elsevier.
3.2.4. Atomic Layer Deposition
The atomic layer deposition (ALD) method is a recently developed and facile strategy for the
element doping of semiconductors. Actually, ALD is a gas-phase deposition process based on
alternate surface reactions of the substrates, and the ALD method possesses several advantages,
such as good reproducibility, considerable conformality, and excellent uniformity [
53
]. Consequently,
the ALD method is considered as a promising strategy for the preparation of doped and composite
photocatalysts [
54
]. For example, Pore et al. [
55
] prepared a series of N-TiO
2
films via employing the
ALD processes. In this study, TiCl
4
was used as the titanium precursor and there were two ALD cycles
during the fabrication process: (i) a thin layer of TiN was grown from the TiCl
4
and NH
3
; and (ii) TiO
2
was deposited on the surface of TiN layer from TiCl
4
and H
2
O, meanwhile the as-prepared TiN layer
was part-oxidized to TiO
2
, thus resulting in the TiO
2−x
N
x
. Moreover, the nitrogen concentration of
the obtained TiO
2−x
N
x
could be well controlled via changing the ratio of TiN and TiO
2
deposition
cycles. Similarly, Lee et al. [
56
] reported a facile and effective vapor-phase synthesis strategy to
prepare a conformal N-TiO
2
thin film based on the ALD process. As shown in Figure 7, the fabrication
process of the corresponding N-TiO
2
film involved four main steps: (i) pulse the TiCl
4
vapor on the
surfaces of a substrate to produce a monolayer of chemisorbed TiCl
x
species; (ii) remove the remaining
unreacted TiCl
4
and corresponding HCl byproducts using nitrogen gas; (iii) NH
4
OH as the nitrogen
source was subsequently pulsed to generate a mixture of gaseous H
2
O and NH
3
, which react with the
as-prepared TiCl
x
species to obtain the N-TiO
2
; and (iv) remove the unreacted precursors and HCl
byproducts again. This cycle could be repeated to achieve the N-TiO
2
film with the desired thickness.
The as-prepared N-TiO
2
exhibited significantly enhanced photocatalytic degradation performance for
organic pollutants solely driven by the solar irradiation.

Catalysts 2019,9, 122 10 of 32
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Figure 7. Schematic illustration demonstrating the synthesis process of the N-doped TiO
2
conformal
film via the ALD method. Adapted with permission from Reference [56]. Copyright (2017) Wiley.
3.2.5. Sol-Gel and Combustion Method
Compared with the abovementioned synthesis approaches, the sol-gel and combustion method
is a facile and low-cost strategy for the preparation of various semiconductors and the corresponding
hybrid semiconductors. With the merits of simplicity and the possibility of controlling the synthesis
conditions, the sol-gel methods have been well developed and several extended sol-gel techniques
have been invented to fabricate new types of semiconductor photocatalysts. For example, Albrbar et
al. [57] reported the synthesis of a series of mesoporous anatase TiO
2
powders doped by N, and S, as
well as the N,S co-doped anatase TiO
2
powder using a non-hydrolytic sol-gel process. During the gel
synthesis process, titaniumtetrachloride and titaniumisopropoxide were used as the precursor of Ti,
dimethylsulfoxide (DMSO) was used as the precursor of S, and NH
3
was used as the precursor of N.
For the preparation of S-doped TiO
2
, the obtained gel derived from the solvent of DMSO was calcined
in air, while N and S co-doped TiO
2
was obtained when the gel was annealed in the atmosphere of
NH
3
. In addition, the pristine TiO
2
and corresponding N-doped TiO
2
was further obtained via
calcining the gel derived from the solvent of cyclohexane in air and NH
3
, respectively. In their studies,
the photocatalytic activities of the samples were evaluated via the degradation of dye C.I. Reactive
Orange16 in water under the irradiation of visible light. The obtained results showed that the N-
doped TiO
2
exhibited better visible-light photocatalytic activity compared with the pristine TiO
2
and
S-doped TiO
2
. Similarly, the sol-gel method is also versatile enough to be combined with other
materials synthesis techniques. Most recently, Rajoriya et al. [58] successfully fabricated a samarium
(Sm) and nitrogen (N) co-doped TiO
2
photocatalyst through an ultrasound-assisted sol-gel process
(Figure 8), where they found that after doping TiO
2
with Sm and N, the photocatalytic degradation
performance of the TiO
2
for 4-acetamidophenol was greatly improved owing to the significantly
improved separation efficiency of the photo-generated electron–hole pair.
Figure 7.
Schematic illustration demonstrating the synthesis process of the N-doped TiO
2
conformal
film via the ALD method. Adapted with permission from Reference [56]. Copyright (2017) Wiley.
3.2.5. Sol-Gel and Combustion Method
Compared with the abovementioned synthesis approaches, the sol-gel and combustion method is
a facile and low-cost strategy for the preparation of various semiconductors and the corresponding
hybrid semiconductors. With the merits of simplicity and the possibility of controlling the synthesis
conditions, the sol-gel methods have been well developed and several extended sol-gel techniques have
been invented to fabricate new types of semiconductor photocatalysts. For example,
Albrbar et al. [57]
reported the synthesis of a series of mesoporous anatase TiO
2
powders doped by N, and S, as well
as the N,S co-doped anatase TiO
2
powder using a non-hydrolytic sol-gel process. During the gel
synthesis process, titaniumtetrachloride and titaniumisopropoxide were used as the precursor of Ti,
dimethylsulfoxide (DMSO) was used as the precursor of S, and NH
3
was used as the precursor of N.
For the preparation of S-doped TiO
2
, the obtained gel derived from the solvent of DMSO was calcined
in air, while N and S co-doped TiO
2
was obtained when the gel was annealed in the atmosphere
of NH
3
. In addition, the pristine TiO
2
and corresponding N-doped TiO
2
was further obtained via
calcining the gel derived from the solvent of cyclohexane in air and NH
3
, respectively. In their
studies, the photocatalytic activities of the samples were evaluated via the degradation of dye C.I.
Reactive Orange16 in water under the irradiation of visible light. The obtained results showed that the
N-doped TiO
2
exhibited better visible-light photocatalytic activity compared with the pristine TiO
2
and S-doped TiO
2
. Similarly, the sol-gel method is also versatile enough to be combined with other
materials synthesis techniques. Most recently, Rajoriya et al. [
58
] successfully fabricated a samarium
(Sm) and nitrogen (N) co-doped TiO
2
photocatalyst through an ultrasound-assisted sol-gel process
(Figure 8), where they found that after doping TiO
2
with Sm and N, the photocatalytic degradation
performance of the TiO
2
for 4-acetamidophenol was greatly improved owing to the significantly
improved separation efficiency of the photo-generated electron–hole pair.

Catalysts 2019,9, 122 11 of 32
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Figure 8. Schematic illustrating the ultrasound assisted sol-gel synthesis process of the Sm/N doped
TiO2. Adapted with permission from Reference [58]. Copyright (2019) Elsevier.
4. Heterojunctions Construction
Besides the abovementioned heteroatoms doping strategy, constructing heterojunctions in
photocatalysts is also considered as one of the most promising approaches for improving the
photocatalysis performance of semiconductors due to its feasibility and effectiveness for the spatial
separation of electron–hole pairs. More specifically, the heterojunction is defined as the formed
interface between two semiconductors with the unequal band structure, which can form band
alignments [59,60]. In fact, there have been several types of heterojunction structures, which could be
considered as the conventional heterojunction structures, and the new generation of heterojunction
structures.
4.1. Conventional Heterojunctions
In general, the conventional heterojunctions can be classified as three types depending on the
different band gaps of the composite semiconductors, which are type I with a straddling gap, type II
with a staggered gap, and type III with a broken gap (Figure 9) [59]. As for the type I heterojunction,
the VB and CB of semiconductor A are lower and higher than the corresponding VB and CB of
semiconductor B, respectively. As a result, the photo-generated electrons and holes transfer to the CB
and VB of semiconductor B, which is negative for the separation of electron–hole pairs. Moreover,
the redox reaction of the composite semiconductors with a type I heterojunction will conduct on the
surface of semiconductor B with a lower redox potential, therefore the redox ability of the whole
photocatalyst may be suppressed. Meanwhile, in the composite semiconductor system with type II
heterojunctions, the VB and CB of semiconductor A are higher than that of semiconductor B, thus the
photo-generated electrons will migrate from the CB of semiconductor A to that of semiconductor B
with a lower reduction potential, and the corresponding holes in the VB of semiconductor B will
migrate to semiconductor A with a lower oxidation potential, thus a spatial separation of electron–
hole pairs will be completed. However, the band gap of the two semiconductors will not overlap in
the type III heterojunctions, and as a result, there is no transmission or separation of electrons and
holes between semiconductor A and semiconductor B. Consequently, the type II heterojunction is the
most effective structure for improving the photocatalysis performance of semiconductors, and has
received a great deal of research attention.
Figure 8.
Schematic illustrating the ultrasound assisted sol-gel synthesis process of the Sm/N doped
TiO2. Adapted with permission from Reference [58]. Copyright (2019) Elsevier.
4. Heterojunctions Construction
Besides the abovementioned heteroatoms doping strategy, constructing heterojunctions in
photocatalysts is also considered as one of the most promising approaches for improving the
photocatalysis performance of semiconductors due to its feasibility and effectiveness for the spatial
separation of electron–hole pairs. More specifically, the heterojunction is defined as the formed interface
between two semiconductors with the unequal band structure, which can form band alignments [
59
,
60
].
In fact, there have been several types of heterojunction structures, which could be considered as the
conventional heterojunction structures, and the new generation of heterojunction structures.
4.1. Conventional Heterojunctions
In general, the conventional heterojunctions can be classified as three types depending on the
different band gaps of the composite semiconductors, which are type I with a straddling gap, type II
with a staggered gap, and type III with a broken gap (Figure 9) [
59
]. As for the type I heterojunction,
the VB and CB of semiconductor A are lower and higher than the corresponding VB and CB of
semiconductor B, respectively. As a result, the photo-generated electrons and holes transfer to the CB
and VB of semiconductor B, which is negative for the separation of electron–hole pairs. Moreover,
the redox reaction of the composite semiconductors with a type I heterojunction will conduct on the
surface of semiconductor B with a lower redox potential, therefore the redox ability of the whole
photocatalyst may be suppressed. Meanwhile, in the composite semiconductor system with type II
heterojunctions, the VB and CB of semiconductor A are higher than that of semiconductor B, thus the
photo-generated electrons will migrate from the CB of semiconductor A to that of semiconductor
B with a lower reduction potential, and the corresponding holes in the VB of semiconductor B will
migrate to semiconductor A with a lower oxidation potential, thus a spatial separation of electron–hole
pairs will be completed. However, the band gap of the two semiconductors will not overlap in the
type III heterojunctions, and as a result, there is no transmission or separation of electrons and holes
between semiconductor A and semiconductor B. Consequently, the type II heterojunction is the most
effective structure for improving the photocatalysis performance of semiconductors, and has received
a great deal of research attention.

Catalysts 2019,9, 122 12 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 12 of 32
Figure 9. Schematic illustrating the photocatalysis mechanism of the three different types of
heterojunction photocatalysts: (a) type-I, (b) type-II, and (c) type-III. Adapted with permission from
Reference [59]. Copyright (2017) Wiley.
Up to now, several type-II heterojunction photocatalysts have been developed by creating two
different phases in the same semiconductor, or directly compositing different semiconductors
together [60,61]. For example, Yu et al. [62] once created the anatase-brookite dual-phase in a TiO
2
photocatalyst to form a type-II heterojunction via hydrolyzing the titanium tetraisopropoxide in
water and an ethanol-H
2
O mixture solution. They found that the co-presence of brookite and anatase
phases in the TiO
2
significantly enhanced the photocatalysis performance. After that, Uddin et al. [63]
successfully fabricated the mesoporous SnO
2
-ZnO heterojunction photocatalysts using a two-step
synthesis strategy. Furthermore, they had carefully examined the band alignment, the results showed
that the obtained SnO
2
-ZnO heterojunction photocatalyst possessed a type-II band alignment and
exhibited higher photocatalytic activity for the degradation of methyl blue in water than that of the
individual SnO
2
and ZnO nanocatalysts (Figure 10). Apart from the inorganic semiconductors,
organic semiconductors could also be incorporated with the semiconductors to form the type-II
heterojunction. For example, Shirmardi et al. [64] used polyaniline (PANI) as the organic
semiconductor combined with ZnSe nanoparticles via a simple and cost-effective co-precipitation
method in the ambient conditions. The obtained ZnSe/PANI nanocomposites exhibited obvious
enhancement in the photocatalytic performance compared to that of the pristine ZnSe nanoparticles.
Figure 9.
Schematic illustrating the photocatalysis mechanism of the three different types of
heterojunction photocatalysts: (
a
) type-I, (
b
) type-II, and (
c
) type-III. Adapted with permission from
Reference [59]. Copyright (2017) Wiley.
Up to now, several type-II heterojunction photocatalysts have been developed by creating
two different phases in the same semiconductor, or directly compositing different semiconductors
together [
60
,
61
]. For example, Yu et al. [
62
] once created the anatase-brookite dual-phase in a TiO
2
photocatalyst to form a type-II heterojunction via hydrolyzing the titanium tetraisopropoxide in water
and an ethanol-H
2
O mixture solution. They found that the co-presence of brookite and anatase
phases in the TiO
2
significantly enhanced the photocatalysis performance. After that, Uddin et al. [
63
]
successfully fabricated the mesoporous SnO
2
-ZnO heterojunction photocatalysts using a two-step
synthesis strategy. Furthermore, they had carefully examined the band alignment, the results showed
that the obtained SnO
2
-ZnO heterojunction photocatalyst possessed a type-II band alignment and
exhibited higher photocatalytic activity for the degradation of methyl blue in water than that of the
individual SnO
2
and ZnO nanocatalysts (Figure 10). Apart from the inorganic semiconductors, organic
semiconductors could also be incorporated with the semiconductors to form the type-II heterojunction.
For example, Shirmardi et al. [
64
] used polyaniline (PANI) as the organic semiconductor combined with
ZnSe nanoparticles via a simple and cost-effective co-precipitation method in the ambient conditions.
The obtained ZnSe/PANI nanocomposites exhibited obvious enhancement in the photocatalytic
performance compared to that of the pristine ZnSe nanoparticles.

Catalysts 2019,9, 122 13 of 32
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Figure 10. (a) Nanostructures of SnO
2
−ZnO composite photocatalysts. (b) The corresponding
photocatalytic performances of SnO
2
–ZnO (red line with square dots), SnO
2
(green line with triangle
dots), and ZnO (blue line with circle dots). Adapted with permission from Reference [63]. Copyright
(2012) American Chemical Society.
4.2. New Generation of Heterojunctions
Although the conventional type-II heterojunctions are capable of spatially separating the photo-
generated electron–hole pairs, there remain several critical limitations, such as the relatively weak
redox ability due to the lower reduction and oxidation potentials, and the suppressed migration of
electrons and holes due to the electrostatic repulsion [59]. Recently, in order to overcome the
abovementioned limitations, a new generation of heterojunctions have been developed, including the
p-n heterojunctions, the surface heterojunctions, the Z-scheme heterojunctions, and the
semiconductor/carbon heterojunctions. Here we will give a brief introduction of each kind of these
newly developed heterojunctions.
4.2.1. p–n Heterojunctions
The p-n heterojunctions could be obtained by incorporating a p-type semiconductor with an n-
type semiconductor, and it has been proved that the formation of p-n heterojunctions are effective
for improving the photocatalytic performance of composite catalysts [65,66]. In general, before the
irradiation of light, there is an internal electric field in the region closed to the p-n interface due to the
electron–hole diffusion tendency of the composite semiconductors system with unequal Fermi levels
[59,67]. Alternatively, when the composite semiconductors are irradiated by a light, and the energy
state of the photon is beyond the band gaps of both p-type and n-type semiconductors, electron–hole
pairs will be generated in the corresponding semiconductors. However, due to the presence of an
internal electric field, the photo-generated electrons and holes will transfer to the CB of the n-type
semiconductor and the VB of p-type semiconductor, respectively. Furthermore, it has been proved
that this spatial separation of the photo-generated electron–hole pairs is much more efficient
compared with that of conventional type-II heterojunction because of the synergy of the internal
electric field and band alignment [59,68]. As a result, a variety of composite semiconductors with the
p-n heterojunctions have been created for the application of photocatalysis. For example, Wen et al.
[69] reported the fabrication of a BiOI/CeO
2
p-n junction using a facile in situ chemical bath method.
The result demonstrated that the BiOI/CeO
2
composite with a mole ratio of 1:1 exhibited a superior
photocatalytic performance for the decomposition of bisphenol A (BPA) and methylene orange under
visible light irradiation. Most recently, as shown in Figure 11, our group reported a facile method for
the preparation of SnS
2
/MoO
3
hollow nanotubes based on the hydrothermal method [70]. The
obtained SnS
2
/MoO
3
hollow nanotubes exhibit a typical p-n heterojunction structure, and a
synergistic effect between MoO
3
and SnS
2
was proven to yield an optimal hydrogen peroxide
production performance.
Figure 10.
(
a
) Nanostructures of SnO
2−
ZnO composite photocatalysts. (
b
) The corresponding
photocatalytic performances of SnO
2
–ZnO (red line with square dots), SnO
2
(green line with
triangle dots), and ZnO (blue line with circle dots). Adapted with permission from Reference [
63
].
Copyright (2012) American Chemical Society.
4.2. New Generation of Heterojunctions
Although the conventional type-II heterojunctions are capable of spatially separating the
photo-generated electron–hole pairs, there remain several critical limitations, such as the relatively
weak redox ability due to the lower reduction and oxidation potentials, and the suppressed
migration of electrons and holes due to the electrostatic repulsion [
59
]. Recently, in order to
overcome the abovementioned limitations, a new generation of heterojunctions have been developed,
including the p-n heterojunctions, the surface heterojunctions, the Z-scheme heterojunctions, and the
semiconductor/carbon heterojunctions. Here we will give a brief introduction of each kind of these
newly developed heterojunctions.
4.2.1. p–n Heterojunctions
The p-n heterojunctions could be obtained by incorporating a p-type semiconductor with an
n-type semiconductor, and it has been proved that the formation of p-n heterojunctions are effective
for improving the photocatalytic performance of composite catalysts [
65
,
66
]. In general, before
the irradiation of light, there is an internal electric field in the region closed to the p-n interface
due to the electron–hole diffusion tendency of the composite semiconductors system with unequal
Fermi levels [59,67].
Alternatively, when the composite semiconductors are irradiated by a light,
and the energy state of the photon is beyond the band gaps of both p-type and n-type semiconductors,
electron–hole pairs will be generated in the corresponding semiconductors. However, due to the
presence of an internal electric field, the photo-generated electrons and holes will transfer to the CB of
the n-type semiconductor and the VB of p-type semiconductor, respectively. Furthermore, it has been
proved that this spatial separation of the photo-generated electron–hole pairs is much more efficient
compared with that of conventional type-II heterojunction because of the synergy of the internal electric
field and band alignment [
59
,
68
]. As a result, a variety of composite semiconductors with the p-n
heterojunctions have been created for the application of photocatalysis. For example,
Wen et al. [69]
reported the fabrication of a BiOI/CeO
2
p-n junction using a facile in situ chemical bath method.
The result demonstrated that the BiOI/CeO
2
composite with a mole ratio of 1:1 exhibited a superior
photocatalytic performance for the decomposition of bisphenol A (BPA) and methylene orange under
visible light irradiation. Most recently, as shown in Figure 11, our group reported a facile method for the
preparation of SnS
2
/MoO
3
hollow nanotubes based on the hydrothermal method [
70
]. The obtained
SnS
2
/MoO
3
hollow nanotubes exhibit a typical p-n heterojunction structure, and a synergistic effect
between MoO
3
and SnS
2
was proven to yield an optimal hydrogen peroxide production performance.

Catalysts 2019,9, 122 14 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 14 of 32
Figure 11. Schematic illustration of the SnS
2
/MoO
3
hollow nanotubes and its photocatalysis
mechanism with a two-channel pathway. Adapted with permission from Reference [70]. Copyright
(2018) Royal Society of Chemistry.
4.2.2. Surface Heterojunctions
As reported before, a surface heterojunction can be created between two crystal facets of a single
semiconductor [59,71]. For example, Yu et al. [72] proved that the formation of a heterojunction
between the (001) and (101) facets in TiO
2
contribute significantly toward the enhancement of
photocatalytic activity. This method enables the construction of a heterojunction on the surface of a
single semiconductor, which is less costly because only one semiconductor is used. They also
demonstrate that there is an optimal ratio for the (001) and (101) facets in the anatase TiO
2
for the
improvement of its photocatalysis performance. Subsequently, Gao et al. [73] found that the surface
heterojunction of TiO
2
could be self-adjusted, and its photocatalytic activity could be significantly
improved via combining a proper surface heterojunction with the Schottky junction. Apart from the
TiO
2
, Bi-based semiconductors could also be employed for the design of photocatalysts with surface
heterojunctions. Most recently, as shown in Figure 12, Lu et al. [74] synthesized a tetragonal BiOI
photocatalyst by regulating the amount of water in the hydrolysis process at room temperature. The
as-prepared photocatalyst possessed a typical surface heterojunction structure between (001) facets
and (110) facets, and exhibited a promoted photocatalytic performance for the degradation of organic
contaminants in water under visible light.
Figure 11.
Schematic illustration of the SnS
2
/MoO
3
hollow nanotubes and its photocatalysis
mechanism with a two-channel pathway. Adapted with permission from Reference [
70
].
Copyright (2018) Royal Society of Chemistry.
4.2.2. Surface Heterojunctions
As reported before, a surface heterojunction can be created between two crystal facets of a single
semiconductor [
59
,
71
]. For example, Yu et al. [
72
] proved that the formation of a heterojunction
between the (001) and (101) facets in TiO
2
contribute significantly toward the enhancement of
photocatalytic activity. This method enables the construction of a heterojunction on the surface
of a single semiconductor, which is less costly because only one semiconductor is used. They also
demonstrate that there is an optimal ratio for the (001) and (101) facets in the anatase TiO
2
for the
improvement of its photocatalysis performance. Subsequently, Gao et al. [
73
] found that the surface
heterojunction of TiO
2
could be self-adjusted, and its photocatalytic activity could be significantly
improved via combining a proper surface heterojunction with the Schottky junction. Apart from
the TiO
2
, Bi-based semiconductors could also be employed for the design of photocatalysts with
surface heterojunctions. Most recently, as shown in Figure 12, Lu et al. [
74
] synthesized a tetragonal
BiOI photocatalyst by regulating the amount of water in the hydrolysis process at room temperature.
The as-prepared photocatalyst possessed a typical surface heterojunction structure between (001) facets
and (110) facets, and exhibited a promoted photocatalytic performance for the degradation of organic
contaminants in water under visible light.

Catalysts 2019,9, 122 15 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 15 of 32
Figure 12. (a,b) Schematic illustrating the growth of TiO2 nanosheets at different conditions. (c) UV-
vis images of the related samples. (d) Photocatalytic degradation efficiency of different catalysts for
methyl orange. (e) Schematic demonstrating the migration of electrons and holes in the surface
heterojunction. Adapted with permission from Reference [74]. Copyright (2018) Elsevier.
4.2.3. Z-Scheme Heterojunctions
Z-scheme heterojunctions were constructed to overcome the limitation of the lower redox
potential of the heterojunction systems. [59,75] In general, the Z-scheme heterojunction is composed
of two different semiconductors and an electron acceptor/donor pair. During the photocatalysis
process, the photo-generated electrons/holes will transfer from the matrix semiconductor to the
coupled semiconductor through the electron acceptor/donor pair or an electron mediator. As a result,
the electrons/holes will accumulate on different semiconductors with higher redox potentiasl, and an
effective spatial separation of electron–hole pairs is also realized. Up to now, the Z-scheme
heterojunctions have been well developed, and various photocatalysts with well-designed Z-scheme
heterojunctions have been invented for the wastewater treatment. [75] For example, Wu et al. [76]
reported the fabrication of the Ag2CO3/Ag/AgNCO composite photocatalyst via a simple in situ ion
exchange method. The obtained composite photocatalyst possessed the Z-scheme heterojunction and
exhibited a highly efficient degradation ratio of rhodamine B and the reduction of Cr (VI) under the
driving of visible light. They proved that the significantly enhanced photocatalytic activity could be
attributed to the low resistance for the interfacial charge transfer and desirable absorption capability.
Recently, considering the relative high cost of the common used electron mediators (e.g., Pt, Ag, and
Au), a new generation of Z-heterojunctions without the electron mediators have been invented for
wastewater treatment, which is named as the direct Z-scheme system [59]. For example, Lu et al. [77]
synthesized a CuInS2/Bi2WO6 composite catalyst with a direct Z-scheme heterojunction via the in situ
Figure 12.
(
a
,
b
) Schematic illustrating the growth of TiO
2
nanosheets at different conditions. (
c
) UV-vis
images of the related samples. (
d
) Photocatalytic degradation efficiency of different catalysts for methyl
orange. (
e
) Schematic demonstrating the migration of electrons and holes in the surface heterojunction.
Adapted with permission from Reference [74]. Copyright (2018) Elsevier.
4.2.3. Z-Scheme Heterojunctions
Z-scheme heterojunctions were constructed to overcome the limitation of the lower redox
potential of the heterojunction systems. [
59
,
75
] In general, the Z-scheme heterojunction is composed
of two different semiconductors and an electron acceptor/donor pair. During the photocatalysis
process, the photo-generated electrons/holes will transfer from the matrix semiconductor to the
coupled semiconductor through the electron acceptor/donor pair or an electron mediator. As a
result, the electrons/holes will accumulate on different semiconductors with higher redox potentiasl,
and an effective spatial separation of electron–hole pairs is also realized. Up to now, the Z-scheme
heterojunctions have been well developed, and various photocatalysts with well-designed Z-scheme
heterojunctions have been invented for the wastewater treatment. [
75
] For example, Wu et al. [
76
]
reported the fabrication of the Ag
2
CO
3
/Ag/AgNCO composite photocatalyst via a simple in situ ion
exchange method. The obtained composite photocatalyst possessed the Z-scheme heterojunction and
exhibited a highly efficient degradation ratio of rhodamine B and the reduction of Cr (VI) under the
driving of visible light. They proved that the significantly enhanced photocatalytic activity could be
attributed to the low resistance for the interfacial charge transfer and desirable absorption capability.
Recently, considering the relative high cost of the common used electron mediators (e.g., Pt, Ag,
and Au), a new generation of Z-heterojunctions without the electron mediators have been invented for

Catalysts 2019,9, 122 16 of 32
wastewater treatment, which is named as the direct Z-scheme system [
59
]. For example, Lu et al. [
77
]
synthesized a CuInS
2
/Bi
2
WO
6
composite catalyst with a direct Z-scheme heterojunction via the in
situ hydrothermal growth of Bi
2
WO
6
on the surface of CuInS
2
networks. The obtained composite
photocatalysts with an optimal Z-scheme exhibited a superior visible light degradation performance
of the tetracycline hydrochloride in water than that of the pristine CuInS
2
and Bi
2
WO
6
. The improved
photocatalytic activity was attributed to the formed intimate interface contact, which ensured a good
interfacial charge transfer ability (Figure 13).
Catalysts 2018, 8, x FOR PEER REVIEW 16 of 32
hydrothermal growth of Bi2WO6 on the surface of CuInS2 networks. The obtained composite
photocatalysts with an optimal Z-scheme exhibited a superior visible light degradation performance
of the tetracycline hydrochloride in water than that of the pristine CuInS2 and Bi2WO6. The improved
photocatalytic activity was attributed to the formed intimate interface contact, which ensured a good
interfacial charge transfer ability (Figure 13).
Figure 13. Schematic illustrating the interfacial electron transfer process and possible photocatalytic
mechanism of CuInS2/Bi2WO6 with the Z-scheme heterojunction. Adapted with permission from
Reference [77]. Copyright (2019) Elsevier.
4.2.4. Semiconductor/Carbon Heterojunctions
Carbonaceous nanomaterials have been widely employed for the design of novel photocatalysts
due to their advantages of high surface area, good conductivity, and chemical stability. In general,
the most commonly used carbonaceous materials for combining with semiconductors involves the
carbon dots (CDs), carbon nanotubes (CNTs), and graphene [78].
The CDs as typical nanocarbon materials have been widely used to enhance the photocatalytic
activity of semiconductors owing to their intriguing optical and electronic properties, low chemical
toxicity, adjustable photoluminescence, and the distinct quantum effect [79]. For example, Long et al.
[80] used carbon dots (CDs) to couple with the BiOI with highly exposed (001) facets to form a
composition of CDs/BiOI. Furthermore, the obtained CDs/BiOI composite exhibited a greatly
improved photocatalytic activity for the degradation of organic dyes in water. It has been proved that
the incorporated CDs in the semiconductor formed a CDs/BiOI heterojunction, which was able to
construct numerous electron surface trap sites and was beneficial for enhancing the visible light
absorption range as well as the charge separation. Recently, Zhao et al. [81] reported the fabrication
of carbon quantum dots (CQDs)/TiO2 nanotubes (TNTs) composite via an improved hydrothermal
method. The CQDs were incorporated on the surface of the TNTs, and played a vital role in
improving the visible light photocatalytic performance of the composite. As shown in Figure 14, they
demonstrated that there were three advantages for the formation of CQDs/TiO2: i) the CQDs could
effectively trap the photo-generated electrons from TNTs and suppress the recombination of electron-
hole pairs, ii) the up-conversion photoluminescence property of CQDs could further improve the
visible light utilization efficiency of CQDs/TNTs, and iii) the hetero-structure formed between the
CQDs and the TNTs could prolong the life of the photogenerated electron and hole pairs.
Figure 13.
Schematic illustrating the interfacial electron transfer process and possible photocatalytic
mechanism of CuInS
2
/Bi
2
WO
6
with the Z-scheme heterojunction. Adapted with permission from
Reference [77]. Copyright (2019) Elsevier.
4.2.4. Semiconductor/Carbon Heterojunctions
Carbonaceous nanomaterials have been widely employed for the design of novel photocatalysts
due to their advantages of high surface area, good conductivity, and chemical stability. In general,
the most commonly used carbonaceous materials for combining with semiconductors involves the
carbon dots (CDs), carbon nanotubes (CNTs), and graphene [78].
The CDs as typical nanocarbon materials have been widely used to enhance the photocatalytic
activity of semiconductors owing to their intriguing optical and electronic properties, low chemical
toxicity, adjustable photoluminescence, and the distinct quantum effect [
79
]. For example,
Long et al. [80]
used carbon dots (CDs) to couple with the BiOI with highly exposed (001) facets
to form a composition of CDs/BiOI. Furthermore, the obtained CDs/BiOI composite exhibited a
greatly improved photocatalytic activity for the degradation of organic dyes in water. It has been
proved that the incorporated CDs in the semiconductor formed a CDs/BiOI heterojunction, which was
able to construct numerous electron surface trap sites and was beneficial for enhancing the visible
light absorption range as well as the charge separation. Recently, Zhao et al. [
81
] reported the
fabrication of carbon quantum dots (CQDs)/TiO
2
nanotubes (TNTs) composite via an improved
hydrothermal method. The CQDs were incorporated on the surface of the TNTs, and played a vital
role in improving the visible light photocatalytic performance of the composite. As shown in Figure 14,
they demonstrated that there were three advantages for the formation of CQDs/TiO
2
: (i) the CQDs
could effectively trap the photo-generated electrons from TNTs and suppress the recombination of
electron-hole pairs, (ii) the up-conversion photoluminescence property of CQDs could further improve
the visible light utilization efficiency of CQDs/TNTs, and (iii) the hetero-structure formed between the
CQDs and the TNTs could prolong the life of the photogenerated electron and hole pairs.

Catalysts 2019,9, 122 17 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 17 of 32
Figure 14. Schematic illustration indicating the photocatalysis mechanism of the CQDs/TNTs
photocatalyst. Adapted with permission from Reference [81]. Copyright (2018) Elsevier.
CNTs are typical nanocarbon materials with highly sp
2
-ordered structures, and thus exhibit an
excellent metallic conductivity, which could form a Schottky barrier junction between the CNT and
semiconductors; as reported before, the Schottky barrier junction could effectively increase the
recombination time of electron–hole pairs [78,82]. Moreover, CNTs could accept electrons in the
composite system with semiconductors due to its large electron-storage capacity, which is beneficial
for retarding or hindering the electron–hole recombination. As a result, a variety of semiconductor-
CNT composite photocatalysts have been developed. For example, Miribangul et al. [83] prepared a
TiO
2
/CNT composite via a simple hydrothermal method. The influence of the CNT concentration in
the TiO
2
-CNT composites on their photocatalytic activity was investigated and the 0.3 wt% CNT
content in TiO
2
/CNT composite could offer the highest photocatalytic degradation of Sudan (I) in
UV–vis light. Apart from the TiO
2
, some of the other semiconductors can also be employed to
composite with CNT, such as the CNT/LaVO
4
composite photocatalyst developed by Xu et al. [84].
As shown in Figure 15, with the presence of CNT, the photocatalytic activity of a CNT/LaVO
4
composite was greatly improved due to the synergistic effect between CNT and LaVO
4
, therefore the
corresponding photocatalytic degradation rate of CNT/LaVO
4
composite for organic contaminant is
2 times that of pure LaVO
4
.
Figure 14.
Schematic illustration indicating the photocatalysis mechanism of the CQDs/TNTs
photocatalyst. Adapted with permission from Reference [81]. Copyright (2018) Elsevier.
CNTs are typical nanocarbon materials with highly sp
2
-ordered structures, and thus exhibit
an excellent metallic conductivity, which could form a Schottky barrier junction between the CNT
and semiconductors; as reported before, the Schottky barrier junction could effectively increase the
recombination time of electron–hole pairs [
78
,
82
]. Moreover, CNTs could accept electrons in the composite
system with semiconductors due to its large electron-storage capacity, which is beneficial for retarding
or hindering the electron–hole recombination. As a result, a variety of semiconductor-CNT composite
photocatalysts have been developed. For example, Miribangul et al. [
83
] prepared a TiO
2
/CNT composite
via a simple hydrothermal method. The influence of the CNT concentration in the TiO
2
-CNT composites
on their photocatalytic activity was investigated and the 0.3 wt % CNT content in TiO
2
/CNT composite
could offer the highest photocatalytic degradation of Sudan (I) in UV–vis light. Apart from the TiO
2
,
some of the other semiconductors can also be employed to composite with CNT, such as the CNT/LaVO
4
composite photocatalyst developed by Xu et al. [
84
]. As shown in Figure 15, with the presence of CNT,
the photocatalytic activity of a CNT/LaVO
4
composite was greatly improved due to the synergistic effect
between CNT and LaVO
4
, therefore the corresponding photocatalytic degradation rate of CNT/LaVO
4
composite for organic contaminant is 2 times that of pure LaVO4.
Catalysts 2018, 8, x FOR PEER REVIEW 17 of 32
Figure 14. Schematic illustration indicating the photocatalysis mechanism of the CQDs/TNTs
photocatalyst. Adapted with permission from Reference [81]. Copyright (2018) Elsevier.
CNTs are typical nanocarbon materials with highly sp
2
-ordered structures, and thus exhibit an
excellent metallic conductivity, which could form a Schottky barrier junction between the CNT and
semiconductors; as reported before, the Schottky barrier junction could effectively increase the
recombination time of electron–hole pairs [78,82]. Moreover, CNTs could accept electrons in the
composite system with semiconductors due to its large electron-storage capacity, which is beneficial
for retarding or hindering the electron–hole recombination. As a result, a variety of semiconductor-
CNT composite photocatalysts have been developed. For example, Miribangul et al. [83] prepared a
TiO
2
/CNT composite via a simple hydrothermal method. The influence of the CNT concentration in
the TiO
2
-CNT composites on their photocatalytic activity was investigated and the 0.3 wt% CNT
content in TiO
2
/CNT composite could offer the highest photocatalytic degradation of Sudan (I) in
UV–vis light. Apart from the TiO
2
, some of the other semiconductors can also be employed to
composite with CNT, such as the CNT/LaVO
4
composite photocatalyst developed by Xu et al. [84].
As shown in Figure 15, with the presence of CNT, the photocatalytic activity of a CNT/LaVO
4
composite was greatly improved due to the synergistic effect between CNT and LaVO
4
, therefore the
corresponding photocatalytic degradation rate of CNT/LaVO
4
composite for organic contaminant is
2 times that of pure LaVO
4
.
Figure 15.
Schematic illustration indicating the reaction mechanism of the photocatalytic procedure of
CNT/LaVO
4
composite catalyst. Adapted with permission from Reference [
84
]. Copyright (2019) Elsevier.

Catalysts 2019,9, 122 18 of 32
Recently, graphene as a newly developed nanocarbon material has attracted numerous research
attention in the area of photocatalysts due to its extraordinary physical properties, including superior
charge transport ability, unique optical properties, high thermal conductivity, large specific surface area,
and good mechanical strength [
78
,
85
,
86
]. Up to now, a myriad of attempts has been carried out to couple
the graphene with various semiconductors to further improve their photocatalytic activity. According to
the previous reports, the first graphene composite semiconductor for photocatalysis was prepared
by Zhang and co-workers [
87
]. They fabricated a TiO
2
(P25)-graphene composite with a chemically
bonding structure via a one-step hydrothermal reaction. As reported, there are three contributions of
the graphene for the photocatalytic activity: (i) enhancing the adsorption capacity of pollutants, (ii)
extending light absorption range, and (iii) improving charge transportation and separation efficiency.
As a result, the photodegradation of the obtained TiO
2
(P25)-graphene composite for methylene blue was
significantly improved, and was superior to that of the bare P25 and the commonly reported P25-CNTs
composite. After that, numerous photocatalysts based on the composite graphene-semiconductors have
been invented for the treatment of wastewater. Most recently, in order to overcome the limitation of
the poor homogenous dispersion of graphene, as shown in Figure 16, Isari et al. [
88
] created a ternary
nanocomposite catalyst (Fe-doped TiO
2
/rGO) derived from Fe-doped TiO
2
and reduced graphene oxide
via a simple sol-gel method. They proved that the band gap of Fe-TiO
2
/rGO could be significantly
decreased compared with that of the pristine TiO
2
, and the obtained Fe-doped TiO
2
/rGO exhibited an
effective decontamination performance for rhodamine B in water.
Catalysts 2018, 8, x FOR PEER REVIEW 18 of 32
Figure 15. Schematic illustration indicating the reaction mechanism of the photocatalytic procedure
of CNT/LaVO
4
composite catalyst. Adapted with permission from Reference [84]. Copyright (2019)
Elsevier.
Recently, graphene as a newly developed nanocarbon material has attracted numerous research
attention in the area of photocatalysts due to its extraordinary physical properties, including superior
charge transport ability, unique optical properties, high thermal conductivity, large specific surface
area, and good mechanical strength [78,85,86]. Up to now, a myriad of attempts has been carried out
to couple the graphene with various semiconductors to further improve their photocatalytic activity.
According to the previous reports, the first graphene composite semiconductor for photocatalysis
was prepared by Zhang and co-workers [87]. They fabricated a TiO
2
(P25)-graphene composite with
a chemically bonding structure via a one-step hydrothermal reaction. As reported, there are three
contributions of the graphene for the photocatalytic activity: i) enhancing the adsorption capacity of
pollutants, ii) extending light absorption range, and iii) improving charge transportation and
separation efficiency. As a result, the photodegradation of the obtained TiO
2
(P25)-graphene
composite for methylene blue was significantly improved, and was superior to that of the bare P25
and the commonly reported P25-CNTs composite. After that, numerous photocatalysts based on the
composite graphene-semiconductors have been invented for the treatment of wastewater. Most
recently, in order to overcome the limitation of the poor homogenous dispersion of graphene, as
shown in Figure 16, Isari et al. [88] created a ternary nanocomposite catalyst (Fe-doped TiO
2
/rGO)
derived from Fe-doped TiO
2
and reduced graphene oxide via a simple sol-gel method. They proved
that the band gap of Fe-TiO
2
/rGO could be significantly decreased compared with that of the pristine
TiO
2
, and the obtained Fe-doped TiO
2
/rGO exhibited an effective decontamination performance for
rhodamine B in water.
Figure 16. Schematic illustration demonstrating the photocatalytic mechanism of Fe-TiO
2
/rGO
catalyst for contaminant under solar irradiation. Adapted with permission from Reference [88].
Copyright (2018) Elsevier.
5. Morphology Regulation of the Composite Photocatalysts
Apart from the intrinsic characteristics of semiconductors, the corresponding catalysts with
different morphologies may result in different photocatalytic activities and different application
processes [89]. Recently, morphology modification of the photocatalysts have attracted more and
more attention owing to further improvements in their application performance, not only for the
photocatalytic performance but also for the application techniques. With this in mind, in this section
Figure 16.
Schematic illustration demonstrating the photocatalytic mechanism of Fe-TiO
2
/rGO
catalyst for contaminant under solar irradiation. Adapted with permission from Reference [
88
].
Copyright (2018) Elsevier.
5. Morphology Regulation of the Composite Photocatalysts
Apart from the intrinsic characteristics of semiconductors, the corresponding catalysts with
different morphologies may result in different photocatalytic activities and different application
processes [
89
]. Recently, morphology modification of the photocatalysts have attracted more and
more attention owing to further improvements in their application performance, not only for the
photocatalytic performance but also for the application techniques. With this in mind, in this section
we will briefly summarize the recent achievements of the composite photocatalysts with different
morphologies of 0D, 1D, 2D, and 3D materials.

Catalysts 2019,9, 122 19 of 32
5.1. Nanoparticles (0D)
Generally, the 0D materials are characterized as spherically shaped with nano-scaled dimensions.
Nanoparticles as a typical 0D material have been widely used in the area of photocatalysis with the
merits of large surface area, simple synthesis methods, and easy to be functionalized [
90
]. Up to now,
several synthesis approaches have been invented, among which the sol-gel method, hydrothermal
method, and solvothermal method could be the most-used techniques for the fabrication of 0D
composite photocatalysts.
5.1.1. Sol-Gel Method
The sol-gel process is a commonly used and effective strategy for the preparation of various
inorganic materials, especially for the metal oxides based on the corresponding precursors, and it
has several merits including being low cost, processed at low-temperature, and the fine control
of the product’s chemical composition. Therefore, the sol-gel process is one of the most-used
techniques for the preparation of composite semiconductor photocatalysts [
58
]. For example,
Vaiano et al. [91]
immobilized the N-doped TiO
2
nanoparticles (NPs) on glass spheres via the sol-gel
method. Through regulating the synthesis conditions, and employing the Triton X-100 as the surface
active agent, the obtained N-doped TiO
2
NPs/glass spheres exhibited a good photocatalytic activity
for methylene blue and eriochrome black-T in water under UV and visible light irradiation. Moreover,
the composite catalyst was easy to be separated from the reaction mixture with a good durability.
Recently,
Chen et al. [92]
prepared a Ni-Cu-Zn ferrite@SiO
2
@TiO
2
composite via a simple sol-gel
method. With the immobilization of Ag and magnetic ferrite, the composite photocatalysts exhibited
comparatively good photodegradation performance for the methylene blue under a visible light source
with lower power. Moreover, the composite catalysts can be easily separated using a magnet and can
be reused well without significant loss of photocatalytic activity (Figure 17).
Catalysts 2018, 8, x FOR PEER REVIEW 19 of 32
we will briefly summarize the recent achievements of the composite photocatalysts with different
morphologies of 0D, 1D, 2D, and 3D materials.
5.1. Nanoparticles (0D)
Generally, the 0D materials are characterized as spherically shaped with nano-scaled
dimensions. Nanoparticles as a typical 0D material have been widely used in the area of
photocatalysis with the merits of large surface area, simple synthesis methods, and easy to be
functionalized [90]. Up to now, several synthesis approaches have been invented, among which the
sol-gel method, hydrothermal method, and solvothermal method could be the most-used techniques
for the fabrication of 0D composite photocatalysts.
5.1.1. Sol-Gel Method
The sol-gel process is a commonly used and effective strategy for the preparation of various
inorganic materials, especially for the metal oxides based on the corresponding precursors, and it has
several merits including being low cost, processed at low-temperature, and the fine control of the
product’s chemical composition. Therefore, the sol-gel process is one of the most-used techniques for
the preparation of composite semiconductor photocatalysts [58]. For example, Vaiano et al. [91]
immobilized the N-doped TiO2 nanoparticles (NPs) on glass spheres via the sol-gel method. Through
regulating the synthesis conditions, and employing the Triton X-100 as the surface active agent, the
obtained N-doped TiO2 NPs/glass spheres exhibited a good photocatalytic activity for methylene
blue and eriochrome black-T in water under UV and visible light irradiation. Moreover, the
composite catalyst was easy to be separated from the reaction mixture with a good durability.
Recently, Chen et al. [92] prepared a Ni-Cu-Zn ferrite@SiO2@TiO2 composite via a simple sol-gel
method. With the immobilization of Ag and magnetic ferrite, the composite photocatalysts exhibited
comparatively good photodegradation performance for the methylene blue under a visible light
source with lower power. Moreover, the composite catalysts can be easily separated using a magnet
and can be reused well without significant loss of photocatalytic activity (Figure 17).
Figure 17. (a) The cycling test of the catalytic performance. (b) Dye removal capacity by adsorption
and degradation for different cycles. (c) Digital photos demonstrating the recyclability by using an
external magnetic field. Adapted with permission from Reference [92]. Copyright (2017) Elsevier.
5.1.2. Hydrothermal Methods
The hydrothermal method is a wet-chemistry method for synthesizing single crystals. Through
the hydrothermal method, a great deal of crystalline phases that are not stable at the melting point
can be obtained [93]. As a result, numerous semiconductor nanoparticles with different surface
(a) (b)
(c)
Figure 17.
(
a
) The cycling test of the catalytic performance. (
b
) Dye removal capacity by adsorption
and degradation for different cycles. (
c
) Digital photos demonstrating the recyclability by using an
external magnetic field. Adapted with permission from Reference [92]. Copyright (2017) Elsevier.
5.1.2. Hydrothermal Methods
The hydrothermal method is a wet-chemistry method for synthesizing single crystals. Through the
hydrothermal method, a great deal of crystalline phases that are not stable at the melting point
can be obtained [
93
]. As a result, numerous semiconductor nanoparticles with different surface
morphologies and compositions can also be prepared using the hydrothermal method. As a

Catalysts 2019,9, 122 20 of 32
representative work, Wu et al. [
94
] fabricated the F-doped flower-like TiO
2
nanoparticle on the
surface of Ti via a low-temperature hydrothermal process. They reported that the presence of
HF in water and the hydrothermal reaction time play an important role in the formation of the
F-doped flower-like TiO
2
nanostructures. Through regulating the synthesis parameters, the obtained
F-doped TiO
2
flower-like nanomaterials exhibited a superior photoelectrochemical activity for the
photodegradation of organic pollutants compared with P-25. They also demonstrated that the
improved photoelectrochemical activity of the F-doped TiO
2
flower-like nanomaterials was mainly
due to the larger surface area and the enhanced visible light harvest capacity. Additionally, magnetic
composite photocatalysts can also be synthesized using the hydrothermal method, such as the
magnetic CoFe
2
O
4
/Ag/Ag
3
VO
4
photocatalysts fabricated by Jing and co-workers [
95
]. During this
study, the as-prepared CoFe
2
O
4
nanoparticles were dispersed in the solutions with AgNO
3
and
Na
3
VO
4
, and the mixture suspensions were hydrothermally treated to prepare CoFe
2
O
4
/Ag/Ag
3
VO
4
composites. Through controlling the weight ratios of CoFe
2
O
4
in the composite system, the optimal
CoFe
2
O
4
/Ag/Ag
3
VO
4
composite exhibited significantly improved photocatalytic activity toward
the degradation of various contaminants including methyl orange, tetracycline, and could even kill
Escherichia coli solely under the driving of visible light. Moreover, with the advantage of having a good
magnetic response property, the corresponding CoFe
2
O
4
/Ag/Ag
3
VO
4
composite could be facilely
collected from the water by applying an extra magnetic field (Figure 18).
Catalysts 2018, 8, x FOR PEER REVIEW 20 of 32
morphologies and compositions can also be prepared using the hydrothermal method. As a
representative work, Wu et al. [94] fabricated the F-doped flower-like TiO2 nanoparticle on the surface
of Ti via a low-temperature hydrothermal process. They reported that the presence of HF in water
and the hydrothermal reaction time play an important role in the formation of the F-doped flower-
like TiO2 nanostructures. Through regulating the synthesis parameters, the obtained F-doped TiO2
flower-like nanomaterials exhibited a superior photoelectrochemical activity for the
photodegradation of organic pollutants compared with P-25. They also demonstrated that the
improved photoelectrochemical activity of the F-doped TiO2 flower-like nanomaterials was mainly
due to the larger surface area and the enhanced visible light harvest capacity. Additionally, magnetic
composite photocatalysts can also be synthesized using the hydrothermal method, such as the
magnetic CoFe2O4/Ag/Ag3VO4 photocatalysts fabricated by Jing and co-workers [95]. During this
study, the as-prepared CoFe2O4 nanoparticles were dispersed in the solutions with AgNO3 and
Na3VO4, and the mixture suspensions were hydrothermally treated to prepare CoFe2O4/Ag/Ag3VO4
composites. Through controlling the weight ratios of CoFe2O4 in the composite system, the optimal
CoFe2O4/Ag/Ag3VO4 composite exhibited significantly improved photocatalytic activity toward the
degradation of various contaminants including methyl orange, tetracycline, and could even kill
Escherichia coli solely under the driving of visible light. Moreover, with the advantage of having a
good magnetic response property, the corresponding CoFe2O4/Ag/Ag3VO4 composite could be
facilely collected from the water by applying an extra magnetic field (Figure 18).
Figure 18. (a) Magnetic separation performance of the CoFe2O4/Ag/Ag3VO4 composite. (b) The
absorption spectra of methyl orange solutions over time in the presence of CoFe2O4/Ag/Ag3VO4
(under visible light λ ≥ 440 nm) and the UV–vis absorption spectrum of CoFe2O4/Ag/Ag3VO4. (c) The
evolution of the absorption spectra of methyl orange solutions over time in the presence of
CoFe2O4/Ag/Ag3VO4 (under visible light λ ≥ 550 nm). (d) Photocatalytic degradation of tetracycline
with different samples under visible light irradiation. Adapted with permission from Reference [95]
Copyright (2016) Elsevier.
5.2. Nanofibers/Nanorods (1D)
Recently, nanofibrous photocatalysts have been intensively studied owing to their unique long
aspect ratio, large surface area, and being easily functionalized. Up to now, various strategies had
been developed to synthesize the 1D materials with different morphology like: wires, belts, rods,
tubes, and rings [61,89,96], among which, the hydrothermal method and electrospinning are the
(a) (b)
(c) (d)
Figure 18.
(
a
) Magnetic separation performance of the CoFe
2
O
4
/Ag/Ag
3
VO
4
composite. (
b
) The absorption
spectra of methyl orange solutions over time in the presence of CoFe
2
O
4
/Ag/Ag
3
VO
4
(under visible light
λ≥
440 nm) and the UV–vis absorption spectrum of CoFe
2
O
4
/Ag/Ag
3
VO
4
. (
c
) The evolution of the
absorption spectra of methyl orange solutions over time in the presence of CoFe
2
O
4
/Ag/Ag
3
VO
4
(under
visible light
λ≥
550 nm). (
d
) Photocatalytic degradation of tetracycline with different samples under visible
light irradiation. Adapted with permission from Reference [95] Copyright (2016) Elsevier.
5.2. Nanofibers/Nanorods (1D)
Recently, nanofibrous photocatalysts have been intensively studied owing to their unique long aspect
ratio, large surface area, and being easily functionalized. Up to now, various strategies had been developed
to synthesize the 1D materials with different morphology like: wires, belts, rods, tubes, and rings [
61
,
89
,
96
],
among which, the hydrothermal method and electrospinning are the most-used techniques. Consequently,

Catalysts 2019,9, 122 21 of 32
in this part, we present the development of composite semiconductors with nanofibrous morphology
derived from the electrospinning method and hydrothermal method for the treatment of wastewater.
5.2.1. Hydrothermal Method
As mentioned above, the hydrothermal method is capable of synthesizing various inorganics
with different morphologies, including the nanofibrous materials. For example, Yang et al. [
97
] once
reported the fabrication of a novel TiO
2
nanofibers with a shell of anatase nanocrystals based on the
hydrothermal process. Actually, the whole fabrication process included three steps: First, the H
2
Ti
3
O
7
nanofibers were obtained from the anatase TiO
2
particles and NaOH solutions via hydrothermal
method. After that, the as-prepared H
2
Ti
3
O
7
nanofibers were treated using a dilute acid solution
under certain hydrothermal condition to generate the anatase nanocrystal shell on the outside. Finally,
the H
2
Ti
3
O
7
phase was converted to TiO
2
(B) phase after a heat treatment while the anatase nanocrystal
shell remained unchanged. Owing to the well-matched phase interfaces, which ensures the charge
transfer across the interfaces, the recombination of electron-hole pairs was effectively suppressed and
the corresponding photoactivity was significantly enhanced. Most importantly, they demonstrated
that these nanofibrous photocatalysts possess specific surface areas similar to the commercial P25
powder, and the fibril morphology endowed them with a good recyclability from water, which is
critically important in practical applications. Recently, our group also carried out a series of studies
on the synthesis of nanofibrous photocatalysts via employing the hydrothermal method such as the
bimetallic AuPd alloy nanoparticles deposited on MoO
3
nanowires [
98
]. As shown in Figure 19, MoO
3
nanowires were firstly prepared from Mo powder and H
2
O
2
via the hydrothermal method. Then,
the as-prepared MoO
3
nanowires were used as the substrates to synthesize the MoO
3
/Au-Pd bimetallic
alloy nanowires via a simple chemical reduction method. As expected, the MoO
3
/Au–Pd bimetallic
alloy nanowires exhibited a good photocatalytic degradation performance for trichloroethylene (TCE)
under the driving of visible light. Similarly, the composite nanowires could be easily separated from
the reaction slurry in a short time after the reaction.
Catalysts 2018, 8, x FOR PEER REVIEW 21 of 32
most-used techniques. Consequently, in this part, we present the development of composite
semiconductors with nanofibrous morphology derived from the electrospinning method and
hydrothermal method for the treatment of wastewater.
5.2.1. Hydrothermal Method
As mentioned above, the hydrothermal method is capable of synthesizing various inorganics
with different morphologies, including the nanofibrous materials. For example, Yang et al. [97] once
reported the fabrication of a novel TiO
2
nanofibers with a shell of anatase nanocrystals based on the
hydrothermal process. Actually, the whole fabrication process included three steps: First, the H
2
Ti
3
O
7
nanofibers were obtained from the anatase TiO
2
particles and NaOH solutions via hydrothermal
method. After that, the as-prepared H
2
Ti
3
O
7
nanofibers were treated using a dilute acid solution
under certain hydrothermal condition to generate the anatase nanocrystal shell on the outside. Finally,
the H
2
Ti
3
O
7
phase was converted to TiO
2
(B) phase after a heat treatment while the anatase nanocrystal
shell remained unchanged. Owing to the well-matched phase interfaces, which ensures the charge
transfer across the interfaces, the recombination of electron-hole pairs was effectively suppressed and
the corresponding photoactivity was significantly enhanced. Most importantly, they demonstrated
that these nanofibrous photocatalysts possess specific surface areas similar to the commercial P25
powder, and the fibril morphology endowed them with a good recyclability from water, which is
critically important in practical applications. Recently, our group also carried out a series of studies
on the synthesis of nanofibrous photocatalysts via employing the hydrothermal method such as the
bimetallic AuPd alloy nanoparticles deposited on MoO
3
nanowires [98]. As shown in Figure 19, MoO
3
nanowires were firstly prepared from Mo powder and H
2
O
2
via the hydrothermal method. Then, the
as-prepared MoO
3
nanowires were used as the substrates to synthesize the MoO
3
/Au-Pd bimetallic
alloy nanowires via a simple chemical reduction method. As expected, the MoO
3
/Au–Pd bimetallic
alloy nanowires exhibited a good photocatalytic degradation performance for trichloroethylene (TCE)
under the driving of visible light. Similarly, the composite nanowires could be easily separated from
the reaction slurry in a short time after the reaction.
Figure 19. Schematic illustrating the band structure of MoO
3
/Au-Pd composite photocatalyst and the
possible reaction mechanism. Adapted with permission from Reference [98]. Copyright (2018)
Elsevier.
5.2.2. Electrospinning Method
Electrospinning is considered as a promising way to synthesize nanofibers with several
advantages, such as easy operation, low cost, and scalable [99–101]. In general, there are four major
Figure 19.
Schematic illustrating the band structure of MoO
3
/Au-Pd composite photocatalyst and the
possible reaction mechanism. Adapted with permission from Reference [
98
]. Copyright (2018) Elsevier.
5.2.2. Electrospinning Method
Electrospinning is considered as a promising way to synthesize nanofibers with several advantages,
such as easy operation, low cost, and scalable [
99
–
101
]. In general, there are four major parts in an
electrospinning device: (i) an electrical power supplier, (ii) a metallic needle, (iii) syringes with the

Catalysts 2019,9, 122 22 of 32
polymer solution, and (iv) a conductive collector. Meanwhile, several process parameters, such as the
polymer-based solution concentration, the viscosity of solution, the flow rate of the syringe driver, and the
electric field power, could also be well-regulated to manipulate the morphology of fibers. During the
electrospinning process, the solution is injected through a metallic needle via a syringe with a constant
pump speed. At the same time, a voltage is applied on the metallic needle; therefore, the solution
droplet will be charged, and then a Taylor cone will be generated when the electronic force is enough
to overcome the surface tension. Following this, a liquid jet is formed between the grounded collector
and the needle. The generated jets will be stretched by an electrostatic repulsion force until it reaches the
collector; meanwhile, the solvent will rapidly evaporate during this process. Finally, the jets are solidified
and the corresponding nanofibers are collected on the collector [100].
As for the applications of photocatalysis, high specific surface area is required to provide more
active sites for the redox reaction. More specifically, electrospun nanofibers as forefront fibrous
materials have attracted considerable research attention in the area of photocatalysis due to its several
advantages of large surface area, extremely high aspect ratio, and ease of functionalization [
102
,
103
].
For example, Zhang et al. [
104
] reported the fabrication of a flexible and hierarchical mesoporous TiO
2
nanoparticle (TiO
2
NP) modified TiO
2
nanofiber composites via the combination of electrospinning and
in situ polymerization method. At first, flexible TiO
2
nanofibers were prepared via the electrospinning
and the subsequently consuming process with the dopant of yttrium. After that, the as-prepared
TiO
2
nanofibers were used as a template for the incorporation of TiO
2
NPs by utilizing a bifunctional
benzoxazine as the carrier through a calcination process in the N
2
atmosphere. The as-prepared
membranes exhibited remarkable photocatalytic activity towards organic dyes in water; moreover,
it could be reused well via simply rinsing with water, and without time-consuming separation
procedures owing to the long aspect ratio and good mechanical property of the composite nanofibers.
In recent years, our group has carried out several works on the design of electrospun nanofibrous
photocatalysts [
105
–
109
]. As a representative sample, a BiOCl
0.3
/BiOBr
0.3
/BiOI
0.4
/PAN composite
fibrous catalyst was fabricated via combining the electrospinning and sol-gel method [
109
]. As shown
in Figure 20, the obtained composite photocatalyst exhibited a typical fibril structure with a good
uniformity, and the corresponding field emission transmission electron microscope (FE-TEM) image
demonstrated a highly crystalline structure in the composite fibers with a clear lattice spacing relating to
the (112) plane of BiOCl, the (110) plane of BiOBr, and the (200) plane of BiOI; therefore, a heterojunction
structure was generated via a close contact of the composite semiconductors. After a visible-light driven
photocatalysis performance evaluation, it was found that the obtained BiOCl
0.3
/BiOBr
0.3
/BiOI
0.4
/PAN
fiber displayed the highest photocatalytic degradation performance of TCE. Moreover, it was concluded
that the improved visible-light driven photocatalytic activity is caused by the interfacial contact of a
heterojunction and the inhibition of the recombination rate of the electron–hole pairs.
Catalysts 2018, 8, x FOR PEER REVIEW 22 of 32
parts in an electrospinning device: (i) an electrical power supplier, (ii) a metallic needle, (iii) syringes
with the polymer solution, and (iv) a conductive collector. Meanwhile, several process parameters,
such as the polymer-based solution concentration, the viscosity of solution, the flow rate of the
syringe driver, and the electric field power, could also be well-regulated to manipulate the
morphology of fibers. During the electrospinning process, the solution is injected through a metallic
needle via a syringe with a constant pump speed. At the same time, a voltage is applied on the
metallic needle; therefore, the solution droplet will be charged, and then a Taylor cone will be
generated when the electronic force is enough to overcome the surface tension. Following this, a
liquid jet is formed between the grounded collector and the needle. The generated jets will be
stretched by an electrostatic repulsion force until it reaches the collector; meanwhile, the solvent will
rapidly evaporate during this process. Finally, the jets are solidified and the corresponding
nanofibers are collected on the collector. [100]
As for the applications of photocatalysis, high specific surface area is required to provide more
active sites for the redox reaction. More specifically, electrospun nanofibers as forefront fibrous
materials have attracted considerable research attention in the area of photocatalysis due to its several
advantages of large surface area, extremely high aspect ratio, and ease of functionalization [102,103].
For example, Zhang et al. [104] reported the fabrication of a flexible and hierarchical mesoporous
TiO2 nanoparticle (TiO2 NP) modified TiO2 nanofiber composites via the combination of
electrospinning and in situ polymerization method. At first, flexible TiO2 nanofibers were prepared
via the electrospinning and the subsequently consuming process with the dopant of yttrium. After
that, the as-prepared TiO2 nanofibers were used as a template for the incorporation of TiO2 NPs by
utilizing a bifunctional benzoxazine as the carrier through a calcination process in the N2 atmosphere.
The as-prepared membranes exhibited remarkable photocatalytic activity towards organic dyes in
water; moreover, it could be reused well via simply rinsing with water, and without time-consuming
separation procedures owing to the long aspect ratio and good mechanical property of the composite
nanofibers. In recent years, our group has carried out several works on the design of electrospun
nanofibrous photocatalysts [105–109]. As a representative sample, a BiOCl0.3/BiOBr0.3/BiOI0.4/PAN
composite fibrous catalyst was fabricated via combining the electrospinning and sol-gel method [109].
As shown in Figure 20, the obtained composite photocatalyst exhibited a typical fibril structure with
a good uniformity, and the corresponding field emission transmission electron microscope (FE-TEM)
image demonstrated a highly crystalline structure in the composite fibers with a clear lattice spacing
relating to the (112) plane of BiOCl, the (110) plane of BiOBr, and the (200) plane of BiOI; therefore, a
heterojunction structure was generated via a close contact of the composite semiconductors. After a
visible-light driven photocatalysis performance evaluation, it was found that the obtained
BiOCl0.3/BiOBr0.3/BiOI0.4/PAN fiber displayed the highest photocatalytic degradation performance of
TCE. Moreover, it was concluded that the improved visible-light driven photocatalytic activity is
caused by the interfacial contact of a heterojunction and the inhibition of the recombination rate of
the electron–hole pairs.
Figure 20. SEM image of pristine PAN fibers (a) and BiOClx/BiOBry/BiOIz composite fibers (b). (c) FE-
TEM image of BiOClx/BiOBry/BiOIz fibers. (d) Lattice-resolved image for BiOClx/BiOBry/BiOIz
(e)
(b) (e)
(a)
(c) (d)
Figure 20.
SEM image of pristine PAN fibers (
a
) and BiOCl
x
/BiOBr
y
/BiOI
z
composite
fibers (
b
). (
c
) FE-TEM image of BiOCl
x
/BiOBr
y
/BiOI
z
fibers. (
d
) Lattice-resolved image for
BiOCl
x
/BiOBr
y
/BiOI
z
nanofibers. (
e
) Schematic indicating the photocatalytic degradation of TCE.
Adapted with permission from Reference [109]. Copyright (2016) Elsevier.

Catalysts 2019,9, 122 23 of 32
5.3. Nanosheets (2D)
Semiconductor nanosheets are typical 2D nanomaterials and have attracted significant attention
in the research area of photocatalysis for their larger surface area and tunable structures. Up to
now, a great deal of semiconductor nanosheets have been synthesized via various strategies
for different applications. The hydrothermal process is one of the most used strategies for the
preparation of 2D semiconductor photocatalysts for the application of wastewater treatment [
110
].
Through the hydrothermal process, various nanosheets derived from a single semiconductor or
multi-semiconductors could be synthesized. For example, Chen et al. [
111
] prepared TiO
2
-based
nanosheets (TNS) via the alkaline hydrothermal treatment of commercial P25. They reported that
the as-prepared TNS exhibited much higher specific surface area and much stronger adsorption for
crystal violet molecules than the raw P25. Furthermore, the TNS could be effectively regenerated using
a H
2
O
2
-assisted photocatalysis process, showing great potential for dealing with the high-chroma
dye wastewater. Besides TiO
2
, various nanosheets derived from different semiconductors could also
be fabricated using a hydrothermal process, such as the WO
3
nanosheet/K
+
Ca
2
Nb
3
O
10−
ultrathin
nanosheet synthesized by Ma et al. [
112
] via a facile hydrothermal assembly of WO
3
nanosheets and
ultrathin K
+
Ca
2
Nb
3
O
10−
nanosheets. They demonstrated that the composite nanosheets possess
2D/2D heterojunctions and display remarkably enhanced photocatalytic activity compared to the
pristine WO
3
and K
+
Ca
2
Nb
3
O
10−
nanosheets, which were mainly caused by the strongly coupled
hetero-interfaces that provided more active sites for reactions and band structure. Additionally,
some other methods, such as the solvothermal or photo-reduction methods, could also be employed
for the preparation of composite nanosheets. For example, Wang et al. [
113
] fabricated the Bi
12
O
15
Cl
6
nanosheets with a narrowed band gap via a simple and facile solvothermal method followed by
a simple thermal treatment. The obtained Bi
12
O
15
Cl
6
nanosheets exhibited a good photocatalytic
degradation performance of bisphenol A solely under the driving of visible light, and the reaction
rate of the composite nanosheets was 13.6 and 8.7 times faster than those of BiOCl and TiO
2
(P25), respectively. In addition, the as-prepared Bi1
2
O
15
Cl
6
nanosheets possessed good stability
and recyclability during the photocatalytic process. As shown in Figure 21, our group recently
developed a Pt/BiOI composite nanosheet via a photo-reduction method in ambient conditions [
114
],
where the as-prepared Pt/BiOI composites exhibited a flower-like structure and could effectively
photocatalytically degrade the rhodamine B and phenol under visible-light irradiation (
λ
> 420 nm),
where the degradation rate was superior to that of pure BiOI. Moreover, it was found that the content
of Pt in the composite plays a vital important role on the photoactivity, and it was found that the
optimal ratio of Pt to BiOI in the composite was 3%. It was concluded that the enhanced photocatalytic
activity of the Pt/BiOI composite was caused by the superior electron transfer ability with the presence
of an appropriate amount of Pt.

Catalysts 2019,9, 122 24 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 24 of 32
Figure 21. (a,b) SEM images of the obtained Pt/BiOI composite nanosheets. (c,d) HR-SEM images of
BiOI nanosheets and Pt/BiOI composite nanosheets, respectively. (e–g) HR-TEM images of Pt/BiOI
composite nanosheets. (h) Element mappings of Pt, Bi, O, and I for the Pt/BiOI composite nanosheets.
Adapted with permission from Reference [114]. Copyright (2017) Elsevier.
5.4. Frameworks (3D)
In recent years, there have been a great number of works reporting a new generation of
composite photocatalysts with 3D frameworks [115]. Actually, the 3D photocatalysts with well-
deigned frameworks show great advantages such as a large specific surface area, high adsorptive
capacity, good structure stability, good mass transfer ability, and a large number of exposed active
sites, which make them promising candidates for the highly efficient photodegradation of
contaminants in water. In general, the 3D composite photocatalysts could be obtained via two
approaches, which are to directly construct a photocatalyst with 3D frameworks (type I), or
compositing the photocatalysts with a template with 3D frameworks (type II).
Through employing the commonly reported synthesis methods of various 3D frameworks, such
as the sol–gel process, in situ assembly, and template methods, various 3D photocatalysts with
different characteristics have be fabricated [116]. The sol-gel process is a well-developed strategy to
synthesize aerogels, and some of the produced aerogels, such as the SiO
2
aerogels, have been
commercialized [117]. In general, there are two stages for the sol-gel process method: first, a precursor
(e.g., metal alkoxide) is subjected to the hydrolysis and condensation reactions to form a wet gel,
during which time, numerous networks are generated between the alkoxide groups; subsequently,
Figure 21.
(
a
,
b
) SEM images of the obtained Pt/BiOI composite nanosheets. (
c
,
d
) HR-SEM images of
BiOI nanosheets and Pt/BiOI composite nanosheets, respectively. (
e
–
g
) HR-TEM images of Pt/BiOI
composite nanosheets. (
h
) Element mappings of Pt, Bi, O, and I for the Pt/BiOI composite nanosheets.
Adapted with permission from Reference [114]. Copyright (2017) Elsevier.
5.4. Frameworks (3D)
In recent years, there have been a great number of works reporting a new generation of
composite photocatalysts with 3D frameworks [
115
]. Actually, the 3D photocatalysts with well-deigned
frameworks show great advantages such as a large specific surface area, high adsorptive capacity,
good structure stability, good mass transfer ability, and a large number of exposed active sites,
which make them promising candidates for the highly efficient photodegradation of contaminants in
water. In general, the 3D composite photocatalysts could be obtained via two approaches, which are to
directly construct a photocatalyst with 3D frameworks (type I), or compositing the photocatalysts with
a template with 3D frameworks (type II).
Through employing the commonly reported synthesis methods of various 3D frameworks, such as
the sol–gel process, in situ assembly, and template methods, various 3D photocatalysts with different
characteristics have be fabricated [
116
]. The sol-gel process is a well-developed strategy to synthesize
aerogels, and some of the produced aerogels, such as the SiO
2
aerogels, have been commercialized [
117
].

Catalysts 2019,9, 122 25 of 32
In general, there are two stages for the sol-gel process method: first, a precursor (e.g., metal alkoxide) is
subjected to the hydrolysis and condensation reactions to form a wet gel, during which time, numerous
networks are generated between the alkoxide groups; subsequently, the formed wet gels are sufficiently
dried to obtain aerogels. As a matter of course, a photocatalytic aerogel can be obtained using a
metal alkoxide precursor with an appropriate photocatalytic activity. For example,
Dagan et al. [118]
prepared a series of highly porous TiO
2
aerogels via the sol-gel method and they also proved that the
photocatalytic degradation performance of the TiO
2
aerogels for organic contaminants is much better
than that of a commercial TiO
2
(P25). Besides, various photoactive metal oxides, metal silylamide, or
their composite aerogels have been developed. However, due to the limitation of sol-gel processes,
some metal oxides or metal chalcogenides are not able to be synthesized into aerogels, and the obtained
aerogel photocatalysts usually suffer from low crystallinity. Therefore, a new generated strategy,
namely an assembly method, has been invented to construct aerogels based on various nanoscale units
with different morphologies and chemical properties. As reported before [
116
], there are three typical
steps for the assembly process: (i) fabrication of the building blocks, (ii) preparing the dispersion of
the building blocks with appropriated concentration, and (iii) solidified the suspension of building
blocks to form a 3D monolith. Based on this principle,
Heiligtag et al. [119]
developed a 3D framework
Au-TiO
2
photocatalysts with a preformed TiO
2
nanoparticles as the blocking units without using any
templates. Through modifying the surface of anatase TiO
2
nanoparticles with trizma, the nanoparticles
undergo an oriented attachment process during gelation and finally result in well-bonded networks.
Moreover, based on the above-mentioned aerogel synthesis methods, various phototcatalytic aerogels
can also be prepared via employing the preformed aerogels as the templates, such as a C
3
N
4
aerogel
that was fabricated by Kailasam and co-workers [
120
] via preparing a C
3
N
4
/SiO
2
composite aerogel
based on the sol-gel method at first, and then remove the SiO
2
via treating the composite in 4 M
NH4HF2(Figure 22).
Catalysts 2018, 8, x FOR PEER REVIEW 25 of 32
the formed wet gels are sufficiently dried to obtain aerogels. As a matter of course, a photocatalytic
aerogel can be obtained using a metal alkoxide precursor with an appropriate photocatalytic activity.
For example, Dagan et al. [118] prepared a series of highly porous TiO2 aerogels via the sol-gel
method and they also proved that the photocatalytic degradation performance of the TiO2 aerogels
for organic contaminants is much better than that of a commercial TiO2 (P25). Besides, various
photoactive metal oxides, metal silylamide, or their composite aerogels have been developed.
However, due to the limitation of sol-gel processes, some metal oxides or metal chalcogenides are
not able to be synthesized into aerogels, and the obtained aerogel photocatalysts usually suffer from
low crystallinity. Therefore, a new generated strategy, namely an assembly method, has been
invented to construct aerogels based on various nanoscale units with different morphologies and
chemical properties. As reported before [116], there are three typical steps for the assembly process:
(i) fabrication of the building blocks, (ii) preparing the dispersion of the building blocks with
appropriated concentration, and (iii) solidified the suspension of building blocks to form a 3D
monolith. Based on this principle, Heiligtag et al. [119] developed a 3D framework Au-TiO2
photocatalysts with a preformed TiO2 nanoparticles as the blocking units without using any
templates. Through modifying the surface of anatase TiO2 nanoparticles with trizma, the
nanoparticles undergo an oriented attachment process during gelation and finally result in well-
bonded networks. Moreover, based on the above-mentioned aerogel synthesis methods, various
phototcatalytic aerogels can also be prepared via employing the preformed aerogels as the templates,
such as a C3N4 aerogel that was fabricated by Kailasam and co-workers [120] via preparing a
C3N4/SiO2 composite aerogel based on the sol-gel method at first, and then remove the SiO2 via
treating the composite in 4 M NH4HF2 (Figure 22).
Figure 22. Schematic illustration indicating the synthesis process of porous carbon nitride and silica
aerogels based on the sol-gel method and the digital photos of corresponding aerogels. Adapted with
permission from Reference [120]. Copyright (2011) Royal Society of Chemistry.
As for the fabrication of type II 3D photocatalysts, an appropriate 3D porous substrate should
be prepared before loading the active substance on its frameworks. Considering the requirements for
high photoreactivity and good service performance, the aerogels/hydrogels derived from ceramics
or carbon are mostly preferred. For example, Li et al. [121] fabricated a ternary magnetic composite
of Fe3O4@TiO2/SiO2 aerogel via combining the sol-gel process and a hydrothermal treatment. During
the fabrication process, Fe3O4 microspheres were first synthesized via the hydrothermal method; after
that, Fe3O4@TiO2 core shell microspheres were fabricated via an in situ reaction method. The used
SiO2 aerogel was derived from the industrial fly ash via a common sol-gel method. Finally, the as-
prepared Fe3O4@TiO2 core shell microspheres and SiO2 aerogel were combined via the hydrothermal
method. According to their report, the obtained Fe3O4@TiO2/SiO2 aerogel exhibited an enhanced
photocatalytic activity for the degradation of rhodamine B dye under visible light irradiation, and
the aerogel could be facilely collected after the reaction due to its good magnetic separation
performance. Interestingly, as shown in Figure 23, Jiang et al. [122] recently developed a separation-
Figure 22.
Schematic illustration indicating the synthesis process of porous carbon nitride and silica
aerogels based on the sol-gel method and the digital photos of corresponding aerogels. Adapted with
permission from Reference [120]. Copyright (2011) Royal Society of Chemistry.
As for the fabrication of type II 3D photocatalysts, an appropriate 3D porous substrate should be
prepared before loading the active substance on its frameworks. Considering the requirements for
high photoreactivity and good service performance, the aerogels/hydrogels derived from ceramics or
carbon are mostly preferred. For example, Li et al. [
121
] fabricated a ternary magnetic composite of
Fe
3
O
4
@TiO
2
/SiO
2
aerogel via combining the sol-gel process and a hydrothermal treatment. During the
fabrication process, Fe
3
O
4
microspheres were first synthesized via the hydrothermal method; after that,
Fe
3
O
4
@TiO
2
core shell microspheres were fabricated via an in situ reaction method. The used SiO
2
aerogel was derived from the industrial fly ash via a common sol-gel method. Finally, the as-prepared

Catalysts 2019,9, 122 26 of 32
Fe
3
O
4
@TiO
2
core shell microspheres and SiO
2
aerogel were combined via the hydrothermal method.
According to their report, the obtained Fe
3
O
4
@TiO
2
/SiO
2
aerogel exhibited an enhanced photocatalytic
activity for the degradation of rhodamine B dye under visible light irradiation, and the aerogel could
be facilely collected after the reaction due to its good magnetic separation performance. Interestingly,
as shown in Figure 23, Jiang et al. [
122
] recently developed a separation-free PANI/TiO
2
3D hydrogel
for the continuous photocatalytic degradation of various contaminants in water. In their studies,
the PANI hydrogel with 3D frameworks was synthesized via the polymerization of aniline. During the
gelling process, the TiO
2
nanoparticles (P25) were incapsulated in the hydrogels. As a result,
the obtained PANI/TiO
2
composite hydrogel exhibited an intriguing capacity for removing organic
contaminants from water, which was mainly caused by the synergistic effect of adsorption enrichment
of hydrogel and the in situ photocatalytic degradation of TiO
2
. Moreover, the presented separation-free
characteristics in the obtained bulk materials indicate a good recyclability of the composite hydrogel.
Catalysts 2018, 8, x FOR PEER REVIEW 26 of 32
free PANI/TiO
2
3D hydrogel for the continuous photocatalytic degradation of various contaminants
in water. In their studies, the PANI hydrogel with 3D frameworks was synthesized via the
polymerization of aniline. During the gelling process, the TiO
2
nanoparticles (P25) were incapsulated
in the hydrogels. As a result, the obtained PANI/TiO
2
composite hydrogel exhibited an intriguing
capacity for removing organic contaminants from water, which was mainly caused by the synergistic
effect of adsorption enrichment of hydrogel and the in situ photocatalytic degradation of TiO
2
.
Moreover, the presented separation-free characteristics in the obtained bulk materials indicate a good
recyclability of the composite hydrogel.
Figure 23. Schematic illustration demonstrating the synthesis process of the 3D PANI/TiO
2
composite
hydrogel. Adapted with permission from Reference [122]. Copyright (2015) Wiley.
6. Summary and Perspectives
In summary, in order to address the worldwide concerned issues of water pollutions, various
photocatalysis processes based on different photocatalysts have been developed; meanwhile,
numerous efforts have been made to further improve the photocatalytic activity of the catalysts based
on the semiconducors. In this review, the recent progress in the development of composite
semiconductor photocatalysts for wastewater treatment is presented, including the most-used
strategies to narrow the band gap of semiconductors, to retard the recombination of the photo-
generated electron-hole pairs, to enhance the visible light adsorption capacity, as well as to increase
the reaction ratio between the photocatalysts and contaminants. Moreover, the composite catalyts
with different morphologies and the corresponding photocatlytic performance were also
summarized.
Although great development of the photocatalysis process has been obtained, there are still
several problems yet to be addressed to further improve the practical application performance of the
photocatalysis. Therefore, some plausible perspectives for the developing trend of composite
photocatalysts for the wasterwater treatment are proposed based on the presented studies: i) the
existing synthesis methods are relative complex, high cost, and harmful to the environment to some
degree, thus a more facile, highly efficent, and green method is anticipated; ii) the mechanism of the
composite semicondutor photocatalysts are still confusing and some of them are unpersuasive,
therefore much more effort is needed for the basic studies of the catalytic mechanisms; and iii) the
practical use are limitted because the collection and reuse of the catalysts in water are still
inconvenient due to their small size and poor mechanical property, therefore novel photocatalysts
with easy collection property or new hybrid devices based on the composite of photocatalysts with
selected substrates (e.g., polymers, metals) are proposed. Finally, we anticipate that this review can
provide some useful guidance for the design of next generation of photocatlysts for the wastewater
remediation.
Funding: This work was supported by the Technology Development Program (S2598148) funded by the
Ministry of SMEs and Startups (MSS, Korea) and the Commercialization Promotion Agency for R&D Outcomes
Figure 23.
Schematic illustration demonstrating the synthesis process of the 3D PANI/TiO
2
composite
hydrogel. Adapted with permission from Reference [122]. Copyright (2015) Wiley.
6. Summary and Perspectives
In summary, in order to address the worldwide concerned issues of water pollutions, various
photocatalysis processes based on different photocatalysts have been developed; meanwhile, numerous
efforts have been made to further improve the photocatalytic activity of the catalysts based on the
semiconducors. In this review, the recent progress in the development of composite semiconductor
photocatalysts for wastewater treatment is presented, including the most-used strategies to narrow the
band gap of semiconductors, to retard the recombination of the photo-generated electron-hole pairs,
to enhance the visible light adsorption capacity, as well as to increase the reaction ratio between the
photocatalysts and contaminants. Moreover, the composite catalyts with different morphologies and
the corresponding photocatlytic performance were also summarized.
Although great development of the photocatalysis process has been obtained, there are still
several problems yet to be addressed to further improve the practical application performance of
the photocatalysis. Therefore, some plausible perspectives for the developing trend of composite
photocatalysts for the wasterwater treatment are proposed based on the presented studies: (i) the
existing synthesis methods are relative complex, high cost, and harmful to the environment to some
degree, thus a more facile, highly efficent, and green method is anticipated; (ii) the mechanism of
the composite semicondutor photocatalysts are still confusing and some of them are unpersuasive,
therefore much more effort is needed for the basic studies of the catalytic mechanisms; and (iii)
the practical use are limitted because the collection and reuse of the catalysts in water are still
inconvenient due to their small size and poor mechanical property, therefore novel photocatalysts with
easy collection property or new hybrid devices based on the composite of photocatalysts with selected

Catalysts 2019,9, 122 27 of 32
substrates (e.g., polymers, metals) are proposed. Finally, we anticipate that this review can provide
some useful guidance for the design of next generation of photocatlysts for the wastewater remediation.
Funding:
This work was supported by the Technology Development Program (S2598148) funded by the Ministry
of SMEs and Startups (MSS, Korea) and the Commercialization Promotion Agency for R&D Outcomes (COMPA)
funded by the Ministry of Science and ICT (MSIT) [2018_RND_002_0064, Development of 800 mAh/g pitch
carbon coating.
Acknowledgments:
This work was supported by the Technology Development Program (S2598148) funded
by the Ministry of SMEs and Startups (MSS, Korea) and the Commercialization Promotion Agency for R&D
Outcomes (COMPA) funded by the Ministry of Science and ICT (MSIT) [2018_RND_002_0064, Development of
800 mAh/g pitch carbon coating.
Conflicts of Interest: The authors declare no conflict of interest.
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