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;
[email protected] (J.G.); [email protected] (Y.Z.); [email protected] (Y.-J.H.)
* Correspondence: [email protected]; 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 2018, 8, x FOR PEER REVIEW 2 of 32

Catalysts 2019, 9, 122 the advanced oxidation processes (AOPs) have been extensively explored to remove
Nowadays, 2 of 32

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
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/H2O),
an extremely strong oxidizing property with a high oxidation potential of 2.80 V/SHE (·OH/H2 O),
such that it can non-selectively oxidize the contaminants and finally convert them to CO2, H2O, or
such that it can non-selectively oxidize the contaminants and finally convert them to CO2 , H2 O, or small
small inorganic ions in a short time [17,18]. In most cases, the ·OH could be produced with the
inorganic ions in a short time [17,18]. In most cases, the ·OH could be produced with the presence
presence of one or more primary oxidants, and/or energy sources or catalysts. Therefore, the typical
of one or more primary oxidants, and/or energy sources or catalysts. Therefore, the typical AOPs
AOPs could be classified as Fenton reactions, the electrochemical advanced oxidation processes, and
could be classified as Fenton reactions, the electrochemical advanced oxidation processes, and the
the heterogeneous photocatalysis [17]. Compared with the traditional water remediation techniques,
heterogeneous photocatalysis [17]. Compared with the traditional water remediation techniques,
the AOPs exhibit many advantages, which include: (1) the contaminants are directly destroyed or
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
reduced in the water body, rather than simply coagulated or filtrated from the water, thus the secondary
secondary pollution could be avoided; (2) the AOPs are suitable for a wide range of contaminants
pollution could be avoided; (2) the AOPs are suitable for a wide range of contaminants including some
including some inorganics and pathogens because of their robust non-selectively oxidizability; and
inorganics and pathogens because of their robust non-selectively oxidizability; and (3) no hazardous
(3) no hazardous byproducts will be generated due to the final reduction products of the AOPs being
byproducts will be generated due to the final reduction products of the AOPs being just CO2 , H2 O,
just CO2, H2O, or small inorganic ions. With the abovementioned merits, the AOPs have attracted
or small inorganic ions. With the abovementioned merits, the AOPs have attracted significant attention
significant attention from both scientific research and industrial processing [19].
from both scientific research and industrial processing [19].
Solar energy is a green, costless, and inexhaustible energy resource. Effective utilization of solar
Solar energy is a green, costless, and inexhaustible energy resource. Effective utilization of
energy is of vital importance for enhancing the sustainability of industry, reducing pollution, and
solar energy is of vital importance for enhancing the sustainability of industry, reducing pollution,
retarding global warming. Consequently, solar energy has been widely used in a range of
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
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
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
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
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
energy is needed and no toxic byproduct will be generated; therefore, it is a green chemical
[21,22]. Actually, the core of photocatalytic AOPs are photocatalysts; semiconductors as the most
technique [21,22]. Actually, the core of photocatalytic AOPs are photocatalysts; semiconductors as the
employed heterogeneous photocatalysis for the AOPs have attained considerable development since
most employed heterogeneous photocatalysis for the AOPs have attained considerable development
Fujishima et al. [23] carried out the first photo-catalyzed AOP based on the titanium-oxide (TiO2) in
since Fujishima et al. [23] carried out the first photo-catalyzed AOP based on the titanium-oxide
1972. Up to now, a myriad of photocatalytic AOPs have been designed for water treatment based on
(TiO2 ) in 1972. Up to now, a myriad of photocatalytic AOPs have been designed for water treatment
various semiconductors. In general, semiconductors are light-sensitive because of their unique
based on various semiconductors. In general, semiconductors are light-sensitive because of their
electronic structure with a filled valence band (VB) and an empty conduction band (CB) [18,21].
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
Figure 1 and Equations (1)–(6) demonstrate the basic reaction process of a semiconductor to generate the
the photocatalytic radicals, which could be decomposed in the following steps: i) photons with a
photocatalytic radicals, which could be decomposed in the following steps: (i) photons with a certain
certain energy are absorbed by the semiconductor; ii) the absorbed photons with energy greater than
energy are absorbed by the semiconductor; (ii) the absorbed photons with energy greater than the band
the band gap energy (Eb) of semiconductors lead to the formation of electrons in the CB and
gap energy (Eb ) of semiconductors lead to the formation of electrons in the CB and corresponding holes
corresponding holes in the VB; and iii) the generated electron–hole pairs will migrate to the surface
in the VB; and (iii) the generated electron–hole pairs will migrate to the surface of semiconductors for
of semiconductors for redox reactions, and fast recombination in nanoseconds will happen at the
redox reactions, and fast recombination in nanoseconds will happen at the same time (it should be
same time (it should be mentioned that this process is negative for the AOPs, which shall be
mentioned that this process is negative for the AOPs, which shall be suppressed [21,22]).
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

Catalysts 2018, 8, x FOR PEER REVIEW 3 of 32

Figure 1. Schematic illustration of the photocatalytic reaction process of a semiconductor. Adapted

Excitation: Photon (hv) + Semiconductor → e− CB + h+ VB (1)
with permission from Reference [18]. Copyright (2012) Elsevier.
− +
Recombination: e + h → energy (2)
Excitation: Photon (hv) + Semiconductor
+ →e −CB +h
+VB (1)
Oxidation of H2 O: H2 O + h VB → •OH + H+ (3)
Recombination: e− + h+ → energy (2)
Reduction of adsorbed O2 : O2 + e− → O2 •− (4)
Oxidation of H2O: H2O + h+VB → •OH + H+ (3)
Reaction with H+ : O2 •− + H+ → •OOH (5)
Reduction of adsorbed O2: O2 + e → O2•
− − (4)
Electrochemical
Reaction with H+ :•O
reduction: OOH + •OOH → H2 O2 + O2
2•− + H+ → •OOH (5) (6)

However, it remainsElectrochemical
a significant challenge
reduction: to•OOH
fabricate → H2O2 + O2visible light photocatalyst
a high-efficiency
+ •OOH (6)
solely based on an individual semiconductor photocatalyst. For example,
However, it remains a significant challenge to fabricate a high-efficiency2 visible light
the TiO , as the most used
photocatalyst, possesses various advantages with excellent chemical stability,
photocatalyst solely based on an individual semiconductor photocatalyst. For example, the TiO2, aslarge surface area, non-toxicity,
and low cost [24];
the most used however, its wide
photocatalyst, energy
possesses bandadvantages
various gap (3.0–3.2 eV)excellent
with means itchemical
can onlystability,
be excitedlargeby the
UV light (λ <
surface 400non-toxicity,
area, nm), such that andless
low than 5% of
cost [24]; the irradiated
however, its widesolar energy
energy band cangap be effectively
(3.0–3.2 used [25].
eV) means
it can only be excited by the UV light (λ < 400 nm), such that less than 5%
Moreover, the fast recombination speed of electron–hole pairs seriously limits the further improvement of of the irradiated solar
energy can beactivity
its photocatalytic effectively used
[18,22]. On [25].
theMoreover,
other hand, thealthough
fast recombination
the recentlyspeed of electron–hole
developed visible light pairs
response
seriously limits the further improvement of its photocatalytic activity [18,22].
semiconductors have a lower energy band gap (<3 eV), such as BiOX (X = I or Br) [26], they still suffer On the other hand,
although the recently developed visible light response semiconductors have a lower energy band gap
from serious photo-corrosion problems in aqueous media via redox reactions and the fast recombination of
(<3 eV), such as BiOX (X = I or Br) [26], they still suffer from serious photo-corrosion problems in
electron–hole pairs during the reaction process. Therefore, it is highly urgent to find an effect strategy to
aqueous media via redox reactions and the fast recombination of electron–hole pairs during the
further improve
reaction the performance
process. Therefore, itofissemiconductor
highly urgent to photocatalysts.
find an effect strategy to further improve the
From ancient times, people have
performance of semiconductor photocatalysts. recognized that the incorporation of two or more constituent
materialsFrom
couldancient
obtaintimes,
various composite
people materials with
have recognized intriguing
that the properties
incorporation of twosuperior
or moreto the individual
constituent
components.
materials Nowadays,
could obtaina myriad
various of functional
composite composite
materials withmaterials
intriguinghave been developed
properties superior for to different
the
individual
applications components.
[27,28]. Nowadays,
Actually, the enhanceda myriad of functional
performance ofcomposite
a composite materials
materialhaveis been
mainly developed
attributed to
for different
the synergistic applications
effect [27,28]. Actually,
of its individual constituent thematerials;
enhancedmeanwhile,
performancethis of aprinciple
composite material
is also is
appropriate
mainly attributed to the synergistic effect of its individual constituent
to the design of semiconductor photocatalysts. Up to now, there have been numerous pioneering studiesmaterials; meanwhile, this
principle is also appropriate to the design of semiconductor photocatalysts. Up to now, there have
reporting the design and fabrication of composite semiconductor photocatalysts via various methods,
been numerous pioneering studies reporting the design and fabrication of composite semiconductor
such as doping heteroatoms or constructing heterojunctions via directly compositing with individual
photocatalysts via various methods, such as doping heteroatoms or constructing heterojunctions via
semiconductors or carbonaceous
directly compositing nanomaterials,
with individual semiconductorsamongorothers. Therefore,
carbonaceous as shown in
nanomaterials, Scheme
among 1, in this
others.
review, we aim to provide a systematic appraisal of the recent development
Therefore, as shown in Scheme 1, in this review, we aim to provide a systematic appraisal of the in the design and fabrication
of various
recent composite
development photocatalysts
in the designfor andthe application
fabrication of wastewater
of various composite treatment. Meanwhile,
photocatalysts for the some
representative
applicationphotocatalysts with composite
of wastewater treatment. Meanwhile, structures and morphologies
some representative from with
photocatalysts the atomic
composite scale to
structures
macroscopic andare
scale morphologies from thethe
reviewed. Finally, atomic
current scale to macroscopic
developing status,scale are reviewed.
challenges, Finally, the
and evolution trend of
current developing
the composite semiconductor status,photocatalysts
challenges, and evolution trend
for wastewater of the composite
remediation semiconductor
are briefly proposed.
photocatalysts for wastewater remediation are briefly proposed.

Scheme 1. The schematic illustration demonstrating the design and synthesis strategies for
composite photocatalysts.
Catalysts 2018, 8, x FOR PEER REVIEW 4 of 32

Scheme 1. The schematic illustration demonstrating the design and synthesis strategies for composite
Catalysts 2019, 9, 122 4 of 32
photocatalysts.

2. 2.
Principle ofof
Principle the Semiconductor
the Photocatalysts
Semiconductor forfor
Photocatalysts Wastewater
WastewaterRemediation
Remediation
AsAs mentioned
mentioned above,
above,thethetrace
tracecontaminants
contaminants (e.g.,
(e.g.,phenol,
phenol, chlorophenol,
chlorophenol, oxalic
oxalicacid)
acid)derived
derived
from
from thethedyeing
dyeingindustry,
industry,petrochemical
petrochemicalindustry,industry, and and thethe agricultural chemicals are
agricultural chemicals are quite
quite difficult
difficultto
toremove
removefrom from the the
waterwater
due to due
the tolowthe low concentration
concentration and complex and compositions
complex compositions [4]. A
[4]. A photocatalytic
photocatalytic degradation method is considered as the most
degradation method is considered as the most promising strategy to deal with this problem. promising strategy to deal with this
problem.
According According to the previous
to the previous studiesstudies
[18,29,30],[18,29,30], as shown
as shown in Figure
in Figure 2, the2, the basic
basic mechanism
mechanism of of
the
the photocatalytic degradation process of a contaminant could be characterized
photocatalytic degradation process of a contaminant could be characterized as the following steps: as the following steps:
i) (i)
thethe target contaminants
target contaminants transfer
transferfromfrom thethe water
waterbodybody to to
thethe
surface
surface of of
thethe
photocatalysts,
photocatalysts, inin
which
which
thethemigration
migration rate ofof
rate corresponding
corresponding contaminants
contaminants may
may bebe influenced
influenced bybythethemorphology
morphology andandsurface
surface
properties
properties of ofthethecatalysts (e.g.,
catalysts surface
(e.g., surface area, porosity,
area, andand
porosity, surface charges);
surface charges);ii) the
(ii)contaminants
the contaminants are
adsorbed
are adsorbed on theon surface of catalysts
the surface with photon
of catalysts with photonexcitedexcited
reaction sites, therefore
reaction a high asurface
sites, therefore area
high surface
ofarea
the catalysts can provide more active sites for the reaction; iii) the redox
of the catalysts can provide more active sites for the reaction; (iii) the redox reactions of the reactions of the photon
activated sites withsites
photon activated the adsorbed contaminants
with the adsorbed and the degraded
contaminants intermediates
and the degraded are produced,
intermediates which
are produced,
are finally
which aredegraded to CO2toand
finally degraded CO2Hand 2O; H iv)2 O;part
(iv)of theofgenerated
part the generated intermediates
intermediates andandthetheresultant
resultant
mineralization products (CO 2 and H 2 O) desorb from the surface of
mineralization products (CO2 and H2 O) desorb from the surface of catalysts to expose the active catalysts to expose the active sites
sites
forfor
the subsequent reactions; and v) the desorbed intermediates transfer from
the subsequent reactions; and (v) the desorbed intermediates transfer from the interface of catalysts the interface of catalysts
andand water
watertotothe thebulk
bulkliquid,
liquid,and
andpart
part of of the
the intermediates
intermediates will will repeat
repeatthe theprocedure
procedurei–v i–vuntil
untilthey
theyare
are completely degraded to CO 2 and H 2 O. Based on the abovementioned
completely degraded to CO2 and H2 O. Based on the abovementioned principles of the semiconductor principles of the
semiconductor
photocatalystsphotocatalysts for water contaminants
for water contaminants degradation, degradation,
five main criteria five main
for the criteria
designfor ofthe
an design
effective
ofphotocatalyst
an effective photocatalyst could be proposed as follow: 1) a semiconductor
could be proposed as follow: (1) a semiconductor with a lower Eg is preferred so that with a lower Eg isthe
preferred
electron–hole pair could be excited easier; (2) the photon absorption capacity of the catalysts shallofbe
so that the electron–hole pair could be excited easier; 2) the photon absorption capacity
theascatalysts shall betoasgenerate
high as possible high as more
possible to generatepairs;
electron–hole more(3)electron–hole
the recombination pairs; process
3) the recombination
of electron–hole
process of electron–hole pairs must be prevented as much as possible
pairs must be prevented as much as possible to enhance the quantum efficiency of the photo-generated to enhance the quantum
efficiency
electron–hole pairs; (4) the surface area of the catalysts shall be large to provide moreshall
of the photo-generated electron–hole pairs; 4) the surface area of the catalysts be large
reaction sites;
toand
provide(5) the chemical and physical structures of photocatalysts must be stable and be beneficial forbe
more reaction sites; and 5) the chemical and physical structures of photocatalysts must the
stable
massand be beneficial
transfer in water.forTothe
meetmass
thetransfer in water. To
abovementioned meet the abovementioned
requirements, requirements,
a variety of strategies have been a
variety
developed of strategies have been
for the design, some developed
of the most-usedfor the design,
strategies some
willof bethe most-usedinstrategies
summarized this review.will be
summarized in this review.

Figure 2. 2.
Figure Schematic diagram
Schematic diagramdemonstrating
demonstratingthe
theremoval
removalofofcontaminants
contaminants in
in water
water with the presence
presence of
of photocatalysts
photocatalysts[18,29,30].
[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., TiO2 ) 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 Fe3+ , Co3+ , Mo5+ , Ru3+ , Ag+ , Cu2+ , Rb+ , Cr3+ , V4+ , 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., TiO2 ); 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 H2 /H2 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 TiO2 [42], and the results
showed that N was the most effective dopant for the improvement of visible-light photocatalysis of
TiO2 because the p states of N can narrow the band gap of N-doped TiO2 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 TiO2 could be
classified as the substitutional type and interstitial type (Figure 3), the substitutional type N-doped
TiO2 is attributed to the oxygen replacement, while the interstitial type is attributed to the additional
N element in the lattice of TiO2 [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.
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Figure 3. Schematic
Figure diagram
3. Schematic demonstrating
diagram the the
demonstrating N doping in the
N doping lattice
in the of of
lattice TiO 2. Adapted
TiO withwith
2 . Adapted
permission from Reference [41]. Copyright (2011) Royal Society of Chemistry.
permission from Reference [41]. Copyright (2011) Royal Society of Chemistry.

3.2.1.
3.2.1. Magnetron
Magnetron Sputtering
Sputtering Method
Method
TheThe magnetron
magnetron sputtering
sputtering method
method is widely
is widely usedusedfor for
the the preparation
preparation of various
of various hybrid
hybrid
semiconductors. For example, Kitano et al. [44] fabricated nitrogen-substituted
semiconductors. For example, Kitano et al. [44] fabricated nitrogen-substituted TiO TiO thin films by
2 2 thin films by using
a radio frequency magnetron sputtering (RF-MS)
using a radio frequency magnetron sputtering (RF-MS) method. The method. The N 2 /Ar gas mixtures with
N2/Ar gas mixtures with different
concentration of N was used as the sputtering gas. They
different concentration of N2 was used as the sputtering gas. They systematically
2 systematically investigated the influence
investigated the of
nitrogen content on the properties of the obtained
influence of nitrogen content on the properties of the obtained N-TiO 2 thin N-TiO2 thin films via regulating the of
films via regulating the concentration
N2 in the sputtering
concentration of N2 in the gases. Meanwhile,
sputtering gases.they proved that
Meanwhile, theythe extentthat
proved of substitution
the extent ofofsubstitution
oxygen positions
of
with N in the lattice of TiO as well as the surface morphologies of
oxygen positions with N in the lattice of TiO2 as well as the surface morphologies of TiO2 could be
2 TiO 2 could be controlled well.
As a result, the visible light absorption capacity of the obtained
controlled well. As a result, the visible light absorption capacity of the obtained N-TiO 2 was obviously enhanced
N-TiO2 was obviously with
bands up
enhanced withto bands
550 nm, upand it was
to 550 nm,found
and it that
was the band
found red
that theshift
bandextent was extent
red shift closelywasrelated to the
closely content
related
of the substituted N element
to the content of the substituted N element in the TiO lattice. Moreover, they found that the as-prepared
2 in the TiO2 lattice. Moreover, they found that the as- 2 N-TiO
photocatalyst
prepared N-TiO2 exhibited
photocatalystan optimized
exhibited photocatalysis reactivity withreactivity
an optimized photocatalysis the N contentwith of the6%. This result
N content
was because
of 6%. This result of the
wasexcessive
becausesubstituted
of the excessiveN, which causes theN,formation
substituted which causes of undesirable
the formationTi3+ species
of
and acts as
undesirable the
Ti3+ recombination
species and acts as centers to decrease thecenters
the recombination photocatalytic activity
to decrease [44]. Apart from
the photocatalytic the TiO2 ,
activity
[44].some
Apartother
from N-doped
the TiO2semiconductors
, some other N-doped could also be preparedcould
semiconductors basedalso
on the RF-MS method.
be prepared based on Recently,
the
Salah et al. [45] fabricated a series of N-doped ZnO nanoparticles films
RF-MS method. Recently, Salah et al. [45] fabricated a series of N-doped ZnO nanoparticles films by by employing the RF-MS
method.the
employing AsRF-MS
shown method.
in FigureAs 4, shown
the obtained
in FigureN-doped
4, the ZnO filmsN-doped
obtained exhibitedZnO an improved response
films exhibited an to
the visibleresponse
improved light, and possessed
to the significantly
visible light, enhancedanddegradation/mineralization
possessed significantlyperformance enhanced for
degradation/mineralization performance for 2-chlorophenol (2-CP), 4-chlorophenol (4-CP),solely
2-chlorophenol (2-CP), 4-chlorophenol (4-CP), and 2,4-dichlorophenoxyaceticacid (2,4-D) under
and 2,4-
the drive of natural sunlight.
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
Figure 4.
4. (a)
(a) The
The degradation and (b) mineralization of N-doped
N-doped ZnOZnO films
filmsfor
for2-CP,
2-CP,4-CP,
4-CP,and
and2,4-D.
2,4-
D.
(c)(c)
TheThe stabilityofofpristine
stability pristineZnO
ZnO and
and N-doped
N-doped ZnO ZnO film.
film.(d)
(d)The
Thestability and
stability andreusability of an
reusability of N-
an
doped
N-doped ZnO ZnOfilm forfor
film thethe
degradation
degradationof of2-CP.
2-CP.Adapted
Adaptedwithwithpermission
permissionfrom
from Reference
Reference [45].
[45].
Copyright
Copyright (2016)
(2016) Elsevier.
Elsevier.

3.2.2. Ion
3.2.2. Ion Implantation
Implantation Method
Method
The ion
The ion implantation
implantation method method as as aa typical
typical materials
materials engineering
engineering strategy strategy thatthat can
can effectively
effectively
regulate the physical, chemical, and electronic properties of semiconductors,
regulate the physical, chemical, and electronic properties of semiconductors, and the operation and the operation process
does not involve any other elements except the selected element, which
process does not involve any other elements except the selected element, which ensures the purity ensures the purity of the
of
dopant [46]. Moreover, owing to the controllable parameters of ion
the dopant [46]. Moreover, owing to the controllable parameters of ion beam implantation, such as beam implantation, such as
ion element, ion energy, ion density, uniformity of ion beam, and
ion element, ion energy, ion density, uniformity of ion beam, and the doping efficiency, ion beamthe doping efficiency, ion beam
implantation is
implantation is aa powerful
powerful approach
approach for for the
the heteroatom
heteroatom dopingdoping of of semiconductors.
semiconductors. For For example,
example,
Tang et al. [47] fabricated an N-doped TiO layer with macrospores on a
Tang et al. [47] fabricated an N-doped TiO2 layer with macrospores on a titanium substrate by using
2 titanium substrate by using the
plasma-based ion implantation method. The fabrication process involves
the plasma-based ion implantation method. The fabrication process involves four steps: i) a helium four steps: (i) a helium plasma
was employed
plasma to generate
was employed He bubbles
to generate in the substrate,
He bubbles (ii) an oxygen
in the substrate, ii) an plasma
oxygentreatment and a followed
plasma treatment and a
annealing in air were used to obtain rutile and anatase
followed annealing in air were used to obtain rutile and anatase phases of TiO , (iii) an Ar ion sputtering
2 phases of TiO2, iii) an Ar ion method
was used tomethod
sputtering exposure was theused
He bubbles on thethe
to exposure surface; and (iv)on
He bubbles thethepre-treated
surface; and samples were
iv) the doped by
pre-treated
nitrogenwere
samples though dopedthe by
nitrogen
nitrogen beam ion implantation
though the nitrogen beam method. ion Moreover,
implantation co-doping
method.of two or more
Moreover, co-
non-metallic anions into a semiconductor photocatalyst (e.g., TiO ) could
doping of two or more non-metallic anions into a semiconductor2 photocatalyst (e.g., TiO2) could also be realized using thealso
ion
implantation
be realized using method.
the ion For example, Song
implantation et al. For
method. [48]example,
preparedSong C/N-implanted single-crystalline
et al. [48] prepared C/N-implanted rutile
TiO nanowire arrays by using carbon and nitrogen ions beam to treat the
single-crystalline rutile TiO2 nanowire arrays by using carbon and nitrogen ions beam to treat the as-
2 as-prepared TiO 2 nanowire
arrays. After
prepared TiO2annanowire
annealingarrays.
treatment,
Aftertheanobtained
annealing C/N-doped
treatment,TiO the2 nanowire
obtained arrays
C/N-dopedexhibitedTiOa2
superior visible
nanowire arrayslight response
exhibited activity, which
a superior was
visible attributed
light response to the synergistic
activity, which effect
wasbetween
attributedthe to
doped
the
C and N atoms. Their work proved that the co-doped C and N
synergistic effect between the doped C and N atoms. Their work proved that the co-doped in the lattice of TiO 2 not only greatly
C and N
improves
in the of
the lattice visible
TiO2light absorption
not only greatlycapability,
improvesbut thealso enhances
visible the separating
light absorption and transferring
capability, but also
property of photo-generated electron–hole pairs (Figure 5).
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
Figure 5. (a) UV–vis
5. (a) UV–vis absorption
absorption spectra
spectra of
of TiO
TiO22 and
and various
various doped
doped TiO
TiO2 .2. (b)
(b) Linear
Linear sweep
sweep
voltammograms
voltammograms of C/N-TiO22 and TiO22. (c) Photo-response of TiO22 and the various doped
of C/N-TiO and TiO . (c) Photo-response of TiO and the various doped TiOTiO22
samples
samples under
under visible
visible light.
light. (d)
(d) Incident
Incident photon-to-current
photon-to-current conversion
conversion efficiency
efficiency spectra
spectra of
of TiO
TiO22 and
and
various doped TiO . Adapted with permission from Reference [48]. Copyright (2018)
various doped TiO2. Adapted with permission from Reference [48]. Copyright (2018) Wiley.
2 Wiley.

3.2.3. Chemical Vapor Deposition Method

3.2.3. Chemical Vapor Deposition Method
Chemical vapor deposition (CVD) is a low-cost and scalable technique, which can directly
Chemical vapor deposition (CVD) is a low-cost and scalable technique, which can directly grow
grow a solid-phase material from a gas phase containing specific precursors. The CVD method
a solid-phase material from a gas phase containing specific precursors. The CVD method has been
has been widely used for the fabrication of semiconductors and the corresponding composite of
widely used for the fabrication of semiconductors and the corresponding composite of oxides,
oxides, sulfides, nitrides, and other mixed anion materials [49]. For example, Lee et al. [50] prepared
sulfides, nitrides, and other mixed anion materials [49]. For example, Lee et al. [50] prepared TiO2
TiO2 composite materials doped by C (TiOC) and N (TiON) with the titanium tetraisopropoxide
composite materials doped by C (TiOC) and N (TiON) with the titanium tetraisopropoxide (TTIP),
(TTIP), oxygen, and NH3 as the precursors via combing the CVD method with a fluidized bed.
oxygen, and NH3 as the precursors via combing the CVD method with a fluidized bed. The results
The results demonstrated that the visible light photocatalysis performance of the composite TiO2
demonstrated that the visible light photocatalysis performance of the composite TiO2 (e.g., TiON)
(e.g., TiON) was significantly improved compared to the commercial TiO2 catalyst (P25, Degussa).
was significantly improved compared to the commercial TiO2 catalyst (P25, Degussa). Similarly,
Similarly, Kafizas et al. [51] employed a combinatorial atmospheric pressure chemical vapor deposition
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
(cAPCVD) method to prepare an anatase TiO2 film with a gradating N content. The obtained TiO2
exhibited a gradating substitutional (Ns ) and interstitial (Ni ) nitrogen concentration, and the transition
film exhibited a gradating substitutional (Ns) and interstitial (Ni) nitrogen concentration, and the
process from predominantly Ns -doped TiO2 to Ns /Ni mixtures, and finally to purely Ni -doped TiO2
transition process from predominantly Ns-doped TiO2 to Ns/Ni mixtures, and finally to purely Ni-
was precisely characterized. In addition, the UV and visible light photocatalytic activities of the
doped TiO2 was precisely characterized. In addition, the UV and visible light photocatalytic activities
obtained N-doped TiO2 were evaluated. As a result, this work demonstrated that Ni -doped anatase
of the obtained N-doped TiO2 were evaluated. As a result, this work demonstrated that Ni-doped
TiO2 results in a better visible light photocatalytic activity than that of predominantly Ns -doping.
anatase TiO2 results in a better visible light photocatalytic activity than that of predominantly Ns-
They proved that the different influences of substitutional and interstitial nitrogen doping on the
doping. They proved that the different influences of substitutional and interstitial nitrogen doping
photocatalytic activity of TiO2 were due to that the greater stability of electron–holes in Ni -doped TiO2
on the photocatalytic activity of TiO2 were due to that the greater stability of electron–holes in Ni-
compare with that of Ns -doped TiO2 , while the propensity of the Ns -doped TiO2 for recombination is
doped TiO2 compare with that of Ns-doped TiO2, while the propensity of the Ns-doped TiO2 for
greater. This result indicated that the doped structures is well-deigned to improve the photocatalytic
recombination is greater. This result indicated that the doped structures is well-deigned to improve
activity of a semiconductor. Additionally, the CVD could also be combined with other materials
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
Catalysts 2019, 9, 122 9 of 32

Catalysts 2018, 8, x FOR PEER REVIEW 9 of 32

synthesis strategy; for example, as shown in Figure 6, Youssef et al. [52] prepared the N-doped
anatase films
N-doped via afilms
anatase one-step
via a low-frequency plasma enhanced
one-step low-frequency chemical vapor
plasma enhanced deposition
chemical (PECVD)
vapor deposition
process. Furthermore,
(PECVD) they demonstrated
process. Furthermore, that this method
they demonstrated that thisdid not need
method didthe
notsubsequential annealing
need the subsequential
step or post-incorporation of the doping agent, and the as–prepared N-TiO film exhibited
annealing step or post-incorporation of the doping agent, and the as–prepared 2N-TiO2 film exhibited good
visible-light-induced photocatalytic performance.
good visible-light-induced photocatalytic performance.

Figure 6. Schematic
Schematic view
view of the capacitively-coupled
capacitively-coupled low frequency
frequency PECVD reactor. Adapted with
permission from Reference [52]. Copyright (2017) Elsevier.

3.2.4. Atomic
3.2.4. Atomic Layer
Layer Deposition
Deposition
The atomic
The atomic layer
layer deposition
deposition (ALD) (ALD) method
method is is aa recently
recently developed
developed and and facile
facile strategy
strategy for for the
the
element doping of semiconductors. Actually, ALD is a gas-phase
element doping of semiconductors. Actually, ALD is a gas-phase deposition process based on deposition process based on
alternate surface reactions of the substrates, and the ALD method
alternate surface reactions of the substrates, and the ALD method possesses several advantages, suchpossesses several advantages,
such
as as good
good reproducibility,
reproducibility, considerable
considerable conformality,
conformality, and excellent
and excellent uniformity
uniformity [53].[53]. Consequently,
Consequently, the
the ALD method is considered as a promising strategy for the preparation
ALD method is considered as a promising strategy for the preparation of doped and composite of doped and composite
photocatalysts [54].
photocatalysts [54]. For
For example,
example, Pore Pore et
et al.
al. [55]
[55] prepared
prepared aa series
series of of N-TiO
N-TiO22 films
films via
via employing
employing the the
ALD processes.
ALD processes. In Inthis
thisstudy,
study, TiCl
TiCl4 was
4 wasused
used as the titanium
as the titanium precursor
precursorand there were were
and there two ALD twocycles
ALD
during the fabrication process: (i) a thin layer of TiN was grown from
cycles during the fabrication process: i) a thin layer of TiN was grown from 4the TiCl4 3and NH the TiCl and NH ; and (ii)3;TiO
and2
was
ii) deposited
TiO on the surface
2 was deposited on theof TiN layer
surface of TiNfrom TiClfrom
layer 4 andTiClH2 O, meanwhile
4 and the as-prepared
H2O, meanwhile TiN layer
the as-prepared
was part-oxidized
TiN to TiO2 , thusto
layer was part-oxidized resulting
TiO2, thusin theresulting
TiO2−x Nin x . Moreover,
the TiO2−xthe Nx. nitrogen
Moreover, concentration
the nitrogen of
the obtained TiO
concentration of the N could
2−x obtained
x be well controlled via changing the ratio of TiN
TiO2−xNx could be well controlled via changing the ratio2of TiN and and TiO deposition
cycles.
TiO Similarly,
2 deposition Lee et
cycles. al. [56] reported
Similarly, a facile
Lee et al. [56] and effective
reported a facile and vapor-phase synthesis strategy
effective vapor-phase synthesis to
prepare a conformal N-TiO
strategy to prepare a conformal 2 thin film based on the ALD process. As shown in
N-TiO2 thin film based on the ALD process. As shown in Figure 7, Figure 7, the fabrication
process
the of the corresponding
fabrication N-TiO2 film involved
process of the corresponding N-TiO2 four main steps:
film involved four(i)main
pulsesteps:
the TiCl 4 vapor
(i) pulse theon the4
TiCl
surfaces
vapor onof a substrate
the surfaces of toaproduce
substrate a monolayer
to produceof chemisorbed
a monolayer of TiCl x species; (ii)
chemisorbed TiClremove
x species;the(ii)
remaining
remove
unreacted TiCl and
the remaining unreacted
4 corresponding HCl byproducts using nitrogen
TiCl4 and corresponding HCl byproducts using nitrogen gas; (iii) NH OH as the nitrogen
4 gas; (iii) NH4OH
source
as was subsequently
the nitrogen source was pulsed to generatepulsed
subsequently a mixture of gaseous
to generate H2 O andofNH
a mixture 3 , which
gaseous Hreact
2O and with NH the3,
as-prepared TiCl species to obtain the N-TiO ; and (iv) remove the
which react with the as-prepared TiClx species to obtain the N-TiO2; and (iv) remove the unreacted
x 2 unreacted precursors and HCl
byproductsand
precursors again.
HClThis cycle could
byproducts be repeated
again. This cycle to could
achieve bethe N-TiO2tofilm
repeated with the
achieve the desired
N-TiO2 film thickness.
with
The desired
the as-prepared N-TiO2 The
thickness. exhibited significantly
as-prepared N-TiO enhanced
2 exhibitedphotocatalytic
significantly degradation
enhancedperformance
photocatalytic for
organic pollutants solely driven by the solar irradiation.
degradation performance for organic pollutants solely driven by the solar irradiation.
Catalysts 2019, 9, 122 10 of 32

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Figure 7.
Figure 7. Schematic
Schematic illustration
illustration demonstrating
demonstrating the
the synthesis
synthesis process
process of
of the
the N-doped
N-doped TiO
TiO2 conformal
conformal
2
film via the ALD method. Adapted with permission from Reference [56]. Copyright (2017)
film via the ALD method. Adapted with permission from Reference [56]. Copyright (2017) Wiley. Wiley.

3.2.5. Sol-Gel and Combustion Method

Compared
Compared with with thetheabovementioned
abovementionedsynthesis synthesisapproaches,
approaches,the thesol-gel
sol-geland
andcombustion
combustion method
method is
aisfacile
a facileandandlow-cost
low-cost strategy
strategyforforthe
thepreparation
preparationofofvarious
varioussemiconductors
semiconductorsand and the
the corresponding
hybrid semiconductors. With the merits of simplicity and the possibility of controlling the synthesis
conditions,
conditions, the thesol-gel
sol-gelmethods
methodshave have been well
been developed
well developed andandseveral extended
several sol-gel
extended techniques
sol-gel have
techniques
been
have invented
been invented to fabricate new types
to fabricate new of semiconductor
types photocatalysts.
of semiconductor For example,
photocatalysts. AlbrbarAlbrbar
For example, et al. [57]
et
reported the synthesis
al. [57] reported of a series
the synthesis of a of mesoporous
series anatase
of mesoporous TiO2 powders
anatase TiO2 powdersdopeddoped
by N,by and
N,S,and
as well
S, as
as
welltheasN,S co-doped
the N,S co-doped anatase TiOTiO
anatase 2 powder
2 powder using
usinga non-hydrolytic
a non-hydrolytic sol-gel
sol-gelprocess.
process.During
During thethe gel
synthesis process, titaniumtetrachloride and titaniumisopropoxidetitaniumisopropoxide were were used
used as
as the
the precursor
precursor of of Ti,
Ti,
dimethylsulfoxide (DMSO) was used as the precursor of S, and NH33 was was used
used as
as the
the precursor
precursor of of N.
N.
For the preparation
preparation of S-dopedS-doped TiOTiO22, the obtained gel derived from the solvent of DMSO was calcined
in air, while N and and SS co-doped
co-doped TiO TiO22waswasobtained
obtainedwhenwhenthe thegelgel was
was annealed
annealed in in
thethe atmosphere
atmosphere of
of
NH NH 3 . In
3. In addition,
addition, thethe pristineTiO
pristine TiO2 2 andcorresponding
and correspondingN-doped N-dopedTiO TiO22was
was further
further obtained
obtained via
calcining the thegelgelderived
derivedfrom fromthethe solvent
solvent of cyclohexane
of cyclohexane in airinand
airNHand NH3 , respectively.
3, respectively. In their In their
studies,
studies, the photocatalytic
the photocatalytic activitiesactivities of the were
of the samples samples were evaluated
evaluated via the degradation
via the degradation of dye C.I. ofReactive
dye C.I.
Reactive
Orange16Orange16
in waterinunder watertheunder the irradiation
irradiation of visible
of visible light. light. The obtained
The obtained results
results showed
showed thatthat
the the
N-
N-doped
doped TiOTiO 2 exhibited
2 exhibited better
better visible-light
visible-light photocatalytic
photocatalytic activity
activity compared
compared withwith
the the pristine
pristine TiO TiO
2 and 2
and S-doped
S-doped TiO2TiO 2 . Similarly,
. Similarly, the the sol-gel
sol-gel method
method is also
is also versatileenough
versatile enoughtotobe becombined
combined with with other
materials synthesis techniques. Most recently, Rajoriya et al. [58] successfully fabricated a samarium
(Sm) and nitrogen
nitrogen (N) (N) co-doped
co-doped TiO TiO22 photocatalyst
photocatalyst through an ultrasound-assisted
ultrasound-assisted sol-gel process
(Figure 8), where they they found
found that
that after
after doping
doping TiOTiO22 with Sm and N, N, the
the photocatalytic
photocatalytic degradation
degradation
performance of the TiO TiO22 for 4-acetamidophenol was greatly improved owing to the significantly
improved separation efficiency efficiency ofof the
the photo-generated
photo-generated electron–hole
electron–holepair. pair.
Catalysts 2019, 9, 122 11 of 32
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Figure
Figure 8. Schematic
Schematic illustrating the ultrasound assisted sol-gel synthesis process of
of the
the Sm/N
Sm/N doped
TiO22.. Adapted
Adapted with
with permission
permission from
from Reference
Reference [58].
[58]. Copyright
Copyright (2019)
(2019) Elsevier.
Elsevier.

4. Heterojunctions
4. Heterojunctions Construction
Construction
Besides the
Besides the abovementioned
abovementioned heteroatoms
heteroatoms doping
doping strategy,
strategy, constructing
constructing heterojunctions
heterojunctions in in
photocatalysts is also considered as one of the most promising approaches
photocatalysts is also considered as one of the most promising approaches for improving the for improving the
photocatalysis performance
photocatalysis performance of of semiconductors
semiconductors due due to
to its
its feasibility
feasibility and
and effectiveness
effectiveness for
for the
the spatial
spatial
separation of
separation ofelectron–hole
electron–holepairs. More
pairs. specifically,
More the heterojunction
specifically, the heterojunctionis defined as the formed
is defined as the interface
formed
interface between two semiconductors with the unequal band structure, which can form[59,60].
between two semiconductors with the unequal band structure, which can form band alignments band
alignments [59,60]. In fact, there have been several types of heterojunction structures, which couldthe
In fact, there have been several types of heterojunction structures, which could be considered as be
conventional
considered asheterojunction
the conventionalstructures, and thestructures,
heterojunction new generation of heterojunction
and the new generationstructures.
of heterojunction
structures.
4.1. Conventional Heterojunctions
In general, the
4.1. Conventional conventional heterojunctions can be classified as three types depending on the
Heterojunctions
different band gaps of the composite semiconductors, which are type I with a straddling gap, type II
In general, the conventional heterojunctions can be classified as three types depending on the
with a staggered gap, and type III with a broken gap (Figure 9) [59]. As for the type I heterojunction,
different band gaps of the composite semiconductors, which are type I with a straddling gap, type II
the VB and CB of semiconductor A are lower and higher than the corresponding VB and CB of
with a staggered gap, and type III with a broken gap (Figure 9) [59]. As for the type I heterojunction,
semiconductor B, respectively. As a result, the photo-generated electrons and holes transfer to the CB
the VB and CB of semiconductor A are lower and higher than the corresponding VB and CB of
and VB of semiconductor B, which is negative for the separation of electron–hole pairs. Moreover,
semiconductor B, respectively. As a result, the photo-generated electrons and holes transfer to the CB
the redox reaction of the composite semiconductors with a type I heterojunction will conduct on the
and VB of semiconductor B, which is negative for the separation of electron–hole pairs. Moreover,
surface of semiconductor B with a lower redox potential, therefore the redox ability of the whole
the redox reaction of the composite semiconductors with a type I heterojunction will conduct on the
photocatalyst may be suppressed. Meanwhile, in the composite semiconductor system with type II
surface of semiconductor B with a lower redox potential, therefore the redox ability of the whole
heterojunctions, the VB and CB of semiconductor A are higher than that of semiconductor B, thus the
photocatalyst may be suppressed. Meanwhile, in the composite semiconductor system with type II
photo-generated electrons will migrate from the CB of semiconductor A to that of semiconductor
heterojunctions, the VB and CB of semiconductor A are higher than that of semiconductor B, thus the
B with a lower reduction potential, and the corresponding holes in the VB of semiconductor B will
photo-generated electrons will migrate from the CB of semiconductor A to that of semiconductor B
migrate to semiconductor A with a lower oxidation potential, thus a spatial separation of electron–hole
with a lower reduction potential, and the corresponding holes in the VB of semiconductor B will
pairs will be completed. However, the band gap of the two semiconductors will not overlap in the
migrate to semiconductor A with a lower oxidation potential, thus a spatial separation of electron–
type III heterojunctions, and as a result, there is no transmission or separation of electrons and holes
hole pairs will be completed. However, the band gap of the two semiconductors will not overlap in
between semiconductor A and semiconductor B. Consequently, the type II heterojunction is the most
the type III heterojunctions, and as a result, there is no transmission or separation of electrons and
effective structure for improving the photocatalysis performance of semiconductors, and has received
holes between semiconductor A and semiconductor B. Consequently, the type II heterojunction is the
a great deal of research attention.
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
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Figure 9. 9.
Figure Schematic illustrating
Schematic the the
illustrating photocatalysis
photocatalysismechanism
mechanism of the three
of the different
three types
different of of
types
heterojunction
heterojunctionphotocatalysts: (a) (a)
photocatalysts: type-I, (b) (b)
type-I, type-II, andand
type-II, (c) type-III. Adapted
(c) type-III. with
Adapted permission
with from
permission from
Reference [59].
Reference Copyright
[59]. (2017)
Copyright Wiley.
(2017) Wiley.

UpUp to now,
to now, several
several type-II
type-II heterojunction
heterojunction photocatalysts
photocatalysts have have been developed
been developed by creatingby creating
two
two different
different phasesphases
in theinsame the same semiconductor,
semiconductor, or directly
or directly compositing
compositing different
different semiconductors
semiconductors
together
together [60,61].
[60,61]. ForFor example,
example, YuYu et al.
et al. [62][62] once
once created
created thethe anatase-brookite
anatase-brookite dual-phase
dual-phase in in a TiO
a TiO 2 2

photocatalyst
photocatalyst totoform
formaatype-II
type-II heterojunction
heterojunction via viahydrolyzing
hydrolyzingthe titanium
the titaniumtetraisopropoxide
tetraisopropoxide in water
in
andand
water an ethanol-H
an ethanol-H 2 O 2O
mixture
mixture solution.
solution.TheyThey found
found that the theco-presence
co-presenceofofbrookite
brookite andand anatase
anatase
phases
phases in in
thethe
TiOTiO 2 significantly
2 significantly enhanced
enhanced thethe photocatalysis
photocatalysis performance.
performance. After
After that,
that, Uddin
Uddin et al.
et al. [63]
[63]
successfully
successfully fabricated
fabricated thethe mesoporous
mesoporous SnO SnO 2 -ZnO
2-ZnO heterojunction
heterojunction photocatalysts
photocatalysts usingusing a two-step
a two-step
synthesis
synthesis strategy.
strategy. Furthermore,
Furthermore, they
they hadhad carefully
carefully examined
examined thethe band
band alignment,
alignment, thethe results
results showed
showed
that
that thethe obtained
obtained SnOSnO 2 -ZnO
2-ZnO heterojunction
heterojunction photocatalyst
photocatalyst possessed
possessed a type-II
a type-II band
band alignment
alignment andand
exhibited
exhibited higher
higher photocatalytic
photocatalytic activity
activity forfor
thethe degradation
degradation of methyl
of methyl blueblue in water
in water thanthan that
that of of
thethe
individual
individual SnOSnO2 2 andZnO
and ZnO nanocatalysts
nanocatalysts (Figure(Figure10).10).Apart
Apartfrom the the
from inorganic semiconductors,
inorganic semiconductors, organic
semiconductors
organic semiconductorscould alsocould be also
incorporated with the semiconductors
be incorporated to form theto
with the semiconductors type-II
form heterojunction.
the type-II
For example, Shirmardi
heterojunction. For example, et al. [64] used polyaniline
Shirmardi et al. [64](PANI) as the
used organic semiconductor
polyaniline (PANI) as the combined
organicwith
ZnSe nanoparticles
semiconductor combined via awith
simpleZnSeandnanoparticles
cost-effective via co-precipitation
a simple andmethod in the ambient
cost-effective conditions.
co-precipitation
The obtained
method ZnSe/PANI
in the ambient nanocomposites
conditions. The obtained exhibited obvious
ZnSe/PANI enhancement in
nanocomposites the photocatalytic
exhibited obvious
performance compared to that of the pristine ZnSe nanoparticles.
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.
10. (a) Nanostructures
Nanostructures of of SnO
SnO22−
−ZnO
ZnO composite photocatalysts.
photocatalysts. (b)
(b) The corresponding
corresponding
photocatalytic performances of SnO –ZnO (red line with square dots), SnO
performances of SnO2 –ZnO (red line with square dots), SnO2 (green
2 2 (green line with triangle
line with
dots), and
triangle ZnOand
dots), (blue line(blue
ZnO with line
circle dots).
with Adapted
circle dots). with permission
Adapted from Reference
with permission from [63]. Copyright
Reference [63].
(2012) American
Copyright (2012) Chemical
AmericanSociety.
Chemical Society.

4.2. New Generation

4.2. New Generation of
of Heterojunctions
Heterojunctions
Although theconventional
Although the conventionaltype-II
type-II heterojunctions
heterojunctions are capable
are capable of spatially
of spatially separating
separating the
the photo-
photo-generated electron–hole
generated electron–hole pairs,remain
pairs, there there remain
severalseveral
criticalcritical limitations,
limitations, such as such
the as the relatively
relatively weak
weak redox ability due to the lower reduction and oxidation potentials, and
redox ability due to the lower reduction and oxidation potentials, and the suppressed migration the suppressedof
migration of electrons
electrons and holes dueand to holes due to therepulsion
the electrostatic electrostatic
[59].repulsion
Recently,[59]. Recently,
in order in orderthe
to overcome to
overcome the abovementioned
abovementioned limitations,
limitations, a new a new
generation generation of heterojunctions
of heterojunctions have been
have been developed, developed,
including the
including the p-n heterojunctions, the surface heterojunctions, the Z-scheme
p-n heterojunctions, the surface heterojunctions, the Z-scheme heterojunctions, and heterojunctions, and the
the
semiconductor/carbon heterojunctions.Here
semiconductor/carbon heterojunctions. Herewewewill
willgive
give aa brief
brief introduction
introduction of of each
each kind
kind of
of these
these
newly developed heterojunctions.
newly developed heterojunctions.
4.2.1. p–n Heterojunctions
4.2.1. p–n Heterojunctions
The p-n heterojunctions could be obtained by incorporating a p-type semiconductor with an
The p-n heterojunctions could be obtained by incorporating a p-type semiconductor with an n-
n-type semiconductor, and it has been proved that the formation of p-n heterojunctions are effective
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
for improving the photocatalytic performance of composite catalysts [65,66]. In general, before the
the irradiation of light, there is an internal electric field in the region closed to the p-n interface
irradiation of light, there is an internal electric field in the region closed to the p-n interface due to the
due to the electron–hole diffusion tendency of the composite semiconductors system with unequal
electron–hole diffusion tendency of the composite semiconductors system with unequal Fermi levels
Fermi levels [59,67]. Alternatively, when the composite semiconductors are irradiated by a light,
[59,67]. Alternatively, when the composite semiconductors are irradiated by a light, and the energy
and the energy state of the photon is beyond the band gaps of both p-type and n-type semiconductors,
state of the photon is beyond the band gaps of both p-type and n-type semiconductors, electron–hole
electron–hole pairs will be generated in the corresponding semiconductors. However, due to the
pairs will be generated in the corresponding semiconductors. However, due to the presence of an
presence of an internal electric field, the photo-generated electrons and holes will transfer to the CB of
internal electric field, the photo-generated electrons and holes will transfer to the CB of the n-type
the n-type semiconductor and the VB of p-type semiconductor, respectively. Furthermore, it has been
semiconductor and the VB of p-type semiconductor, respectively. Furthermore, it has been proved
proved that this spatial separation of the photo-generated electron–hole pairs is much more efficient
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
compared with that of conventional type-II heterojunction because of the synergy of the internal
field and band alignment [59,68]. As a result, a variety of composite semiconductors with the p-n
electric field and band alignment [59,68]. As a result, a variety of composite semiconductors with the
heterojunctions have been created for the application of photocatalysis. For example, Wen et al. [69]
p-n heterojunctions have been created for the application of photocatalysis. For example, Wen et al.
reported the fabrication of a BiOI/CeO2 p-n junction using a facile in situ chemical bath method.
[69] reported the fabrication of a BiOI/CeO2 p-n junction using a facile in situ chemical bath method.
The result demonstrated that the BiOI/CeO2 composite with a mole ratio of 1:1 exhibited a superior
The result demonstrated that the BiOI/CeO2 composite with a mole ratio of 1:1 exhibited a superior
photocatalytic performance for the decomposition of bisphenol A (BPA) and methylene orange under
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
visible light irradiation. Most recently, as shown in Figure 11, our group reported a facile method for
preparation of SnS2 /MoO3 hollow nanotubes based on the hydrothermal method [70]. The obtained
the preparation of SnS2/MoO3 hollow nanotubes based on the hydrothermal method [70]. The
SnS2 /MoO3 hollow nanotubes exhibit a typical p-n heterojunction structure, and a synergistic effect
obtained SnS2/MoO3 hollow nanotubes exhibit a typical p-n heterojunction structure, and a
between MoO3 and SnS2 was proven to yield an optimal hydrogen peroxide production performance.
synergistic effect between MoO3 and SnS2 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.
11. Schematic
Schematic illustration
illustration of SnS22/MoO
of the SnS /MoO3 3 hollow
hollow nanotubes
nanotubes and
and its photocatalysis
mechanism with a two-channel pathway.
mechanism with a two-channel pathway. Adapted with permission from Reference [70]. Copyright
Adapted with permission from Reference [70].
(2018) Royal
Copyright Society
(2018) of Chemistry.
Royal Society of Chemistry.

4.2.2. Surface
4.2.2. Surface Heterojunctions
Heterojunctions
As reported
As reported before,
before, aa surface
surface heterojunction
heterojunction can can be
be created
created between
between two two crystal
crystal facets
facets ofof aa single
single
semiconductor [59,71]. For example, Yu et al. [72] proved that the formation
semiconductor [59,71]. For example, Yu et al. [72] proved that the formation of a heterojunction of a heterojunction
between the
between the (001)
(001) and
and (101)
(101) facets
facets inin TiO contribute significantly
TiO22 contribute significantly toward
toward the the enhancement
enhancement of of
photocatalytic activity. This method enables the construction of
photocatalytic activity. This method enables the construction of a heterojunction on thea heterojunction on surface
the surfaceof a
of a single
single semiconductor,
semiconductor, which
which is less
is less costly
costly because
because onlyone
only onesemiconductor
semiconductorisis used. used. They
They also
also
demonstrate that there is an optimal ratio for the (001) and (101) facets in the anatase TiO2 for the
demonstrate that there is an optimal ratio for the (001) and (101) facets in the anatase TiO 2 for the
improvement of
improvement of its
its photocatalysis performance. Subsequently,
photocatalysis performance. Subsequently, Gao Gao etet al.
al. [73]
[73] found
found that
that the
the surface
surface
heterojunction of
heterojunction of TiO
TiO22 could
could bebe self-adjusted,
self-adjusted, and and its
its photocatalytic activity could
photocatalytic activity could be be significantly
significantly
improved via combining a proper surface heterojunction with the
improved via combining a proper surface heterojunction with the Schottky junction. Apart Schottky junction. Apart
from from
the
the TiO ,
TiO2, Bi-based
2 Bi-based semiconductors could also be employed for the design of
semiconductors could also be employed for the design of photocatalysts with surface photocatalysts with
surface heterojunctions.
heterojunctions. Most recently,
Most recently, as shown as shown
in Figurein Figure
12, Lu 12, Lu [74]
et al. et al.synthesized
[74] synthesized a tetragonal
a tetragonal BiOI
BiOI photocatalyst by regulating the amount of water in the hydrolysis process
photocatalyst by regulating the amount of water in the hydrolysis process at room temperature. The at room temperature.
The as-prepared
as-prepared photocatalyst
photocatalyst possessed
possessed a typical
a typical surface
surface heterojunctionstructure
heterojunction structurebetween
between (001)
(001) facets
facets
and (110)
and (110) facets,
facets, and
and exhibited
exhibited aa promoted
promoted photocatalytic
photocatalytic performance
performance for for the
the degradation
degradation of of organic
organic
contaminants in water under visible
contaminants in water under visible light. light.
Catalysts 2019, 9, 122 15 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 15 of 32

Figure 12. (a,b)

Figure 12. (a,b) Schematic
Schematicillustrating
illustratingthe
thegrowth
growthofofTiO 2 nanosheets
TiO at different conditions. (c) UV-vis
2 nanosheets at different conditions. (c) UV-
images of the related samples. (d) Photocatalytic degradation efficiency
vis images of the related samples. (d) Photocatalytic degradation efficiency of different catalysts
of different for methyl
catalysts for
orange. (e) Schematic demonstrating the migration of electrons and holes in the surface
methyl orange. (e) Schematic demonstrating the migration of electrons and holes in the surface heterojunction.
Adapted with permission
heterojunction. frompermission
Adapted with Reference [74].
fromCopyright
Reference (2018) Elsevier. (2018) Elsevier.
[74]. Copyright
4.2.3. Z-Scheme Heterojunctions
4.2.3. Z-Scheme Heterojunctions
Z-scheme heterojunctions were constructed to overcome the limitation of the lower redox
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
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
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
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
coupled semiconductor through the electron acceptor/donor pair or an electron mediator. As a result,
result, the electrons/holes will accumulate on different semiconductors with higher redox potentiasl,
the electrons/holes will accumulate on different semiconductors with higher redox potentiasl, and an
and an effective spatial separation of electron–hole pairs is also realized. Up to now, the Z-scheme
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 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]
heterojunctions have been invented for the wastewater treatment. [75] For example, Wu et al. [76]
reported the fabrication of the Ag2 CO3 /Ag/AgNCO composite photocatalyst via a simple in situ ion
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
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
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
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.
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,
Recently, considering the relative high cost of the common used electron mediators (e.g., Pt, Ag, and
and Au), a new generation of Z-heterojunctions without the electron mediators have been invented for
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
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]
Catalysts 2018, 8, x FOR PEER REVIEW 16 of 32
synthesized a CuInS2 /Bi2 WO6 composite catalyst with a direct Z-scheme heterojunction via the in
situ hydrothermal growth of Bi2 WO6 on the surface of CuInS2 networks. The obtained composite
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
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 Bi2 WO6 . The improved
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
photocatalytic activity was attributed to the formed intimate interface contact, which ensured a good
interfacial charge transfer ability (Figure 13).
interfacial charge transfer ability (Figure 13).

Figure 13.
Figure 13. Schematic
Schematic illustrating
illustrating the the interfacial
interfacial electron
electron transfer
transfer process
process and
and possible
possible photocatalytic
photocatalytic
mechanism of CuInS /Bi WO with the Z-scheme heterojunction. Adapted with
mechanism of CuInS2 /Bi2 WO6 with the Z-scheme heterojunction. Adapted with permission from
2 2 6 permission from
Reference [77].
Reference [77]. Copyright
Copyright (2019)
(2019) Elsevier.
Elsevier.

4.2.4.
4.2.4. Semiconductor/Carbon Heterojunctions
Semiconductor/Carbon Heterojunctions
Carbonaceous
Carbonaceous nanomaterials
nanomaterials have have been
been widely
widely employed
employed for for the
the design
design of of novel
novel photocatalysts
photocatalysts
due
due toto their
their advantages
advantages of of high
high surface
surface area,
area, good
good conductivity,
conductivity, and and chemical
chemical stability.
stability. In In general,
general,
the
the most commonly used carbonaceous materials for combining with semiconductors involves the
most commonly used carbonaceous materials for combining with semiconductors involves the
carbon
carbon dots
dots (CDs),
(CDs), carbon
carbon nanotubes
nanotubes (CNTs),
(CNTs),and andgraphene
graphene[78]. [78].
The
The CDs
CDs as as typical
typical nanocarbon
nanocarbon materials
materials have
have been
been widely
widely usedused toto enhance
enhance the the photocatalytic
photocatalytic
activity
activity of semiconductors owing to their intriguing optical and electronic properties, low
of semiconductors owing to their intriguing optical and electronic properties, low chemical
chemical
toxicity, adjustablephotoluminescence,
toxicity, adjustable photoluminescence, andand the distinct
the distinct quantum quantum effect
effect [79]. For[79].
example,ForLong example,
et al.
Long et al. [80] used carbon dots (CDs) to couple with the BiOI with
[80] used carbon dots (CDs) to couple with the BiOI with highly exposed (001) facets to form a highly exposed (001) facets
to form a composition
composition of CDs/BiOI. of CDs/BiOI.
Furthermore,Furthermore,
the obtained the obtained
CDs/BiOICDs/BiOI
composite composite
exhibitedexhibited
a greatly a
greatly
improved improved photocatalytic
photocatalytic activity
activity for for the degradation
the degradation of organicof organic
dyes dyesItin
in water. water.
has It has been
been proved that
proved that the incorporated CDs in the semiconductor formed a CDs/BiOI
the incorporated CDs in the semiconductor formed a CDs/BiOI heterojunction, which was able to heterojunction, which was
able to construct
construct numerous numerous
electronelectron
surfacesurface trapand
trap sites siteswasandbeneficial
was beneficial for enhancing
for enhancing the visible
the visible light
light absorption
absorption range range
as wellasaswell as the separation.
the charge charge separation.
Recently,Recently,
Zhao et al. Zhao et al. [81]the
[81] reported reported the
fabrication
fabrication of carbon quantum dots (CQDs)/TiO
of carbon quantum dots (CQDs)/TiO2 nanotubes (TNTs) 2 nanotubes (TNTs) composite via
composite via an improved hydrothermal an improved
hydrothermal
method. The CQDs method. The incorporated
were CQDs were incorporated
on the surface on theof surface
the TNTs, of the
and TNTs,
playedandaplayed a vital
vital role in
role in improving the visible light photocatalytic performance of the composite.
improving the visible light photocatalytic performance of the composite. As shown in Figure 14, they As shown in Figure 14,
they demonstrated
demonstrated that there
that there werewerethreethree advantages
advantages forformation
for the the formation of CQDs/TiO
of CQDs/TiO 2 : (i)
2: i) the CQDsthe CQDs
could
could effectively
effectively trap thetrap the photo-generated
photo-generated electronselectrons
from TNTs from andTNTs and suppress
suppress the recombination
the recombination of
of electron-
electron-hole pairs, (ii) the up-conversion photoluminescence property
hole pairs, ii) the up-conversion photoluminescence property of CQDs could further improve theof CQDs could further improve
the visible
visible lightlight utilization
utilization efficiency
efficiency ofofCQDs/TNTs,
CQDs/TNTs,and andiii)(iii)the
thehetero-structure
hetero-structureformed
formed between
between the
CQDs andand thethe TNTs
TNTs could
couldprolong
prolongthe thelife
lifeof
ofthe
thephotogenerated
photogeneratedelectron electronand andhole
holepairs.
pairs.
Catalysts 2019, 9, 122 17 of 32
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Catalysts 2018, 8, x FOR PEER REVIEW 17 of 32

Figure 14. Schematic illustration indicating the photocatalysis mechanism of the CQDs/TNTs
Figure 14. Schematic illustration indicating the photocatalysis mechanism of the CQDs/TNTs
photocatalyst. Adapted with permission from Reference [81]. Copyright (2018) Elsevier.
photocatalyst.
Figure 14.Adapted
Schematicwith permission
illustration from Reference
indicating [81]. Copyright
the photocatalysis (2018)ofElsevier.
mechanism the CQDs/TNTs
photocatalyst. Adapted with permission from Reference [81].2Copyright (2018) Elsevier.
CNTs are typical nanocarbon materials with highly sp -ordered structures, and thus exhibit an
CNTs are typical nanocarbon materials with highly sp2 -ordered structures, and thus exhibit
excellent metallic conductivity, which could form a Schottky barrier junction between the CNT and
an excellent CNTs are typical
metallic nanocarbonwhich
conductivity, materials with
could highly
form sp2-ordered
a Schottky structures,
barrier and thus
junction exhibit
between thean CNT
semiconductors; as reported before, the Schottky barrier junction could effectively increase the
excellent metallic conductivity,
and semiconductors; as reported which
before, could
the form a Schottky
Schottky barrier barrier junction
junction could between the CNT
effectively and the
increase
recombination time of electron–hole pairs [78,82]. Moreover, CNTs could accept electrons in the
semiconductors;
recombination ofas reported before, pairs the Schottky barrier junction
couldcould effectively increase the
compositetime system electron–hole
with semiconductors [78,82].
due to Moreover, CNTs
its large electron-storage accept
capacity,electrons
which in the composite
is beneficial
recombination time of electron–hole pairs [78,82]. Moreover, CNTs could accept electrons in the
systemforwith semiconductors
retarding or hinderingdue to its large electron-storage
the electron–hole recombination. As capacity,
a result,which
a varietyis beneficial for retarding
of semiconductor-
composite system with semiconductors due to its large electron-storage capacity, which is beneficial
CNT composite
or hindering photocatalysts
the electron–hole have been developed.
recombination. As a result,For example,
a varietyMiribangul et al. [83] prepared
of semiconductor-CNT a
composite
for retarding or hindering the electron–hole recombination. As a result, a variety of semiconductor-
TiO /CNT
photocatalysts
2 composite
have been via a simple
developed. hydrothermal
Forbeen
example, method.
Miribangul The influence
et al. [83] of the CNT
preparedetaal. concentration
TiO 2 /CNT in
composite
CNT composite photocatalysts have developed. For example, Miribangul [83] prepared a
the TiOhydrothermal
via a simple 2-CNT composites on their photocatalytic activity was investigated and the 0.3 wt% CNT
method. The influence of the CNT concentration in the TiO -CNT composites
TiO2/CNT composite via a simple hydrothermal method. The influence of the CNT concentration 2 in
content in TiO2/CNT composite could offer the highest photocatalytic degradation of Sudan (I) in
on their
the photocatalytic
TiO2-CNT compositesactivityon was investigated
their photocatalyticand the 0.3 wt
activity was % investigated
CNT contentand in TiO /CNT
the 20.3 wt%composite
CNT
UV–vis light. Apart from the TiO2, some of the other semiconductors can also be employed to
couldcontent
offer the highest
in TiO 2/CNT photocatalytic
composite could degradation of Sudan
offer the highest (I) in UV–vis
photocatalytic light. Apart
degradation from(I)
of Sudan theinTiO2 ,
composite with CNT, such as the CNT/LaVO4 composite photocatalyst developed by Xu et al. [84].
some UV–vis
of the light.semiconductors
other Apart from thecan TiOalso
2, some
be of the other
employed to semiconductors
composite with
As shown in Figure 15, with the presence of CNT, the photocatalytic activity of a CNT/LaVO4
can also
CNT, such beas employed
the to
CNT/LaVO 4
composite
composite with
photocatalystCNT, such
developed as the CNT/LaVO
by Xu et al. 4 composite photocatalyst developed by Xu et al. [84].
[84]. As shown in Figure 15, with the presence of CNT,
composite was greatly improved due to the synergistic effect between CNT and LaVO4, therefore the
As shown in activity
the photocatalytic Figure 15,
of awith the presence
CNT/LaVO of CNT,was thegreatly
photocatalytic activitytoofthe a CNT/LaVO
synergisticis4effect
corresponding photocatalytic degradation 4 composite
rate of CNT/LaVO improved
4 composite fordueorganic contaminant
composite was greatly improved due to the synergistic effect between CNT and LaVO4, therefore the
between CNT
2 times and
that of LaVO 4 , therefore
pure LaVO 4. the corresponding photocatalytic degradation rate of CNT/LaVO4
corresponding photocatalytic degradation rate of CNT/LaVO4 composite for organic contaminant is
composite for organic contaminant is 2 times that of pure LaVO4 .
2 times that of pure LaVO4.

Figure 15. Schematic illustration indicating the reaction mechanism of the photocatalytic procedure of
CNT/LaVO4 composite catalyst. Adapted with permission from Reference [84]. Copyright (2019) Elsevier.
Catalysts 2018, 8, x FOR PEER REVIEW 18 of 32

Figure 15. Schematic illustration indicating the reaction mechanism of the photocatalytic procedure
of CNT/LaVO4 composite catalyst. Adapted with permission from Reference [84]. Copyright (2019)
Catalysts 2019, 9, 122
Elsevier. 18 of 32

Recently, graphene as a newly developed nanocarbon material has attracted numerous research
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
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
charge transport ability, unique optical properties, high thermal conductivity, large specific surface area,
area, and good mechanical strength [78,85,86]. Up to now, a myriad of attempts has been carried out
and good mechanical strength [78,85,86]. Up to now, a myriad of attempts has been carried out to couple
to couple the graphene with various semiconductors to further improve their photocatalytic activity.
the graphene with various semiconductors to further improve their photocatalytic activity. According to
According to the previous reports, the first graphene composite semiconductor for photocatalysis
the previous reports, the first graphene composite semiconductor for photocatalysis was prepared
was prepared by Zhang and co-workers [87]. They fabricated a TiO2 (P25)-graphene composite with
by Zhang and co-workers [87]. They fabricated a TiO2 (P25)-graphene composite with a chemically
a chemically bonding structure via a one-step hydrothermal reaction. As reported, there are three
bonding structure via a one-step hydrothermal reaction. As reported, there are three contributions of
contributions of the graphene for the photocatalytic activity: i) enhancing the adsorption capacity of
the graphene for the photocatalytic activity: (i) enhancing the adsorption capacity of pollutants, (ii)
pollutants, ii) extending light absorption range, and iii) improving charge transportation and
extending light absorption range, and (iii) improving charge transportation and separation efficiency.
separation efficiency. As a result, the photodegradation of the obtained TiO2 (P25)-graphene
As a result, the photodegradation of the obtained TiO2 (P25)-graphene composite for methylene blue was
composite for methylene blue was significantly improved, and was superior to that of the bare P25
significantly improved, and was superior to that of the bare P25 and the commonly reported P25-CNTs
and the commonly reported P25-CNTs composite. After that, numerous photocatalysts based on the
composite. After that, numerous photocatalysts based on the composite graphene-semiconductors have
composite graphene-semiconductors have been invented for the treatment of wastewater. Most
been invented for the treatment of wastewater. Most recently, in order to overcome the limitation of
recently, in order to overcome the limitation of the poor homogenous dispersion of graphene, as
the poor homogenous dispersion of graphene, as shown in Figure 16, Isari et al. [88] created a ternary
shown in Figure 16, Isari et al. [88] created a ternary nanocomposite catalyst (Fe-doped TiO2/rGO)
nanocomposite catalyst (Fe-doped TiO2 /rGO) derived from Fe-doped TiO2 and reduced graphene oxide
derived from Fe-doped TiO2 and reduced graphene oxide via a simple sol-gel method. They proved
via a simple sol-gel method. They proved that the band gap of Fe-TiO2 /rGO could be significantly
that the band gap of Fe-TiO2/rGO could be significantly decreased compared with that of the pristine
decreased compared with that of the pristine TiO2 , and the obtained Fe-doped TiO2 /rGO exhibited an
TiO2, and the obtained Fe-doped TiO2/rGO exhibited an effective decontamination performance for
effective decontamination performance for rhodamine B in water.
rhodamine B in water.

Figure 16.
Figure 16. Schematic illustration demonstrating
Schematic illustration demonstrating the photocatalytic
the photocatalytic mechanism
mechanism ofof Fe-TiO
Fe-TiO/rGO
2/rGO
2
catalyst for contaminant under solar irradiation.
catalyst for contaminant under solar irradiation. Adapted
Adapted with permission from Reference [88].
with permission from Reference [88].
Copyright (2018)
Copyright (2018) Elsevier.
Elsevier.

5. Morphology Regulation of the Composite Photocatalysts

Photocatalysts
Apart from the
the intrinsic
intrinsic characteristics
characteristics of
of semiconductors,
semiconductors, the corresponding
corresponding catalysts with
different morphologies may result in in different
different photocatalytic
photocatalytic activities
activities and
and different
different application
application
processes [89].
[89]. Recently, morphology modification of the photocatalysts have attracted more and
more attention owing to further
further improvements
improvements in their
their application
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 2018, 8, x FOR PEER REVIEW 19 of 32

we will2019,
Catalysts briefly
9, 122summarize the recent achievements of the composite photocatalysts with different
19 of 32
morphologies of 0D, 1D, 2D, and 3D materials.

5.1. Nanoparticles
5.1. Nanoparticles (0D)
(0D)
Generally, the
Generally, the0D0D
materials are characterized
materials as spherically
are characterized shaped with
as spherically nano-scaled
shaped dimensions.
with nano-scaled
NanoparticlesNanoparticles
dimensions. as a typical 0Dasmaterial have0D
a typical been widely have
material used in the area
been of photocatalysis
widely used in the with
area the
of
merits of large surface
photocatalysis area,
with the simple
merits of synthesis methods,
large surface area, and easysynthesis
simple to be functionalized [90]. easy
methods, and Up totonow,
be
several synthesis
functionalized approaches
[90]. Up to now,have beensynthesis
several invented, among which
approaches havethe sol-gel
been method,
invented, hydrothermal
among which the
method,
sol-gel and solvothermal
method, hydrothermal method
method, could be the most-used
and solvothermal techniques
method for most-used
could be the the fabrication of 0D
techniques
composite
for photocatalysts.
the fabrication of 0D composite photocatalysts.

5.1.1. Sol-Gel
5.1.1. Sol-Gel Method
Method
The sol-gel
The sol-gel process
process is is aa commonly
commonly used used and
and effective
effective strategy
strategy forfor the
the preparation
preparation of of various
various
inorganic materials,
inorganic materials,especially
especiallyfor forthe
themetal
metal oxides
oxides based
based on on
thethe corresponding
corresponding precursors,
precursors, andand it
it has
has several merits including being low cost, processed at low-temperature,
several merits including being low cost, processed at low-temperature, and the fine control of the and the fine control
of the product’s
product’s chemicalchemical
composition.composition.
Therefore,Therefore, the sol-gel
the sol-gel process process
is one is one of the
of the most-used most-used
techniques for
techniques for the preparation of composite semiconductor photocatalysts
the preparation of composite semiconductor photocatalysts [58]. For example, Vaiano et al. [91] [58]. For example,
Vaiano et al. [91]
immobilized immobilized
the N-doped TiO2the N-doped TiO
nanoparticles 2 nanoparticles
(NPs) on glass spheres(NPs)via onthe
glass spheres
sol-gel via the
method. sol-gel
Through
method. Through
regulating regulating
the synthesis the synthesis
conditions, conditions,
and employing theand employing
Triton X-100 asthe theTriton X-100
surface as the
active surface
agent, the
active agent, the obtained N-doped TiO NPs/glass spheres exhibited a good
obtained N-doped TiO2 NPs/glass spheres exhibited a good photocatalytic activity for methylene
2 photocatalytic activity
for methylene
blue blue and black-T
and eriochrome eriochrome black-Tunder
in water in waterUVunder
and UV and visible
visible light irradiation.
light irradiation. Moreover,
Moreover, the
the composite
composite catalyst
catalyst waswaseasyeasy to be
to be separated
separated from
from thethe reactionmixture
reaction mixturewith witha agood
gooddurability.
durability.
Recently, Chen
Recently, Chen etet al.
al.[92]
[92]prepared
preparedaaNi-Cu-Zn
Ni-Cu-Znferrite@SiO
ferrite@SiO22@TiO composite via
@TiO22 composite via aa simple
simple sol-gel
sol-gel
method. With
method. With the
the immobilization
immobilization of of Ag
Ag and
and magnetic
magnetic ferrite,
ferrite, the
the composite
composite photocatalysts
photocatalysts exhibited
exhibited
comparatively good photodegradation performance for the methylene blue under a visiblesource
comparatively good photodegradation performance for the methylene blue under a visible light light
with lower
source withpower. Moreover,
lower power. the composite
Moreover, catalystscatalysts
the composite can be easily
can beseparated using a magnet
easily separated using a and can
magnet
be reused
and can bewell without
reused significant
well without loss of photocatalytic
significant activity (Figure
loss of photocatalytic activity17).
(Figure 17).

(a) (b)

(c)

Figure
Figure 17. (a) The cycling test of the catalytic performance. (b)
(b) Dye removal capacity
capacity by adsorption
adsorption
and
and degradation
degradation for
for different
different cycles.
cycles. (c)
(c) Digital
Digital photos
photos demonstrating
demonstrating the
the recyclability
recyclability by
by using
using an
an
external
external magnetic
magnetic field. Adapted
Adapted with permission from Reference [92]. Copyright (2017) Elsevier.

5.1.2. Hydrothermal
5.1.2. Hydrothermal Methods
Methods
The hydrothermal
The hydrothermal method
methodisisaawet-chemistry
wet-chemistrymethod
methodforfor
synthesizing single
synthesizing crystals.
single Through
crystals. the
Through
hydrothermal
the method,
hydrothermal a great
method, deal
a great of of
deal crystalline
crystallinephases
phasesthat
thatare
arenot
notstable
stable at
at the
the melting point
melting point
can be obtained [93]. As a result, numerous semiconductor nanoparticles with different
can be obtained [93]. As a result, numerous semiconductor nanoparticles with different surface surface
morphologies and compositions can also be prepared using the hydrothermal method. As a
Catalysts 2019, 9, 122 20 of 32
Catalysts 2018, 8, x FOR PEER REVIEW 20 of 32

representative
morphologies work, Wu et al. [94]
and compositions canfabricated the F-doped
also be prepared usingflower-like TiO2 nanoparticle
the hydrothermal method. As onathe
surface
representative work, Wu et al. [94] fabricated the F-doped flower-like TiO2 nanoparticle on the surface of
of Ti via a low-temperature hydrothermal process. They reported that the presence
HFof in
Ti water and the hydrothermal
via a low-temperature reaction
hydrothermal time They
process. play reported
an important that therole in the of
presence formation
HF in waterof the
and theflower-like
F-doped hydrothermal TiOreaction
2 time play
nanostructures. an important
Through role
regulating in the
the formation
synthesis of the F-doped
parameters, theflower-
obtained
like TiOTiO
F-doped 2 nanostructures. Through regulating
2 flower-like nanomaterials the synthesis
exhibited a superior parameters, the obtained F-doped
photoelectrochemical activityTiO
for2the
flower-like nanomaterials exhibited a superior photoelectrochemical
photodegradation of organic pollutants compared with P-25. They also demonstrated that activity for thethe
photodegradation
improved of organic pollutants
photoelectrochemical activity ofcompared
the F-doped withTiOP-25. They also demonstrated that the
2 flower-like nanomaterials was mainly
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
due to the photocatalysts
composite larger surface areacanand thebe
also enhanced
synthesizedvisibleusing
light harvest capacity. Additionally,
the hydrothermal method, such magnetic
as the
composite photocatalysts can also be synthesized using the hydrothermal
magnetic CoFe2 O4 /Ag/Ag3 VO4 photocatalysts fabricated by Jing and co-workers [95]. During method, such as thethis
magnetic CoFe2O4/Ag/Ag3VO4 photocatalysts fabricated by Jing and co-workers [95]. During this
study, the as-prepared CoFe2 O4 nanoparticles were dispersed in the solutions with AgNO3 and
study, the as-prepared CoFe2O4 nanoparticles were dispersed in the solutions with AgNO3 and
Na3 VO4 , and the mixture suspensions were hydrothermally treated to prepare CoFe2 O4 /Ag/Ag3 VO4
Na3VO4, and the mixture suspensions were hydrothermally treated to prepare CoFe2O4/Ag/Ag3VO4
composites. Through controlling the weight ratios of CoFe2 O4 in the composite system, the optimal
composites. Through controlling the weight ratios of CoFe2O4 in the composite system, the optimal
CoFe2 O4 /Ag/Ag3 VO4 composite exhibited significantly improved photocatalytic activity toward
CoFe2O4/Ag/Ag3VO4 composite exhibited significantly improved photocatalytic activity toward the
the degradation
degradation of of various
various contaminants
contaminants including
including methyl
methyl orange,
orange, tetracycline,
tetracycline, andand
couldcould
eveneven
killkill
Escherichia
Escherichiacoli solely
coli under
solely under thethe
driving of of
driving visible
visiblelight. Moreover,
light. Moreover, with
withthethe
advantage
advantage of of
having
havinga good
a
magnetic response property, the corresponding CoFe O /Ag/Ag
good magnetic response property, the corresponding CoFe2O4/Ag/Ag3VO4 composite could be
2 4 3 VO 4 composite could be facilely
collected from the from
facilely collected waterthe
bywater
applying an extraan
by applying magnetic field (Figure
extra magnetic 18). 18).
field (Figure

(a) (b)

(c) (d)

Figure18.18.
Figure (a)(a) Magnetic
Magnetic separation
separation performance
performance of the
of the CoFe 2 O4CoFe 2O4/Ag/Ag
/Ag/Ag 3VO4 composite.
3 VO4 composite. (b) The(b) The
absorption
absorption
spectra spectra
of methyl of methyl
orange orange
solutions solutions
over time in the over timeofinCoFe
presence the 2presence
O4 /Ag/Ag of 3CoFe 2O4/Ag/Ag
VO4 (under 3VOlight
visible 4

(under visible light λ ≥ 440 nm) and the UV–vis absorption spectrum of CoFe O /Ag/Ag
λ ≥ 440 nm) and the UV–vis absorption spectrum of CoFe2 O4 /Ag/Ag3 VO4 . (c) The evolution of the
2 4 3VO 4. (c) The
evolutionspectra
absorption of theofabsorption spectra
methyl orange of methyl
solutions orange
over time solutions
in the presenceover time
of CoFe in the presence of
2 O4 /Ag/Ag3 VO4 (under
CoFe 2O4/Ag/Ag3VO4 (under visible light λ ≥ 550 nm). (d) Photocatalytic degradation of tetracycline
visible light λ ≥ 550 nm). (d) Photocatalytic degradation of tetracycline with different samples under visible
with
light different samples
irradiation. Adaptedunder visible lightfrom
with permission irradiation.
ReferenceAdapted with permission
[95] Copyright from Reference [95]
(2016) Elsevier.
Copyright (2016) Elsevier.
5.2. Nanofibers/Nanorods (1D)
5.2. Nanofibers/Nanorods (1D)
Recently, nanofibrous photocatalysts have been intensively studied owing to their unique long aspect
Recently,
ratio, large surfacenanofibrous photocatalysts
area, and being have been intensively
easily functionalized. Up to now,studied
various owing to their
strategies unique
had been long
developed
aspect ratio, large surface area, and being easily functionalized. Up to now, various strategies had
to synthesize the 1D materials with different morphology like: wires, belts, rods, tubes, and rings [61,89,96],
been developed
among to synthesize method
which, the hydrothermal the 1D materials with different
and electrospinning morphology
are the most-usedlike: wires, belts,
techniques. rods,
Consequently,
tubes, and rings [61,89,96], among which, the hydrothermal method and electrospinning are the
Catalysts 2019, 9, 122 21 of 32

Catalysts 2018, 8, x FOR PEER REVIEW 21 of 32

in this part, we present the development of composite semiconductors with nanofibrous morphology
most-used techniques. Consequently, in this part, we present the development of composite
derived from the electrospinning method and hydrothermal method for the treatment of wastewater.
semiconductors with nanofibrous morphology derived from the electrospinning method and
hydrothermal method for the treatment of wastewater.
5.2.1. Hydrothermal Method
As Hydrothermal
5.2.1. mentioned above, Methodthe hydrothermal method is capable of synthesizing various inorganics
with different morphologies, including the nanofibrous materials. For example, Yang et al. [97] once
As mentioned above, the hydrothermal method is capable of synthesizing various inorganics
reported the fabrication
with different of a novel
morphologies, TiO2 nanofibers
including withmaterials.
the nanofibrous a shell of For
anatase nanocrystals
example, Yang et al.based on the
[97] once
hydrothermal
reported the fabrication of a novel TiO2 nanofibers with a shell of anatase nanocrystals based on2 Ti
process. Actually, the whole fabrication process included three steps: First, the H the3 O7
nanofibers
hydrothermalwereprocess.
obtained from the
Actually, the anatase TiO2 particles
whole fabrication process and NaOHthree
included solutions via hydrothermal
steps: First, the H2Ti3O7
method.
nanofibersAfter that,
were the as-prepared
obtained H2 Ti3 O7TiO
from the anatase nanofibers
2 particleswere treatedsolutions
and NaOH using a dilute acid solution
via hydrothermal
under certain hydrothermal condition to generate the anatase nanocrystal shell
method. After that, the as-prepared H2Ti3O7 nanofibers were treated using a dilute acid solution on the outside. Finally,
theunder
H2 Ti3certain
O7 phase was converted
hydrothermal to TiOto2 (B)
condition phasethe
generate after a heatnanocrystal
anatase treatment while
shell onthethe
anatase
outside.nanocrystal
Finally,
shell
theremained
H2Ti3O7 phaseunchanged. Owing
was converted to to
TiO the well-matched
2(B) phase
phase after a heat interfaces,
treatment whilewhich ensures
the anatase the charge
nanocrystal
shell remained
transfer across theunchanged.
interfaces, theOwing to the well-matched
recombination phase interfaces,
of electron-hole pairs waswhich ensures
effectively the charge
suppressed and
transfer across the interfaces, the recombination of electron-hole pairs was
the corresponding photoactivity was significantly enhanced. Most importantly, they demonstratedeffectively suppressed and
thethese
that corresponding
nanofibrous photoactivity
photocatalystswas significantly
possess specificenhanced.
surface Most importantly,
areas similar to they demonstrated
the commercial P25
that these nanofibrous photocatalysts possess specific surface areas similar
powder, and the fibril morphology endowed them with a good recyclability from water, which is to the commercial P25
powder,
critically and the fibril
important morphology
in practical endowedRecently,
applications. them with oura group
good recyclability
also carriedfrom
out awater,
serieswhich is
of studies
critically important in practical applications. Recently, our group also carried
on the synthesis of nanofibrous photocatalysts via employing the hydrothermal method such as the 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 MoO3 nanowires [98]. As shown in Figure 19, MoO3
bimetallic AuPd alloy nanoparticles deposited on MoO3 nanowires [98]. As shown in Figure 19, MoO3
nanowires were firstly prepared from Mo powder and H2 O2 via the hydrothermal method. Then,
nanowires were firstly prepared from Mo powder and H2O2 via the hydrothermal method. Then, the
the as-prepared MoO3 nanowires were used as the substrates to synthesize the MoO3 /Au-Pd bimetallic
as-prepared MoO3 nanowires were used as the substrates to synthesize the MoO3/Au-Pd bimetallic
alloy nanowires via a simple chemical reduction method. As expected, the MoO3 /Au–Pd bimetallic
alloy nanowires via a simple chemical reduction method. As expected, the MoO3/Au–Pd bimetallic
alloy nanowires exhibited a good photocatalytic degradation performance for trichloroethylene (TCE)
alloy nanowires exhibited a good photocatalytic degradation performance for trichloroethylene (TCE)
under
under thethe
driving
drivingofofvisible
visiblelight.
light.Similarly,
Similarly, thethe composite nanowirescould
composite nanowires couldbebeeasily
easily separated
separated from
from
thethe
reaction slurry in a short time after the reaction.
reaction slurry in a short time after the reaction.

Figure 19. Schematic illustrating the band structure of MoO3/Au-Pd composite photocatalyst and the
Figure 19. Schematic illustrating the band structure of MoO3 /Au-Pd composite photocatalyst and the
possible reaction mechanism. Adapted with permission from Reference [98]. Copyright (2018)
possible reaction mechanism. Adapted with permission from Reference [98]. Copyright (2018) Elsevier.
Elsevier.
5.2.2. Electrospinning Method
5.2.2. Electrospinning Method
Electrospinning is considered as a promising way to synthesize nanofibers with several advantages,
such asElectrospinning
easy operation,islow
considered
cost, and as a promising
scalable way
[99–101]. to synthesize
In general, there nanofibers withparts
are four major several
in an
advantages, such as easy operation, low cost, and scalable [99–101]. In general, there are four major
electrospinning device: (i) an electrical power supplier, (ii) a metallic needle, (iii) syringes with the
Catalysts 2019, 9, 122 22 of 32

Catalysts 2018, 8, x FOR PEER REVIEW 22 of 32

polymer solution, and (iv) a conductive collector. Meanwhile, several process parameters, such as the
polymer-based
parts in ansolution concentration,
electrospinning device: (i)theanviscosity
electricalofpower
solution, the flow
supplier, (ii) arate of theneedle,
metallic syringe driver,
(iii) syringesand the
electric field
with thepower,
polymer could alsoand
solution, be well-regulated
(iv) a conductivetocollector.
manipulate the morphology
Meanwhile, of fibers.
several process During the
parameters,
electrospinning
such as theprocess, the solution
polymer-based solutionis injected through
concentration, thea metallic
viscosity needle via a the
of solution, syringe
flow with
rate ofa constant
the
pumpsyringe
speed.driver,
At theand same thetime,
electric field power,
a voltage is appliedcouldon also
thebe well-regulated
metallic to manipulate
needle; therefore, the
the solution
morphology of fibers. During the electrospinning process, the solution
droplet will be charged, and then a Taylor cone will be generated when the electronic force is enough is injected through a metallic
needle via
to overcome theasurface
syringetension.
with a constant
Following pump this,speed.
a liquidAt the
jet issame
formed time,between
a voltagethe is grounded
applied on collector
the
metallic needle; therefore, the solution droplet will be charged, and then a Taylor cone will be
and the needle. The generated jets will be stretched by an electrostatic repulsion force until it reaches the
generated when the electronic force is enough to overcome the surface tension. Following this, a
collector; meanwhile, the solvent will rapidly evaporate during this process. Finally, the jets are solidified
liquid jet is formed between the grounded collector and the needle. The generated jets will be
and the corresponding nanofibers are collected on the collector [100].
stretched by an electrostatic repulsion force until it reaches the collector; meanwhile, the solvent will
As for the
rapidly applications
evaporate during of this
photocatalysis,
process. Finally, high the specific surface
jets are area isand
solidified required to provide more
the corresponding
activenanofibers
sites for arethecollected
redox reaction. More
on the collector. [100] specifically, electrospun nanofibers as forefront fibrous
materials Ashave attracted considerable research attention in the area of photocatalysis
for the applications of photocatalysis, high specific surface area is required to provide more due to its several
active sites
advantages for the
of large redoxarea,
surface reaction. More high
extremely specifically,
aspect electrospun
ratio, and ease nanofibers as forefront fibrous
of functionalization [102,103].
materialsZhang
For example, have attracted considerable
et al. [104] reportedresearch attentionof
the fabrication in athe area ofand
flexible photocatalysis
hierarchicalduemesoporous
to its several TiO2
advantages
nanoparticle (TiOof2 large surface area,
NP) modified TiOextremely high aspect ratio, and ease of functionalization [102,103].
2 nanofiber composites via the combination of electrospinning and
For example, Zhang et al. [104] reported the fabrication of a flexible and hierarchical mesoporous
in situ polymerization method. At first, flexible TiO2 nanofibers were prepared via the electrospinning
TiO2 nanoparticle (TiO2 NP) modified TiO2 nanofiber composites via the combination of
and the subsequently consuming process with the dopant of yttrium. After that, the as-prepared
electrospinning and in situ polymerization method. At first, flexible TiO2 nanofibers were prepared
TiO2 nanofibers were used as a template for the incorporation of TiO NPs by utilizing a bifunctional
via the electrospinning and the subsequently consuming process with2 the dopant of yttrium. After
benzoxazine as the carrier
that, the as-prepared TiOthrough a calcination process in the N atmosphere. The as-prepared
2 nanofibers were used as a template for the2 incorporation of TiO2 NPs by
membranes
utilizingexhibited
a bifunctional remarkable
benzoxazine photocatalytic activityatowards
as the carrier through calcination organic
processdyes
in theinNwater; moreover,
2 atmosphere.

it could
The be reused well
as-prepared via simply
membranes exhibitedrinsing with water,
remarkable and without
photocatalytic activitytime-consuming
towards organic dyes separation
in
water; moreover,
procedures owing to the it could
longbeaspect
reusedratiowell and
via simply rinsing with water,
good mechanical property andofwithout time-consuming
the composite nanofibers.
separation
In recent years,procedures
our groupowing to the long
has carried outaspect
several ratioworks
and good on themechanical
design property of the composite
of electrospun nanofibrous
photocatalysts [105–109]. As a representative sample, a BiOCl0.3 /BiOBr0.3 /BiOI0.4of
nanofibers. In recent years, our group has carried out several works on the design electrospun
/PAN composite
nanofibrous photocatalysts [105–109]. As a representative sample, a BiOCl0.3/BiOBr0.3/BiOI0.4/PAN
fibrous catalyst was fabricated via combining the electrospinning and sol-gel method [109]. As shown
composite fibrous catalyst was fabricated via combining the electrospinning and sol-gel method [109].
in Figure 20, the obtained composite photocatalyst exhibited a typical fibril structure with a good
As shown in Figure 20, the obtained composite photocatalyst exhibited a typical fibril structure with
uniformity, and the corresponding
a good uniformity, field emission
and the corresponding transmission
field emission electron
transmission microscope
electron microscope (FE-TEM)
(FE-TEM) image
demonstrated a highly crystalline
image demonstrated structure structure
a highly crystalline in the composite fibers with
in the composite a clear
fibers with lattice
a clear spacing relating to
lattice spacing
the (112) plane
relating to of
theBiOCl, the (110)
(112) plane planethe
of BiOCl, of (110)
BiOBr, andofthe
plane (200)and
BiOBr, planetheof BiOI;
(200) therefore,
plane of BiOI;atherefore,
heterojunctiona
structure was generated
heterojunction via awas
structure close contact via
generated of the composite
a close contact semiconductors. After a visible-light
of the composite semiconductors. Afterdriven
a
visible-light driven photocatalysis performance evaluation, it was
photocatalysis performance evaluation, it was found that the obtained BiOCl0.3 /BiOBr0.3 /BiOI0.4 /PAN found that the obtained
BiOCl0.3/BiOBr
fiber displayed the 0.3 /BiOI0.4photocatalytic
highest /PAN fiber displayed the highest
degradation photocatalytic
performance of TCE.degradation
Moreover, performance
it was concludedof
TCE. Moreover, it was concluded that the improved visible-light
that the improved visible-light driven photocatalytic activity is caused by the interfacial contact driven photocatalytic activity is of a
caused by the interfacial contact of a heterojunction and the inhibition of the recombination rate of
heterojunction and the inhibition of the recombination rate of the electron–hole pairs.
the electron–hole pairs.

(a) (b) (e)

(e)

(c) (d)

Figure
20. 20. SEM
SEMimage of pristine
image PAN fibers
of pristine PAN (a) and BiOCl
fibers (a)x/BiOBr
and y/BiOI
BiOCl z composite fibers (b). (c) FE-
Figure x /BiOBry /BiOIz composite
TEM image of BiOClx/BiOBry/BiOIz fibers. (d) Lattice-resolved image for BiOClx/BiOBry/BiOIz
fibers (b). (c) FE-TEM image of BiOClx /BiOBry /BiOIz fibers. (d) Lattice-resolved image for
BiOClx /BiOBry /BiOIz 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 TiO2 -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 H2 O2 -assisted photocatalysis process, showing great potential for dealing with the high-chroma
dye wastewater. Besides TiO2 , various nanosheets derived from different semiconductors could also
be fabricated using a hydrothermal process, such as the WO3 nanosheet/K+ Ca2 Nb3 O10 − ultrathin
nanosheet synthesized by Ma et al. [112] via a facile hydrothermal assembly of WO3 nanosheets and
ultrathin K+ Ca2 Nb3 O10 − nanosheets. They demonstrated that the composite nanosheets possess
2D/2D heterojunctions and display remarkably enhanced photocatalytic activity compared to the
pristine WO3 and K+ Ca2 Nb3 O10 − 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 Bi12 O15 Cl6
nanosheets with a narrowed band gap via a simple and facile solvothermal method followed by
a simple thermal treatment. The obtained Bi12 O15 Cl6 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 TiO2
(P25), respectively. In addition, the as-prepared Bi12 O15 Cl6 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.
Figure 21. (a,b)
(a,b) SEM
SEM images
images ofof the
theobtained
obtainedPt/BiOI
Pt/BiOI composite
composite nanosheets.
nanosheets. (c,d)
(c,d) HR-SEM
HR-SEM images
images of
of
BiOI nanosheets and Pt/BiOI composite nanosheets, respectively. (e–g) HR-TEM images
BiOI nanosheets and Pt/BiOI composite nanosheets, respectively. (e–g) HR-TEM images of Pt/BiOI of Pt/BiOI
composite nanosheets.
composite nanosheets. (h)
(h) Element
Element mappings
mappings ofof Pt,
Pt, Bi,
Bi, O,
O, and
and II for
for the
the Pt/BiOI
Pt/BiOI composite
composite nanosheets.
nanosheets.
Adapted with permission from Reference [114]. Copyright (2017)
Adapted with permission from Reference [114]. Copyright (2017) Elsevier. Elsevier.

5.4. Frameworks (3D)

In recent years,
years, there have been a great number number of works works reporting
reporting a new new generation
generation of
composite
compositephotocatalysts
photocatalystswith with3D3D
frameworks
frameworks [115]. Actually,
[115]. the 3Dthe
Actually, photocatalysts with well-deigned
3D photocatalysts with well-
frameworks show great
deigned frameworks showadvantages such as asuch
great advantages largeasspecific
a largesurface
specificarea, higharea,
surface adsorptive capacity,
high adsorptive
good structure stability, good mass transfer ability, and a large number of exposed
capacity, good structure stability, good mass transfer ability, and a large number of exposed active active sites,
which
sites, make
whichthem
make promising candidatescandidates
them promising for the highlyforefficient
the highlyphotodegradation of contaminants in
efficient photodegradation of
water. In general,
contaminants in the 3D composite
water. In general,photocatalysts could be
the 3D composite obtained via two
photocatalysts approaches,
could be obtainedwhichviaare to
two
directly construct
approaches, whicha photocatalyst withconstruct
are to directly 3D frameworks (type I), or compositing
a photocatalyst the photocatalysts
with 3D frameworks (type I),with
or
acompositing
template withthe3D frameworks with
photocatalysts (typeaII).
template with 3D frameworks (type II).
Through
Throughemploying
employingthe thecommonly
commonlyreported
reportedsynthesis
synthesis methods
methods ofof
various
various 3D3Dframeworks,
frameworks, such as
such
the sol–gel
as the process,
sol–gel in situ
process, in assembly, and template
situ assembly, methods,
and template various various
methods, 3D photocatalysts with different
3D photocatalysts with
characteristics have be fabricated
different characteristics [116]. The [116].
have be fabricated sol-gelThe
process
sol-gelis aprocess
well-developed strategy to strategy
is a well-developed synthesize to
aerogels, and some of the produced aerogels, such
synthesize aerogels, and some of the produced aerogels, as the SiO aerogels, have been commercialized
2 such as the SiO2 aerogels, have been [117].
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,
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
Catalysts 2018,
subjected to 8,
thex FOR PEER REVIEW
hydrolysis and condensation reactions to form a wet gel, during which time, numerous 25 of 32

networks are generated between the alkoxide groups; subsequently, the formed wet gels are sufficiently
the formed
dried wet aerogels.
to obtain gels are sufficiently
As a matter dried to obtain
of course, aerogels. As a matter
a photocatalytic aerogelofcan
course, a photocatalytic
be obtained using a
metal alkoxide precursor with an appropriate photocatalytic activity. For example, Dagan et activity.
aerogel can be obtained using a metal alkoxide precursor with an appropriate photocatalytic al. [118]
For example,
prepared Dagan
a series et al.porous
of highly [118] prepared a series
TiO2 aerogels of highly
via the porous TiO
sol-gel method aerogels
and2they via thethat
also proved sol-gel
the
method and they also proved that the photocatalytic degradation performance of the
photocatalytic degradation performance of the TiO2 aerogels for organic contaminants is much better TiO2 aerogels

for organic
than that of acontaminants
commercial TiO is much better than that of a commercial TiO2 (P25). Besides, various
2 (P25). Besides, various photoactive metal oxides, metal silylamide, or
photoactive
their composite metal oxides,
aerogels metal
have beensilylamide,
developed.orHowever,
their composite
due to theaerogels have
limitation been developed.
of sol-gel processes,
However, due to the limitation of sol-gel processes, some metal oxides or metal chalcogenides
some metal oxides or metal chalcogenides are not able to be synthesized into aerogels, and the obtained are
not ablephotocatalysts
aerogel to be synthesized into aerogels,
usually andlow
suffer from the obtained aerogel
crystallinity. photocatalysts
Therefore, usually suffer
a new generated from
strategy,
low crystallinity. Therefore, a new generated strategy, namely an assembly method,
namely an assembly method, has been invented to construct aerogels based on various nanoscale units has been
invented to construct aerogels based on various nanoscale units with different morphologies
with different morphologies and chemical properties. As reported before [116], there are three typical
and
chemical properties. As reported before [116], there are three typical steps for the assembly process:
steps for the assembly process: (i) fabrication of the building blocks, (ii) preparing the dispersion of
(i) fabrication of the building blocks, (ii) preparing the dispersion of the building blocks with
the building blocks with appropriated concentration, and (iii) solidified the suspension of building
appropriated concentration, and (iii) solidified the suspension of building blocks to form a 3D
blocks to form a 3D monolith. Based on this principle, Heiligtag et al. [119] developed a 3D framework
monolith. Based on this principle, Heiligtag et al. [119] developed a 3D framework Au-TiO2
Au-TiO2 photocatalysts with a preformed TiO2 nanoparticles as the blocking units without using any
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
templates. Through modifying the surface of anatase TiO2 nanoparticles with trizma, the
undergo an oriented attachment process during gelation and finally result in well-bonded networks.
nanoparticles undergo an oriented attachment process during gelation and finally result in well-
Moreover, based on the above-mentioned aerogel synthesis methods, various phototcatalytic aerogels
bonded networks. Moreover, based on the above-mentioned aerogel synthesis methods, various
can also be prepared via employing the preformed aerogels as the templates, such as a C3 N4 aerogel
phototcatalytic aerogels can also be prepared via employing the preformed aerogels as the templates,
that was fabricated by Kailasam and co-workers [120] via preparing a C3 N4 /SiO2 composite aerogel
such as a C3N4 aerogel that was fabricated by Kailasam and co-workers [120] via preparing a
based on the sol-gel method at first, and then remove the SiO2 via treating the composite in 4 M
C3N4/SiO2 composite aerogel based on the sol-gel method at first, and then remove the SiO2 via
NH4 HF2 (Figure 22).
treating the composite in 4 M NH4HF2 (Figure 22).

Figure 22.
Figure 22. Schematic
Schematic illustration
illustration indicating
indicating the
the synthesis
synthesis process
process of
of porous
porous carbon
carbon nitride
nitride and
and silica
silica
aerogels based
aerogels based on
on the
the sol-gel
sol-gel method
method and
and the
the digital
digital photos
photos of
of corresponding
corresponding aerogels.
aerogels. Adapted
Adapted with
with
permission from Reference [120]. Copyright (2011) Royal Society of Chemistry.
permission from Reference [120]. Copyright (2011) Royal Society of Chemistry.

As for
As for the
thefabrication
fabricationofoftype typeIIII3D
3Dphotocatalysts,
photocatalysts, anan appropriate
appropriate 3D3D porous
porous substrate
substrate should
should be
be prepared before loading the active substance on its frameworks. Considering
prepared before loading the active substance on its frameworks. Considering the requirements the requirements for
high photoreactivity
high photoreactivityand andgood
goodservice
serviceperformance,
performance, thethe aerogels/hydrogels
aerogels/hydrogels derived
derived from
from ceramics
ceramics or
or carbon are mostly preferred. For example, Li et al. [121] fabricated a ternary
carbon are mostly preferred. For example, Li et al. [121] fabricated a ternary magnetic composite of magnetic composite
of 3Fe
Fe O43O 4@TiO
@TiO 2/SiO
2 /SiO 2 aerogel
2 aerogel via
via combining
combining thethe sol-gel
sol-gel process
process andand a hydrothermal
a hydrothermal treatment.
treatment. During
During the
the fabrication
fabrication process,
process, Fe3 OFe
4 O 4 microspheres
3microspheres were were
first first synthesized
synthesized via via
the the hydrothermal
hydrothermal method;
method; after after
that,
that,
Fe 3 O4Fe3O4@TiO
@TiO 2 core 2 core
shellshell microspheres
microspheres werewere fabricated
fabricated via anviainan inreaction
situ situ reaction
method.method. The SiO
The used used2
SiO2 aerogel
aerogel was derived
was derived from thefrom the industrial
industrial fly ash flyvia ash via a common
a common sol-gel method.
sol-gel method. Finally,
Finally, the the as-
as-prepared
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-
Catalysts 2019, 9, 122 26 of 32

Fe3 O4 @TiO2 core shell microspheres and SiO2 aerogel were combined via the hydrothermal method.
According to their report, the obtained Fe3 O4 @TiO2 /SiO2 aerogel exhibited an enhanced photocatalytic
activity for the degradation of rhodamine B dye under visible light irradiation, and the aerogel could
Catalysts 2018, 8, x FOR PEER REVIEW 26 of 32
be facilely collected after the reaction due to its good magnetic separation performance. Interestingly,
as shown
free in Figure
PANI/TiO 23, Jiang et al. [122] recently developed a separation-free PANI/TiO 3D hydrogel
2 3D hydrogel for the continuous photocatalytic degradation of various2contaminants
for the continuous
in water. In their photocatalytic
studies, the PANI degradation of various
hydrogel with 3Dcontaminants
frameworks in water.
was In their studies,
synthesized via the
the PANI hydrogel with 3D frameworks was synthesized via the polymerization of aniline.
polymerization of aniline. During the gelling process, the TiO2 nanoparticles (P25) were incapsulated During the
gelling process, the
in the hydrogels. As TiO 2 nanoparticles
a result, the obtained (P25) were incapsulated
PANI/TiO in the hydrogels. As a result,
2 composite hydrogel exhibited an intriguing
the obtained PANI/TiO 2 composite hydrogel exhibited an
capacity for removing organic contaminants from water, which was mainly intriguing capacity for removing
caused organic
by the synergistic
contaminants from water, which was mainly caused by the synergistic effect of
effect of adsorption enrichment of hydrogel and the in situ photocatalytic degradation of TiO2.adsorption enrichment
of hydrogelthe
Moreover, andpresented
the in situseparation-free
photocatalytic degradation of in
characteristics TiO 2 . Moreover,
the the presented
obtained bulk separation-free
materials indicate a good
characteristics in the obtained bulk
recyclability of the composite hydrogel. materials indicate a good recyclability of the composite hydrogel.

Figure 23.
Figure 23. Schematic
Schematic illustration
illustration demonstrating
demonstratingthe
thesynthesis
synthesisprocess
processof
ofthe
the3D
3DPANI/TiO
PANI/TiO22 composite
composite
hydrogel. Adapted
hydrogel. Adapted with
with permission
permission from
from Reference
Reference [122].
[122]. Copyright
Copyright (2015)
(2015) Wiley.
Wiley.

6.
6. Summary
Summary and
and Perspectives
Perspectives
In
In summary,
summary, in in order
order toto address
address thethe worldwide
worldwide concerned
concerned issuesissues of
of water
water pollutions,
pollutions, various
various
photocatalysis
photocatalysisprocesses
processes based
basedon different photocatalysts
on different have been
photocatalysts havedeveloped; meanwhile,meanwhile,
been developed; numerous
efforts
numeroushaveefforts
been have
madebeen to further
made to improve
further the photocatalytic
improve activity of
the photocatalytic the catalysts
activity based on
of the catalysts the
based
semiconducors. In this review, the recent progress in the development
on the semiconducors. In this review, the recent progress in the development of composite of composite semiconductor
photocatalysts
semiconductorforphotocatalysts
wastewater treatment is presented,
for wastewater including
treatment is the most-used
presented, strategiesthe
including to narrow
most-usedthe
band gap of semiconductors, to retard the recombination of the photo-generated
strategies to narrow the band gap of semiconductors, to retard the recombination of the photo- electron-hole pairs,
to enhanceelectron-hole
generated the visible light adsorption
pairs, to enhance capacity, as well
the visible lightas adsorption
to increase capacity,
the reaction ratioas
as well between the
to increase
photocatalysts
the reaction ratioandbetween
contaminants. Moreover, theand
the photocatalysts composite
contaminants.catalytsMoreover,
with different morphologies
the composite and
catalyts
the corresponding photocatlytic performance were also summarized.
with different morphologies and the corresponding photocatlytic performance were also
Although great development of the photocatalysis process has been obtained, there are still
summarized.
several problems
Although yet development
great to be addressed to further
of the improveprocess
photocatalysis the practical application
has been obtained, performance
there are stillof
the photocatalysis. Therefore, some plausible perspectives for the developing
several problems yet to be addressed to further improve the practical application performance of the trend of composite
photocatalysts
photocatalysis. for the wasterwater
Therefore, treatmentperspectives
some plausible are proposed forbased
the on the presented
developing trendstudies: (i) the
of composite
existing
photocatalysts for the wasterwater treatment are proposed based on the presented studies: some
synthesis methods are relative complex, high cost, and harmful to the environment to i) the
degree,
existing thus a more
synthesis facile, highly
methods efficent,
are relative and green
complex, method
high cost, andisharmful
anticipated;
to the(ii) the mechanism
environment to some of
the composite
degree, thus a semicondutor
more facile, highly photocatalysts
efficent, and aregreen
still confusing
method is and some of ii)
anticipated; them
the are unpersuasive,
mechanism of the
therefore much more effort is needed for the basic studies of the
composite semicondutor photocatalysts are still confusing and some of them are unpersuasive,catalytic mechanisms; and (iii)
the practical
therefore muchusemore
are limitted becausefor
effort is needed thethe
collection
basic studiesand reuse
of the of the catalysts
catalytic in water
mechanisms; andare
iii)still
the
inconvenient
practical usedue aretolimitted
their small size and
because thepoor mechanical
collection andproperty,
reuse oftherefore novel photocatalysts
the catalysts in water are with still
easy collectiondue
inconvenient property
to their or new
smallhybrid devices
size and poorbased on the composite
mechanical of photocatalysts
property, therefore with selected
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
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.

References
1. Carpenter, S.R.; Caraco, N.F.; Correll, D.L.; Howarth, R.W.; Sharpley, A.N.; Smith, V.H. Nonpoint pollution
of surface waters with phosphorus and nitrogen. Ecol. Appl. 1998, 8, 559–568. [CrossRef]
2. Jarup, L. Hazards of heavy metal contamination. Br. Med. Bull. 2003, 68, 167–182. [CrossRef] [PubMed]
3. Dudgeon, D.; Arthington, A.H.; Gessner, M.O.; Kawabata, Z.I.; Knowler, D.J.; Leveque, C.; Naiman, R.J.;
Prieur-Richard, A.H.; Soto, D.; Stiassny, M.L.J.; et al. Freshwater biodiversity: Importance, threats, status
and conservation challenges. Biol. Rev. 2006, 81, 163–182. [CrossRef] [PubMed]
4. Ribeiro, A.R.; Nunes, O.C.; Pereira, M.F.R.; Silva, A.M.T. An overview on the advanced oxidation processes
applied for the treatment of water pollutants defined in the recently launched Directive 2013/39/EU.
Environ. Int. 2015, 75, 33–51. [CrossRef] [PubMed]
5. Kolpin, D.W.; Furlong, E.T.; Meyer, M.T.; Thurman, E.M.; Zaugg, S.D.; Barber, L.B.; Buxton, H.T.
Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams, 1999-2000: A national
reconnaissance. Environ. Sci. Technol. 2002, 36, 1202–1211. [CrossRef] [PubMed]
6. Schwarzenbach, R.P.; Escher, B.I.; Fenner, K.; Hofstetter, T.B.; Johnson, C.A.; von Gunten, U.; Wehrli, B.
The challenge of micropollutants in aquatic systems. Science 2006, 313, 1072–1077. [CrossRef]
7. Radjenovic, J.; Sedlak, D.L. Challenges and opportunities for electrochemical processes as next-generation
technologies for the treatment of contaminated water. Environ. Sci. Technol. 2015, 49, 11292–11302. [CrossRef]
8. Jiang, J.Q. The role of coagulation in water treatment. Curr. Opin. Chem. Eng. 2015, 8, 36–44. [CrossRef]
9. Lekang, O.I.; Bomo, A.M.; Svendsen, I. Biological lamella sedimentation used for wastewater treatment.
Aquac. Eng. 2001, 24, 115–127. [CrossRef]
10. Ali, I. Water treatment by adsorption columns: Evaluation at ground level. Sep. Purif. Rev. 2014, 43, 175–205.
[CrossRef]
11. Oe, T.; Koide, H.; Hirokawa, H.; Okukawa, K. Performance of membrane filtration system used for water
treatment. Desalination 1996, 106, 107–113. [CrossRef]
12. Joss, A.; Zabczynski, S.; Gobel, A.; Hoffmann, B.; Loffler, D.; McArdell, C.S.; Ternes, T.A.; Thomsen, A.;
Siegrist, H. Biological degradation of pharmaceuticals in municipal wastewater treatment: Proposing a
classification scheme. Water Res. 2006, 40, 1686–1696. [CrossRef] [PubMed]
13. Mamba, G.; Mishra, A. Advances in magnetically separable photocatalysts: Smart, recyclable materials for
water pollution mitigation. Catalysts 2016, 6, 34. [CrossRef]
14. Lee, S.Y.; Park, S.J. TiO2 photocatalyst for water treatment applications. J. Ind. Eng. Chem. 2013, 19, 1761–1769.
[CrossRef]
15. Van der Hoek, J.P.; Bertelkamp, C.; Verliefde, A.R.D.; Singhal, N. Drinking water treatment technologies in
Europe: State of the art-challenges-research needs. J. Water Supply Res. Technol.-Aquac. 2014, 63, 124–130.
[CrossRef]
16. Gogate, P.R.; Pandit, A.B. A review of imperative technologies for wastewater treatment I:
Oxidation technologies at ambient conditions. Adv. Environ. Res. 2004, 8, 501–551. [CrossRef]
17. Oturan, M.A.; Aaron, J.J. Advanced oxidation processes in water/wastewater treatment: Principles and
applications. a review. Crit. Rev. Environ. Sci. Technol. 2014, 44, 2577–2641. [CrossRef]
Catalysts 2019, 9, 122 28 of 32

18. Pelaez, M.; Nolan, N.T.; Pillai, S.C.; Seery, M.K.; Falaras, P.; Kontos, A.G.; Dunlop, P.S.M.; Hamilton, J.W.J.;
Byrne, J.A.; O’Shea, K.; et al. A review on the visible light active titanium dioxide photocatalysts for
environmental applications. Appl. Catal. B-Environ. 2012, 125, 331–349. [CrossRef]
19. Comninellis, C.; Kapalka, A.; Malato, S.; Parsons, S.A.; Poulios, L.; Mantzavinos, D. Advanced oxidation
processes for water treatment: Advances and trends for R&D. J. Chem. Technol. Biot. 2008, 83, 769–776.
20. Sansaniwal, S.K.; Sharma, V.; Mathur, J. Energy and exergy analyses of various typical solar energy
applications: A comprehensive review. Renew. Sustain. Energy Rev. 2018, 82, 1576–1601. [CrossRef]
21. Mills, A.; Davies, R.H.; Worsley, D. Water-purification by semiconductor photocatalysis. Chem. Soc. Rev.
1993, 22, 417–425. [CrossRef]
22. Mills, A.; LeHunte, S. An overview of semiconductor photocatalysis. J. Photochem. Photobiol. A Chem. 1997,
108, 1–35. [CrossRef]
23. Fujishima, A.; Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972, 238,
37. [CrossRef] [PubMed]
24. Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.L.; Horiuchi, Y.; Anpo, M.; Bahnemann, D.W.
Understanding TiO2 photocatalysis: Mechanisms and materials. Chem. Rev. 2014, 114, 9919–9986. [CrossRef]
[PubMed]
25. Tong, H.; Ouyang, S.X.; Bi, Y.P.; Umezawa, N.; Oshikiri, M.; Ye, J.H. Nano-photocatalytic materials:
Possibilities and challenges. Adv. Mater. 2012, 24, 229–251. [CrossRef] [PubMed]
26. An, H.Z.; Du, Y.; Wang, T.M.; Wang, C.; Hao, W.C.; Zhang, J.Y. Photocatalytic properties of BiOX (X = Cl, Br,
and I). Rare Metals 2008, 27, 243–250. [CrossRef]
27. Azeez, A.A.; Rhee, K.Y.; Park, S.J.; Hui, D. Epoxy clay nanocomposites—Processing, properties and
applications: A review. Compos. Part B-Eng. 2013, 45, 308–320. [CrossRef]
28. Dhand, V.; Mittal, G.; Rhee, K.Y.; Park, S.J.; Hui, D. A short review on basalt fiber reinforced polymer
composites. Compos. Part B-Eng. 2015, 73, 166–180. [CrossRef]
29. Chong, M.N.; Jin, B.; Chow, C.W.K.; Saint, C. Recent developments in photocatalytic water treatment
technology: A review. Water Res. 2010, 44, 2997–3027. [CrossRef] [PubMed]
30. Ani, I.J.; Akpan, U.G.; Olutoye, M.A.; Hameed, B.H. Photocatalytic degradation of pollutants in petroleum
refinery wastewater by TiO2 - and ZnO-based photocatalysts: Recent development. J. Clean. Prod. 2018, 205,
930–954. [CrossRef]
31. Yu, Z.B.; Chen, X.Q.; Kang, X.D.; Xie, Y.P.; Zhu, H.Z.; Wang, S.L.; Ullah, S.; Ma, H.; Wang, L.Z.; Liu, G.; et al.
Noninvasively modifying band structures of wide-bandgap metal oxides to boost photocatalytic activity.
Adv. Mater. 2018, 30, 1706259. [CrossRef] [PubMed]
32. Choi, W.Y.; Termin, A.; Hoffmann, M.R. The role of metal ion dopants in quantum-sized TiO2 :
Correlation between photoreativity and charge carrier recombination dynamics. J. Phys. Chem. 1994,
98, 13669–13679. [CrossRef]
33. Liu, G.; Wang, L.Z.; Yang, H.G.; Cheng, H.M.; Lu, G.Q. Titania-based photocatalysts-crystal growth, doping
and heterostructuring. J. Mater. Chem. 2010, 20, 831–843. [CrossRef]
34. Zhu, J.F.; Deng, Z.G.; Chen, F.; Zhang, J.L.; Chen, H.J.; Anpo, M.; Huang, J.Z.; Zhang, L.Z.
Hydrothermal doping method for preparation of Cr3+ -TiO2 photocatalysts with concentration gradient
distribution of Cr3+ . Appl. Catal. B-Environ. 2006, 62, 329–335. [CrossRef]
35. Dvoranova, D.; Brezova, V.; Mazur, M.; Malati, M.A. Investigations of metal-doped titanium dioxide
photocatalysts. Appl. Catal. B-Environ. 2002, 37, 91–105. [CrossRef]
36. Bouras, P.; Stathatos, E.; Lianos, P. Pure versus metal-ion-doped nanocrystalline titania for photocatalysis.
Appl. Catal. B-Environ. 2007, 73, 51–59. [CrossRef]
37. Devi, L.G.; Kottam, N.; Murthy, B.N.; Kumar, S.G. Enhanced photocatalytic activity of transition metal ions
Mn2+ , Ni2+ and Zn2+ doped polycrystalline titania for the degradation of Aniline Blue under UV/solar light.
J. Mol. Catal. A Chem. 2010, 328, 44–52. [CrossRef]
38. Serpone, N. Is the band gap of pristine TiO2 narrowed by anion- and cation-doping of titanium dioxide in
second-generation photocatalysts? J. Phys. Chem. B 2006, 110, 24287–24293. [CrossRef]
39. Kudo, A.; Niishiro, R.; Iwase, A.; Kato, H. Effects of doping of metal cations on morphology, activity,
and visible light response of photocatalysts. Chem. Phys. 2007, 339, 104–110. [CrossRef]
40. Chen, J.H.; Yao, M.S.; Wang, X.L. Investigation of transition metal ion doping behaviors on TiO2 nanoparticles.
J. Nanopart. Res. 2008, 10, 163–171. [CrossRef]
Catalysts 2019, 9, 122 29 of 32

41. Dunnill, C.W.; Parkin, I.P. Nitrogen-doped TiO2 thin films: Photocatalytic applications for healthcare
environments. Dalton Trans. 2011, 40, 1635–1640. [CrossRef] [PubMed]
42. Asahi, R.; Morikawa, T.; Irie, H.; Ohwaki, T. Nitrogen-doped titanium dioxide as visible-light-sensitive
photocatalyst: Designs, developments, and prospects. Chem. Rev. 2014, 114, 9824–9852. [CrossRef] [PubMed]
43. Asahi, R.; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y. Visible-light photocatalysis in nitrogen-doped titanium
oxides. Science 2001, 293, 269–271. [CrossRef] [PubMed]
44. Kitano, M.; Funatsu, K.; Matsuoka, M.; Ueshima, M.; Anpo, M. Preparation of nitrogen-substituted TiO2 thin
film photocatalysts by the radio frequency magnetron sputtering deposition method and their photocatalytic
reactivity under visible light irradiation. J. Phys. Chem. B 2006, 110, 25266–25272. [CrossRef] [PubMed]
45. Salah, N.; Hameed, A.; Aslam, M.; Abdel-Wahab, M.S.; Babkair, S.S.; Bahabri, F.S. Flow controlled fabrication
of N doped ZnO thin films and estimation of their performance for sunlight photocatalytic decontamination
of water. Chem. Eng. J. 2016, 291, 115–127. [CrossRef]
46. Mikkelsen, N.J.; Pedersen, J.; Straede, C.A. Ion implantation—The job coater’s supplement to coating
techniques. Surf. Coat. Technol. 2002, 158, 42–47. [CrossRef]
47. Tang, G.Z.; Li, J.L.; Sun, M.R.; Ma, X.X. Fabrication of nitrogen-doped TiO2 layer on titanium substrate.
Appl. Surf. Sci. 2009, 255, 9224–9229. [CrossRef]
48. Song, X.Y.; Li, W.Q.; He, D.; Wu, H.Y.; Ke, Z.J.; Jiang, C.Z.; Wang, G.M.; Xiao, X.H. The “Midas
Touch” transformation of TiO2 nanowire arrays during visible light photoelectrochemical performance
by carbon/nitrogen coimplantation. Adv. Energy Mater. 2018, 8, 1800165. [CrossRef]
49. Chen, X.; Mao, S.S. Titanium dioxide nanomaterials: Synthesis, properties, modifications, and applications.
Chem. Rev. 2007, 107, 2891–2959. [CrossRef]
50. Lee, S.Y.; Park, J.; Joo, H. Visible light-sensitized photocatalyst immobilized on beads by CVD in a fluidizing
bed. Sol. Energy Mater. Sol. Cell 2006, 90, 1905–1914. [CrossRef]
51. Kafizas, A.; Crick, C.; Parkin, I.P. The combinatorial atmospheric pressure chemical vapour deposition
(cAPCVD) of a gradating substitutional/interstitial N-doped anatase TiO2 thin-film; UVA and visible light
photocatalytic activities. J. Photochem. Photobiol. A Chem. 2010, 216, 156–166. [CrossRef]
52. Youssef, L.; Leoga, A.J.K.; Roualdes, S.; Bassil, J.; Zakhour, M.; Rouessac, V.; Ayral, A.; Nakhl, M.
Optimization of N-doped TiO2 multifunctional thin layers by low frequency PECVD process. J. Eur.
Ceram. Soc. 2017, 37, 5289–5303. [CrossRef]
53. George, S.M. Atomic layer deposition: An Overview. Chem. Rev. 2010, 110, 111–131. [CrossRef]
54. Vilhunen, S.H.; Sillanpaa, M.E.T. Atomic layer deposited (ALD) TiO2 and TiO2-x Nx thin film photocatalysts
in salicylic acid decomposition. Water Sci. Technol. 2009, 60, 2471–2475. [CrossRef]
55. Pore, V.; Heikkila, M.; Ritala, M.; Leskela, M.; Areva, S. Atomic layer deposition of TiO2-x Nx thin films for
photocatalytic applications. J. Photochem. Photobiol. A Chem. 2006, 177, 68–75. [CrossRef]
56. Lee, A.; Libera, J.A.; Waldman, R.Z.; Ahmed, A.; Avila, J.R.; Elam, J.W.; Darling, S.B. Conformal nitrogen-doped
TiO2 photocatalytic coatings for sunlight-activated membranes. Adv. Sustain. Syst. 2017, 1, 1600041. [CrossRef]
57. Albrbar, A.J.; Djokic, V.; Bjelajac, A.; Kovac, J.; Cirkovic, J.; Mitric, M.; Janackovic, D.; Petrovic, R.
Visible-light active mesoporous, nanocrystalline N,S-doped and co-doped titania photocatalysts synthesized
by non-hydrolytic sol-gel route. Ceram. Int. 2016, 42, 16718–16728. [CrossRef]
58. Rajoriya, S.; Bargole, S.; George, S.; Saharan, V.K.; Gogate, P.R.; Pandit, A.B. Synthesis and characterization
of samarium and nitrogen doped TiO2 photocatalysts for photo-degradation of 4-acetamidophenol in
combination with hydrodynamic and acoustic cavitation. Sep. Purif. Technol. 2019, 209, 254–269. [CrossRef]
59. Low, J.; Yu, J.; Jaroniec, M.; Wageh, S.; Al-Ghamdi, A.A. Heterojunction photocatalysts. Adv. Mater. 2017, 29,
1601694. [CrossRef]
60. Baek, J.H.; Kim, B.J.; Han, G.S.; Hwang, S.W.; Kim, D.R.; Cho, I.S.; Jung, H.S. BiVO4 /WO3 /SnO2
Double-heterojunction photoanode with enhanced charge separation and visible-transparency for bias-free
solar water-splitting with a perovskite solar cell. ACS Appl. Mater. Interfaces 2017, 9, 1479–1487. [CrossRef]
61. Han, H.S.; Han, G.S.; Kim, J.S.; Kim, D.H.; Hong, J.S.; Caliskan, S.; Jung, H.S.; Cho, I.S.; Lee, J.K.
Indium-tin-oxide nanowire array based CdSe/CdS/TiO2 one-dimensional heterojunction photoelectrode for
enhanced solar hydrogen production. ACS Sustain. Chem. Eng. 2016, 4, 1161–1168. [CrossRef]
62. Yu, J.C.; Yu, J.G.; Ho, W.K.; Zhang, L.Z. Preparation of highly photocatalytic active nano-sized TiO2 particles
via ultrasonic irradiation. Chem. Commun. 2001, 1942–1943. [CrossRef]
Catalysts 2019, 9, 122 30 of 32

63. Uddin, M.T.; Nicolas, Y.; Olivier, C.; Toupance, T.; Servant, L.; Muller, M.M.; Kleebe, H.J.; Ziegler, J.;
Jaegermann, W. Nanostructured SnO2 -ZnO heterojunction photocatalysts showing enhanced photocatalytic
activity for the degradation of organic dyes. Inorg. Chem. 2012, 51, 7764–7773. [CrossRef]
64. Shirmardi, A.; Teridi, M.A.M.; Azimi, H.R.; Basirun, W.J.; Jamali-Sheini, F.; Yousefi, R.
Enhanced photocatalytic performance of ZnSe/PANI nanocomposites for degradation of organic and
inorganic pollutants. Appl. Surf. Sci. 2018, 462, 730–738. [CrossRef]
65. Lee, C.H.; Lee, G.H.; van der Zande, A.M.; Chen, W.C.; Li, Y.L.; Han, M.Y.; Cui, X.; Arefe, G.; Nuckolls, C.;
Heinz, T.F.; et al. Atomically thin p-n junctions with van der Waals heterointerfaces. Nat. Nanotechnol. 2014,
9, 676–681. [CrossRef]
66. Kawazoe, H.; Yanagi, H.; Ueda, K.; Hosono, H. Transparent p-type conducting oxides: Design and fabrication
of p-n heterojunctions. MRS Bull. 2000, 25, 28–36. [CrossRef]
67. Lu, M.X.; Shao, C.L.; Wang, K.X.; Lu, N.; Zhang, X.; Zhang, P.; Zhang, M.Y.; Li, X.H.; Liu, Y.C.
p-MoO3 Nanostructures/n-TiO2 nanofiber heterojunctions: Controlled fabrication and enhanced
photocatalytic properties. ACS Appl. Mater. Interfaces 2014, 6, 9004–9012. [CrossRef]
68. Zhang, L.P.; Jaroniec, M. Toward designing semiconductor-semiconductor heterojunctions for photocatalytic
applications. Appl. Surf. Sci. 2018, 430, 2–17. [CrossRef]
69. Wen, X.J.; Niu, C.G.; Zhang, L.; Zeng, G.M. Novel p-n heterojunction BiOI/CeO2 photocatalyst for wider
spectrum visible-light photocatalytic degradation of refractory pollutants. Dalton Trans. 2017, 46, 4982–4993.
[CrossRef]
70. Zhang, Y.; Park, S.J. Formation of hollow MoO3 /SnS2 heterostructured nanotubes for efficient light-driven
hydrogen peroxide production. J. Mater. Chem. A 2018, 6, 20304–20312. [CrossRef]
71. Wei, Z.D.; Zhao, Y.; Fan, F.T.; Li, C. The property of surface heterojunction performed by crystal facets for
photogenerated charge separation. Comp. Mater. Sci. 2018, 153, 28–35. [CrossRef]
72. Yu, J.G.; Low, J.X.; Xiao, W.; Zhou, P.; Jaroniec, M. Enhanced Photocatalytic CO2 -Reduction Activity of
Anatase TiO2 by Coexposed {001} and {101} Facets. J. Am. Chem. Soc. 2014, 136, 8839–8842. [CrossRef]
73. Gao, S.J.; Wang, W.; Ni, Y.R.; Lu, C.H.; Xu, Z.Z. Facet-dependent photocatalytic mechanisms of anatase TiO2 :
A new sight on the self-adjusted surface heterojunction. J. Alloys Compd. 2015, 647, 981–988. [CrossRef]
74. Lu, J.; Wu, J.; Xu, W.X.; Cheng, H.Q.; Qi, X.M.; Li, Q.W.; Zhang, Y.A.; Guan, Y.; Ling, Y.; Zhang, Z.
Room temperature synthesis of tetragonal BiOI photocatalyst with surface heterojunction between (001)
facets and (110) facets. Mater. Lett. 2018, 219, 260–264. [CrossRef]
75. Li, H.J.; Tu, W.G.; Zhou, Y.; Zou, Z.G. Z-scheme photocatalytic systems for promoting photocatalytic
performance: Recent progress and future challenges. Adv. Sci. 2016, 3, 12. [CrossRef]
76. Wu, X.S.; Hu, Y.D.; Wang, Y.; Zhou, Y.S.; Han, Z.H.; Jin, X.L.; Chen, G. In-situ synthesis of Z-scheme
Ag2 CO3 /Ag/AgNCO heterojunction photocatalyst with enhanced stability and photocatalytic activity.
Appl. Surf. Sci. 2019, 464, 108–114. [CrossRef]
77. Lu, X.Y.; Che, W.J.; Hu, X.F.; Wang, Y.; Zhang, A.T.; Deng, F.; Luo, S.L.; Dionysiou, D.D. The facile fabrication
of novel visible-light-driven Z-scheme CuInS2 /Bi2 WO6 heterojunction with intimate interface contact by in
situ hydrothermal growth strategy for extraordinary photocatalytic performance. Chem. Eng. J. 2019, 356,
819–829. [CrossRef]
78. Leary, R.; Westwood, A. Carbonaceous nanomaterials for the enhancement of TiO2 photocatalysis. Carbon
2011, 49, 741–772. [CrossRef]
79. Li, J.; Liu, K.; Xue, J.; Xue, G.; Sheng, X.; Wang, H.; Huo, P.; Yan, Y. CQDS preluded carbon-incorporated 3D
burger-like hybrid ZnO enhanced visible-light-driven photocatalytic activity and mechanism implication.
J. Catal. 2019, 369, 450–461. [CrossRef]
80. Long, B.; Huang, Y.C.; Li, H.B.; Zhao, F.Y.; Rui, Z.B.; Liu, Z.L.; Tong, Y.X.; Ji, H.B. Carbon Dots Sensitized
BiOI with Dominant {001} Facets for superior photocatalytic performance. Ind. Eng. Chem. Res. 2015, 54,
12788–12794. [CrossRef]
81. Zhao, F.F.; Rong, Y.F.; Wan, J.M.; Hu, Z.W.; Peng, Z.Q.; Wang, B. High photocatalytic performance of
carbon quantum dots/TNTs composites for enhanced photogenerated charges separation under visible light.
Catal. Today 2018, 315, 162–170. [CrossRef]
82. Di, J.; Li, S.X.; Zhao, Z.F.; Huang, Y.C.; Jia, Y.; Zheng, H.J. Biomimetic CNT@TiO2 composite with enhanced
photocatalytic properties. Chem. Eng. J. 2015, 281, 60–68. [CrossRef]
Catalysts 2019, 9, 122 31 of 32

83. Miribangul, A.; Ma, X.L.; Zeng, C.; Zou, H.; Wu, Y.H.; Fan, T.P.; Su, Z. Synthesis of TiO2 /CNT Composites
and its photocatalytic activity toward sudan (I) degradation. Photochem. Photobiol. 2016, 92, 523–527.
[CrossRef]
84. Xu, Y.G.; Liu, J.; Xie, M.; Jing, L.Q.; Xu, H.; She, X.J.; Li, H.M.; Xie, J.M. Construction of novel CNT/LaVO4
nanostructures for efficient antibiotic photodegradation. Chem. Eng. J. 2019, 357, 487–497. [CrossRef]
85. Wang, Y.J.; Shi, R.; Lin, J.; Zhu, Y.F. Significant photocatalytic enhancement in methylene blue degradation
of TiO2 photocatalysts via graphene-like carbon in situ hybridization. Appl. Catal. B-Environ. 2010, 100,
179–183. [CrossRef]
86. Mamaghani, A.H.; Haghighat, F.; Lee, C.-S. Hydrothermal/solvothermal synthesis and treatment of TiO2
for photocatalytic degradation of air pollutants: Preparation, characterization, properties, and performance.
Chemosphere 2019, 219, 804–825. [CrossRef]
87. Zhang, H.; Lv, X.J.; Li, Y.M.; Wang, Y.; Li, J.H. P25-Graphene composite as a high performance photocatalyst.
ACS Nano 2010, 4, 380–386. [CrossRef]
88. Isari, A.A.; Payan, A.; Fattahi, M.; Jorfi, S.; Kakavandi, B. Photocatalytic degradation of rhodamine B
and real textile wastewater using Fe-doped TiO2 anchored on reduced graphene oxide (Fe-TiO2 /rGO):
Characterization and feasibility, mechanism and pathway studies. Appl. Surf. Sci. 2018, 462, 549–564.
[CrossRef]
89. Nasr, M.; Eid, C.; Habchi, R.; Miele, P.; Bechelany, M. Recent progress on titanium dioxide nanomaterials for
photocatalytic applications. ChemSusChem 2018, 11, 3023–3047. [CrossRef]
90. Giberman, D. Against zero-dimensional material objects (and other bare particulars). Philos. Stud. 2012, 160,
305–321. [CrossRef]
91. Vaiano, V.; Sacco, O.; Sannino, D.; Ciambelli, P. Nanostructured N-doped TiO2 coated on glass spheres for
the photocatalytic removal of organic dyes under UV or visible light irradiation. Appl. Catal. B-Environ. 2015,
170, 153–161. [CrossRef]
92. Chen, C.C.; Jaihindh, D.; Hu, S.H.; Fu, Y.P. Magnetic recyclable photocatalysts of Ni-Cu-Zn
ferrite@SiO2 @TiO2 @Ag and their photocatalytic activities. J. Photochem. Photobiol. A Chem. 2017, 334,
74–85. [CrossRef]
93. Somiya, S.; Roy, R. Hydrothermal synthesis of fine oxide powders. Bull. Mater. Sci. 2000, 23, 453–460.
[CrossRef]
94. Wu, G.S.; Wang, J.P.; Thomas, D.F.; Chen, A.C. Synthesis of F-doped flower-like TiO2 nanostructures with
high photoelectrochemical activity. Langmuir 2008, 24, 3503–3509. [CrossRef]
95. Jing, L.Q.; Xu, Y.G.; Huang, S.Q.; Xie, M.; He, M.Q.; Xu, H.; Li, H.M.; Zhang, Q. Novel magnetic
CoFe2 O4 /Ag/Ag3 VO4 composites: Highly efficient visible light photocatalytic and antibacterial activity.
Appl. Catal. B-Environ. 2016, 199, 11–22. [CrossRef]
96. Cho, I.S.; Lee, C.H.; Feng, Y.Z.; Logar, M.; Rao, P.M.; Cai, L.L.; Kim, D.R.; Sinclair, R.; Zheng, X.L.
Codoping titanium dioxide nanowires with tungsten and carbon for enhanced photoelectrochemical
performance. Nat. Commun. 2013, 4, 8. [CrossRef]
97. Yang, D.J.; Liu, H.W.; Zheng, Z.F.; Yuan, Y.; Zhao, J.C.; Waclawik, E.R.; Ke, X.B.; Zhu, H.Y. An Efficient
Photocatalyst Structure: TiO2 (B) Nanofibers with a Shell of Anatase Nanocrystals. J. Am. Chem. Soc. 2009,
131, 17885–17893. [CrossRef]
98. Zhang, Y.; Park, S.J. Bimetallic AuPd alloy nanoparticles deposited on MoO3 nanowires for enhanced
visible-light driven trichloroethylene degradation. J. Catal. 2018, 361, 238–247. [CrossRef]
99. Li, D.; Xia, Y.N. Electrospinning of nanofibers: Reinventing the wheel? Adv. Mater. 2004, 16, 1151–1170.
[CrossRef]
100. Greiner, A.; Wendorff, J.H. Electrospinning: A fascinating method for the preparation of ultrathin fibres.
Angew. Chem. Int. Edit. 2007, 46, 5670–5703. [CrossRef]
101. Reneker, D.H.; Chun, I. Nanometre diameter fibres of polymer, produced by electrospinning. Nanotechnology
1996, 7, 216–223. [CrossRef]
102. Wu, X.H.; Si, Y.; Yu, J.Y.; Ding, B. Titania-based electrospun nanofibrous materials: A new model for organic
pollutants degradation. MRS Commun. 2018, 8, 765–781. [CrossRef]
103. Agarwal, S.; Greiner, A.; Wendorff, J.H. Functional materials by electrospinning of polymers. Prog. Polym. Sci.
2013, 38, 963–991. [CrossRef]
Catalysts 2019, 9, 122 32 of 32

104. Zhang, R.Z.; Wang, X.Q.; Song, J.; Si, Y.; Zhuang, X.M.; Yu, J.Y.; Ding, B. In situ synthesis of flexible
hierarchical TiO2 nanofibrous membranes with enhanced photocatalytic activity. J. Mater. Chem. A 2015, 3,
22136–22144. [CrossRef]
105. Panthi, G.; Park, M.; Kim, H.Y.; Park, S.J. Electrospun Ag-CoF doped PU nanofibers: Effective visible light
catalyst for photodegradation of organic dyes. Macromol. Res. 2014, 22, 895–900. [CrossRef]
106. Panthi, G.; Park, M.; Park, S.J.; Kim, H.Y. PAN Electrospun nanofibers reinforced with Ag2 CO3 nanoparticles:
Highly efficient visible light photocatalyst for photodegradation of organic contaminants in waste water.
Macromol. Res. 2015, 23, 149–155. [CrossRef]
107. Saud, P.S.; Pant, B.; Park, M.; Chae, S.H.; Park, S.J.; El-Newehy, M.; Al-Deyab, S.S.; Kim, H.Y. Preparation and
photocatalytic activity of fly ash incorporated TiO2 nanofibers for effective removal of organic pollutants.
Ceram. Int. 2015, 41, 1771–1777. [CrossRef]
108. Seong, D.B.; Son, Y.R.; Park, S.J. A study of reduced graphene oxide/leaf-shaped TiO2 nanofibers for
enhanced photocatalytic performance via electrospinning. J. Solid State Chem. 2018, 266, 196–204. [CrossRef]
109. Zhang, Y.F.; Park, M.; Kim, H.Y.; Ding, B.; Park, S.J. In-situ synthesis of nanofibers with various ratios of
BiOClx /BiOBry /BiOIz for effective trichloroethylene photocatalytic degradation. Appl. Surf. Sci. 2016, 384,
192–199. [CrossRef]
110. Zhang, D.Q.; Li, G.S.; Li, H.X.; Lu, Y.F. The development of better photocatalysts through composition- and
structure-engineering. Chem. Asian J. 2013, 8, 26–40. [CrossRef]
111. Chen, F.T.; Fang, P.F.; Gao, Y.P.; Liu, Z.; Liu, Y.; Dai, Y.Q. Effective removal of high-chroma crystal violet
over TiO2 -based nanosheet by adsorption-photocatalytic degradation. Chem. Eng. J. 2012, 204, 107–113.
[CrossRef]
112. Ma, X.D.; Jiang, D.L.; Xiao, P.; Jin, Y.; Meng, S.C.; Chen, M. 2D/2D heterojunctions of WO3
nanosheet/K+ Ca2 Nb3 O10 - ultrathin nanosheet with improved charge separation efficiency for significantly
boosting photocatalysis. Catal. Sci. Technol. 2017, 7, 3481–3491. [CrossRef]
113. Wang, C.Y.; Zhang, X.; Song, X.N.; Wang, W.K.; Yu, H.Q. Novel Bi12 O15 Cl6 photocatalyst for the degradation
of bisphenol a under visible-light irradiation. ACS Appl. Mater. Interfaces 2016, 8, 5320–5326. [CrossRef]
114. Zhang, Y.F.; Park, S.J. Fabrication and characterization of flower-like BiOI/Pt heterostructure with enhanced
photocatalytic activity under visible light irradiation. J. Solid State Chem. 2017, 253, 421–429. [CrossRef]
115. Jiang, W.J.; Zhu, Y.F.; Zhu, G.X.; Zhang, Z.J.; Chen, X.J.; Yao, W.Q. Three-dimensional photocatalysts with a
network structure. J. Mater. Chem. A 2017, 5, 5661–5679. [CrossRef]
116. Wan, W.C.; Zhang, R.Y.; Ma, M.Z.; Zhou, Y. Monolithic aerogel photocatalysts: A review. J. Mater. Chem. A
2018, 6, 754–775. [CrossRef]
117. Pierre, A.C.; Pajonk, G.M. Chemistry of aerogels and their applications. Chem. Rev. 2002, 102, 4243–4265.
[CrossRef]
118. Dagan, G.; Tomkiewicz, M. Titanium dioxide aerogels for photocatalytic decontamination of aquatic
environments. J. Phys. Chem. 1993, 97, 12651–12655. [CrossRef]
119. Heiligtag, F.J.; Rossell, M.D.; Suess, M.J.; Niederberger, M. Template-free co-assembly of preformed Au and
TiO2 nanoparticles into multicomponent 3D aerogels. J. Mater. Chem. 2011, 21, 16893–16899. [CrossRef]
120. Kailasam, K.; Epping, J.D.; Thomas, A.; Losse, S.; Junge, H. Mesoporous carbon nitride-silica
composites by a combined sol-gel/thermal condensation approach and their application as photocatalysts.
Energy Environ. Sci. 2011, 4, 4668–4674. [CrossRef]
121. Li, Z.D.; Wang, H.L.; Wei, X.N.; Liu, X.Y.; Yang, Y.F.; Jiang, W.F. Preparation and photocatalytic performance
of magnetic Fe3 O4 @TiO2 core-shell microspheres supported by silica aerogels from industrial fly ash.
J. Alloys Compd. 2016, 659, 240–247. [CrossRef]
122. Jiang, W.J.; Liu, Y.F.; Wang, J.; Zhang, M.; Luo, W.J.; Zhu, Y.F. Separation-free polyaniline/TiO2 3D hydrogel
with high photocatalytic activity. Adv. Mater. Interfaces 2016, 3, 1500502. [CrossRef]

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