Chemistry–Sustainability–Energy–Materials

Accepted Article

Title: Desulfurization through photocatalytic oxidation: a critical review

Authors: Xiaoyu Zhou, Tianyi Wang, Hang Liu, Xiaochun Gao,

Chengyin Wang, and Guoxiu Wang

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To be cited as: ChemSusChem 10.1002/cssc.202002144

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01/2020
ChemSusChem 10.1002/cssc.202002144

REVIEW
Desulfurization through photocatalytic oxidation: a
critical review

Xiaoyu Zhou[a], Tianyi Wang[b], Hang Liu[a], Xiaochun Gao*[b], Chengyin Wang*[a],
Guoxiu Wang*[b]

Accepted Manuscript

This article is protected by copyright. All rights reserved.

ChemSusChem
REVIEW
Abstract: Fuel oil, the most important strategic resource, has been
widely used in industrial applications. However, the sulfur-containing
compounds in fuel oil also present human with huge environmental
issues and health concerns due to the hazardous combustion waste.
To address this problem, the low vulcanization of fuel production
technology has been intensively explored. Compared with traditional
hydrodesulfurization technology, the new-emerged photocatalytic
desulfurization has the advantages of milder operating conditions,
lower energy consumption, and higher efficiency, holding great
prospect to achieve deep desulfurization. Though great efforts have
been made, the desulfurization catalysts still suffer from inferior light
absorption, fast recombination of photocarriers, and poor structure
modification. This review summarizes recent development of
photocatalytic desulfurization, including the desulfurization principle,
current desulfurization challenges, and corresponding solutions.
Particularly, the roles of defect engineering, hybrid coupling, and
structure modifications to the enhancement of photocatalytic
performance are emphasized, respectively. In addition, the
photocatalytic desulfurization mechanism is also introduced with the
·OH and ·O2- radicals as main active species. At last, some
perspectives on the photocatalytic desulfurization are provided which
can further optimize the desulfurization efficiency and guide future
photocatalyst design.
1. Introduction
The steadily growth of the global population, and booming of
economy activities have presented human with an unprecedented
demand for energy supplies, particularly the naturally stored and
low-cost fuel oil.[1] However, rare fuel oil contains sulfur
compounds, such as sulfur ether, mercaptan, thiophene,
benzothiophene, and dibenzothiophene, rising industrial and
environmental challenges for human society. Specifically, sulfur-
containing fuel oil would damage the automobile engines and
deactivate the platinum catalyst used in exhaust gas processors
and electrodes of fuel cells.[2] It is also worth mentioning that the
random release of fuel oil combustion waste, sulfur dioxide (SO 2),
has caused severe acid rain that corrodes buildings and, crops,
changes the pH of soils and rivers, and adversely affects aquatic
life. More worse，excessive exposure to SO2 waste may lead to
respiratory diseases such as asthma and neurological diseases. [4]
Considering the above mentioned negative influences of sulfur-
containing compounds, countries all over the world have
[a] X. Zhou, H. Liu, Prof. C. Wang,
The College of Chemistry and Chemical Engineering
Yangzhou University
180 Si-Wang-Ting Road, Yangzhou, 225002, P. R. China
E-mail: wangcy@yzu.edu.cn
[b] T. Wang, X. Gao, Prof. G. Wang
School of Mathematical and Physical Sciences
University of Technology Sydney
City Campus, Broadway, Sydney, NSW 2007, Australia
E-mail: Xiaochun.Gao@uts.edu.au
Guoxiu.Wang@uts.edu.au
2
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002144
implemented strict standards of the sulfur level in fuel oil via
optimizing fuel oil refining technology and exploring new
desulfurization strategy to degrade the sulfur-containing
hazards.[5]
As regard to the latter desulfurization approach, it can be
classified into physical desulfurization, biological desulfurization,
and chemical desulfurization, respectively (Figure 1a). The former
two methods can be performed under gentle conditions, such as
relative low temperature and ambient pressure. For instance,
adsorption desulfurization (ADS), a promising physical
Accepted Manuscript
technology using zeolite,[6,7] metal organic skeleton,[8] metal and
metal oxide as adsorbents[9,10] to achieve deep desulfurization
(sulfur content < 1 ppm), has advantages of simple manipulation,
economic and environmental benignity. [11] Although ADS can
obtain ultra-high desulfurization efficiency, its adsorption capacity
and adsorbent regeneration are rather limited.[12] Other physical
extraction desulfurization (EDS) technology has also been widely
studied,[13,14] but it is confronted with volatile extraction solvents,
complex extraction agent recovery process, and high recovery
cost.[15] Biological desulfurization (BDS), an emerging fuel
desulfurization method, has attracted intensive research interest
worldwide. However, due to its requirement of complex reaction
equipment, high desulfurization cost, and low efficiency of
biocatalyst, its development is extremely limited. [16] The chemical
oxidation desulfurization (ODS) technology which oxidizes
organic sulfide to sulfoxide or other sulfones, exhibiting the merits
of high desulfurization efficiency and robust catalyst stability. [17-19]
But there are also problems such as high cost, catalyst loss, and
secondary pollution during the desulphurization process.
Therefore, ODS technology has not been applied industrially. So
far, sulfur compounds such as mercaptan and thioether in fuel oil
can be easily removed through the traditional
hydrodesulfurization (HDS) technology. To further reduce the
sulfur and achieve deep desulfurization, harsh operation
conditions for HDS are required, including reacting with hydrogen
at high temperatures and pressures, and using expensive
catalysts.[20] Although it can satisfy the requirements of producing
low-sulfur oil, it also releases toxic hydrogen sulfide gas and
reduce octane number in fuel oil.[21] All these issues (high energy
consumption, high cost, and high by-product harmfulness) lead to
high cost of deep desulfurization.[12] In addition, thiophene and
other polycyclic aromatic hydrocarbons are difficult to be removed
by HDS method due to the existence of steric hindrance and
electronic effect structure. Therefore, researchers need to
develop more efficient desulfurization technologies which can not
only achieve deep desulfurization but also lower the cost and
energy consumption to a rational level.
Recently, photocatalytic oxidation desulfurization (PODS),
referring to the reaction using photocatalyst to generate highly
active radicals to reduce/oxidize C-S-C bond of sulfur-containing
pollutants,[22] has boosted a surge of research interest due to its
economic, green, and high efficient merits. When the irradiation
energy is higher than photocatalyst bandgap, the electrons in the
valence band (VB) are excited and jumped to the conduction band
(CB), leaving the VB positive charged with holes while the CB
negative charged with electrons. At the same time, the
discontinuous bands of semiconductor can allow the
photogenerated electrons and holes with a certain life span to
take part in redox reactions. Specifically, O2 would react with
ChemSusChem
REVIEW
photogenerated electrons to form superoxide radicals (·O2-),
which further combine with electrons to form hydrogen peroxide,
and then hydroxyl radicals (·OH). The holes in the VB would bind
to the water molecules on photocatalyst surface and also produce
·OH radicals with strong oxidative ability.[23,24] These free radicals
have adequate redox ability to oxidize the sulfur-containing
compounds into less harmful or non-hazardous substances. It is
worth to mention that the number of publications and citations on
PODS have witnessed a seven-fold and increase in the past
decade, which shows the importance and rapid development of
this field (Figure 1b and 1c). Considering the limited number of
photocatalytic desulfurization reviews, we believe that it is urgent
and necessary to summarize recent development on PODS.
In this review, we first compare the traditional desulfurization
methods and novel photocatalytic desulfurization as shown in
Figure 1. Special attention is paid to current challenges of
photocatalytic desulfurization, including the insufficient light
absorption ability, fast recombination of photogenerated
electron/hole pairs, and poor structure optimization. We also
present the corresponding solutions to overcome above
mentioned issues in terms of defect engineering, hybrid coupling,
as well as morphology modifications. In addition, the detection of
active species in PODS process and oxidization mechanism are
also discussed. At last, we propose some PODS perspectives and
suggest future development directions. We hope this review
sheds light on the how to construct more efficient PODS
photocatalysts.
2. Challenges of PODS
Since the landmark discovery of Honda-Fujishima effect in early
1970’s, photocatalytic technology has been the focus of the
scientific community, particularly in the research fields of
pollutants degradation, air purification, hydrogen production,
carbon dioxide reduction, and photocatalytic sterilization. [25] It is
until 2002 that TiO2 was reported to oxidize the sulfur-containing
dibenzothiophene (DBT) in acetonitrile, [26] with its concentration
decreasing by 40 % under ultraviolet (UV) illumination for 10 h.
The PODS of TiO2 works only the irradiation excitation energy is
stronger than its bandgap of ~3.2 eV, allowing the electrons in the
VB and holes in the VB ready to generate ultra-active free radicals
(·O2-, ·OH).[27] These free radicals have adequate redox ability to
oxidize the sulfur-containing compounds into less harmful or non-
hazardous substances.[28,29] Since then, the research progress on
PODS has witnessed a significant improvement with a various
range of photocatalysts from metallic inorganic substances to
metal-free organic polymer such as CeO2,[30] Fe2O3,[31] MoO3,[32]
Cu2O,[33] TiO2, [34] SnO2,[35] WO3 [36] and g-C3N4.[37] However, there
are still research obstacles to be addressed, including the
insufficient visible light absorption, fast recombination of
photogenerated electron/hole pairs, and severe aggregations of
photocatalysts.
2.1 Insufficient visible light absorption
The premise of photocatalytic reaction is enabling the
semiconductor to absorb the photon energy when the excited
energy is larger than its bandgap. Taking the most widely
investigated anatase TiO2 as an example, it can only respond to
UV light with wavelength shorter than 387 nm due to its large band
3
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002144
gap of ~ 3.2 eV. Namely, its valid light absorption range only
occupies 5 % of the whole solar spectrum. Thus, anatase TiO2 is
very limited on practical PODS applications. Song et al. reported
that its photocatalytic desulfurization efficiency of benzothiophene
(BT) is only 23.0 % [38] which is far more unsatisfied from the deep
desulfurization. This inferior light absorption phenomenon is also
found on other PODS photocatalysts such as BiVO 4, g-C3N4,
SnO2, and WO3.[39,35,36,40] As is known to all that, the limited light
response to long
Xiaoyu Zhou is now a master student in the
Accepted Manuscript
College of Chemistry and Chemical
Engineering at Yangzhou University (China),
under the supervision of Prof. Chengyin Wang.
His research mainly focuses on photocatalysis
and photocatalytic oxidation desulfurization.
Xiaochun Gao received her Ph. D. degree
from University of Technology Sydney (UTS),
Austrilia in 2020 under Prof. Guoxiu Wang's
supervision. She is currently a research
associate in Prof. Guoxiu Wang’s group at
UTS. Her research focuses on the design of
((Author Portrait))
cathodic materials for metal-sulfur batteries
and graphitic carbon nitrides for photocatalytic
water splitting.
Chengyin Wang received his Ph.D. degree in
physical chemistry from Yangzhou University ((Athor Portrait))
in 2007. He is currently a professor in the
College of Chemistry and Chemical
Engineering at Yangzhou University. His
research interests focus on electrochemistry,
analytical chemistry for materials, functional
materials in energy storage and conversion,
and photocatalysis.
((Author Portrait))
Guoxiu Wang is the Director of the Centre for
Clean Energy Technology and a Distinguished
Professor at University of Technology Sydney
(UTS), Australia. He is an expert in materials
chemistry, electrochemistry, energy storage
and conversion, and battery technologies. His
research interests include lithium-ion batteries,
lithium-air batteries, sodium-ion batteries,
lithium-sulfur batteries, supercapacitors,
hydrogen storage materials, fuel-cells,
graphene, MXene and other 2D functional materials for energy storage and
conversion. Professor Wang has published more than 520 refereed journal
((Author Portrait))
papers with an h-index of 110. His publications have attracted over 40,000
citations.
ChemSusChem
REVIEW
Figure 1. (a) General features of ADS/EDS, BDS, HDS/ODS, and PODS; Number of (b) publications and (c) citations of PODS from 2009-2019 (data from
Web of Science).
wavelength light would result in less excited photocarriers, and
subsequently worse photocatalytic performance.[41,42]
2.2. Fast photocarrier recombination rate
Without rational modifications on the photocatalyst surface
chemistry or optimization on photocatalyst components, a large
portion of excited electrons and holes would recombine again in
the bulk or on the surface of photocatalysts in less than 10 -9 s,
simultaneously releasing the photonic energy via fluorescence or
heat.[43] This definitely leads to a waste of photonic energy and
lower the PODS degradation efficiency. Kang et al. reported that
pure WO3 showed the very high photoluminescence intensity,
indicating the severe recombination of photocarriers. As a result,
its PODS degradation of DBT was only 24 %.[36] Similar
phenomenon is observed with bulk g-C3N4 materials with its
PODS removal of BT is barely 40 %.[44] Therefore, to transfer
more photonic energy to chemical energy, the transport efficiency
of photocarriers must be improved.[45]
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10.1002/cssc.202002144
Accepted Manuscript
2.3. Structure modification
It is widely acknowledged that structure has a significantly
influence on property, and this is exactly true in photocatalytic
system. Under light irradiation, more exposed active sites indicate
more sulfur-containing molecules can be absorbed on the
photocatalyst surface, and thus more probabilities to be
reduced/oxidized compared with those with limited surface area.
Besides, a long irradiation time or intensive reaction activity can
cause the aggregations of photocatalytic nanoparticles, [46] thus
leading to a low catalytic stability and restricting their further
applications. Vu et al. prepared composite of carbon nanotubes
(MWNTs) and TiO2.[47] The surface area of TiO2 and MWNTs/TiO2
composites are 8.44 m2/g and 17.32 m2/g, respectively. The
results show that the DBT conversion of MWNTs/TiO 2 composite
is 80 %, and that of pure TiO2 is only 56 %. The main reason is
that pure TiO2 is easy to agglomerate and its specific surface area
is small, resulting in less reactive sites, which directly limits the
performance of PODS.
ChemSusChem
REVIEW
Figure 2. SEM images of (a) P25, and (b) N-TiO2; (c) XRD patterns; (d) UV-visible diffuse reflectance spectra; (e) Plot of the Kubelka-Munk function against the photon
energy and (f) Time course of DBT removal under visible light irradiation of P25 and N-TiO2 Ref. [48] with permission of Elsevier Ltd.
3. SOLUTIONS TO PODS
To improve the desulfurization performance of photocatalysts,
researchers have proposed many strategies, including (1) defect
engineering by non-metal/metal doping;[48,34,49] (2) coupling with
other semiconductors materials;[50] and (3) optimizing
photocatalyst structure with advanced nanostructures and
introducing substrate material with high specific surface area. [47,51]
3.1. Doping
Doping, including the non-metal doping and mental doping, has
been demonstrated to be one of most important defect
engineering strategy to boost the photocatalytic activity.[52,53]
According to previous reports, doping that introducing impurities
into the semiconductor can effectively tune its electronic structure
with changed CB and VB positions with smaller bandgap,
enhanced redox activity, or faster electron mobility. [54,55] In some
cases, additional electronic states between CB and VB can be
induced, lowering the excited energy and suppressing the
recombination of photogenerated electrons with holes.[56] For
example, some dopants (C, N, P) can narrow the bandgap of TiO2
and result in a hybrid 2p energy level between the CB and the VB,
which significantly enhanced the visible light absorption and
improved photocarrier separation efficiency. [57-60] Li et al.
prepared novel visible light catalyst materials (C/g-C3N4) by
hydrothermally treating a mixture of g-C3N4 and glucose
solution.[61] Compared with pure g-C3N4, C/g-C3N4 exhibits
enhanced visible light absorption, adsorption capacity and
enhanced photocurrent response. O-doped g-C3N4 nanosheets
were prepared by Sun et al.[62] Compared with conventional g-
C3N4, O-doped g-C3N4 nanosheets exhibit greatly improved
photocatalytic activity under visible light, with a 10.7 times
increase in performance at 420 nm. Liu et al. prepared s-doped
g-C3N4 for the first time.[63] The results showed that the S-doped
5
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002144
Accepted Manuscript
g-C3N4 obtained had good photocatalytic activity at > 300 nm and
420 nm, which was 7.2 and 8.0 times higher than the original g-
C3N4, respectively. Zhu et al. synthesized P-doped g-C3N4
mesoporous nanostructured materials by simple co-condensation
of melamine and (hydroxy ethylidene) phosphonic acid. [64] The
results show that P can form chemical bonds with carbon and
nitrogen in the g-C3N4 framework. In addition, the lone pair of
electrons can be delocalized to the p-doped g-C3N4, which acts
as an active site to improve the conductivity and thus the electron
transfer capacity. In addition to non-metal doping, the absorption
ability and electronic conductivity of semiconductors can be
improved by metal doping, rendering an enhancement of
photocarrier migration, diffusion, and separation. [65,66] Therefore,
after doping, the light absorption and photocarrier transfer
process for PODS is believed to be significantly optimized.
3.1.1 Non-metal doping
Non-metal elements such as C, O, N, P, and S can be doped into
the matrix of photocatalysts, which would narrow their bandgap,
and thus effectively extend the light absorption from UV to
visible/infrared region.[67] Zarrabi and co-works synthesized
C/TiO2@(Mobil Composite Matter-41)MCM-41 (CTM-41)
photocatalytic materials.[51] The UV-Visible absorption spectrum
(UV-Vis) indicated the CTM-41 samples exhibited absorption in
the visible range 400-800 nm. Further analysis of UV-Vis
absorption spectrum showed that CTM-41 (Si/Ti = 5) has a higher
visible light absorption capacity from 410 to 600 nm compared to
CTM-41 (Si/Ti = 50). The CHN elemental analysis of the catalysts,
the visible light absorption increases with increasing carbon
content. These illustrate that C-doped TiO2@MCM-41 materials
can improve the absorption in the visible region. The degradation
of DBT under visible light irradiation showed that the
photocatalytic conversion of DBT was as high as 95.6 %. N-doped
CeO2-TiO2 nanomaterials were synthesized using biological
templates by Lu et al.[68] The successful doping of N improved the
visible light absorption efficiency of CeO 2-TiO2 photocatalytic
ChemSusChem 10.1002/cssc.202002144

REVIEW

Accepted Manuscript
Figure 3. The SEM image of a) 0.8 wt% Nd-doped BiVO4; b) Photocatalytic desulfurization of TH by (a') blank, (b') BiVO4, (c') 0.2 wt% Nd-doped BiVO4, (d')
0.6 wt% Nd-doped BiVO4, (e') 0.8 wt% Nd-doped BiVO4 and (f') 1.0 wt% Nd-doped BiVO4); c) Cycling runs of phenol degradation by 0.8 wt % Nd-doped BiVO4
Ref.[52] Copyright 2015, Elsevier Ltd. d) SEM image of Na(x)-CN; e) UV-vis diffuse reflectance spectra; f) (αhν)1/2 vs. hν of g-C3N4 and Na(x)-CN; g) Transient
photocurrent response of g-C3N4 and Na(x)-CN under visible light irradiation; h) PODS of TH in model fuel over g-C3N4 and Na(0.3)-CN; i) Recyclability of
photocatalysts Ref.[53] Copyright 2019, Elsevier Ltd.

materials. The UV-Vis diffuse reflectance spectra (DRS) analysis
of the photocatalyst showed that all the samples were responsive
in the visible 400 nm to 600 nm region. Moreover, the CeO2-TiO2
composites have a broader absorption under visible light
compared to pure TiO2 and CeO2. It shows that N doping leads to
a decrease in the band gap of CeO2-TiO2 composites. The results
of the photocatalytic desulfurization showed that the removal of
DBT reached 93.7 % with 3 h of visible light irradiation. Kalantari
et al. synthesized N-doped TiO2 (N-TiO2) using Degussa P25
(mixture of TiO2 nanoparticles with 85 % rutile and 15% anatase)
and urea as precursors for the removal of DBT. [48] The field
emission scanning electron microscope (FE-SEM) images
indicate that both N-TiO2 and P25 show a spherical structure with
agglomerates (Figure 2a and 2b). It can be observed that both
pure TiO2 and doped TiO2 show spherical morphology with a size
between 30-50 nm, and their particle size is between 30-50 nm.
The FE-SEM and XRD results (Figure 2c) show that N-doping has
no obvious effect on the morphology and crystalline phase of TiO 2
and undoped TiO2 nanoparticles. In addition, according to
(Fourier transform infrared) FT-IR spectra measurement, there
are more surface hydroxyl ground in the N-doped TiO2, which
might further give an enhanced light absorption to visible region
with more photogenerated electrons and holes. This is confirmed
by the UV-Vis diffusion spectra which P25 exhibits a shorter
absorption edge of 395 nm than N-TiO2 of 460 nm (Figure 2d),
with the bandgap decreasing from 3.10 eV to 2.75 eV (Figure 2e).
As a result, the photocatalytic conversion of DBT for N-TiO2 is
around 40.3 % after 4 h under visible irradiation, which is 4.7 times
higher than that of P25 (Figure 2f).
3.1.2 Metal doping
Bismuth vanadate (BiVO4), a promising visible-light-driven
photocatalyst material, has attracted extensive research interest
due to its ultra-high stability.[69] However, BiVO4 exhibits poor light
adsorption ability and severe recombination rate of photocarriers,
resulting in low photocatalytic efficiency.[2] Gao et al. prepared a
series of Ag doped BiVO4 (Ag-BiVO4) via a pH-adjusted
hydrothermal method. They claimed that the hybrid materials
exhibit high crystalline degree and smooth surface when the pH
is adjusted to 7.[39] Compared to pure BiVO4, Ag-BiVO4 shows a
longer visible light absorption edge up to 540 nm. The good
dispersity of Ag particles on the surface of BiVO 4 also assists to
inhibit the recombination of photogenerated electrons and holes

6
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ChemSusChem
REVIEW
Table 1. Summary of the results for the doping in PODS.
Photocatalyst Light source Substance concentration of simulated oil
N-TiO2 55 W Xenon lamp DBT=400 ppm
Ag-BiVO4 400 W metal halide lamp TH=500 ppm
Nd-BiVO4 400 W metal halide lamp TH=500 ppm
mainly due to the enhanced electronic conductivity. The PODS
degradation of thiophene (TH) is up to 95 %. What’s more, Gao
et al. prepared Nd doped BiVO4 composite with a two-dimensional
(2D) long rod-shaped structures which is confirmed by the SEM
image (Figure 3a).[70] It can be found that 1D long rod-shaped
particles appear to have high crystallinity and display mainly thin
particles with borders of several hundred nanometers. The results
of photocatalytic oxidation desulfurization showed that after 210
min of visible light irradiation, the photocatalytic desulfurization
rate of TH by Nd-BiVO4 could reach 90.8 %, which is 2 times
higher than that of bare BiVO4 (Figure 3b). As shown in Figure 3c,
Nd doped BiVO4 exhibits relatively stable performance after five
cycles of phenol degradation, and the photocatalyst does not
show obvious activity loss. This improvement of photocatalytic
performance might mainly due to Nd dopants, which increases
the electronic conductivity of bulk material and thus facilitates the
charge transfer process, inhibiting the recombination of
photogenerated electron and hole composites.
Zhang and co-workers synthesized Na doped g-C3N4 ( Na(x)-
CN) photocatalyst for desulfurization of TH, where x presents the
mass ratio of NaCl/melamine precursor. [71] The Na(x)-CN
nanosheets are helpful for the construction of an efficient fuel oil
PODS system due to its 2D nanostructure (Figure 3d). As is
shown in Figure 3e that the Na(x)-CN samples display red shift at
the absorption edges compared with pure g-C3N4, and this
tendency becomes more obvious with the increasing Na doping
concentration. This observation indicates an enhancement in the
visible light adsorption via Na doping. In Figure 3f, the band gaps
of g-C3N4, Na(0.3)-CN, Na(0.5)-CN and Na(1.0)-CN are 2.70,
2.44, 2.15 and 2.02 eV, respectively. The difference between
band gaps of the samples possibly originates from the lattice
defects and the changes in condensation degree in g-C3N4 with
the Na doping. Figure 3g shows the transient photocurrent
response of g-C3N4 and Na(x)-CN samples under visible light
irradiation. Each Na(x)-CN sample exhibits higher photocurrent
than pure g-C3N4 under irradiation, which indicates that Na doping
can improve the interface charge transfer ability of g-C3N4. Figure
3h shows that Na (0.3)-CN reaches the highest TH conversion
efficiency of 73 % when compared with pure g-C3N4 and other
counterparts, indicating the introduction of Na species is
beneficial to the improvement of photocatalytic performance. As
shown in Figure 3i, the stability of Na doped g-C3N4 material is
studied. From the research results, we can see that the
photocatalyst can be reused for 4 times without deactivation,
indicating that the catalyst has good recyclability and stability. A
7
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002144
Photocatalytic Year of publication Ref.
performance
40.3 % in 240 min 2016 [48]
95 % in 210 min 2013 [39]
90.8 % in 210 min 2015 [70]
Accepted Manuscript
summary of the doping on photocatalytic desulfurization PODS
materials is shown on Table 1.
3.2. Hybrid coupling
The photocarrier separation efficiency can also be improved by
constructing a hybrid structure. When a semiconductor with
smaller bandgap is introduced to a wide bandgap semiconductor,
the light absorption range can be extended to longer wavelength.
In the hybrid structure, due to the difference of energy band of the
semiconductors, the photogenerated carriers will transfer from
higher energy level to lower energy level, [65] which effectively
inhibits the photogenerated electron and hole recombination. This
hybrid coupling strategy might also benefit the PODS
efficiency.[72]
As is known to all that g-C3N4 has a bandgap of 2.7 eV, which
can generate electrons and holes through the excitation of visible
light, and realize the following PODS process. However, the bulk
g-C3N4 shows inferior PODS activity mainly due to its fast
recombination of photogenerated electron/hole pairs.
Recently, g-C3N4 and other metal oxide composites are used for
oxidation desulfurization, including TiO 2/g-C3N4,[50] MoO2/g-
C3N4,[73] g-C3N4/SnO2,[74] and WO3/g-C3N4 nanocomposites.[75]
Wang et al. presented a two-step method to synthesize TiO2/g-
C3N4 with TiO2 nanoparticles successfully deposited on the
surface of g-C3N4 (Figure 4a).[50] The XRD patterns of the samples
with different proportions of TiO2 were given in Figure 4b. It can
be seen that there is no obvious characteristic peak of TiO 2,
indicating that the synthesized TiO2 is amorphous. With the
increasing content of TiO2, the diffraction peak at 13.0°decreases
mainly due to the less g-C3N4 content in the composites.
Compared with bare TiO2, the DBT degradation efficiency of
TiO2/g-C3N4 composite is greatly improved from 79.1 % to 98.9 %,
which indicates that the TiO2/g-C3N4 heterojunction structure has
great help to improve the performance of PODS. It can be seen
from Figure 4c that the desulfurization rate of DBT almost
maintain at similar level after several cycles. Li and co-workers
prepared MXene (Ti3C2) modified g-C3N4 catalysts for PODS.[44]
The g-C3N4 nanosheets were successfully inserted by Ti 3C2,
forming a heterogeneous structure with enhanced interface effect.
Due to the intercalation of Ti3C2 nanosheets, photogenerated
electrons are transferred from g-C3N4 to Ti3C2, which significantly
improving the separation efficiency of photocarriers. The catalytic
system is carried out under normal conditions without additional
oxidant such as H2O2 nor O2. As a result, the g-C3N4/Ti3C2 shows
ChemSusChem 10.1002/cssc.202002144

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Accepted Manuscript
Figure 4. (a) SEM image of the 40 %-TiO2/g-C3N4 catalysts and (b) XRD patterns of the catalysts ((a') pure g-C3N4; (b') 10 % TiO2/g-C3N4; (c') 20 % TiO2/g-
C3N4; (d') 30 % TiO2/g-C3N4; (e') 40 % TiO2/g-C3N4; (f') 50 % TiO2/g-C3N4; (g') pure TiO2). (c) Investigation of recycling of catalyst Ref. [50] with permission of
Elsevier Ltd. (d) Schematic illustration of the fabrication process for CeO2/TiO2 nanotube arrays; (e) SEM image of CeO2/TiO2 nanoarrays; (f) Comparison of
photocatalytic desulfurization activity for CeO2, TiO2 nanoarrays, and CeO2/TiO2 nanoarrays Ref. [76] with permission of Elsevier Ltd. (g) SEM image of the
as-synthesized Cu2O-CeO2 nanocomposite; (h) UV-Vis diffuse reflectance spectra of CeO2 nanoparticles and Cu2O-CeO2; (i) Repeatability of the as-
synthesized Cu2O-CeO2 nanocomposite Ref. [77] with permission of Elsevier Ltd.

an ultra-high TH removal efficiency of 73.57 %. It is worth
mentioning that this composite can effectively activate and utilize
O2 in the air instead of requiring other oxidant, which is a very
valuable research direction of photocatalytic desulfurization.
To further improve the photocatalytic desulfurization
performance of TiO2, amorphous TiO2 nanoparticles were
prepared by a simple sol–gel method and subsequent
incorporation with copper (5-20 wt%) via an electrochemical
method in the presence of a supporting electrolyte,
tetraethylammonium perchlorate (TEAP), to synthesize CuO/TiO2
catalysts.[34] The results showed that Ti3+ surface defects, oxygen
vacancies and CuO acted as the trapping sites for electrons,
preventing the recombination of electrons and holes and
subsequently improving the oxidation ability of CuO/TiO2. The
presence of small bandgap CuO also makes the nanocomposite
responsive to visible light. Inspired by this, Hitam and
colleagues prepared CuO/TiO2-C photocatalysts where C
indicates that C defects were introduced into TiO 2.[78] The coupling
of CuO and introduction of C defects into TiO2 narrow the
bandgap of photocatalyst, enhancing the visible light absorption
from 420 nm to 450 nm. The formation of a large number of Ti-O-
C and O-Ti-C bonds, high specific surface area, and large pore
size not only increase the number of active centers of the
photocatalyst, but also provide a good surface contact, which is
beneficial to the improvement of DBT oxidation desulfurization.
Another TiO2-SiO2 hybrid photocatalyst was also synthesized by
a hydrothermal method.[79] The nanocomposite also shows a
ultra-high DBT desulfurization efficiency of 98.4 % in fuel oil after
5 hours.
Cerium oxide (CeO2), a rare earth metal oxide with very low
price, is a promising photocatalytic material because of its special
electron orbital structure, optical properties, and redox activity.[80]
Compared bare TiO2, CeO2/TiO2 nanocomposite can accelerate
the photoelectron transfer, boost more electron and hole pairs,
and improve the photocatalytic performance.[81] Lu and
colleagues reported a CeO2/TiO2 nanoarrays which was
synthesized by an anodic oxidation and microwave synthesis
method.[76] In details, CeO2/TiO2 nanotube arrays were prepared
according to the following procedure. 10 mmol Ce(NO3)3·6 H2O
and 50 mmol hexamethylene tetraamine (HMT) dispersed in 100
mL of aqueous to form a mixture solution. Then, a piece of TiO 2
nanotube arrays strip was added to the solution. Subsequently,
the microwave chemical reactor was turned on and kept the
microwave frequency of 2450 MHz, the output power of 400 W,
temperature of 75 ˚C for 20 min. After the microwave heated
reaction, the strip was drawn from the flask and washed with
deionized water, and then dried at 80 ˚C for 10 h. Finally,
CeO2/TiO2 nanotube arrays have been synthesized (Figure 4d).
Interestingly, as is shown in Figure 4e, the CeO2 nanoparticles
are highly dispersed on the orifices and surface of TiO2 nanotube

8
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ChemSusChem
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arrays. These arrays are in an average length of 5 µm, a mean
pore diameter of 60 nm, and a wall thickness of about 30 nm,
respectively. The ordered tube array structure is beneficial to the
separation of photogenerated electrons and holes, and speeding
up the transfer of photocarriers. Also, the narrow bandgap of this
hybrid can help to improve the photocatalytic activity by absorbing
more photons. Therefore, the results show that compared with
commercial CeO2 and pure TiO2 nanotube arrays, CeO2/TiO2
nanotube arrays have higher photocatalytic activity, and the
conversion of BT is more than 90 % within 5 h, which indicates
that the introduction of CeO2 can improve the photocatalytic
efficiency of pure TiO2 nanotube arrays (Figure 4f). Zhang and co-
workers presented the N-doped CeO2/TiO2 composite by a facile
impregnation method.[68] It is found that CeO2/TiO2 forms a
heterogeneous structure, which effectively promotes the
separation of photogenerated electrons and holes. As a result,
photocatalytic desulfurization data shows a much higher DBT
removal efficiency of 93.7 % than TiO2.
In addition, previous photocatalytic CO 2 reduction has
demonstrated that a p-n heterostructure can be built between
Cu2O and CeO2.[82] The Cu2O-CeO2 heterojunction gives an
extended visible light absorption and a better inhibition of
electron-hole separation. Motivated by this, Mousavi and co-
workers reported a Cu2O-CeO2 hetero-catalyst by a facile and
one-step sonochemical.[77] As shown in Figure 4g, the Cu2O-CeO2
displays aggregated spherical nanoparticles. More importantly,
Cu2O-CeO2 exhibits a much smaller bandgap of 2.2 eV, which is
0.6 eV lower than that of bare CeO2, indicating an enhancement
of visible light absorption (Figure 4h). Together with the faster
electron coordination due to p-n junction, Cu2O-CeO2 shows a
high TH removal efficiency of 84 % after 3 h with robust cycling
stability under visible light irradiation (Figure 4i).
Hybrid coupling using other semiconductors such as graphene,
carbon nanotube, or constructing multiple components has also
been reported.[83,84] Graphene is a new type of 2D nanomaterials,
which can improve the photocatalytic activity due to its excellent
light absorption and electronic conductivity.[85] The coupling of
graphene with TiO2 has demonstrated the good effects of fast
electron migration, strong surface adsorption, and enhanced
visible light absorption, thus leading to a superior PODS removal
of TH to 94.3 % within 100 min.[86] The synergistic effect of RuO2
acting as an oxidation catalyst and SO42-TiO2 (after TiO2 was
treated with H2SO4, SO42- was uniformly adsorbed on the surface
Table 2. Summary of the results photocatalytic materials in PODS.
Photocatalyst Light source Substance concentration of simulated oil
TiO2/g-C3N4 250 W high pressure Hg lamp DBT=500 ppm
Cu2O-CeO2 400 W Xenon lamp TH=800 ppm
CeO2-TiO2 300 W Xenon lamp BT=200 ppm
N-CeO2/TiO2 300 W Xenon lamp DBT=100 ppm
g-C3N4/Ti3C2 300 W Xenon lamp TH=140ppm
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10.1002/cssc.202002144
of TiO2, and then sintered at 450 °C for 3 hours to obtain SO 42--
TiO2 solid acid) acting as a Lewis acid to capture superoxide
species and activate TH molecules was also reported by Lin et
al.[87] The results show that the conversion of pure TiO 2 for
photocatalytic oxidation of TH is low of 12 %, 0.05 wt%
RuO2/SO42--TiO2 can reach more than 88 %. The photocatalytic
activity of TH is greatly improved by supported RuO2 on the basis
of SO42-TiO2. The synergistic effect of cocatalyst and surface
acidity on TiO2 is the main reason for improving the photocatalytic
oxidation activity of TH. In order to further study the PODS of
multiple metal oxide composites, the researchers studied
Cu/Cu2O/BiVO4/Bi7VO13 composites.[88] In this heterogeneous
Accepted Manuscript
structure, Cu2O increases the light absorption range and inhibits
the photogenic electron hole composite. While Cu enhances the
material conductivity, which is beneficial to the transport of
photogenerated electron. In addition, this hybrid exhibits
Cu/Cu2O/BiVO4/Bi7VO13 nanoparticles with rectangular cube-like
morphology and the size of about 30-100 nm was obtained,
indicating there are more reactive sites to further, improve the
PODS efficiency. As a result, the TH PODS efficiency by
Cu/Cu2O/BiVO4/Bi7VO13 was up to 92 %. Table 2 summarizes all
the publications of hybrid coupling on PODS.
3.2.1 Dye-sensitized technology
Most photocatalysts absorb UV light and very limited visible light,
failing to effectively utilize solar light. Dye sensitization, referring
to the physical or chemical adsorption of dye molecules onto the
surface of photocatalysts, has demonstrated its superior ability to
absorb long-wavelength light.[89,90] This is mainly due to the fact
that the chromogenic groups of organic dyes contain conjugated
double bonds, which can absorb visible light easily under
irradiation. These dyes are mostly organic dyes, metal complexes,
or quantum dots, which can be classified into visible-responsive,
near-infrared-responsive and visible/near-infrared-responsive
dyes according to their spectral response region.[91]
At present, the visible light-responsive organic
metallophthalocyanine are widely used in photocatalytic
desulfurization applications. Zhang and co-workers synthesized
metallophthalocyanine/SnO2 (MTcPc/SnO2) composites using
Sn(OH)4 and MTcPc (M = Mn2+, Fe2+, Zn2+ and Cu2+) as
precursors. The photocatalytic activities of ZnTcPc/SnO2 hybrid
were evaluated by the oxidation of TH in fuel with O2 as the
Photocatalytic Year of publication Ref.
performance
98.9 % in 120 min 2014 [50]
84 % in 180 min 2020 [77]
90 % in 300 min 2015 [76]
93.7 % in 80 min 2020 [68]
73.6% in 180 min 2020 [44]
ChemSusChem
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Figure 5. (a) SEM micrographs of RGO/TiO2; (b) UV–Vis spectra of GO, TiO2 and RGO/TiO2; (c) Photocatalytic activity of RGO/TiO2. [47] with permission of
Elsevier Ltd. (d) SEM images of Ag-AgBr/Al-MCM-41; (e) Wide-angle XRD patterns of 10-60 % Ag-AgBr/Al-MCM-41; (f) Conversion of DBT of 40 % Ag-
AgBr/Al-MCM-41 for four cycles. [92] with permission of Elsevier Ltd.
oxidant. The excited photo-electrons on ZnTcPc could be easily
injected into SnO2 under visible light, thus suppressing
photocarrier recombination and improving solar utilization
efficiency. As a result, the TH degradation rate of sensitized
ZnTcPc/SnO2 composite reached 98.42 % after 3h compared to
pure SnO2 of 30 %.[35] Li et al. proposed the synthesis of
metallophthalocyanine/La0.8Ce0.2NiO3 (MTcPc/LCNO)
photocatalysts by sol-gel and impregnation methods. The results
showed that the MTcPc/LCNO hybrid photocatalyst could
absorbs more visible light and effectively remove DBT from the
model oil with a degradation efficiency of 88% under visible light.
In addition, the catalyst showed a strong cycling ability with only
a slight decrease to 79.6% after 5 cycles. [93] Guo et al. prepared
2, 9-dichloroquinacridone (DCQ)-sensitized TiO2@SBA-15
composite (DCQ-TiO2@SBA-15) for a photocatalytic
desulfurization experiment with a much higher DBT
desulfurization rate of 96.1 % than the un-sensitized TiO2@SBA-
15 in a reaction time of 90 min under visible light. [94] Although the
photocatalysts sensitization has been a research hotspot in
PODS, there is still a need for painstaking exploration in reducing
the cost of photosensitization technology, improving the stability
of the photosensitization process, and finally the photocatalytic
removal efficiency of targeted pollutants. Most photocatalysts
absorb UV light and very limited visible light, failing to effectively
utilize solar light. Dye sensitization, referring to the physical or
chemical adsorption of dye molecules onto the surface of
photocatalysts, has demonstrated its superior ability to absorb
long-wavelength light.[90] This is mainly due to the fact that the
chromogenic groups of organic dyes contain conjugated double
10
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10.1002/cssc.202002144
Accepted Manuscript
bonds, which can absorb visible light easily under irradiation.
These dyes are mostly organic dyes, metal complexes, or
quantum dots, which can be classified into visible-responsive,
near-infrared-responsive and visible/near-infrared-responsive
dyes according to their spectral response region.[91]
3.3. Structure modifications
As is known that TiO2 is an important photocatalyst, but TiO2
nanoparticles are easy to aggregate in the photocatalytic process.
The severe aggregation not only lowers the photocatalytic
desulfurization activity, but also reduces the number of active
sites on the surface of TiO2. In addition, bare TiO2 nanoparticles
require a high cost for filtration recovery and might cause
secondary pollution if deposed randomly. [95] Therefore,
researchers began to use carrier materials with high surface area
to fix and disperse TiO2 nanoparticles. Currently, carbon materials
(carbon nanotubes,[47] graphene,[86] bamboo charcoal[96]), porous
silicon dioxide (MCM-41),[51] porous glass,[97] and metal organic
skeleton (MOFs) [98] have been reported as the supporting matrix
for PODS.[99,100]
Carbon nanomaterials such as carbon nanotubes (MWNTs),
graphene, carbon dots, and carbon nanosheets have been
employed as ideal carrier materials for photocatalysis due to the
advantages of unique morphology, strong adsorption ability, good
conductivity, and high chemical stability. [47] Particularly, due to the
one/two-dimensional structure and special electronic property,
both MWNTs and graphene can pave a “high-speed way” for the
ChemSusChem
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transport of excited photogenerated electrons, and therefore
inhibit the recombination process.[101]
Vu and co-workers designed a MWNTs/TiO2 composite using
MWNTs as the supporting matrix which allowed the TiO 2
nanoparticles evenly dispersed on the surface of MWNTs by a gel
method.[47] MWNTs have a large electricity-storage capacity, and
therefore, it may accept photon-excited electrons in mixtures or
nanocomposites with TiO2, thus retarding or hindering
recombination. The results showed that more than 98 % sulfur
compounds in industrial diesel oil were oxidized and removed by
MWNTs/TiO2 composite photocatalyst. In another similar study,
Ag-TiO2 and MWNTs were used to prepare for the desulfurization
of TH.[102] It was found that Ag and TiO2 nanoparticles were evenly
dispersed on MWNTs, and Ag dopants hindered the
recombination of photogenerated electrons and holes. In addition,
MWNTs enhanced the optical absorption performance of TiO 2.
This photocatalyst combines the concept of metal doping, hybrid
coupling as well as morphology modification, providing valuable
experience for the study of efficient green catalysts.
Zhang et al. proposed a simple hydrothermal method for the
preparation of TiO2 catalyst supported on reduced graphene oxide
(RGO), and applied it to the oxidation and desulfurization of TH in
model fuel.[86] As shown in Figure 5a, TiO2 is evenly distributed on
the surface of graphene and the agglomeration of TiO2
nanoparticles was optimized obviously. The absorption edge of
RGO/TiO2 composites showed a notable red shift from 325 nm to
540 nm compared with pure TiO2 nanoparticles. The excellent
morphology and conductivity of RGO are conducive to the
electron transfer from bulk TiO2 to surface, which is beneficial to
the improvement of PODS performance. The results indicated
that the addition of graphene can improve the response of
titanium dioxide to visible light and enhance its photocatalytic
activity under visible light (Figure 5b). With an RGO mass loading
of 5 %, RGO/TiO2 composite exhibited the highest TH removal
efficiency of 94.3 % in 100 min (Figure 5c).
In addition, other carbon material such as bamboo charcoal
(BC) was also reported as a supporting matrix for the PODS
activity enhancement of TiO2. Zhang et al. reported a TiO2/BC
nanocomposite by a wetting process of which TiO 2 was well
loaded onto skirt and surface of pores of BC. TiO 2/BC
nanocomposite has maintained the original pore structure. [96] The
results show that the DBT conversion of TiO 2/BC was 70 % 160
min. This structure modification can significantly prevent the
Table 3. Summary of the results for the use of support materials in PODS.
Photocatalyst Light source Substance concentration of simulated oil
C/TiO2-MCM41 300W tungsten lamp DBT=300 ppm
Al-MCM-41/Ag- AgBr 165W tungsten lamp DBT=500 ppm
Ag-TiO2/PG 50 W visible LED BT=50 ppm
ATP-CeO2/MoO2 300 W Xenon lamp DBT=200 ppm
CeO2/ATP/g-C3N4 300 W Xenon lamp DBT=200 ppm
11
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10.1002/cssc.202002144
aggregation of TiO2 nanoparticles, maximizing the utilization of
photocatalyst. In addition, TiO2/BC hybrid can exist at the oil-
water phase interface with the photocatalytic oxidation reaction
occurs in the oil phase, while the oxidation products can diffuse
to the water phase without adding any extract.
The porous silicon dioxide (MCM-41) is another ideal carrier
material to enhance the PODS activity mainly due to its uniform
and ordered channel structure, which is conducive to the inhibition
of TiO2 nanoparticles aggregation.[51] In addition, MCM-41 has a
large specific surface area up to 1076.50 m2 g-1for the adsorption
of sulfur-training compounds, and thus could provide more active
sites for PODS reaction. Another related study reported the
Accepted Manuscript
synthesis of Ni nanoparticles coated C/TiO2@MCM-41 catalyst by
ultrasonic dispersion of C/TiO2@MCM-41 in nickel-containing
aqueous solution.[103] The results showed that Ni (II) was reduced
to Ni metallic nanoparticle in the size of about 2.7 nm on the
surface of CTM-41 (Ni/CTM-41) with specific surface area of
754.37 m2 g-1, implying more active sites are provided to improve
the photocatalytic performance. In this photocatalytic
desulfurization reaction system, MCM-41 was used as the carrier,
which was modified by TiO2, and then Ni nanoparticles were
deposited on the surface of TiO2. The results show that Ni
nanoparticles are highly dispersed on the carrier material, the Ni
nanoparticles exhibited the photo desulfurization by providing a
π-complexation adsorption. According to the desulfurization
results, when Ni/CTM-41 was used as catalyst, the photocatalytic
desulfurization rate of DBT was the highest (98.6 %). Pham et al.
prepared a series of Ag-AgBr/Al-MCM-41 nanocomposites by
dispersing Ag-AgBr on mesoporous silica Al-MCM-41 with natural
bentonite as raw material.[92] The physical properties of Ag-
AgBr/Al-MCM-41 were characterized by X-ray diffraction
measurement (Figure 5d) and scanning electron microscopy
(Figure 5e). The results show that the prepared nanocomposites
have a good mesoporous structure with Ag-AgBr particles
uniformly covered on the surface or inside the mesoscopic
channels of Al-MCM-41. In addition, the intensities of these
diffraction peaks were constantly enhanced, thus indicated a
better crystallinity with the increase of AgBr content. Figure 5f
shows that the oxidation desulfurization degree of DBT decreases
slightly with time, but it is still above 90 % after four cycles. The
conversion was kept above 90 % in all experiments, which
indicated that the catalyst had high photocatalytic performance. In
addition, they also reported a successful synthesis of Al-MCM-
Photocatalytic Year of publication Ref.
performance
95.6 % in 300 min 2015 [51]
98 % in 360 min 2018 [92]
83.5 % in 80 min 2018 [97]
95 % in 180 min 2016 [3]
98 % in 180 min 2017 [113]
ChemSusChem 10.1002/cssc.202002144

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Accepted Manuscript
Figure 6. (a) TEM and (b) HRTEM images of CeO2/ATP/g-C3N4; (c) Photocurrent profiles of CeO2/ATP/g-C3N4, CeO2/g-C3N4, g-C3N4 and CeO2/ATP; (d)
Desulfurization rate as a function of time under visible light irradiation Ref. [113] with permission of Elsevier. (e) TEM images and (f) STEM images of Ag-
TiO2/PG; (g) Transient photocurrent responses of TiO2/PG and Ag-TiO2/PG; (h) Photocatalytic activity of 3 % Ag-TiO2/PG for DBT conversion. [97] with
permission of American Chemical Society. (i) TEM images of Cu-BTC and Cu-BTC@TiO2; (j) Schematic of mild synthesis of Cu-BTC@TiO2 microspheres and
their desulfurization performance; (k) Conversion of BT for Cu-BTC and Cu-BTC@TiO2. [61] with permission of MDPI (Basel, Switzerland).

41@Ag/TiO2 nanocomposites via the sol-gel method followed
with water heat treatment.[104] The uniform dispersion of silver
nanoparticles on TiO2 surface improves the visible light
absorption of TiO2 due to the plasma effect. Also, the good
conductivity of silver nanoparticles can facilitate the electron
mobility, suppressing the recombination of photogenerated
electrons and holes,[105] and thus boost the photocatalytic activity
of catalysts significantly. The most important is that the high
specific surface area of Al-MCM-41 carrier favors to provide
abundant photocatalytic active sites, further increasing the DBT
degradation efficiency to 90 % under UV irradiation. When the
temperature increases to 70 °C, the photooxidation
desulfurization efficiency of DBT can reach 100 % even with
visible light irradiation for 2 h.
Apart from MCM-41, researchers have also found zeolites like
TS-1 (Titanium Silicalite-1), SBA-15 (Santa Barbara Amorphous-
15), ZSM-5 (Zeolite Socony Mobil–5), NaX (Sodium-X), and NaY
(Sodium-Y) can be used as supporting materials in photocatalytic

12
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ChemSusChem
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desulfurization experiments. In a study of photocatalytic
desulfurization of DBT, Zhang et al. found that TS-1 has a better
performance compared to pure TiO2 with a good degradation
efficiency of DBT to 75%. This is mainly due to the fact that TS-1
could provide a large surface area for the dispersion of
photocatalyst to generate abundant active radical species and
thus enhances the PODS performance.[106] Naik et al. synthesized
TiO2-SBA-15 nanocomposites using a simple aqueous solution-
based chemical method. The results showed that the TiO 2-SBA-
15 nanocomposites exhibited a high methyl orange removal
efficiency of 81 % even at a very low TiO2 loading of 10 wt%. Guo
et al. also obtained a similar result when employing the
TiO2@SBA-15 composites for photocatalytic oxidative
desulfurization, reaching a high DBT removal rate of 96.1% in a
reaction time of 90 min.[94] Wang and co-workers used the ZSM-
5 material for ultra-deep desulfurization of catalytically cracked
gasoline and achieved excellent desulfurization results. [107] To
further investigate the role of ZSM-5 in PODS, Sahragard et al.
developed ZSM-5/ZnO composites for DBT desulfurization. [108]
The results showed that ZSM-5/ZnO improved the photocatalytic
performance mainly due to the larger specific surface area of
ZSM-5, the stronger adsorption capacity for TH compounds, and
therefore the stronger the photoexcitation capacity for electron-
hole pairs at the active sites.
In addition, the researchers also studied the strong sulfides
adsorption capacity of NaX and NaY zeolite. [109,110] According to
the experimental results, the desulfurization conversion of
Ni/TiO2/NaX nano-zeolite particles was found to be as high as
92.29 %. Acting as photocatalyst carriers, their large surface area
is favorable to disperse the photocatalyst powder, providing more
reactive active sites, and inhibiting the photocatalyst aggregation
phenomenon, which is a good choice for future researchers to
design functional photocatalyst.
The separation and recovery of photocatalyst in photocatalytic
reaction often limits the practical application of photocatalyst.
Attapulgite (ATP) is a natural clay with strong adsorption ability
and is considered as a good supporting material due to its special
pore structure, low cost and environment be nigity. [111] The ATP
with a large specific surface area and abundant active sites, is
often combined with metals and metal oxides to obtain functional
nanocomposites.[112] According to relevant literature, the ATP-
CeO2/MoO2 nanocomposite was synthesized with microwave
assisted method and its photocatalytic desulfurization activity was
studied.[3] Composed of ATP skeleton, CeO2 and MoO2
nanoparticles, the three-dimensional network structure has a
large specific surface area, forming a good electronic
transmission channel, effectively promoting the separation
efficiency of photogenerated electrons and holes. The ATP-
CeO2/MoO2 nanocomposites provide a photocatalyst synthesis
method with high activity and high property value for DBT deep
desulfurization of 98 % in 180 min. Li et al. prepared CeO 2/ATP/g-
C3N4 nanocomposites.[113] With the synergistic effect of the large
adsorption capacity of ATP matrix and the enhanced electron
transport ability of CeO2/g-C3N4, CeO2/ATP/g-C3N4
nanocomposite material (Figure 6a,6b,6c and 6d) has excellent
photocatalytic desulfurization activity, with the DBT removal rate
of near 98 %. Moreover, CeO2/ATP/g-C3N4 shows no obvious
photocatalytic activity deterioration after 8 cycles, indicating its
excellent recyclability. Miao and co-workers prepared BiVO4/g-
C3N4@SiO2 photocatalytic desulfurization by hydrothermal
method with an efficiency of 99 %.[40]
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10.1002/cssc.202002144
Apart from the above mentioned common carrier materials,
researchers also studied other supporting materials such as metal
skeletons and porous glass.[60] Chen et al. used a simple synthetic
method, to obtain a hybrid Ag-TiO2 material distributed on the
porous glass material (PG).[97] It can be seen from (Figure 6e and
6f) that the catalyst maintains the spherical structure without
agglomerations. Figure 6g indicates that due to the hybrid
coupling with Ag nanoparticles and PG onto TiO2, the visible light
absorption is enhanced and the charge transfer progress is
accelerated, leading to a significantly improved photocurrent of
Ag-TiO2/PG. The results show that this material has high visible
light absorption, efficient separation of photogenerated electrons
Accepted Manuscript
and holes, large adsorption surface area and many active sites
for photocatalytic oxidation. Figure 6h show that under visible light
irradiation, the DBT conversion of Ag-TiO2/PG and TiO2/PG are
83.5 % and 58.8 % respectively within 80 minutes. The results
show that Ag-TiO2/PG has higher photocatalytic activity than
TiO2/PG.
Metal organic framework (MOFs) as a new porous structure
material which is considered as an ideal carrier material for
photocatalytic desulfurization in terms of its good adsorption
desulfurization property.[98] Liu et al. successfully synthesized a
core-shell Cu-benzene-1,3,5-tricarboxylic acid (Cu-BTC) @ TiO2
for photocatalytic assisted adsorptive desulfurization of DBT. [61]
Figure 6i show Cu-BTC (left) and Cu-BTC@TiO2 (right) display a
microsphere structure. The surface of Cu-BTC particles was
coated with TiO2 particles. The surface of the microspheres is
zigzag, which may be attributed to the TiO2 particles adhering to
the surface and finally forming the outer layer. Figure 6j show Cu-
BTC@TiO2 synthesis diagram of microspheres and their
desulfurization performance. Firstly, Cu-BTC was prepared in the
first step, and then TiO2 layer was deposited on the surface of Cu-
BTC to form Cu-BTC@TiO2 Microsphere. Under UV light radiation,
Cu-BTC@TiO2 Thiophene sulfide was oxidized to sulfone by
photocatalyst. Figure 6k the model fuel was desulfurized with Cu-
BTC as adsorbent, and the removal rate of BT was less than 30 %,
indicating that the pure Cu-BTC have a very low conversion rate.
Cu-BTC@TiO2 BT desulfurization efficiency reached 86 % in 20
min and the reaction time was more than 99 % in 90 min. The
results show that, Cu-BTC@TiO2 BT conversion is 6.5 times
higher than that of pure Cu-BTC. In this study, the combination of
photocatalysis and adsorption can achieve rapid and deep
desulfurization, which provides a new research idea for the
realization of rapid and deep desulfurization.
Recently, some researchers have studied the desulfurization
capability of the hybrid photocatalyst of MoO3@MOF in the
photocatalytic desulfurization reaction system. [114] The results
show that the synergistic effect of MOFs active surface and MoO 3
catalyst active center improves the desulfurization efficiency of
photocatalytic desulfurization under UV and visible light irradiation.
This study provides a prospect for the preparation of new
photocatalyst materials in photocatalytic desulfurization systems.
Table 3 depicts a summary of the PODS using different types of
support materials
3.4. Other photocatalytic desulfurization methods
In addition, the application of ionic liquids in PODS system is also
reported. Ionic liquid, as a green reaction medium, has stable
chemical properties and strong thermal stability. [115] Because of
the advantages of simple synthesis process and green
ChemSusChem 10.1002/cssc.202002144

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environmental friendless,[116] ionic liquid has been used as an
extraction agent in photocatalytic desulfurization systems. For
example, Wang’s group has proposed that nano-TiO2 was
prepared by microwave irradiation in [Bmim]BF4 ionic liquid.[117]
The prepared ionic liquid containing TiO 2 was used as extraction
agent for desulfurization. The results showed that under mild
conditions, 98.2 % sulfide in fuel oil was removed within 10 hours.
In recent years, amorphous TiO2, ionic liquid and H2O2
photocatalytic desulfurization systems have also been
reported.[118] The results show that under UV irradiation, the
photocatalytic desulfurization efficiency can reach 96.6 %, which
is a promising green photocatalytic desulfurization system.
electrostatically induced self-assembly method.[113] The results
showed that the CeO2/ATP/g-C3N4 exhibits a high DBT removal
efficiency of 95 % after 8 consecutive runs. In a sharp contrast,
CeO2/g-C3N4 displays a reducing degradation rate to 70 % after 8
cycles. The enhanced photocatalytic activity and recyclability of
CeO2/ATP/g-C3N4 were related to the introduction of ATP
skeleton, which improved the stability and integrity of the material.
Bagheri et al. synthesized MoO3-MOF composite for
photocatalytic oxidative desulfurization experiments. [114] It was
found that the PODS efficiency of DBT remained unchanged after
3 cycles with the values of 90 % and 85 % after four and five
cycles, respectively, proving the stable property of MoO3-MOF

Li and co-workers modified g-C3N4 with amphiphilic
[Bmin]3PMo12O40 (BPMO) to form heterogeneous structures.[119]
In the process of photocatalytic desulfurization, BPMO can
adsorb DBT in oil phase and H2O2 in water phase at the same
time, promoting mass transfer at oil-water interface. Due to the
existence of BPMO carrier, g-C3N4 is not only well dispersed but
also forms heterojunction with BPMO, which is conducive to the
separation of photogenerated electrons and holes. The PODS
reaction system composed of BPMO/g-C3N4 and H2O2 solved the
mass transfer problem at the oil-water two-phase interface. This
new photocatalytic desulfurization method provides a new way for
us to study deep desulfurization.
3.5. Recyclability of the catalysts
Although the performance of the catalyst can be significantly
improved after the optimization on morphology and electronic
structure, the catalyst recyclability is also a key issue in the
development of PODS, especially for doped and structure-
modified catalysts. Fortunately, most PODS photocatalysts show
reasonable recyclability performance when re-dispersed into the
pollutant solution. For instance, Li et al. prepared CeO2/
attapulgite (ATP)/g-C3N4 nanocomposites using a facile
Accepted Manuscript
composite. Pham et al. prepared Ti-Al-SBA-15 bimetals from
titanium tetraisopropoxide and natural kaolin clay for the
degradation of DBT by a direct hydrothermal method. [120] The Ti-
Al-SBA-15 showed a reasonable recyclability with its DBT
removal efficiency reduced by about 1.5 % in the fourth cycle.
They also studied the recyclability of Ag-AgBr/Al-MCM-41
nanocomposites for DBT degradation.[104] The catalyst was
recovered by centrifugation and washed several times with
distilled water and ethanol. The Ag@AgBr/Al-SBA-15 catalyst
was reused four times, and the results showed that the DBT
photocatalytic degradation decreased slightly, from 97.40 % to
94.88 %, indicating its stable photocatalytic activity. The
recyclability of the C/TiO2@MCM-41 catalyst was explored by
Zarrabi’s group via testing the cycling performance of DBT
degradation process.[51] The results showed that the DBT removal
rate was almost stay the same value at 94.30 % after 2 cycles.
Despite enhanced recyclability activity has been achieved by
most PODS photocatalysts, the recovery process is still
restrained by the repeated, time-costing powder collection and
washing procedure.[121-123] Therefore, current material synthetic
methods need to be optimized on the materials’ magnetic,
hydrophile-lipophile and particularly the free-standing property,
which can allow them to be easily separated from the pollutant

Figure 7. (a) PODS of TH in MXene (5.0)/GCN model fuel were present with different scavengers; (b) The EPR spectra show that DMPO captures the
of the ·OH and ·O2- radicals in the n-octane of g-C3N4 and M (5.0)/GCN; (c) GC-MS identification for the possible products of Th in PODS over M(5.0)/GCN
for 3 h; (d) Photocatalytic oxidation desulfurization pathway; (e) Ion chromatography spectra of inorganic products SO42- over M(5.0)/GCN for 3 h; (f) Ti3C2
and M(5.0)/GCN, Photocatalytic mechanism of PODS Ref. [44] with permission of Elsevier.

14
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ChemSusChem
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solutions via electrical/magnetic fields, natural sedimentation, and
direct collection.[124-126] In short, for future PODS evaluation, we
should not only emphasize their cycling performance but only pay
attention to the easy-to-recycle recovery techniques, which would
provide more constructive guidance for practical application.
4. Mechanism of PODS
To study the mechanism of PODS, researchers have mainly
adopted active species capture test using electron paramagnetic
resonance spectrometer (EPR) technique for the detection of
active species.[40,127-131] The procedure is similar to PODS, adding
a certain amount of scavenger or charging sufficient N 2. The
ascorbic acid (AA), isopropyl alcohol (IPA), dimethyl sulfoxide
(DMSO), and triethanolamine (TEA) scavengers were employed
for trapping the superoxide radicals (·O2-), hydroxyl radicals (·OH),
electrons (e−) and holes (h+), respectively.[86,34,132-135] While N2
was used for evacuating the oxidant O 2. Besides, gas
chromatography-mass spectrometer (GC-MS) and ion
chromatography are also necessary to identify the possible
organics, intermediates, and inorganic substances.
Li et al. prepared MXene-Ti3C2 (M) modified g-C3N4 composites
and applied them to photocatalytic oxidation denitrification and
desulfurization under visible light. The results show that the
removal rates of pyridine (Pyr) and TH are as high as 245.2 μg g-
1
and 270.7 μg g-1, respectively. Figure 7a gives PODS of TH over
M (5.0)/GCN (Ti3C2 content is 5 wt% in Ti3C2 and g-C3N4
composites) in the presence of various radical scavengers. It can
be concluded that e-, h+, O2, and ·O2- radicals were active species
in the degradation of TH but ·OH has little effect. Figure 7b shows
the EPR spectra of ·OH and ·O2- captured by DMPO (free radical
scavenger). This experiment further confirmed that there was no
·OH radical but only ·O2- radical. Moreover, M(5.0)/GCN has
stronger DMPO- ·O2- signal strength than g-C3N4, which indicates
that the ability of Ti3C2 to generate ·O2- in O2 and e- is enhanced.
Based on this, we can draw a conclusion that in absence of H2O2
and H2O, there is no ·OH radical in the PODS activity, and the
·O2- radical may be an important active substance for TH oxidation
due to the existence of dissolved O2 in n-octane solution. Figure
7c shows the GC-MS spectra of PODS of TH, the peak at 116 m/z
is identified to the sulfone molecule. Combined with the capture
experiments, the pathway of PODS is shown in Figure 7d.[44]
Under visible light irradiation, e- and H+ were produced in Ti3C2/g-
C3N4 composites. The excited photogenerated electrons were
combined with O2 to form ·O2-. TH was combined with H+ to form
a ring intermediate C4H4N+·, which was further transformed into
sulfone molecule after reacting with ·O2-. Then the sulfone was
mineralized by ·O2-. Figure 7e shows the SO42- signal of the final
mineralization product of TH, which was successfully identified by
ion chromatography-spectrum analysis. Based on the above
analysis, combined with the electronic structure diagram, the
reaction mechanism and process diagram are proposed in Figure
7f.
In a case of detect the existence of radicals removal for Ag-
TiO2/PG photocatalyst, the ESR determination using 5, 5-
dimethyl-1-pyrrolin-N-oxide (DMPO) as scavenging agent is
conducted to explore the free radicals. [97] Figure 8 show the
comparison experiments conducted under both dark and visible
light irradiation. No radicals were not detected under dark
15
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002144
Accepted Manuscript
Figure 8. (a) ESR spectra for DMPO-·O2-; (b) DMPO-·OH; (c) TEMPO-h+
of the TiO2/PG and Ag-TiO2/PG materials with dark and visible light
irradiation; (d) schematic diagram of photocarrier transfer in Ag-TiO2/PG
under visible light irradiation Ref. [97] with permission of American Chemical
Society.
conditions, indicating this is a light-driven reaction. The
characteristic peaks of ·O2- radicals and ·OH radicals were found
in visible light. In addition, the Ag-TiO2/PG catalyst showed a
twice enhanced signal intensity of active radicals compared with
TiO2/PG as shown in Figure 8a and Figure 8b. The light-induced
hole (h+) was also tested using 2,2,6,6-tetramethyl-1-piperidine
(TEMPO) as probe molecule. As shown in Figure 8c, ESR signal
of h+ was not found in dark condition. Under the same illumination
condition, the signal intensity corresponding to the h +
characteristic peak of Ag-TiO2/PG was significantly higher than
that of TiO2/PG, indicating the coupling of Ag and TiO2
nanoparticles contributes to the separation of photogenerated
electrons and holes. In the process of photodegradation,
photogenerated electron e- reacts with O2 to form ·O2-, and hole
(h+) reacts with OH- and H2O to form ·OH. These results indicate
that both photoinduced electrons and holes contribute to the
photodegradation process of Ag-TiO2/PG photocatalyst, leading
to the increase of active substance concentration, that is, ·OH,
·O2- and holes are all active substances for photocatalytic
oxidative desulfurization. The experimental results prove that both
photogenerated electrons and holes play a role in the PODS
reaction for Ag-TiO2/PG hybrid.
To further explore the photocatalytic reaction mechanism of Ag-
TiO2/PG composites, the conduction band position (E CB) and
valence band position (EVB) of TiO2 were calculated according to
the following:
EVB = X + 0.5 Eg - Ee (1)
ECB = EVB - Eg (2)
Where X value represents (the electronegativity of the
semiconductor) of TiO2 (5.81 eV), Eg is the bandgap of TiO2 (3.1
eV), and Ee is the energy of hydrogen atom (-4.5 eV). Therefore,
the EVB and ECB of TiO2 are calculated to be is 2.86 eV and -0.24
eV, respectively. Figure 8d illustrates that under visible light,
(surface plasmon resonance) SPR Ag played an important role in
excitation of light-induced electrons, and would not compound
with photogenerated holes, these electrons combine with O 2
ChemSusChem
REVIEW
adsorbed on the surface of the material to produce ·O2-. In
addition, there are ESR signals of h+ and ·OH in Ag-TiO2/PG
system, which proves that the holes (h +) generated on the valence
band of TiO2 reacted with H2O or OH- to produce ·OH. In the
process of photocatalytic oxidation, DBT and BT were oxidized by
active radicals - ·O2-, ·OH and h+. The material is a porous
nanostructure with high specific surface area of 131.2 m 2 g-1,
which can adsorb H2O, OH-, O2 and organic molecules, and
provide abundant active sites for photocatalytic oxidation reaction.
This is conducive to the improvement of photocatalytic oxidation
performance. The results showed that the conversion of DBT and
BT were 95.2 % and 92.1 %, respectively.
In their exploration of the PODS mechanism of CeO2/ATP/g-
C3N4, Li et al. used the ESR technique to track the response
species.[113] As derived from ESR characterization in Figure 9a
and Figure 9b, the CeO2/ATP/g-C3N4 only shows the
characteristic signals of DMPO-·OH under visible light irradiation,
indicating ·OH plays an important role in photocatalytic
desulfurization. The experimental results show that the addition of
TBA caused a significant suppressed effect with the
photocatalytic desulfurization conversion reducing from 98 % to
60 % (Figure 9c). This may be due to the fact that the addition of
TBA to the photocatalytic solution resulted in the trapping of ·OH
radicals, which affected the photocatalytic performance. In
addition, TEOA leads to a slight deactivation of the photocatalyst
which implies that holes are also the active species for PODS.
From GC-MS analysis in Figure 9d, we can see DBT was oxidized
to its corresponding counterpart of sulfones (DBTO 2) from 0.5 h
to 3 h. Figure 9e illustrates that the CB and VB of g-C3N4 are -
0.91 eV and 1.79 eV respectively, which are more positive than
those of CeO2 (-0.53 eV and 2.67 eV). Moreover, g-C3N4 and
CeO2 possess a more suppressing the recombination of
Figure 9. ESR spectra for (a) DMPO-·OH; (b) DMPO-·O2-; (c)Effects of different scavengers on the degradation of DBT in the presence of CeO2/ATP/g-C3N4
samples; (d) GC–MS analysis; (e) Photocatalytic desulfurization mechanism of CeO2/ATP/g-C3N4 Ref. [113] with permission of Elsevier Ltd; (f) Mechanisms for
the photocatalytic reaction of RGO/TiO2 Ref. [86] with permission of Elsevier Ltd.
16
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002144
photogenerated electrons and holes. At the same time, holes in
the VB of g-C3N4 are not able to oxidize OH- to produce ·OH,
because the potential of holes in the VB of g-C3N4 (1.79 eV) is not
as high as the OH-/·OH (1.99 eV) redox potential.[132] It is
concluded from the active substance capture experiments that
·OH radical are used as the main active substances in the PODS
process to convert DBT molecules into DBTO2. While the holes
have a relatively weak oxidation capacity but are also involved in
the desulfurization reaction. Based on the above studies, the
authors propose the following desulfurization mechanism:
CeO2/ATP/g-C3N4+ hv →CeO2 (e-)+ g-C3N4 (h+) (1)
e-+H2O2→OH-+·OH
Accepted Manuscript
(2)
H++OH-→·OH (3)
+·OH (h+) → (4)
(4)
matched energy band structure, which facilitates the transfer of
photogenerated electrons from g-C3N4 to CeO2, thus effectively
As is shown in Figure 9f, the PODS mechanism of RGO/TiO2
nanoparticles revealed that the excellent photocatalytic activity
attributed to the high electron mobility of graphene, the
enhancement of surface adsorption for thiophene molecules and
strong visible absorption.[86] First, at the initial stage of
photocatalytic desulfurization, TH, H2O2 and oxygen molecules
rapidly reach an adsorption-desorption equilibrium on the catalyst
surface. Then, RGO/TiO2 is excited by visible light to produce
photogenerated electrons and holes for the degradation of TH in
n-octane. The photogenerated electrons in the CB of TiO2 migrate
rapidly to the RGO surface, thus effectively inhibiting the
complexation of photogenerated electrons with holes. Afterwards,
the holes on the VB of TiO2 directly oxidized TH to C4H4S+, and
ChemSusChem
REVIEW
the O2 molecules and H2O2 adsorbed on the RGO surface reacted
with the migrating e- to produce ·OH and ·O2 radicals. The ·OH
and ·O2 radicals further oxidize C4H4S+ to produce C4H4SO2.
5. CONCLUSION AND OUTLOOK
Desulfurization is widely acknowledged as an efficient strategy to
produce clear fuel oil toward industrial applications. Compared to
traditional desulfurization methods, photocatalytic desulfurization
is regarded as a more green, economic, and high-efficient
desulfurization technology to achieve deep desulfurization. This
paper reviews recent progress of PODS in the past decade, from
its background, working principle to the challenges along with the
corresponding solutions: 1) defect engineering including the non-
metal doping and metal doping mainly aims to enhance the light
absorption ability of photocatalysts by narrowing their bandgap or
facilitate the charge transfer process by improving their electronic
conductivity; 2) While hybrid coupling targets to form
heterostructures to increase the photocarrier separation efficiency
by providing more active electrons and holes for PODS reaction;
3) Structure modification is also necessary to optimize the contact
between different nanocomponents, preventing the nanoparticle
aggregations and maximizing the utilization of the core
photocatalyst. Additionally, the PODS mechanism was also
identified by tracking free radicals using different scavenging
agents or other auxiliary techniques.
Though notable improvements have been made in the field of
PODS catalysis, there remain some problems to be addressed for
future design of PODS photocatalysts: 1) The bandgap and redox
activity of photocatalyst should be well balanced as an over-
narrow bandgap usually diminishes the strong photocatalytic
activity due to the lower CB/VB positions. 2) Low-cost materials,
particularly the metal-free materials such as carbonaceous-based
and carbon/boron nitrides-based photocatalysts should be well
developed. The widely investigated metallic compounds and
noble metal (Ag, Au, Pt) nanoparticles are easy to produce
pollution and/or increase the PODS cost. 3) After photocatalytic
desulfurization, it is very difficult to recycle and reuse catalysts
from fuel. Most photocatalysts are powder and dispersed in
solution which means the recycling process needs extra high-
speed centrifugation or high vacuum condition. Thus, free-
standing photocatalyst with abundant pores that are easy to
collected from fuel oil and absorb sulfur-containing compounds
should be paid to more attention. The regeneration performance
of PODS photocatalysts should be emphasized particularly for
future industrialization applications. However, current PODS
regeneration performance is severely restrained by the thermal-
/photo-stability of photocatalyst, and the nonnegligible weight loss
of photocatalyst due to the complex and low-efficient powder
collection process. Thus, researchers should pay more attention
on the development of ultra-stable photocatalysts with high
thermal stability and superior anti-photocorrosion ability. In
addition, the PODS materials need to be optimized on their
magnetic, hydrophile-lipophile, and particularly the free-standing
property, which can allow them to be easily separated from the
pollutant solutions and thus reduces the weight loss during the
repeated desulfurization process. Besides, more advanced in-situ
active species detection methods and theoretical analysis on the
identification of the active sites of photocatalyst are necessary to
17
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002144
reveal the deeper kinetic chemistry of PODS, which are believed
to be the next breakthrough of this research area.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant Nos. 21375116), a project funded by
the priority academic program development of Jiangsu higher
education institutions (PAPD).
Keywords: photocatalytic desulfurization•doping•hybrid
Accepted Manuscript
coupling• structure modification
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ChemSusChem 10.1002/cssc.202002144

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Entry for the Table of Contents

Accepted Manuscript
Photocatalytic desulfurization is the most promising deep desulfurization method. This review summarizes recent progress of
photocatalytic desulfurization and emphasizes the roles of defect engineering, hybrid coupling, and structure modifications toward the
enhancement of photocatalytic performance.

20
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