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Efficient catalyst development for deep aerobic

photocatalytic oxidative desulfurization: recent
advances, confines, and outlooks

Iqrash Shafiq, Sumeer Shafique, Parveen Akhter, Ghulam Abbas,

Ahsanulhaq Qurashi & Murid Hussain

To cite this article: Iqrash Shafiq, Sumeer Shafique, Parveen Akhter, Ghulam Abbas, Ahsanulhaq
Qurashi & Murid Hussain (2021): Efficient catalyst development for deep aerobic photocatalytic
oxidative desulfurization: recent advances, confines, and outlooks, Catalysis Reviews, DOI:
10.1080/01614940.2020.1864859

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Published online: 04 Jan 2021.

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CATALYSIS REVIEWS
[Link]

ARTICLE

Efficient catalyst development for deep aerobic

photocatalytic oxidative desulfurization: recent advances,
confines, and outlooks
Iqrash Shafiqa,b1, Sumeer Shafiquea1, Parveen Akhterc, Ghulam Abbasd,
Ahsanulhaq Qurashie, and Murid Hussain a
a
Department of Chemical Engineering, COMSATS University Islamabad, Lahore Campus, Lahore,
Pakistan; bDepartment of Health, Safety & Environment (HSE), Refinery Division, Pak-Arab Refinery
Limited “Company” (PARCO), Karachi, Pakistan; cDepartment of Chemistry, The University of Lahore,
Lahore, Pakistan; dDepartment of Chemical Engineering, University of Gujrat, Gujrat, Pakistan;
e
Department of Chemistry, Khalifa University, Abu Dhabi, United Arab Emirates

ABSTRACT ARTICLE HISTORY

The supply of environmentally friendly petroleum products has Received 10 October 2020
extreme importance in ensuring a reliable healthy climate glob­ Accepted 10 December 2020
ally. The elimination of obstinate sulfur complexes is an enor­ KEYWORDS
mous task in the current challenging legislative situation for fuel Photocatalytic
refining companies. The conversion of these obstinate sulfur desulfurization; refractory
complexes is challenging in the progression of deeper photo­ sulfur compounds;
catalytic oxidative desulfurization. As an eco-friendly, inexpen­ sulfur-free liquid fuels;
sive and non-lethal oxidant with bountiful accessibility, oxygen oxygen; different catalytic
prevailing in the air is utilized in the deep photocatalytic oxida­ systems
tive desulfurization process as a reliable substitute for hydro­
peroxide and other expensive hydroperoxide derivatives.
However, the superlative activation of oxygen under light irra­
diations is hitherto a challenge. This potential review critically
analyzes the recent strategies employed for the development of
efficient materials for the progression of deep aerobic photo­
catalytic oxidative desulfurization system for the removal of
obstinate sulfur complexes. Furthermore, the associated tech­
nologies influencing the deep photocatalytic oxidative desulfur­
ization performances have been identified and significant
parameters for the process optimization are evaluated to
address the forthcoming challenges.

CONTACT Murid Hussain drmhussain@[Link] Postal Address: Department of Chemical

Engineering, COMSATS University Islamabad, Lahore, Pakistan.
1
Both authors contributed equally.
© 2021 Taylor & Francis
2 I. SHAFIQ ET AL.

1. Introduction
With a growing energy mandate worldwide; crude oil secures a key position in
the cumulative global energy resource. Crude oil is mainly comprised of hydro­
carbons such as straight chains, aromatic rings, heteroatoms, and other assort­
ments such as nitrogen, oxygen, organosulfur compounds, etc., which usually
persist even in refined specialty end-products including gasoline, aviation fuels,
and diesel.[1–6] The diminution in the exploration and production of global
crude oil reserves lean toward the global dependency over heavier crude oils,
comprising these heteroatoms.[7–9] Thus, increasing the sulfur-contents in the
petroleum refinery streams.
The presence of these organo-sulfur compounds inclines to the reforming catalyst
deactivation and initiates corrosion issues in process equipment, piping, and
tankage.[10–12] These organo-sulfur compounds turn out to be the source of SOx
emissions upon combustion, subsequently causing air pollution, acid rain, and global
warming.[13–15] For instance, the presence of SOx and moisture in the atmosphere
produces sulfuric acid either by a heterogenous or homogenous pathway, accelerating
the erosion of the historical building, adverse upshot on soil chemistry, foliage damage,
and disturbing the pH of water bodies with low buffer capacities and subsequently
jeopardize the marine life.[16–24] In conjunction with acid rain, SOx also promotes the
tropospheric ozone and acid smog formation.[25–27] Moreover, breathing in a toxic
climate could outcome numerous health concerns such as asthma, heart disease, and
respiratory syndrome.[10,18] In Malaysia, 19.48% of deaths in 2012 were owing to
diseases related to the respiratory system.[28]
In general regulations, the sulfur-content is expressed as ppm (by weight).
The refinery product with zero-sulfur is highly desirable, but the sulfur persists
even in ultra-refined refinery products. For diesel, US EPA sets a determined
permissible sulfur content of 15 ppm.[29,30] Japan and Europe decide on an
extra strict sulfur-level of 10 ppm.[31,32] Canada bounds the maximum per­
missible sulfur-content of 15 ppm.[33] Superfluous sulfur emission regulations
could be expected globally very soon.[34–36] To comply with forthcoming
sulfur regulations, the petroleum refineries may face several challenges to
minimalize the adverse effects of sulfur on health and the environment.
Therefore, special consideration has been remunerated toward the investiga­
tion of more efficient sulfur-removal technologies.
The sulfur-removal technologies can be generally characterized into two
categories: HDS technology and non-HDS technology.[37,38] The most com­
monly used method for sulfur-removal is hydrodesulfurization (HDS). HDS is
an efficient technology sufficient for the removal of most of the aliphatic and
acyclic organosulfur compounds.[39–43] The requirements of achieving high
temperatures (200–450°C), high pressures (3–6 MPa), hydrogen demands,
and expensive catalyst makes HDS less capable of producing superlative
desulfurization efficiencies.[44–47] However, this technology is particularly
 CATALYSIS REVIEWS 3

more expensive and less effective in the desulfurization of DBT and its
derivatives, owing to the steric hindrance faced during the hydrogenation
pathway.[31,48–50] Furthermore, the HDS reactivity for DMDBT (a butyl aro­
matic sulfur-containing compound) and its derivatives are quite
restricted.[51–54] Besides, HDS stimulates negative influence over the octane
number of treated products and impetuses the undesired hydrogenation of
non-sulfur containing aromatic compounds.[55] Owing to the limited effi­
ciency and expensiveness of HDS, the advancement of an effective alternative
deep desulfurization technology is promptly important.[56–59] This is obliga­
tory to commercially introduce an alternative technology such as adsorptive
desulfurization (ADS), [60–65] extraction desulfurization (EDS), [49,66,67] oxida­
tive desulfurization (ODS), [68–71] chemical desulfurization (CDS),[72–74] and
biological desulfurization (BDS).[75–81]
Regardless of the enormous investments in research and development in the
petroleum refining section for exploring the revamping options and new
process units progresses to meet the latest regulatory requirements, the com­
mercially employed desulfurization process is still very expensive. Therefore,
further research is required for the advancement in the innovative catalysts’
synthesis, upgraded reactors design, and novel process development.
However, the aforementioned desulfurization technologies are under the
developmental stages. Single-stage EDS is not sufficient to provide promising
results, else it requires multi-stage extractions to ensure the desired level of
sulfur-contents in the product stream.[82] In ADS, the surface functionality,
porosity, and structure of the adsorbents are not obviously defined and con­
sequently, it is not easy to adjust them for meeting the desired set of
requirements.[83] In BDS, the technology is not adequate for the treatment
of refinery streams, because a sufficient amount of carbon is mineralized
during the BDS pathways, reducing the product quality and hence the process
is not commercially feasible.[84,85]
Recently, the ODS method has grasp noteworthy attention as an auspicious
technology for the deep desulfurization of refinery products owing to its super­
ior selective transformation of organo-sulfur compounds to their corresponding
sulfoxides and sulfones under moderate reaction circumstances.[63,73,86] ODS
bears numerous advantages over other desulfurization technologies, such as the
requirement of moderate reaction circumstances (around 40–100°C and ambi­
ent pressures), lesser capital and operational costs, no hydrogen demands, less
complexity, and higher selectivity in desulfurizing aromatic sulfur compounds
compared to that of HDS.[87–89]
So far, numerous oxidants such as molecular oxygen (O2), [90] ozone
(O3), [91,92] hydrogen peroxide, [93] tert-hydroperoxide[94] have been inves­
tigated in several ODS studies. Among these oxidants, hydrogen peroxide
is the most widely used oxidant for high ODS performances owing to its
high oxygen activation and environmental benevolent characteristic.[9,95]
4 I. SHAFIQ ET AL.

However, the use of hydrogen peroxide for ODS applications requires an

extra separation method afterward the oxidation reactions, declining the
overall reliability and efficiency of the technology.[96,97] Moreover, the
storage and handling of hydrogen peroxide possess fire and explosion
issues and is potentially dangerous.[98]
Recently, molecular oxygen (O2) has received significant attention as an
oxidant for several ODS processes, by which both the oxidation/extraction
processes occur subsequently, therefore eliminating the requirement of the
oxidant separation process.[99–102] Even though molecular oxygen is indubitably
abundantly available and the most cost-effective oxidant, it is inactive due to
a low-energy triplet (3O2) ground state.[98] Several attempts have been made for
the activation of molecular oxygen for the desulfurization applications.[103–109]
However, these attempts require the utilization of pure molecular oxygen, longer
reaction times, and higher temperatures. Nevertheless, high operating tempera­
tures directed the feasibility of side-reactions that reduces the research octane
number of the petroleum stream.[110]
To enhance the ODS efficiencies, the technology was investigated by
integration with other allied technologies such as microwave-ODS,
adsorptive-ODS, extractive-ODS, ultrasound-ODS, electrochemical-ODS,
thermodynamic-ODS, and photocatalytic-ODS.[111–117] Among these
developing integrated technologies photocatalytic oxidative desulfurization
method has revealed exceptional potential owing to its extraordinary
benefits, such as carbon-neutral, chemical reaction driving by photon
rather than high pressures and temperatures, employment of abundantly
available solar energy.[118]
Photocatalysis-assisted desulfurization is grasping sufficient attention in
recent years.[119,120] Considering the importance and advancement of deep
aerobic photocatalytic oxidative desulfurization process (APODS) in the
emerging world, this process has not broadly been reviewed so far to the
best of our acquaintance. Curiously, many available viewpoints and literature
reviews deliberated only the ODS process alone, [38,117,121–127] or discussing
the APODS to a limited extent.[128] However, reviews on APODS are inter­
mittent so far, despite the statistic that reveals the massive research work has
been conducted for the advancement in this field recently. The objective of this
paper is to provide an inclusive framework consequential from the accessible
literature on the progression of deep APODS photocatalysts and the develop­
ment of new contests to alleyway and a break-through advancement in the
commercial desulfurization catalysts to produce sulfur-free refinery products.
Moreover, the APODS photocatalysts presently established in the exploration
centers for the up-gradation of the commercial desulfurization procedures in
petroleum refineries are also discussed.
 CATALYSIS REVIEWS 5

2. Aerobic photocatalytic oxidative desulfurization (APODS)

Photocatalytic technology employs light irradiation for the activation of
a photocatalyst for boosting the progression of a chemical reaction to address
various environmental contamination issues. Photocatalysis is an advanced oxida­
tion process, grasped significant attention since its discovery in the early 1970s by
Fujishima and Honda.[129] This special attention is due to its enhanced performance
in the abatement of an extensive range of hazardous chemicals under illumination,
oxidant and photocatalyst, and revealing sufficient potential in commercial
application.[130–132] The superlative characteristics of photocatalysis include its
operability at moderate conditions, eco-friendliness, sustainability, inexpensively,
non-complexity, and effective conversion of hazardous chemicals into eco-friendly
yields with sufficient selectivity.[133–136]
Visible light-driven photocatalysis has grasped global attention for addres­
sing several environmental contamination concerns, economic characteristics,
energy-efficiency, and specifically owing to high efficiencies.[137–142] Visible
light is abundantly available worldwide due to its high percentage availability
in the solar spectrum.[143] The high-efficiency photocatalysis process requires
firm redox ability and an extensive range of light absorption.[144] However,
single-component photocatalysis embraces a restricted light-capturing range,
inadequate separation of charges, swift electron-hole recombination, and
feeble redox capability.[145] Generally, the narrower bandgap is desirable for
obtaining a photocatalyst with an extensive light absorption range. A negative
conduction band (CB) and high positive valence band (VB) is essential for
enhanced redox ability.[144] So far, the tuning of these two parameters is yet an
enormous challenge.
Being associated with the ODS family, aerobic photocatalytic oxidative desul­
furization (APODS) is well thought out to be an auspicious technology.[146] This
is owing to its non-complexity, effectiveness, inexpensively, truncated energy
consumption, improved safety, and enhanced activity performance. Besides, this
technology is an absolute greener substitute capable of the conversion of toxic
organo-sulfur compounds into eco-friendly products. This procedure is entirely
distinct from EDS and ADS, where organo-sulfur compounds are extracted or
adsorbed, respectively. The operating mechanism includes the chemical reaction
activation utilizing light illumination, air or molecular oxygen as oxidant and
a semiconductor photocatalyst. Numerous research work has been conducted to
synthesize an efficient photocatalyst for the desulfurization of petroleum refinery
streams. Several criteria comprising bandgap energy, textural characteristics,
exposed surface area, specific pore volume, morphological properties, surface
defects, reaction conditions including initial concentration and nature of
organo-sulfur compounds, catalyst dosage, reaction time, air or molecular oxy­
gen flow rate are among the crucial factors for enhancing the cumulative
APODS activity performance.
6 I. SHAFIQ ET AL.

2.1. Process description

Usually, the aerobic photocatalytic oxidative desulfurization (APODS) process

proceeds through two major zones, the photocatalytic oxidation zone, and the
sulfones separation zone, as shown in Figure 1. In the first zone, the feedstock
containing refractory organosulfur compounds are introduced into the photo­
catalytic oxidation reactor, where light irradiations are employed for the
activation of photocatalyst, under the abundant oxygen availability. The orga­
nosulfur compounds present in the feedstock are converted into sulfoxides
and sulfone. In the second zone, the sulfoxides and sulfone produced in the
preceding zone are separated from the system by using the traditional pro­
cesses of adsorption and/or extraction. The generalized reaction occurring in
the entire process is shown in equation (1):

Organosulfur compound + Oxygen Sulfone (1)

The removal of dibenzothiophene (DBT) and its derivatives is the most

challenging task in the commercially used hydrodesulfurization process,
owing to its least reactivity in the HDS system. The APODS process has an
added advantage that these least reactive refractory organosulfur compounds
appear to be the more reactive species in the APODS process, as shown in
equation (2).

+ O2
(2)

Figure 1. Simplified overview of the aerobic photocatalytic oxidative desulfurization process.

 CATALYSIS REVIEWS 7

The APODS technology is not as much of capital and operational expenses

as that of HDS technology, exhibiting its installation feasibility in smaller sized
refining plant and considerable option for newly designed petroleum refi­
neries. The application of the technology is positioned at downstream of the
commercial HDS unit, to process the feed stream with sulfur contents less than
500 ppm, containing only refractory organosulfur compounds.

2.2. Chemistry of APODS process

The basic principle of APODS can be explained as a simple photocatalytic
mechanism of generation, transmission, and utilization of photo-generated
electrons (e−) and holes (h+) for the desulfurization of refractory organo-sulfur
compounds in an aerobic environment under sufficient illumination, as shown
in Figure 2. The aerobic environment can be provided either by the bubbling
of molecular oxygen or by fresh air, depending upon the process design
parameters. The incident beam of light comprising of the photons with energy
content equal to and/or greater than the bandgap energy of the semiconductor
photocatalyst, absorbs on the surface of that semiconductor, subsequently
exciting the electrons from the valence band (VB) to the conduction band
(CB), generating holes in the valence band.
In an aerobic environment, the photogenerated electrons approach the
surface of the semiconductor photocatalyst and reduce the molecular oxygen
(O2) to generate superoxide anion species/radicals (O2•−,O22-), [147,148] which

Figure 2. Schematic illustration of photocatalytic oxidative desulfurization of liquid fuels.

8 I. SHAFIQ ET AL.

can onwards transform into OH• through a series of reactions.[149] These

series of reactions may include the reaction of the oxygen anion radicals
with the surface’s hydroxyl ions (H+) and/or the hydroxyl ions of the adsorbed
water vapors in the air as follows[150–153]:

Photocatalyst + hv (light waves) e−CB+ h+VB (3)

e−CB+ O2 .
O2− (4)
.
O2−+ H+ .
HO2 (5)

2.O2−+ 2 H2OH2 O2 + 2OH− + O2 (6)

.
HO2+ H++ e−CB H2O2 (7)

H2O2+ e−CB .
OH+ OH− (8)

This period is believed to be the initial step in the generation of the highly
unstable, reactive, and oxidized form of thiophene-based organo-sulfur com­
pounds in the addition of these photogenerated anionic radicals at 2/5 position
of the thiophene ring.[154,155] Moreover, the photogenerated superoxide anion
species/radicals (O2•−,O22-) have sufficient capability to oxidize the organo-
sulfur compounds to their corresponding sulfoxides and sulfones.[150]
.
O2−+ 2DBT 2DBTO (9)
.
O2−+ 2DBT 2DBTO2 (10)

In the meantime, the photogenerated holes capture electrons from the

refractory organo-sulfur compounds absorbed on the surface of the semicon­
ductor photocatalyst or by reacting with adsorbed water vapors in the air (H2
O) to generate OH• radicals.[156] The chemical interactions between the OH•
radicals and the photogenerated holes with these unstable, reactive, and
oxidized forms of thiophene-based organosulfur compounds give rise to
a series of oxidation reactions.[157–159]

h+VB+ OH− (ads) .

OH (11)

h+VB+ H2O (ads) .

OH + 2H+ (12)
.
OH + DBTDBTO+ H+ (13)
.
OH + DBT DBTO2 + H+ (14)

Up to the present, the foremost challenge in the development of an efficient

semiconductor photocatalyst is the rapid recombination of photogenerated
electron-hole pairs (Figure 3), owed to the robust coulombic force prevailing
 CATALYSIS REVIEWS 9

Figure 3. Basic conceptualization of the photogeneration process of electron-hole pairs.

between these photogenerated species. On the other hand, the sulfur atom of
the organosulfur compounds has two lone pairs of electrons and thus, the
hydroxyl radicals appeared to be more reactive than that of superoxide
anions.[150,160] Therefore, the oxidation of organosulfur compounds is vividly
reliant on the generation rate of hydroxyl radicals. The recombination of
photogenerated species readily hinders the generation of hydroxyl radicals,
decreasing the oxidation rate of the organosulfur compound. The abundant
availability of oxygen not only initiates the plenteous generation of superoxide
anions and hydroxyl radicals but it also hinders the recombination of photo­
generated electron-hole pairs. The presence of an aerobic environment and/or
the adsorption of oxygen on the semiconductor photocatalyst surface effec­
tively inhibit the recombination of electron-hole by acting as an active electron
trap.[161] Thus, the photogenerated charges are consumed swiftly and the
recombination of photogenerated electron-hole both on the surface and in
the bulk of semiconductor photocatalyst is hindered.
Nevertheless, the significance of the aerobic and anaerobic environment
was comprehensively studied by providing the oxygenated and nitrogenous
environment, respectively, over a mesoporous graphite-based carbonitride
photocatalyst.[162] A series of experiments were performed to investigate the
10 I. SHAFIQ ET AL.

effect of molecular oxygen (O2) in the oxidative desulfurization mechanism. It

was reported that the N2 environment exhibits the DBT desulfurization
efficiency of 41% only, while the O2 environment revealed the desulfurization
efficiency of up to 100% under the same reaction conditions, as shown in
Figure 4. The combined theoretical and experimental results demonstrated
that the presence of molecular oxygen is obligatory for attaining sufficiently
higher desulfurization rates.

2.3. Reactivity of organosulfur compounds

The oxidation reactivities of organosulfur compounds for the aerobic-based

photocatalytic process have been studied by various research groups. There is
an extensive relationship between the oxidation reactivity and the electron
density/stearic hindrance of the organosulfur compounds. The organosulfur
compounds with a more sterically hindered structure restrict the oxygen
approach toward the S-atom, consequentially exhibiting dropped reactivity.
Nevertheless, there is a bit of inconsistency observed in the order of photo­
catalytic oxidation reactivities reported in the literature.
The detailed investigation of the photocatalytic oxidation reactivities of
organosulfur compounds is obligatory for an efficient APODS reactor
design for commercial applications. Wenshuai Zhu et al. reported the
photocatalytic oxidation reactivities of organosulfur compounds in the

Figure 4. Effect of nitrogen (a), and oxygen (b) on the photocatalytic oxidative desulfurization
process .[162]
 CATALYSIS REVIEWS 11

following order: BT > DBT > 4,6-DMDBT.[163] It was proven from experi­
mentation that the order of photocatalytic oxidation reactivities varies by
varying the reaction conditions. Otsuki et al. reported the electron densities
and the reaction rate constant values for most commonly found organo­
sulfur compounds in the petroleum product streams.[164] Experimentations
proved that the oxidation reactivities of organosulfur compounds upsurge
with the increased electron density of S-atom. As per electron density
trends, the oxidation reactivities of organo-sulfur compounds are in the
following order: 4,6-DMDBT > DBT > BT. A similar trend was observed in
the other ODS systems.[165,166] On the other hand, continuous research
work in the ODS field revealed more different trends of oxidation reactivity
as well, such as DBT > 4,6-DMDBT > BT[119,167,168] and DBT > BT >
4,6-DMDBT.[169–171] These orders of reactivities were attributed to the
combined effect of steric hindrance and electron densities. In intermittent
cases, BT > DBT > 4,6-DMDBT order of reactivities is also reported,
[163,172]
which is totally inverse of the electron density concept. It was
reported that this order of reactivities might be due to the utilization of
larger sized oxidizing agents. However, BT and DBT have nearly similar
steric hindrance in their structures, but BT is revealing higher reactivity,
yet having lesser electron density on the sulfur atom. Precisely, there is
great ambiguity persisting in the available literature regarding the order of
photocatalytic oxidation reactivities. Further, the order of oxidation reac­
tivities for organosulfur compounds endorsed by several viewpoints is as
follows [,121,123,126]:

4,6-DMDBT > 4-MDBT > DBT > BT > T.

2.4. Commercial applications

Modern petroleum refineries employ the HDS process for the commercial
level production of marketable refinery products in compliance with
national and international regulatory authorities. Considering the impor­
tance of sulfur removal and the regulatory requirements, the commercia­
lization of alternative desulfurization is extremely important. However, the
APODS process is a brilliant candidate for its consideration for commer­
cialization. The desulfurized product from a conventional refining unit
generally contains several refractory organosulfur compounds such as
4,6-DMDBT and its derivatives. These compounds generally require extre­
mely severe reaction conditions for desulfurization owing to their least
reactivity. Curiously, these compounds are observed to be highly reactive
in the APODS process. Thus, an APODS unit can be designed at down­
stream of the HDS unit for the production of sulfur-free products, as
shown in Figure 5.
12 I. SHAFIQ ET AL.

Figure 5. Integrated approach for the commercialization of photocatalytic desulfurization.

The commercialization of a novel desulfurization technology requires its

feasibility for effectiveness at the commercial scale. The following require­
ments should adequately comply for qualifying a novel desulfurization tech­
nology for commercial applications[30]:

(1) Capital cost: The technology needs the least plant utility requirements is
highly desired.
(2) Operational cost: An untroublesome operational cost is desired.
(3) Technical perspective: Less complicated technology is needed.
(4) Overall compatibility with refinery: Should not cause any functional
issue to adjacent units.
(5) Health, Safety & Environment: Technology with minimum impact on
the surroundings to be preferred.

Accomplishing the aforementioned conditions is likely to be nearly impos­

sible. Yet, this is mandatory for a process technology to compete with the
traditional technology to qualify for commercialization. Though the most
commonly used hydrodesulfurization technology does not fully comply
with these criteria, still the technology is being used widely due to its
outstanding performance for the desulfurization of sulfur-rich streams. In
our opinion, APODS technology is a brilliant candidate to be considered as
a substitute for deep desulfurization systems by integrating with the HDS
technology.
 CATALYSIS REVIEWS 13

3. Deep APODS performances

In semiconductor photocatalysis, a narrow bandgap is desired for the effective
utilization of solar energy, whereas a wider bandgap is desired for the achieve­
ment of adequate redox tendency on a single-component semiconductor
photocatalyst. Besides, the deficiency of appropriate compatibility between
the light receptive range and the firm redox ability for a single-component
semiconductor photocatalyst confines its range of applications. Several
attempts have been reported such as enhancing the surface areas of photo­
catalysts, doping with other metal and/or nonmetal elements, and using the
combination of two or more semiconductors, etc.

3.1. Enhancing the surface area

Nowadays numerous photocatalysts are available for the proceeding of the
aerobic photocatalytic desulfurization reactions. Day by day new and more
effective photocatalysts are being developed. However, the activity perfor­
mance of all these photocatalysts is seriously restricted by the high agglomera­
tion capability. This undesired agglomeration of small-sized photocatalyst
particles leads toward the inhibition of APODS reactivity greatly. To resolve
the aforementioned issue, the use of support material is a promising technique
for the development of photocatalytic materials capable of generating super­
lative results. Several research groups have studied the effects of using the
support materials for the enhancement of the surface area of material to
reduce the agglomeration and make it possible to develop plentiful accessible
reaction sites. Herein, the advances in enhancing the exposed surface area of
semiconductor photocatalysts reported in recent years are briefly discussed
and also summarized in Table 1.

3.1.1. Colloidal silica

Carbon nitride (C3N4) is among the most common photocatalysts widely used
for dye degradation, CO2 reduction, water splitting, and associated depollu­
tion applications under visible light irradiations.[176–182] C3N4 is an efficient
photocatalyst with a bandgap of 2.7 eV.[183] It is worth mentioning that the
specific surface area of carbon nitride is very small, i.e. around 14.9 m2/g .[184]
Yunfeng Zhu et al. reported the synthesis of novel graphitic carbon nitride
with the mesoporous structure using the SiO2 template etching technique.[162]
The as-synthesized mpg-C3N4 photocatalyst revealed extraordinary aerobic
performance by completely desulfurizing the organosulfur compounds in
90 minutes. The comparison of g-C3N4 and mpg-C3N4 photocatalysts was
also studied to investigate the effect of surface area enhancement. It can be
seen from Figure 6 that the mesoporous catalyst with improved specific sur­
face area (194 m2/g) exhibited far better aerobic desulfurization performance
 14

Table 1. Summary of the modifications for the enhancement of the exposed surface area of the semiconductor photocatalysts.
I. SHAFIQ ET AL.

Surface Catalyst Activity

Catalyst area dosage Sulfur (Percent
Sr Photocatalyst Support Synthesis method Light Source (m2/g) (gL−1) Reactor (ppm) Conversion %) Ref
[162]
01 g-C3N4 SiO2 Hydrothermal 300 W xenon lamp (visible light) 194 10 100 ml Closed glass vessel BT 99.9% in 90 min
100
DBT 99.9% in 90 min
100
4,6-DMDBT 99.9% in 70 min
100
[173]
02 MoO3 TMU-5 Facile in situ synthesis 300 W xenon lamp (UV and Visible 557 2.5 Cylindrical quartz UV DBT 95.6% in 60 min
(MOF) method light) reactor 521
[146]
03 R-PcFe Ti-MCM Hydrothermal Visible light 366 2 Homemade instrument DBT 95.6% in 120 min
-41 1000
[174]
04 TiO2 Cu-BTC Hydrothermal 300 W high-pressure mercury lamp 901 - 100 ml photochemical BT 86% in 20 min
(UV light) reactor 1000
DBT 95% in 20 min
1000
[175]
05 TiO2 SiO2 Hydrothermal 300 W xenon lamp (UV light) 659 50 100 mL three mouth glass BT 88% in 60 min
reactor 50
DBT 100% in 60 min
50
4,6-DMDBT 96% in 60 min
50
 CATALYSIS REVIEWS 15

Figure 6. Effect of exposed surface area with C3N4 (a), and mpg-C3N4 (b) on the photocatalytic
oxidative desulfurization process .[162]

that of g-C3N4. The mpg-C3N4 photocatalyst desulfurized DBT completely in

90 minutes, while g-C3N4 hardly achieved 41% in 110 minutes.

3.1.2. Metal-organic framework

MoO3 is a well-known photocatalyst used for various photocatalytic
applications.[185] The activity performance of MoO3 can be further enhanced
by increasing the exposed surface area. Minoo Bagheri et al. reported the
enhancement of the surface area of MoO3 catalyst by using MOF.[173] 5 wt%
MoO3 was added on the TMU-5 support (surface area 591 m2/g) to obtain the
desired photocatalyst. The photocatalyst exhibited excellent aerobic photoca­
talytic desulfurization performance by achieving 95.6% efficiency in 60 min­
utes. However, the photocatalyst exhibited poor recyclability.

3.1.3. MCM-41
MCM-41 is an extensively explored mesoporous molecular sieve with a high
surface of around 1000 m2/g.[186] The presence of limited acid sites and no
surface charge presence makes it an inefficient catalytic candidate.[187]
However, the incorporation of titanium (Ti4+) could transform it into
a competent photocatalyst.[188,189] Ran Liu et al. reported the loading of
R-PcFe over Ti-MCM-41 to obtain an efficient photocatalyst for aerobic
desulfurization application.[146] The photocatalyst revealed the 95.6% removal
16 I. SHAFIQ ET AL.

of DBT at optimized experimental conditions. However, the photocatalyst

exhibited impressive recyclability.

3.1.4. Core-shell Cu-BTC

The integration of photocatalytic desulfurization and adsorptive desulfuriza­
tion is considered to be a capable combination of the deep desulfurization
applications.[190] Jing Liu et al. reported the synthesis of Cu-BTC@TiO2
microspheres.[174] The TiO2 shell was employed as the photocatalytic oxidiz­
ing agent, while Cu-BTC was employed as the adsorbent for the oxidation
products. Characterization revealed the jagged surface of the photocatalyst,
confirming the generation of an external layer of TiO2 particles over Cu-BTC.
The as-synthesized combined-desulfurizer exhibited outstanding desulfuriza­
tion results by converting 95% of DBT within 20 minutes. This high efficiency
was attributed to the efficient electron-holes transfers over the photocatalyst.
Kinetic studies revealed the pseudo-first-order reaction mechanism.

3.1.5. Silica (H2O2-assisted synthesis)

Xin Li et al. reported the hydrothermal synthesis of TiO2-SiO2-H using
hydroperoxide.[175] Several photocatalysts were synthesized by varying the
Ti/Si ratio and investigated for desulfurization performance for model oil
under UV light in the aerobic environment. The as-synthesized catalyst
revealed excellent desulfurization performance due to improved surface area,
enhanced radiations adsorption, and lessened electron/hole recombination.
Besides good desulfurization performance, the photocatalyst exhibited excel­
lent selectivity and regeneration capability.
Based on the experimental findings discussed above, it is worth mentioning
that the selection of appropriate support material is crucial for the develop­
ment of the photocatalyst with enhanced desulfurization performance. These
support materials significantly improve the textural properties of the photo­
catalyst material by not only enhancing the surface area but by reducing the
agglomeration of the particles, increasing the dispersion rate, enhancing the
availability of the more active site, high light-harvesting capability, low elec­
tron/hole recombination possibility, and above-all expressively generating the
sulfones adsorption capability in the photocatalytic materials, therefore boost­
ing the photocatalytic desulfurization performance, as shown in Figure 7.

3.2. Doping with other elements

TiO2 is the most explored photocatalyst owing to its high chemical stability,
non-toxicity, inexpensively, and photocatalytic activity performance.[120]
Nevertheless, few restrictions, such as wide bandgap and more electron-hole
recombination characteristics encumber its photocatalytic performance.[191,192]
Thus, several techniques have been investigated to improve the photochemical
 CATALYSIS REVIEWS 17

Figure 7. Effect of using support material for the enhancement of photocatalytic desulfurization
efficiency.

characteristics of TiO2, specifically doping with nonmetal anions and transition

or noble metal ions. This technique promotes the charge separation capability,
hinders the recombination of photogenerated electron-hole pairs, and contrib­
uted toward visible light responsivity.[193] Several research groups have studied
the effects of doping of metal and nonmetals in the crystal lattice of the
photocatalyst for the enhancement of charge separation capability of the mate­
rial and enhancing the light-responsive range to harvest a maximum portion of
the light irradiations. Herein, the advances in doping of metal ions and non­
metal ions into the semiconductor photocatalysts reported in recent years are
briefly discussed and also summarized in Table 2.

3.2.1. Ru-TiO2
Feng Lin et al. reported loading of RuO2 (0.045 wt%) on sulfated TiO2 and
investigated the as-prepared photocatalyst for aerobic desulfurization perfor­
mance of thiophene. Several characterization techniques were employed to
investigate the surface acidity and crystallinity of TiO2. The characterizations
revealed that the synergistic effect of RuO2 resulted in the capturing of more
superoxide active species and boosted the photocatalytic performance.[116]

3.2.2. Cu-TiO2
CNC Hitam et al. reported the synthesis of amorphous TiO2 by sol-gel method
and successive CuO doped amorphous TiO2 (5–20 wt% incorporation of Cu).
The as-prepared catalyst revealed richness in Ti-O-Cu bonds, oxygen vacan­
cies, and Ti3+ surface defects. Ti-O-N bonds were also found in the photo­
catalyst due to the usage of ammonium salt in the synthesis process. The
photocatalyst was tested over DBT desulfurization and revealed to be follow­
ing pseudo-first-order.[194]
 18

Table 2. Summary of the doping of metal ions and nonmetal ions into the semiconductor photocatalysts.
I. SHAFIQ ET AL.

Dopant Catalyst Activity

Catalyst quantity dosage Sulfur (Percent
Sr Photocatalyst Dopant Synthesis method Light Source (wt%) (gL−1) Reactor (ppm) Conversion %) Ref
[116]
01 SO42−-TiO2 Ru Incipient wetness method 300 W high-pressure 0.045 1 Pyrex reaction cell ThP 88% in 180 min
mercury lamp 600
[194]
02 TiO2 Cu Sol-gel method Visible light 5–20 1 Batch reactor DBT 99% in 90 min
100
[153]
03 TiO2 N Ultrasonic assisted impregnation 55 W xenon lamp - 3 100 ml Pyrex reactor DBT 40.3% in
reaction method 400 240 min
[195]
04 TiO2 Zr Urea gelation/co-precipitation 300 W xenon lamp (UV - 50 100 ml three-mouth BT 99.8% in
method light) glass reactor 50 240 min
DBT 99.6% in
50 120 min
4,6-DMDBT 99.9% in 30 min
50
[196]
05 α-MoO3 Ag Photoreduction process 500 W xenon lamp 5 1.5 Glass reactor ThP 98.3% in
(visible light) 500 270 min
[197]
06 TiO2 Fe, N Ultrasonic assisted impregnation 55 W xenon lamp 0.5 3 100 ml Pyrex reactor DBT 59.8% in
(co-doped) reaction method 400 240 min
[198]
07 g-C3N4 Na Simple mixed-calcination pathway 300 W xenon lamp - 5 Sealed reactor ThP 99% in 360 min
(visible light) 200
[48]
08 BiVO4 Ag Hydrothermal synthesis 400 W metal halide lamp - 0.0015 - ThP 95% in 210 min
500
 CATALYSIS REVIEWS 19

3.2.3. N-TiO2
Kaveh Kalantari et al. reported the synthesis of N-TiO2 by ultrasonic-assisted
direct impregnation technique. In the synthesis of N-TiO2, urea was used as
N source and TiO2-P25 was used as a titania source. The successful incorpora­
tion of nitrogen in titania lattice was confirmed by FTIR and XPS. A redshift
was observed in the light absorption range and the photocatalyst response was
observed in the visible light range. The as-synthesized photocatalyst was tested
for the desulfurization performance of DBT and compared to that of TiO2-
P25. N-TiO2 revealed improved catalytic performance. Besides, the photoca­
talyst revealed acceptable recyclability.[153]

3.2.4. Zr-TiO2
Wei Zhang et al. reported the synthesis of Zr-loaded TiO2 prepared via the co-
precipitation method. The as-prepared photocatalyst was employed as
a combined photocatalyst-adsorbent purpose. The as-prepared material
revealed enhanced UV irradiation adsorption capacity with improved selec­
tivity toward various organosulfur compounds. The calcination temperature
and Ti/Zr ratio were optimized at 500 and 5:5, respectively. The photocatalytic
material revealed enhanced aerobic desulfurization performance by achieving
99.6% desulfurization with 120 minutes. The photocatalyst exhibited excellent
activity over multiple recycling experimental runs.[195]

3.2.5. Ag-α-MoO3
YanZhong Zhen et al. reported the synthesis of Ag-α-MoO3 by the photo­
reduction method. The as-prepared photocatalyst revealed excellent thiophene
desulfurization performance compared to that of α-MoO3. The experimental
results proved that the superoxide species and holes were the prime species
driving the overall desulfurization process, demonstrating the potential of Ag-
α-MoO3 for desulfurization applications. The repeated recycled experimental
runs confirmed the admirable stability of the as-synthesized photocatalyst.[196]

3.2.6. Fe-N-TiO2
Kaveh Kalantari et al. reported the synthesis of Fe-N co-doped TiO2 prepared
via ultrasonic-assisted direct impregnation technique. The co-doping of N and
Fe-TiO2 consequent in increasing the specific surface area and decreased
crystallite size. The as-prepared photocatalyst was investigated for aerobic
desulfurization performance of DBT under visible light. The co-doped photo­
catalyst was far more efficient than that of a mono-doped counterpart. This
improved performance was attributed to the extension of the light adsorption
range due to the co-doping of iron and nitrogen. This co-doping promotes the
separation of photogenerated charges and inhibits the electron-hole recombi­
nation. Furthermore, the dopant loading was optimized at 0.5 wt%.[197]
20 I. SHAFIQ ET AL.

3.2.7. Na/g-C3N4
Xibiao Zhang et al. reported the NaCl-assisted doping of Na in g-C3N4 via
a mixed-calcination method. The chemical, structural, and photophysical
properties of the as-synthesized photocatalyst were demonstrated using
several characterization techniques and compared to that of pure g-C3N4.
The synthesis method results in the production of a porous and highly
dispersed structure, contributing to increasing the light-harvesting cap­
ability and narrowed recombination of photogenerated electron-hole pairs.
The as-synthesized catalyst revealed excellent thiophene desulfurization
performance.[198]

3.2.8. Ag-BiVO4
Xiao-Ming Gao et al. reported the synthesis of a series of visible-light respon­
sive Ag-doped BiVO4 photocatalysts via hydrothermal technique. A reliable
relationship among the preparation procedure, material structure, and physi­
cochemical properties was observed. The crystallinity of material increased
gradually by increasing the pH, in addition to light-harvesting capability
owing to the phase transformation from tetragonal to monoclinic phase. The
material synthesis at neutral pH revealed extraordinary aerobic photocatalytic
oxidative desulfurization performance by transforming 95% of sulfides within
210 minutes. Moreover, the as-synthesized photocatalyst revealed improved
exposed surface area.[48]
Based on the experimental findings discussed above, it is worth mentioning
that the selection of an appropriate doping metal ion or nonmetal anion is
crucial for the development of the photocatalyst with improved desulfuriza­
tion performance. These dopants expressively improve the bandgap of the
photocatalytic semiconductor materials, confirms the accessibility of the addi­
tional active site, extended light-responsive range, improved light absorption
tendency, little photogenerated electron/hole recombination opportunity, and
thus enhancing the photocatalytic desulfurization performance, as shown in
Figure 8.

3.3. Combination of semiconductors

In single-component semiconductor photocatalysis, the swift recombination
of photogenerated electron-hole restricts its wide applications, as the recom­
bination of charges consequents into the truncated quantum efficiency and
deprives the catalytic activity.[199] The combination of two or more than two
semiconductors generates a heterogeneous structure, which will possibly be
able to address this problem by providing a wider light photon absorption
range and hindering the recombination of photogenerated electron-hole.[200]
In the combination with two or more than two semiconductors, the swift
recombination of photogenerated electron-hole is prevented by the shifting of
 CATALYSIS REVIEWS 21

Figure 8. Effect of metal doping for the enhancement of photocatalytic desulfurization efficiency.

charges from the energy levels of one semiconductor photocatalyst to the

energy levels of an adjacent one.[201] The association between the energy levels
of the different semiconductors in the heterogeneous structure provides an
enduring and efficient separation of photogenerated charges. Therefore,
research groups are more focused on developing novel and prolific hetero­
geneous semiconductor structures. Herein, the advances in the development
of heterogeneous semiconductor photocatalysts reported in recent years are
briefly discussed and also summarized in Table 3.

3.3.1. MTcPc/SnO2
Gai Zhang et al. reported the in-situ hydrothermal synthesis of a composite
series of metal phthalocyanine/SnO2 (MTcPc/SnO2). The morphological,
structural, and physicochemical characteristics of as-prepared composites
were investigated by several characterization techniques. The photocatalytic
activities of these composites were evaluated under visible light irradiations
for the desulfurization performance on a model solution containing thio­
phene in an aerobic environment, as shown in Figure 9. The aerobic photo­
catalytic desulfurization activities were found in following order:
ZnPcTc/SnO2 > CuPcTc/SnO2 > MnPcTc/SnO2 > FePcTc/SnO2 > SnO2.
The formation of heterojunction between SnO2 and MPcTc significantly
enhanced the photocatalytic performance of the photocatalyst due to the
transfer of electrons from the valence band of phthalocyanine to the con­
duction band of SnO2. This easy transfer rate tends to the effective separation
of charges and prevents the chances of photogenerated charges recombina­
tion. The ZnPcTc/SnO2 exhibited the highest thiophene aerobic photocata­
lytic degradation performance.[202]
 22

Table 3. Summary of the heterogenous material forming by combination of two semiconductor photocatalysts.
I. SHAFIQ ET AL.

Catalyst Activity
Coupling Catalyst dosage Sulfur (Percent
Sr Photocatalyst Photocatalyst Synthesis method Light Source (gL−1) Reactor (ppm) Conversion %) Ref
[202]
01 ZnTcPc SnO2 In situ hydrothermal 400 W halogen lamp (visible light) 20 100 ml Glass flask ThP 98.55% in
800 180 min
[203]
02 ZnTcPc g-C3N4 In situ hydrothermal 400 W halogen lamp (visible light) 20 100 ml Glass flask ThP 84.4% in 90 min
800
[204]
03 CeO2 ATP (attapulgite) Facile precipitation method 300 W xenon lamp (Visible light) - Photocatalytic reaction DBT 87% in 240 min
apparatus 200
(GHX-2)
[205]
04 Bi2S3 Bi2WO6 Multistep process 400 W halogen lamp (visible light) 0.8 - ThP 100% in 90 min
500
[206]
05 Mn3O4 Ag2WO4 Microwave-assisted 400 W medium pressure mercury lamp 1.2 Pyrex reaction cell ThP 100% in 60 min
coprecipitation route (visible light) 600
[207]
06 AgI α-MoO3 Facile hydrothermal method 400 W metal halide lamp (visible light) 2 50 mL quartz tube reactor ThP 97.5% in 120 min
500
[208]
07 Cu2O BiVO4 Pechini sol-gel method 400 W Osram lamp 1 - ThP 92% in 150 min
(Visible light) 800
[209]
08 AgI Bi2O3 glycothermal method 400 W Osram lamp 1 - DBT 93% in 120 min
(Visible light) 800
[210]
09 Ti3C2 g-C3N4 Ultrasonic assisted synthesis 300 W xenon lamp (Visible light) 2.5 - ThP 99% in 180 min
140
[211]
10 Cu2O CeO2 Single-step sonochemical 400 W Osram lamp 0.8 - ThP 84% in 30 min
method (Visible light) 800
 CATALYSIS REVIEWS 23

Figure 9. Photocatalytic desulfurization performance of different MTcPc/SnO2 .[202]

3.3.2. ZnTcPc/g-C3N4
Gai Zhang et al. reported the in-situ hydrothermal synthesis of zinc phthalo­
cyanine/g-C3N4 (ZnTcPc/g-C3N4). The morphological, structural, and physico­
chemical characteristics of the as-prepared composite were investigated by
several characterization techniques. The photocatalytic activity of the composite
material was evaluated under visible light irradiations for the desulfurization
performance on a model solution containing thiophene in an aerobic environ­
ment. The as-synthesized heterogenous material exhibited superior activity
performance compared to that of pure g-C3N4. The heterojunction presented
improved distribution and wider response to visible light irradiations. A novel
interaction between the two semiconductor materials was observed, allowing
the swift transfer of charges between the adjacent energy levels.[203]

3.3.3. CeO2/ATP
Fengqin Wu et al. reported the synthesis of Er3+:CeO2/ATP (attapulgite)
nanocomposites by a single-step facile precipitation method. The formation
of heterogenous structure consequents in the generation of oxygen vacancy
intermediation, which significantly contributes toward the swift photogener­
ated electrons transfer and hinders the recombination of these charges. The
mass ratio of ATP and Er3+:CeO2 was optimized at 10:4 to reach the maximum
aerobic photocatalytic oxidative desulfurization efficiency.[204]
24 I. SHAFIQ ET AL.

3.3.4. Bi2WO6/Bi2S3
Li Guo reported the synthesis of Fe3O4@SiO2/Bi2WO6/Bi2S3 (F-BWO-BS) by
the multistep process with novel magnetic properties. The formation of hetero­
genous structure results in improving the optical absorption capability and
widen the visible light absorption range. The photogenerated holes were the
key driving species for enhanced activity performance. The experimental find­
ings verified the magnetic characteristics of as-synthesized composite material.
Moreover, the material exhibited excellent recyclability and stability.[205]

3.3.5. Mn3O4/Ag2WO4
Ahmed Shawky reported the synthesis of Mn3O4/Ag2WO4 heterostructure by
a simple microwave-assisted coprecipitation method. The optimized mass
ratio of Mn3O4 and Ag2WO4 materials revealed the noticeable narrowing of
bandgap, extension of light absorption range, improved charges separation
and preventing the recombination of photogenerated electron-holes. The as-
prepared composite material was investigated for aerobic photocatalytic oxi­
dative desulfurization performance for thiophene under visible light irradia­
tions and completely degraded thiophene within an hour. The as-prepared
composite material revealed superior recyclability and stability.[206]

3.3.6. AgI/α-MoO3
Yanzhong Zhen et al. reported the synthesis of a novel Ag/AgI/α-MoO3
composite structure. The morphology, composition, optical, and charge
transfer characteristics were evaluated by several characterization techni­
ques. The as-synthesized heterogenous structure revealed extraordinary
aerobic oxidative performance approaching over 97% degradation for thio­
phene. The photogenerated holes, hydroxyl radicals, and oxygen superoxide
radicals were reported to be the most dominant conversion species. CO2,
SO3 and H2O were detected as the final end-products received after miner­
alization of thiophene. The verification of these end-products generations
was verified by the formation of BaCO3 and BaSO4 by reacting with
Ba(NO3)2.[207]

3.3.7. Cu2O/BiVO4/Bi7VO13
Mehdi Mousavi-Kamazani et al. reported the facile sol-gel synthesis of the
bismuth vanadate and copper oxide composites. The amounts of reactant
precursors were optimized. [Link] ratio was found optimum for Cu:Bi:V ele­
ments were adjusted to obtain the heterojunction of rectangular-cubes mor­
phology with high surface area and small-sized cubes of around 50 nm.
Impressive light-harvesting and electron-holes generation were observed by
the as-synthesized material under visible light irradiation. Interestingly, cop­
per is doped on the heterojunction to enhance the conductivity and improving
the aerobic oxidative catalytic performance.[208]
 CATALYSIS REVIEWS 25

3.3.8. AgI/Bi2O3
Mehdi Mousavi-Kamazani reported glycothermal synthesis of flower-like
AgI/Bi2O3 composite by using Tween 80 surfactant. The experiment-based
degradation mechanism findings suggested that the photogenerated holes and
oxygen superoxide species were the dominant species of the overall oxidation
process. The formation of specific morphology, Z-scheme system resulted in
improved light-harvesting, superior separation of charges and swift transfer of
electron-hole pairs. These characteristics were cumulatively consequent for
the exhibition of excellent aerobic photocatalytic oxidative efficiency.
Moreover, the as-synthesized heterojunction revealed acceptable recyclability
and stability.[209]

3.3.9. Ti3C2/g-C3N4
Bolun Li reported the ultrasonic-assisted synthesis of Ti3C2/g-C3N4 composite
and evaluated for aerobic oxidative desulfurization performance for thiophene
under visible light irradiations. The photoelectric and structural properties of
the as-synthesized composite were investigated by several characterization
techniques. The successful intercalation of both semiconductors enhanced
the transfer of electrons from g-C3N4 to Ti3C2 structure and prevents the
recombination of photogenerated charges. DFT studies and experimental
analysis revealed that the photogenerated holes were the primary driving
species for the desulfurization mechanism, while the oxygen superoxide radi­
cals and photogenerated electrons provided the promotional role in the overall
conversion process. Ti3C2/g-C3N4 composite revealed high desulfurization
efficiency, higher photocatalytic activity, and virtuous stability and
recyclability.[210]

3.3.10. Cu2O-CeO2
Mehdi Mousavi-Kamazani et al. reported the single-step sonochemical synth­
esis of Cu2O-CeO2 nanocomposites and evaluated for aerobic oxidative desul­
furization performance for thiophene under visible light irradiations. The
characterization techniques revealed that the CuO-CeO2 was produced in
the absence of ultrasonic irradiations, rather than Cu2O-CeO2. The as-
synthesized nanocomposite resulted in high photocatalytic oxidation perfor­
mance compared to that of CuO-CeO2 owing to the synergistic effect of
photogenerated electrons, improved light-harvesting capability, and improved
charges separation. The as-synthesized nanocomposite revealed good stability
and recyclability.[211]
Based on the experimental findings discussed above, it is worth mentioning
that the selection of an appropriate combination of semiconductor photoca­
talysts for synthesizing heterojunctions is very crucial for the development of
the photocatalyst with improved desulfurization performance. The strategy of
synthesizing heterojunctions expressively improves the bandgap of the
26 I. SHAFIQ ET AL.

Figure 10. Effect of synthesizing heterogeneous materials by the combination of two or more
semiconductors for enhancement of photocatalytic desulfurization efficiency.

photocatalytic heterojunction structures, extended light-responsive range,

improved light absorption tendency, inhibits the photogenerated electron/
hole recombination by the shifting of photogenerated charge carriers from
the energy levels of one semiconductor photocatalyst to the energy levels of
adjacent one (as shown in Figure 10), and thus enhancing the photocatalytic
desulfurization performance.

4. Process optimization
The selection of optimal parameters is crucial in enhancing the efficiency
of the aerobic photocatalytic desulfurization process.[98,212] Wenshuai Zhu
et al. reported an attempt to investigating the aerobic photocatalytic
desulfurization process performance for DBT removal from model oil in
different reaction conditions. The desulfurization efficiency was very low,
as shown in Figure 11, around 2.1% and 7.8%, when using UV light and
extractant only, respectively. However, the grouping of extractant and UV
light in the aerobic environment slightly raised the efficiency to 9.5%, as
shown in the figure. Interestingly, isobutyl aldehyde was added to the UV
system, in an aerobic environment. This combination resulted in an
elevated photocatalytic desulfurization performance up to 63.4%, which
is still not compliant with the deep desulfurization goal. Stimulatingly, the
deep eutectic solvent (DES) was introduced into the system and the
desulfurization performance surprisingly jumped to 96.3%, conquering
the deep desulfurization goal. Moreover, the research group investigated
the influence of replacing the air flowrate with nitrogen gas. The activity
 CATALYSIS REVIEWS 27

Figure 11. Desulfurization efficiency of different combinations of photocatalytic desulfurization

systems .[163]

performance was radically reduced to just 10.8%. Furthermore, the

absence of UV irradiation resulted in providing 11.6% efficiency only.
Summarizing, the above investigation revealed that isobutyl aldehyde can
be utilized for the enhancement of active species production under UV
irradiation in an aerobic environment and both air as oxidant and deep
eutectic solvent as extractant played a vital role in improving photocata­
lytic desulfurization performance.[163]
In addition to these parameters, numerous other factors are responsible for
regulating the aerobic photocatalytic desulfurization performances such as the
initial concentration of organosulfur compounds, the flow rate of oxygen or
air, the temperature of the reactor, and the catalyst dosage. These imperative
factors are discussed below:

4.1. The initial concentration of S-compound

The initial concentration of the organosulfur compound in the reaction
solution is a dynamic factor in driving the overall photocatalytic efficiency.
Literature shows that the lower the concentration of organosulfur com­
pounds in the feed stream, the higher will be the photocatalytic desulfuriza­
tion performance.[98,132,163,194,195] It is worth mentioning that the increase in
the initial concentration of organosulfur compounds, lower will be the
photocatalytic performance. This is most likely due to the adhesion of
a high number of organosulfur compounds over the surface of the
28 I. SHAFIQ ET AL.

photocatalyst, in addition to the interruption of the light irradiation passage.

Up to the present time, the relating trend is observed for the photocatalytic
abatement of other organic compounds such as paracetamol, ibuprofen,
bisphenol A, and chloroaniline.[213–216]

4.2. Temperature

The temperature of the reaction solution is observed to be a critical factor in

regulating the photocatalytic desulfurization efficiencies. Literature shows
that the lower temperature favors the photocatalytic desulfurization of orga­
nosulfur compounds.[210] Bolun Li et al. investigated the effect of tempera­
ture on the photocatalytic desulfurization efficiency. The PL spectra of the
same catalyst were examined at room temperature and 40°C. It was observed
that the PL spectra of the catalyst sample at 40°C was much stronger than
that at room temperature, which represents the swift recombination of
photogenerated electron-hole at higher temperatures. Moreover, higher tem­
peratures will result in the release of dissolved oxygen from the reaction
solution, consequent in the declination of the availability of oxidation spe­
cies, which was beneficial in the production of photogenerated charge
carriers.[210]

4.3. Oxidant flowrate

The bubbling flowrate of an oxidant such as air or oxygen is found beneficial
in enhancing the photocatalytic desulfurization performance.[48,141,163,166]
Xingye Zeng et al. revealed that the activity performance is facilitated gen­
erally by oxygen bubbling, while the activity is suppressed by nitrogen
bubbling.[98] At a flow rate of 40 mL/min, the organosulfur compound
removal was declined to 24%, representing that the oxidation was completely
seized, this little performance is just indicating the extraction by using an
extractant. The lack of oxygen can facilitate the recombination of charge
carriers, declining the desulfurization ability.[217] At zero bubbling, the
organosulfur compound removal was enhanced to 94.1%, representing that
the oxidation reaction was carried out by using the dissolved oxygen. The
bubbling of oxygen at 20 mL/min further facilitated the photocatalytic
desulfurization, while the increase of oxygen flow rate to 40 mL/min
impacted negligible effect over the photocatalytic desulfurization because
the adequate amount of oxygen was dissolved into the reaction solution at
a lower flowrate as well. Several research groups have studied the effect of
oxidant flowrate at >100 mL/min[146] and 300 mL/min, [197] indicating
a slight decline in the photocatalytic performance, which was attribute to
the adhesion of organosulfur molecules over the surface of the photocatalyst
and interrupting the passage of light irradiations.[218]
 CATALYSIS REVIEWS 29

4.4. Catalyst dosage

The catalyst dosage is another crucial aspect in achieving high aerobic

photocatalytic desulfurization performances.[132,146,196,197,206,207,219] It is
much vibrant that the increase in catalyst dosage will sufficiently increase
the number of available active sites for the proceeding of organosulfur
compounds adsorption along with the light photons, consequently facilitat­
ing the bulk production of photogenerated charge carriers. In the prevailing
time, the incremental dosing beyond the optimal value may lead to the
catalyst aggregates formation reducing the exposed surface area, resulting
in low desulfurization performance. Furthermore, these catalyst aggregates
may interrupt the passage of light, declining the production of charge
carriers.[132]

5. Associated facilities
It is valued revealing that besides the aforesaid emphasized parameters accom­
plished for achieving superlative aerobic photocatalytic oxidative desulfuriza­
tion performance, several supplementary decisive characteristics are intact,
which also demands sufficient attention. These parameters include the selec­
tion of oxidant compatible extractant and/or adsorbent for the enhancement
of aerobic photocatalytic oxidative desulfurization efficiency, in addition to the
efficient catalyst availability.

5.1. Extractants

This is mandatory for an efficient solvent or extractant to bear excellent

extractability for sulfides and/or sulfones. Besides, lacking in contributing
contaminants to the refined product, environment friendliness, non-
noxious, and sufficiently stable for reusability.[220] Therefore, the selection of
extractant is among the crucial factors for the achievement of high desulfur­
ization performances. Hitherto, traditional solvents including water, metha­
nol, dimethylformamide, and acetonitrile have been sightseen.[48,112,221,222]
Nevertheless, their reusability and environmental concerns have been laid
down for the development or exploration of an efficient extractant.[223,224]

5.1.1. Ionic liquids

The captivating characteristics of ionic liquids such as the capability of being
liquid over a wider temperature range, chemical and thermal stability, and
approximately negligible vapor pressure owing to ionic character make them
the key focus for utilizations as a greener extraction agent.[225] Moreover,
a wide range of ionic constituents’ availability makes the researchers able to
design an ionic liquid with targeted extraction requirements.[226]
30 I. SHAFIQ ET AL.

5.1.2. Deep eutectic solvents

Stimulated by ionic liquids, deep eutectic solvents (DES), well-known low-cost
extractants were explored. DESs contain a hydrogen-bond donor (HBD) and
a hydrogen-bond acceptor (HBA). DESs are as much efficient as ILs, accom­
panied by inexpensive and environment-friendly synthesis techniques.
Literature shows that the exploitation of DES as an extractant can be beneficial
to attain 96.3% desulfurization performance, while the absence of DES con­
sequent into the decline of performance down to 63.4%.[163]

5.2. Adsorbents

The adsorption tendency of an adsorbent for a specific specie is exceedingly

dependent on the nature of that specie along with the surface properties of the
adsorbent.[195] Likewise, for efficient adsorbance of 4,6-DMDBT molecules
(~0.59 × 0.89 nm size), an adsorbent having <1 nm pore size is
recommended.[14] In addition to pore size, the enhanced surface area of
adsorbent is a crucial factor in achieving high adsorption efficiencies. To
date, numerous adsorbent materials have been established for improved
adsorption of sulfides such as Ce/MCM-41, Ni/Al-MCM-41, CuO-SBA-15,
Cu/ZrO2, metal halides/MCM-41, La/MCM-41, nano-crystalline NaY, het­
eroatom zeolites, Y-zeolites, MCM-22, SBA-15, and several ZrO2-based
adsorbents.[227]

6. Summary and outlook

This critical review on aerobic photocatalytic oxidative desulfurization is
envisioned to summarize the topical tactics and stratagems established for
synthesizing an efficient photocatalyst. Several alterations have been carried
out for overwhelming the inadequacies being faced by single-component
photocatalysts. These adjustment approaches include the enrichment of the
accessible active sites for activity enhancement, cultivating the photon harvest­
ing propensity, and upgrading the photogenerated charges separation effi­
ciency. This is well elaborated that the adequate selection of support
material is crucial in obtaining a well-dispersed textural photocatalyst having
sufficient capability of overcoming the agglomeration issue, therefore attaining
plentiful active sites. To address the agglomeration challenge 2D materials
based on MOS2 and MoOxSy could be potential candidates to improve the
process performance and improve dispersivity of the photocatalyst. Moreover,
Sulfur-based semiconductor 2D transition metal dichalcogenides (TMDCs)
could provide additional surface properties to improve the overall perfor­
mance. Additionally, the insertion of supplementary elements into the crystal
lattice of a single-component photocatalyst has been confirmed to boost the
captivation of visible light owing to the bandgap narrowing and subsequent
 CATALYSIS REVIEWS 31

inhibition of electron-hole recombination tendency. Likewise, the combina­

tion of two or more semiconductor photocatalysts with the tuned orientation
of valence and conduction bands boots the photogenerated charges separation
capability. In this pursuit heterostructures combining 2D TMDCs and n-type
semiconductor oxide could improve charge separation or insulting these
photocatalyst systems with dielectric materials with ultrafine loading to
improve surface passivation which can improve the charge separation and
equally ameliorate stability of the photocatalytic system. The aforesaid statis­
tics offer much beneficial intuition for designing an efficient photocatalyst with
plentiful active sites, heightened light-harvesting tendency, prolonged exis­
tence of electron-hole pairs, for providing superlative desulfurization applica­
tions. Moreover, the synthesizing strategies, supporting allied facilities such as
extractants and adsorbents, and process optimization factors such as the
preliminary concentration of organosulfur compounds, temperature, oxidant
flow rate, and catalyst dosage optimization are expansively deliberated.

Acknowledgment
We are grateful to our colleagues at COMSATS University Islamabad and Pak-Arab Refinery
Limited for healthy discussions.

Funding
This research did not receive external funding.

ORCID
Murid Hussain [Link]

Conflict of Interest
The author declares no conflict of interest.

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