catalysts

Review
A Short Review of Aerobic Oxidative Desulfurization of Liquid
Fuels over Porous Materials
Bo Yuan 1 , Xiaolin Li 1, * and Yinyong Sun 2, *

1 Institute of Intelligent Manufacturing Technology, Shenzhen Polytechnic, Shenzhen 518055, China;

yuanbo@szpt.edu.cn
2 MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of
Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
* Correspondence: lixiaolin0427@szpt.edu.cn (X.L.); yysun@hit.edu.cn (Y.S.); Tel.: +86-755-26731941 (X.L.)

Abstract: Oxidative desulfurization (ODS) has attracted much attention owing to the mild working
conditions and effective removal of the aromatic sulfur-containing compounds which are difficult to
desulfurize using the industrial hydrodesulfurization (HDS) technique. Molecular oxygen in ambient
air have been recognized as an ideal oxidant in ODS due to its easy availability, non-toxicity and
low cost in recent years. However, molecular oxygen activation under mild operating conditions
is still a challenge. Porous materials and their composites have drawn increasing attention due to
their advantages, such as high surface area and confined pore space, along with their stability. These
merits contribute to the fast diffusion of oxygen molecules and the formation of more exposed active
sites, which make them ideal catalysts for aerobic oxidation reactions. The confined space pore size
offers a means of catalytic activity and durability improvement. This gives rise to copious attention
toward the porous catalysts in AODS. In this review, the progress in the characteristics and AODS
catalytic activities of porous catalysts is summarized. Then, emphasis on the molecular oxygen



activation mechanism is traced. Finally, the breakthroughs and challenges of various categories of

 porous catalysts are concluded.
Citation: Yuan, B.; Li, X.; Sun, Y. A
Short Review of Aerobic Oxidative Keywords: aerobic oxidation; oxidative desulfurization; porous materials; catalysis; liquid fuels
Desulfurization of Liquid Fuels over
Porous Materials. Catalysts 2022, 12,
129. https://doi.org/10.3390/
catal12020129 1. Introduction
Academic Editor: Haralampos Sulfur oxide (SOx ) emissions released from the combustion of residual sulfur com-
N. Miras pounds in liquid fuels causes severe environmental pollution, such as haze and acid rain [1].
Received: 25 November 2021
To reduce pollution, numerous countries have issued a series of stringent regulations to
Accepted: 18 January 2022
limit the sulfur content in liquid fuels. Therefore, government departments all over the
Published: 21 January 2022
world issued a series of environmental protection regulations to limit the sulfur content in
liquid fuels. In 2006, the US Environmental Protection Agency stipulated that the sulfur
Publisher’s Note: MDPI stays neutral
content in diesel fuel should not exceed 15 ppm, while the Euro V norms require that the
with regard to jurisdictional claims in
sulfur content in liquid fuels is reduced to less than 10 ppm [2].
published maps and institutional affil-
To meet the current sulfur content standards, many liquid fuels desulfurization tech-
iations.
nologies have been developed. Currently, the most adopted desulfurization method in
industry is hydrodesulfurization (HDS) technology, which demands high temperatures
and pressures (>630 K, >8 MPa), and large consumption of hydrogen. Furthermore, al-
Copyright: © 2022 by the authors.
though HDS is effective for aliphatic organic sulfur compounds, mercaptans, thioethers
Licensee MDPI, Basel, Switzerland. and disulfides, it is ineffective for the removal of aromatic heterocyclic sulfur compounds
This article is an open access article in liquid fuels, especially large-molecular thiophene compounds, such as benzothiophene
distributed under the terms and (BT), dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT) and their alkyl
conditions of the Creative Commons derivatives [3,4].
Attribution (CC BY) license (https:// To solve the above problems, non-HDS technologies have been developed, such as
creativecommons.org/licenses/by/ adsorptive desulfurization (ADS) [5–8], extractive desulfurization (EDS) [9–12], oxidative
4.0/). desulfurization (ODS) [13–15], and biodesulfurization (BDS) [16,17]. Among them, ODS

Catalysts 2022, 12, 129. https://doi.org/10.3390/catal12020129 https://www.mdpi.com/journal/catalysts

Catalysts 2022, 12, 129 2 of 20

integrated with adsorption/extraction is receiving increasing attention, due to its non-

hydrogen consumption, enhanced efficiency, mild reaction conditions, low cost, stronger
operability, and practicability [18–21].
In the 1970s, some researchers began to use oxidizing gases containing nitrogen oxides
to remove sulfides and nitrides contained in petroleum. Guth [22] first used nitrogen oxide
as a chemical oxidant and methanol as an extractant to oxidize and remove sulfur and
nitrogen compounds from petroleum. However, the ODS technology did not gain much
importance until 2000, when stringent environmental regulations were declared. The oxi-
dants commonly used in the oxidative desulfurization process are mainly NO2 [23], organic
peracids [24], hydrogen peroxide (H2 O2 ) [25–28], organic hydrogen peroxide such as tert-
butyl hydroperoxide (TBHP) and cumene hydroperoxide (CHP) [29–31], ozone [32–38], and
air [39–41]. The oxidation capacity, reaction by-products, and prices of common oxidants in
ODS reactions are shown in Table 1 [42]. From the perspective of environmental protection,
hydrogen peroxide is considered to be a greener oxidant due to the by-product of the reac-
tion being H2 O, and its oxidizing ability is high. The ODS mechanism regarding various
oxidants have already been extensively discussed in previous review articles [42,43].

Table 1. Common oxidants and their oxidizing properties in ODS reactions of liquid fuels [42].

Active Oxygen Oxidizing Power Price

Oxidants Byproduct Safety & Handling
(%) (V vs. SHE) (EUR/Kg)
Causes serious eye damage
May cause respiratory irritation
H2 O2 (30 wt%) 14.1(47.1) +1.78 H2 O 145
Causes skin irritation
Keep from contact with clothing
Very toxic to aquatic life
Ozone 33.3 +2.07 SO2 Must be contained within -
ozone-resistant tubing and pipes
Flammable liquid and vapor
Causes severe skin burns and
eye damage
t-BuOOH(TBHP) 17.8 - t-BuOH May cause genetic defects 64
and cancer
Use only under a chemical
fume hood
Combustible liquid
CumOOH(CHP) 10.5 - CumOH May be fatal if swallowed 95
Avoid inhalation of vapor or mist
May intensify fire; oxidizer
Causes severe skin burns and
KO2 45.0 +1.56 OH- eye damage 835
Use only under a chemical
fume hood
Flammable liquid and vapor
Organic peracid
Organic acid Causes severe skin burns and
(peracetic acid at 21.1 +1.81 345
(acetic acid) eye damage;
100 wt%)
Avoid contact with skin and eyes
Contains gas under pressure, may
Air 23.2 +1.23 (O2 ) None explode if heated 0
Store in a well-ventilated place

Basically, hydrogen peroxide is a 30% aqueous solution, which leads to a biphasic

reaction system, increasing the mass transfer resistance between the oily and aqueous phase.
Furthermore, the reaction system that uses H2 O2 as the oxidant often requires the addition
of a polar solvent or phase transfer agent to promote the mass transfer between different
Catalysts 2022, 12, 129 3 of 20

phases. Most of the polar solvents are toxic, which undoubtedly increases the threats to
environmental protection [44,45]. Alongside the environmental issues, the hydroperoxide
also exhibit fire and explosion concerns [46]. An organic hydrogen peroxide, such as TBHP,
CHP, etc. can be miscible with oil, so there is no need to add polar solvents or phase transfer
agents to avoid the above problems. However, the organic alcohol’s byproducts generated
from organic hydrogen peroxide would be a contamination and affect the quality of liquid
fuel products. Due to abundant sources, low cost and high environmental safety, air or
oxygen have been increasingly used as an oxidant in oxidative desulfurization systems in
recent years [47,48].
ODS with O2 , also known as aerobic ODS (AODS), is gradually attracting interest.
However, the activation of O2 is still challenging under comparatively mild conditions since
its ground state lies in triplet(3O2 ) with low energy [49,50]. Generally, this reaction has been
carried out in pure O2 at either high temperatures or elevated pressures, and it has usually
required non-recyclable sacrificial agents. Therefore, the key issue in this field is to develop
high-performance catalysts, aiming to reduce the requirement for O2 activation [51,52].
As green chemistry and catalytic technology have been leaping forward, a noticeable
progress has been achieved in the study on the AODS catalyst. Photocatalysis has shown
a remarkable achievement in the activation of molecular oxygen [53–55]. A wide range
of catalysts such as polyoxomolybdates [39], metal-organic framework materials [56,57],
reduced graphene oxide (rGO) [58], boron nitride [59], precious metals [60], porphyrin [61],
and metal oxides [62] have been reported.
Among them, the use of porous materials is highly desirable due to their large surface
area and remarkable activity. The porous structure design is proposed to contribute
to superior O2 diffusion, more exposed active sites, tunable electronic structure, thus
facilitating activation of O2 . Furthermore, the confined space inside the pores could (i) create
intimate contacts between the reactants and catalysts; (ii) offer particular microenvironment
for the products formation; (ii) increase the power and energy densities of the pore confined
fluids; (iii) make the surface active sites abundant; (iv) accommodate and isolate active
sites, enhancing stability and selectivity of exposed surface active centers; and (v) facilitate
the ion and electron transport, resulting in a tunable electronic structure and activation of
molecular oxygen. The above confinement effects enable the thermodynamics and kinetics
of the reaction be regulated, which eventually lead to catalytic performance enhancement.
Accordingly, the most recent available literature on development attempts for the
commercially feasible and efficient porous materials AODS catalysts during the last decade
is critically reviewed. In this review, the catalytic systems are first classified into porous
metal oxides, molecular sieve and mesoporous silica, metal-organic frameworks, porous
graphene, boron nitride-based materials, etc. Then, the structure and AODS performance
developments of various porous catalysts made so far are summarized. The catalytic
mechanism is also analyzed for each catalyst. Finally, based on a comparative analysis of
the porous AODS catalysts, the limitations and prospects encountering in the development
process are deliberated.

2. Porous Metal Oxides

Metal oxides had been used as catalysts for aerobic oxidative desulfurization exten-
sively due to their low cost, facile synthesis, and superior catalytic performance [63,64].
Moreover, porous structure catalysts exhibited a higher catalytic activity since more active
sites are be exposed on their surface. On the other hand, the AODS process was classified
as a gas-liquid-solid triple-phase reaction. The design of a hierarchical structure to enhance
the mass transfer of O2 from the gas-liquid interface to active sites undoubtedly played
an important role in improving the apparent activity of catalyst. Therefore, porous metal
oxides might be a promising candidate for the AODS process. In this section, porous
metal oxides catalysts including molybdenum containing mixed metal oxides (MMOs),
tungsten oxide, vanadium pentoxide was summarized in Table 2 and the AODS mechanism
was analyzed.
Catalysts 2022, 12, 129 4 of 20

Table 2. Comparison on the catalytic performance of porous metal oxides as AODS catalysts.

BET Model Reaction Reaction

Catalyst Catalyst Oil Model Solution Sulfur Oxidant Activity Ref.
(m2 /g) Amount (ppm) Temperature Time
Volume
BT(500) 100 ◦ C 360 min 97%
Ce-Mo-O 14 100 mg 20 g Decalin DBT(500) O2 100 ◦ C 480 min 99% [62]
4,6-DMDBT(200) 100 ◦ C 480 min 99%

Decahydron- BT(500) 360 min 88%

Co2 MoO – 100 mg 20 g DBT(500) Air 120 ◦ C 180 min 100% [65]
aphthalene 4,6-DMDBT(500) 180 min 100%

CoFeMo- BT(500) 360 min ~92%

MMO-2 73.62 20 mg 20 g Diesel DBT(500) Air 100 ◦ C 180 min 99.2% [66]
4,6-DMDBT(500) 180 min 99.2%

CoNiMo- Decahydron- BT (500) 110 ◦ C 120 min 60%

HNT-2 114.7 20 mg 20 g DBT (500) Air 100 ◦ C 240 min 100% [67]
aphthalene 4,6-DMDBT(500) 110 ◦ C 120 min 100%

3DOM DBT(200) 120 ◦ C 480 min 99%

WOx -400
14.2 10 mg 20 mL Dodecane 4-MDBT(200) Air 120 ◦ C 480 min 99% [68]
4,6-DMDBT(200) 120 ◦ C 240 min 99%
DBT(500) 120 ◦ C 360 min 99.7%
DBT(600) 120 ◦ C 360 min 98.7%
α-V2 O5 - 10 mg 50 mL
Decahydron- DBT(800) Air 120 ◦ C 360 min 97.2%
nanosheets DBT(1000) 120 ◦ C 360 min 95.5% [69]
aphthalene
4-MDBT(500) 120 ◦ C 360 min 96.1%
4,6-DMDBT(500) 120 ◦ C 360 min 92%
DBT(200) 100%
T-Nb2 O5 22.1 50 mg 20 mL Dodecane 4-MDBT(200) O2 130 ◦ C 420 min 100% [70]
4,6-DMDBT(200) 96%

Among them, molybdenum containing mixed metal oxides (MMOs), which possess
advantages of cheap affordability, excellent stability, and a tunable electronic structure, are
the most promising catalysts for aerobic application.
Shi et al. [62] synthesized a mesoporous Ce-Mo-O catalyst, which was proved to
be highly active for aerobic oxidative desulfurization. The dibenzothiophene and 4,6-
dimethyldibenzothiophene were almost completely converted without any additional
sacrificial agent at 100 ◦ C with O2 bubbled in at ambient pressure, and the conversion
of benzothiophene could reach 97%. It was assumed that oxygen was first activated by
Ce species in the catalyst to form some reactive oxygen species. Subsequently, these
oxygen species were further oxidized DBT into DBTO2 with the assistance of Mo species in
the catalyst.
Zhang et al. [65] prepared a Co-Mo-O bimetallic oxide catalyst. It could oxidize 92.2%
DBT at 120 ◦ C in a reaction time of 1 h and air flow of 30 mL/min. The high performance
benefited from the synergistic effect of Co and Mo. The Co sites could first exhibit the
activation of O2 and then the active oxygen species further reacted with Mo sites before
oxidation of sulfur-containing compounds.
Song et al. [66] synthesized durable Co-Fe-Mo layered mixed metallic oxides and
realized complete conversion of DBT in 1.5 h at 120 ◦ C with an air flow rate of 40 mL/min.
The catalysts could be repeated eight times without an obvious decrease in reactivity. The
authors reported that with the decrease of Mo content, the oxygen vacancies increased,
thus the AODS performance was improved.
Liu et al. [67] fabricated hierarchical hollow Co-Ni-Mo-O mixed metallic-oxide nan-
otubes as catalysts in AODS. The catalyst achieved complete conversion of DBT and
4,6-DMDBT at 100 ◦ C with an air flow rate of 25 mL/min. The improved AODS catalytic
performance was attributed to the well-exposed metal centers, high concentrated oxygen
vacancies and desired electronic structure, as shown in Figure 1.
Zhang et al. [68] successfully prepared a three-dimensional hierarchical porous tung-
sten oxide (3DOM) catalyst with rich oxygen defects for aerobic oxidative desulfurization of
4,6-dimethyldibenzothiophene. The unique hierarchical porous structure successfully elim-
inated the steric hindrance effect of 4,6-DMDBT. The as-prepared 3DOM WOx-400 showed
the aerobic oxidative desulfurization of over 99% in 4 h with an air flow of 100 mL/min, as
depicted in Figure 2A. Moreover, sulfur removal remained at 99% after 5-time cycles, as
 vacancies and desired electronic structure, as shown in Figure 1.
Song et al. [66] synthesized durable Co-Fe-Mo layered mixed metallic oxides and
realized complete conversion of DBT in 1.5 h at 120 °C with an air flow rate of 40 mL/min.
The catalysts could be repeated eight times without an obvious decrease in reactivity. The
authors reported that with the decrease of Mo content, the oxygen vacancies increased,
Catalysts 2022, 12, 129 thus the AODS performance was improved. 5 of 20
Liu et al. [67] fabricated hierarchical hollow Co-Ni-Mo-O mixed metallic-oxide
nanotubes as catalysts in AODS. The catalyst achieved complete conversion of DBT and
shown in Figure
4,6-DMDBT 2B,°C
at 100 which
withwould
an air meet
flow the
raterequirement
of 25 mL/min.for The
industrial production
improved of clean
AODS catalytic
•−
diesel. The abundant oxygen defects facilitated the activation of O to O
performance was attributed to the well-exposed metal centers, high concentrated
2 2 , which boosted
oxygen
the ODS efficiency.
vacancies and desired electronic structure, as shown in Figure 1.

Figure 1. Proposed Catalytic Mechanism of Aerobic Oxidation of DBT Over CoNiMo Catalysts [67].

Zhang et al. [68] successfully prepared a three-dimensional hierarchical porous

tungsten oxide (3DOM) catalyst with rich oxygen defects for aerobic oxidative
desulfurization of 4,6-dimethyldibenzothiophene. The unique hierarchical porous
structure successfully eliminated the steric hindrance effect of 4,6-DMDBT. The as-
prepared 3DOM WOx-400 showed the aerobic oxidative desulfurization of over 99% in 4
h with an air flow of 100 mL/min, as depicted in Figure 2A. Moreover, sulfur removal
remained at 99% after 5-time cycles, as shown in Figure 2B, which would meet the
requirement for industrial production of clean diesel. The abundant oxygen defects
Figure1.1. Proposed
facilitated
Figure Proposed
the activation
Catalytic O2 to O• of
CatalyticofMechanism
Mechanism ,ofwhich
Aerobic Oxidation
boosted
Aerobic of
theof
Oxidation ODSDBTefficiency.
DBT OverCoNiMo
Over CoNiMoCatalysts
Catalysts[67].
[67].

Zhang et al. [68] successfully prepared a three-dimensional hierarchical porous

tungsten oxide (3DOM) catalyst with rich oxygen defects for aerobic oxidative
desulfurization of 4,6-dimethyldibenzothiophene. The unique hierarchical porous
structure successfully eliminated the steric hindrance effect of 4,6-DMDBT. The as-
prepared 3DOM WOx-400 showed the aerobic oxidative desulfurization of over 99% in 4
h with an air flow of 100 mL/min, as depicted in Figure 2A. Moreover, sulfur removal
remained at 99% after 5-time cycles, as shown in Figure 2B, which would meet the
requirement for industrial production of clean diesel. The abundant oxygen defects
facilitated the activation of O2 to O• , which boosted the ODS efficiency.

Figure2.2.(A)
Figure (A) Aerobic
Aerobic ODSODS
tests tests on various
on various sulfur compounds at 120 ◦ C at
sulfur compounds and120 °C and (B)
(B) recycling recycling
performance
performance
of of the 3DOM
the 3DOM WOx-400 WOx-400
sample [68]. sample [68].

Furthermore, orthorhombic vanadium pentoxide is always proposed to be advanta-

geous for molecular oxygen (O2 ) absorption and activation, thus it is a competent candidate
in aerobic reactions.
Recently, Wang et al. [69] synthesized an atomic-layered α-V2O5 nanosheets (5–7 layers),
resulting in a 99.7% sulfur removal of dibenzothiophene (less than 2 ppm) at 120 ◦ C within
6 h and an air velocity of 100 mL/min. In this process, O2 free from air is activated to O2•− by
α-V2 O5 nanosheets, which subsequently oxidize sulfur compounds to their corresponding
sulfones,
Figure 2. realizing
(A) AerobicdeepODS
desulfurization.
tests on various sulfur compounds at 120 °C and (B) recycling
performance
Yu et.al of thesynthesized
[70] 3DOM WOx-400 sample [68]. niobium pentoxide (T-Nb2 O5 ) with elevated
an orthorhombic
ratio of high-index planes, first for aerobic oxidative desulfurization (ODS) of the refractory
aromatic sulfide. Compared with amorphous or pseudohexagonal mesoporous structure
Nb2 O5 , the 650 ◦ C—T-Nb2 O5 within 7 h had a 100% sulfur removal rate, showing its
excellent catalytic performance. Moreover, the cycle experiments confirm the stability of the
prepared 650 ◦ C—T-Nb2 O5 after 8 regeneration processes, showing a promising prospect
of NbOx-based materials for ODS under mild conditions.

3. Composites of Mesoporous Silica and Metal Oxides

Mixed oxides of transition metals were among the best studied catalysts for the
oxidation of sulfur-containing compounds with atmospheric oxygen. However, fewer
active sites were exposed in many bulk metal oxides due to the aggregation phenomenon.
Thus, many carriers were developed to improve the dispersion of active species. The
Catalysts 2022, 12, 129 6 of 20

catalytic performance comparison on composites of mesoporous silica and metal oxides

was listed in Table 3.

Table 3. Comparison on the AODS catalytic performance of mesoporous silica/metal oxides composites.

BET Catalyst Model Model Sulfur Reaction Reaction

Catalyst Oil Oxidant Activity Ref.
(m2 /g) Amount Solution (ppm) Temperature Time
Volume
5 wt%V2 O5 / Decahydron-
547 50 mg 50 mL DBT (500) Air 120 ◦ C 480 min 99.3% [71]
SBA-15 aphthalene
DBT (500) 99.9%
WO3 / 167 10 mg 20 mL Decalin 4-MDBT(200) O2 120 ◦ C 480 min 98.2% [72]
MMS-500 4,6-DMDBT(200) 92.3%
DBT (500) 120 ◦ C 90 min 100%
CoMo-0.5IL-SBA 196 0.2 wt% 30 mL Decalin BT (500) Air 120 ◦ C 180 min 100% [73]
3-MBT (500) 120 ◦ C 360 min 57%
[(C8 H17 )3 NCH3 ]3 - DBT (500) 300 min 100%
PMo12 O40 / – 25 mg 20 mL Decalin Air 120 °C 420 min 100% [74]
γ-MMS 4-MDBT(500)

Wang et al. [71] reported a V2 O5 /SBA-15 composites synthesized by the impregnation

methods. It was found that sulfur removal of DBT could reach 99.3% in the molecular
oxygen-based system using ionic liquid extraction. Moreover, this reaction system was
proved to be potential in practical application. The porous carrier (SBA-15) improved
the dispersion of V2 O5 , which made more active sites exposed than bulk materials. The
Catalysts 2022, 12, x FOR PEER REVIEW
oxidative desulfurization efficiency for various organosulfur compounds was found in7 of 22
the
following order: 4,6-DMDBT < 4-MDBT < DBT, as shown in Figure 3.

Figure 3.
Figure 3. Sulfur
Sulfurremoval
removalofof
oils with
oils different
with S-concentrations
different (a), and
S-concentrations (a), substrates (b). Experimental
and substrates (b). Exper-
conditions:
imental T = 120 °C,
conditions: T =V(oil)
120 =◦ C,
50 V(oil)
mL, V(Bmim]BF4) = 5 mL, m(catalyst)
= 50 mL, V(Bmim]BF4) = 5 mL,= 0.05 g, v(air) =
m(catalyst) = 100
0.05mL
g,
min−1=[71].
v(air) 100 mL min−1 [71].

Jiang et
Jiang et al.
al. [72]
[72] reported
reported aa novel
novel tungsten
tungsten oxideoxide catalyst
catalyst supported
supported on on magnetic
magnetic
mesoporous silica,
mesoporous silica, where thethe removal
removal of of DBT
DBTcould
couldreach
reach99.9%
99.9%after
after8 8h h
at at
120 °C,◦ C,
120 as
shown
as shown in inFigure
Figure4a. 4a.Moreover,
Moreover,thetheremoval
removal of of 4-methyldibenzothiophene
4-methyldibenzothiophene and 4,6- 4,6-
dimethyldibenzothiophene could
dimethyldibenzothiophene could also
also reach
reach 98.2%
98.2% and
and 92.3%
92.3% under
under the
the same
same conditions,
conditions,
asshown
as shownin inFigure
Figure4b. 4b. FT-IR
FT-IRspectra
spectraindicated
indicatedthat thattungsten
tungstenperoxide
peroxideformed
formedduring
duringthe
the
•
•−
reaction,thus
reaction, thusthetheactive
activespecies
speciesmight
mightbebeOO2 and andtungsten
tungstenperoxide.
peroxide.
For neat polyoxometalate (POM) and ionic liquid, the low surface area (<10 m2 /g)
and good solubility in polar solvents leads to the (b) leaching of catalytically active sites. To
(a)
overcome the limitations and improve the catalytic properties, the active components were
immobilized on supports. Ekaterina A et al. [73] used an SBA-15 anchored Anderson-type
POM as highly heterogeneous catalysts. A 100% DBT removal was achieved within 90 min
at 120 ◦ C at an air flow of 100 mL/min. By immobilization, the POM active center could be
 conditions: T = 120 °C, V(oil) = 50 mL, V(Bmim]BF4) = 5 mL, m(catalyst) = 0.05 g, v(air) = 100 mL
min−1 [71].

Jiang et al. [72] reported a novel tungsten oxide catalyst supported on magnetic
Catalysts 2022, 12, 129 mesoporous silica, where the removal of DBT could reach 99.9% after 8 h at 120 °C, 7 of as
20
shown in Figure 4a. Moreover, the removal of 4-methyldibenzothiophene and 4,6-
dimethyldibenzothiophene could also reach 98.2% and 92.3% under the same conditions,
reused
as shownfiveintimes without
Figure significant
4b. FT-IR spectraloss of catalytic
indicated thatactivity,
tungsten which overcame
peroxide theduring
formed drawbackthe
of neat POM
reaction, the active species might be O• and tungsten peroxide.
thuscatalysts.

(a) (b)

Figure 4.4.(a)
Figure (a)Effects
Effectsofofdifferent
different reaction
reaction temperatures
temperatures on DBT
on DBT removal.
removal. Reaction
Reaction conditions:
conditions: m
m (cat-
(catalyst)
alyst) = 0.01
= 0.01 g,flow
g, air air flow
= 100= mL/min,
100 mL/min, and and V (model
V (model oil)
oil) = 20=mL;
20 mL; (b) Removal
(b) Removal of different
of different sub-
substrates
strates in the
in the desulfurization
desulfurization system.
system. Reaction
Reaction conditions:mm(catalyst)
conditions: (catalyst)= =0.01
0.01g,g,TT== 120
120 ◦°C, air
C, air
flow == 100
flow 100 mL/min,
mL/min, andand VV(model
(modeloil)
oil)==20
20mL
mL[72].
[72].

For neat
Xun et al.polyoxometalate
[74] used magnetic (POM) and ionicsilica
mesoporous liquid, the2low
(γ-Fe surface
O3 @SiO area 2(<10
2 @mSiO ) as amsupport
2/g) and

good
for solubility
an ionic liquidincatalyst
polar solvents
[(C8 H17 )3leads
NCH3to the 12
]3 PMo leaching
O40 . Withof air
catalytically
as an oxidant,active
the sites.
removal To
overcome
of DBT from themodel
limitations and reach
oil could improve100% 120 ◦ C within
theatcatalytic properties, the an
5 h and active components
air flow rate of
were
100 immobilized
mL/min. on supports.
Furthermore, Ekaterina
the catalyst couldA be et al. [73] by
separated used an SBA-15
a magnet anchored
and recycled at
Anderson-type POM as highly heterogeneous catalysts. A 100%
least four times without obvious decrease in the catalytic performance. It was suggested DBT removal was
achieved
that Mo inwithin
[(C8 H1790)3 NCH
min at3 ]3120
PMo°C at40an
12 O air flow
could formof 100 mL/min.
active By immobilization,
per-oxo groups and oxidize DBT the
to
POMits corresponding sulfones.
active center could be reused five times without significant loss of catalytic activity,
which overcame the drawback of neat POM catalysts.
4. Metal-Organic
Xun et al. [74] Frameworks
used magnetic Based Materials silica (γ-Fe2O3@Si@mSiO2) as a support
mesoporous
for anMetal-Organic Frameworks
ionic liquid catalyst [(C8H17(MOFs)
)3NCH3are]3PMokinds
12Oof40. crystalline
With air asporous hybrid
an oxidant, thematerials,
removal
which originate from the coordination bonds formed between
of DBT from model oil could reach 100% at 120 °C within 5 h and an air flow rate metal nodes and organic
of 100
linkers.
mL/min.Generally, MOFsthe
Furthermore, have received
catalyst increasing
could attention
be separated by in various and
a magnet applications
recycledranging
at least
from gas storage
four times withoutto chemical catalysis, in
obvious decrease owing to the excellent
the catalytic tunability
performance. of pore
It was size, shape
suggested that
and functionality [75,76]. The combination of polynuclear metal clusters and organic linkers
make them suitable catalysts for AODS. Furthermore, the high surface area makes MOFs
affordable for accommodation of catalytic active species, thus forming MOF-supported
catalysts. Their AODS catalytic performance is summarized in Table 4.

Table 4. Comparison on the AODS catalytic performance of MOFs-based materials.

BET Model Reaction Reaction

Catalyst Catalyst Oil Model Sulfur Oxidant Activity Ref.
(m2 /g) Amount Solution (ppm) Temperature Time
Volume
POM@NENU-
9N 564 44 mg 50 mL Decalin DBT(500) O2 80 ◦ C 90 min 100% [77]

MIL-101 (Cr) 1850 0.5 g /L 10 mL n-dodecane DBT (200) O2 120 ◦ C 1440 min 99% [56]
MIL-101
(Cr)-NO2 1850 0.04 mmol Cr 20 mL n-dodecane DBT (200) O2 140 ◦ C 270 min 100% [78]

BT(200) 12%
993 5g ambient 120 ◦ C 300 min 99.6%
MFM-300(V) 1.5 g/L n-dodecane DBT(200) air [57]
4,6-DMDBT(200) 98.1%
HPW@MOFs 1102 4.21 mg 60 mL Octane DBT(500) O2 90 ◦ C 240 min 84% [79]
POM@MOF-
199@ 732 2 g /L - Octane DBT (2000) O2 85 ◦ C 180 min 98.5% [80]
MCM-41
CNTs@MOF-
199- 371.45 100 mg 50 mL n-octane DBT (2000) O2 80 ◦ C 180 min 98.3% [81]
Mo16 V2
Catalysts 2022, 12, 129 8 of 20

For example, a MOF (NENU-9N) encased POM catalyst [77] was proved to be able
to realize complete aerobic oxidative desulfurization of DBT at 80 ◦ C for 1.5 h under
the existence of isobutylaldehyde, which was first oxidized to the corresponding peracid
by molecular oxygen and then oxidized DBT to DBT-sulfone. The nanocrystalline MOF
facilitated POMs to overcome the obstacle of poor solubility in non-polar environment.
However, the use of sacrificial agents increases the contamination of liquid fuel products.
Gómez-Paricio et al. [56] reported the desulfurization of DBT and its derivatives using
MIL-101 as catalysts and molecular oxygen as oxidant without the need for sacrificial
aldehydes. The reaction took an induction period of 6 h resulting from the diffusion of the
solvent inside the MIL-101 pores. The authors envisioned that the shorter chain length of
the solvent, the shorter
Catalyststhe2022,induction duration.
12, x FOR PEER REVIEW The DBT could be completely oxidized into
DBT-sulfone at 120 ◦ C and 24 h, with an oxygen balloon under 1 atm. The resulting model
Catalysts 2022, 12, x FOR PEER REVIEW 9 of 2
oil extracted with water realized the complete removal of sulfur. In addition, the catalyst
remained stable after five cycles without any activity reduction, showing a high stability.
Selective quenching experiments confirmed OO2•−
•−
/HOO was
2 /HOO was the thereactive
reactiveoxygen
oxygenspecies
species in the
in the AODS reaction.•
O /HOO  was
About 1%the reactive
solvent oxidation
oxygen
oxidation byproducts
species
byproducts in the was was reaction.
AODS observed.About 1% solven
observed.
oxidation
On this basis, byproducts
Vallés-García et al.was
[78]observed.
studied aOn this
series basis, Vallés-Garcí
of MIL-101(Cr)-X a et al. [78] s
functionalized
with electron withdrawing On this (NObasis,
2 , SO 3 Vallés-García
H or Cl) or et
functionalized
electron al. [78]
donor withstudied
(NH electron
2 or a
CH series
3 ) of MIL-101(Cr)-X
withdrawing
groups, and(NO2, SO
found that the NO functionalized
2 -modified with
MIL-101 electron
was withdrawing
moreCH efficient
3 ) (NO
groups,than ,
2and SO
the H or
parent
3found Cl) or electron
MIL-101(Cr),
that the NO donor
2and (NH2 o
-modified M
other isoreticularCHsolid3) groups, and found that the NO2-modified MIL-101 was more efficient than th
in promoting the AODS of DBT
parent without anyand
MIL-101(Cr), byproduct formation.solid in p
other isoreticular
parent
The initial reaction rate MIL-101(Cr),
was in a good and other
linear isoreticular with
relationship solid thein promoting
oxidation the AODS of
potential of the
DBT withou
any byproduct formation. The initial reaction rate w
any byproduct formation. The initial reaction rate was in a good linear relationship with
substituents on terephthalate ligands, thus MIL-101(Cr)- the oxidation NO2potential
was the mostof theactive catalyst. on terep
substituents
the oxidation potential of the substituents on terephthalate ligands, thus MIL-101(Cr)
Mechanistic studies showed that MIL-101(Cr)-NO NO 2 was
2 was theacting
mostas heterogeneous
active catalyst studie
catalyst. Mechanistic
NO2 was the most active catalyst. Mechanistic studies showed that MIL-101(Cr)- NO2 wa
in thiophenol oxidation and as a radical initiator for the
acting as AODS, as shown
heterogeneous in Figure
catalyst in 5. For
thiophenol oxid
acting as heterogeneous catalyst in thiophenol oxidation and as a radical initiator for th
both reactions, the catalyst can be reused without deactivation,
AODS, as shown keeping
in its
Figure
AODS, as shown in Figure 5. For both reactions, the catalyst can be reused withou
crystallinity
5. For bothandreactions,
with negligible metal leaching.
deactivation, deactivation,
keeping its crystallinity and withkeeping
negligible itsmetal
crystallinity
leaching.and with negli

Figure 5. Proposed Figure 5. Proposed

pathway for the pathway for the aerobic
aerobic oxidation oxidation of
of thiophenol tothiophenol to benzene using
benzene disulphide disulphide usin
as catalyst [78]. 2 as catalyst [78]. Figure 5. Proposed pathway for the aerobic oxidation of
MIL-101(Cr)-NO2 MIL-101(Cr)-NO
MIL-101(Cr)-NO2 as catalyst [78].
Li et al. [57] investigated
Li et al. [57] investigated the AODS performance the AODS performance
of MFM-300(V) of MFM-300(V) in both hydrogen
in both hydrogen-
donating and withdrawing solvents under ambient air atmosphere. The removal of sulfu
donating and withdrawing solvents under ambientLi airetatmosphere.
al. [57] investigated
The removal the AODS performan
of sulfur
content in model oil reached 99.6% and 98.1% for DBT and 4,6-DMDBT, underinambientin
respectively,
content in model oil reached 99.6% and 98.1%donating for DBTand andwithdrawing
4,6-DMDBT,solvents respectively, a
absence of molecular oxygen pumped or bubbled from the gas cylinders. The catalys
absence of molecular oxygen pumped or bubbled content in model
from the gasoilcylinders.
reached 99.6% and 98.1% for D
The catalyst
could be recycled seven times without any significant decrease in aerobic desulfurization
could be recycledperformance.
seven timesMoreover,
without any absence decrease
of molecular oxygen pumped or bubbled
the significant
Catalysts MFM-300(V)
2022, 12, x FOR PEER in aerobic
also REVIEW
showed desulfurization
excellent performance in both
performance. Moreover, the MFM-300(V)
hydrogen-donating
could be recycled
also showed excellent
and hydrogen-withdrawing
seven times
performance
solvent.
without any
As depictedininboth
significa
Figure 6, th
hydrogen-donating and AODS
excellent hydrogen-withdrawing
performance might performance.
solvent.
be attributedMoreover,
As todepicted the
the active MFM-300(V)
inV-sites
Figure
and the also
6,unique sho
porou
excellent AODS structure
performance be hydrogen-donating
attributed to the active and
V-sites andhydrogen-withdrawing
of MFM-300(V), consequently facilitating the in-situ generation of OH radicals
might unique porous so
excellent
structure of MFM-300(V), consequently facilitating O2 /HOO
AODS generation
the in-situ performance  OH
wasradicals.
of might be •−
theattributed
reactive ox
to
oxidation
structure of MFM-300(V), byproducts
consequently was obsert
facilitating
On this basis, Vallés-Ga
functionalized with electron wi
CH3) groups, and found that t
parent MIL-101(Cr), and other i
any byproduct formation. The i
the oxidation potential of the s
NO2 was the most active catalys
acting as heterogeneous catalys
AODS, as shown in Figure 5.
Catalysts 2022, 12, x FOR PEER REVIEW 10 of 22
Catalysts 2022, 12, x FOR PEER REVIEW 10 of 22
Catalysts 2022, 12, 129 9 of 20

Figure 6. Proposed reaction mechanism over MFM-300(V) in ODS of DBT under ambient air
atmosphere
Figure [57]. reaction
Figure6.6.Proposed
Proposed reaction mechanism
mechanism over
over MFM-300(V)
MFM-300(V) in ODS
in ODS of under
of DBT DBT under ambient
ambient air
air atmo-
atmosphere
sphere [57]. [57].
Ding et al. [79] first selected phosphotungstic acid in a host matrix (HPW@MOFs) as
Dingetetal.
Ding
a recyclable al.[79]
and [79] firstselected
first
efficient selected phosphotungstic
catalystphosphotungstic
in the AODS process. acid
acid in
inThe a effect
a hosthost matrix
matrix (HPW@MOFs)
(HPW@MOFs)
of varying as as
the flowrate a
a recyclable
recyclable and and efficient
efficient catalyst
catalyst in in
the the AODS
AODS process.
process. The The effect
effect
of molecular oxygen was investigated for variance between 0 mL/min to 130 mL/min. The of of varying
varying the the flowrate
flowrate of
of molecular
molecular
DBT conversion oxygen
oxygen waswas
increased investigated
investigated
by increasingfor for variance
variance
the between
between
flowrate 0 mL/min
0 mL/min
of molecular toto 130
130
oxygen mL/min.
mL/min.
and The
The
exhibited
DBT
the conversion
DBTbest
conversion increased
increased
ODS performance bybyincreasing
atincreasing thethe
110 mL/min, flowrate
flowrateof molecular
as shown of in
molecular
Figureoxygen andmechanism
7.oxygen
The exhibited
and the
exhibitedof
best
the ODS
best performance
decreased ODS
ODSperformance at 110 mL/min,
performance atat110
high as shown
mL/min,
flowrate inshown
aswas Figure 7. Figure
in
attributed The to
mechanism
7. The
the of decreased
mechanism
shortened contact of
ODS performance
decreased
between DBTODS and at high flowrate
performance
oxygen. at highwas flowrate
In addition, attributed
the effect to
of the
was shortened
attributed
increasing to contact between
the shortened
catalyst dosage was DBT
contact
also
and oxygen.
between
reported DBT
in In and
this addition,
work.oxygen.
ThetheDBTeffect
In of increasing
addition,
conversion the was catalyst
effect dosage
of increasing
significantly was alsoby
catalyst
increased reported
dosage in this
was
increasing also
the
work.
HPW@MOFsThe DBT
reported in this conversion
work.from
dosage The 0% was significantly
DBTtoconversion
3% and 84% was increased by
ofsignificantly increasing
DBT was removed increased the
from HPW@MOFs
by increasing
the model the oil
dosage from
HPW@MOFs
after 240 min.0%dosage
to 3% and
from84% 0% of to DBT was84%
3% and removedof DBTfromwas theremoved
model oil afterthe
from 240model
min. oil
after 240 min.

Figure7.
Figure 7. Effect
Effect of
of air
air and
and OO22 flow rate on DBT
DBT removal
removal rate
rate with
with HPW@MOFs.
HPW@MOFs. Conditions:
Conditions: reaction
reaction
temperature,
temperature, 90◦of
Figure 7. Effect
90 °C; catalyst
C;air 2dosage,
and Odosage,
catalyst 1%on
flow rate
1% the
theDBTmass
mass of normal
normal
removal
of octane;
rateoctane; extracting agent,
with HPW@MOFs.
extracting agent, distilledreaction
Conditions:
distilled water;
water;
reaction time,
temperature, 240
90 min
°C;
reaction time, 240 min [79]. [79].
catalyst dosage, 1% the mass of normal octane; extracting agent, distilled water;
reaction time, 240 min [79].
AA catalyst
catalystsystem
systemof ofPOM@MOF-199@MCM-41(PMM)
POM@MOF-199@MCM-41(PMM) was was designed
designed byby Li
Li et
et al.
al.[80]
[80]
A
designed catalyst
designed for deep system of
deepoxidative POM@MOF-199@MCM-41(PMM)
oxidativedesulfurization
desulfurizationofof
model
model oil oil
under was designed by
O2 atmosphere.
under Li
O2 atmosphere. et al.
The PMM [80]
The
designed
catalyst
PMM for deep
showed
catalyst a oxidative
showed clearly
a clearly desulfurization
nano-porous
nano-porous of model
structure
structureand oildefinitely
and under O2 atmosphere.
definitelyhigher The PMM
higher reactivity
reactivity and
and
catalyst compared
stability
stability showed awith
compared clearly
with the nano-porous
the heteropolyacid
heteropolyacidstructure
only. The
only. and
The DBT
DBTdefinitely higher
conversion
conversion could
couldreactivity
reach up
reach upand to
to
stability
98.5%
98.5% compared
when
when reactedwith
reacted for 33the
for hh at
at 85 ◦°C.
heteropolyacid
85 only.the
Moreover,
C. Moreover, The
the DBT conversion
catalyst
catalyst alsocould
could also
could reach up
be recycled
be recycled and
and to
98.5% when reacted for 3 h at 85 °C. Moreover, the catalyst could also be recycled and
Catalysts2022,
Catalysts 2022,12,
12,129
x FOR PEER REVIEW 11 of 20
10 of 22

reused
reused for
for up
up to
to 10
10cycles
cycleswith
withminimal
minimalefficiency
efficiencyreduction,
reduction, as
asshown
shownin
inFigure
Figure8.8. The
The
pseudo-first-order reaction kinetics was followed.
pseudo-first-order reaction kinetics was followed.

Figure8.8. Stability
Figure Stability test
testresults
resultsof
ofthe
thecatalyst
catalyst[80].
[80].

Gao
Gaoet etal.
al.[81]
[81]synthesized
synthesizedaaseries
seriesofofCNTs@MOF-199-POM
CNTs@MOF-199-POMcatalysts catalysts and
andtested
tested for
for
the oxidative desulfurization performance.
the oxidative desulfurization performance. Of Of all as-prepared catalysts,
as-prepared catalysts, the CNTs@MOF-
199-Mo
199-Mo1616V V22 catalyst showed the best catalytic resultsresults ranging
ranging upup to
to 98.3%
98.3% with
with an
an oxygen
oxygen
flow ◦ C in 180 min. The catalyst was valid from 40 ◦ C to 100 ◦ C.
flow rate
rate of
of 1.5
1.5 L/min
L/min atat 80
80 °C in 180 min. The catalyst is valid from 40 °C to 100 °C. and
and the apparent
the apparent activation
activation energy
energy calculated
calculated fromfrom pseudo-first-order
pseudo-first-order raterate constant
constant was
is 12.89
12.89 kJ/mol,
kJ/mol, as illustrated
as illustrated in Figure
in Figure 9. Itobserved
9. It was was observed thatincrease
that the the increase in agitation
in agitation rate
rate from
from 200 to 800 rpm led to significantly improving in oxidative desulfurization
200 to 800 rpm led to significantly improving in oxidative desulfurization performance performance
from
from70%70%to to 97%.
97%. Moreover,
Moreover,the theas-prepared
as-preparedcatalyst
catalystwas
wastested
testedfor
forreusability
reusabilityandandfound
found
to for up to seven cycles. It was reported that M(O) −
to be usable for up to seven cycles. It was reported that M(O)n n− (M = Mo or V) in
be usable (M = Mo or V) in POM
POM
could
couldcombine
combinewith withthetheoxygen
oxygento toform
formM(OM(O22))nn− and then
− and then oxidize
oxidize DBT
DBT into
into DBT-sulfone.
DBT-sulfone.

Figure9.
Figure 9. Plot
Plotof
ofthe
theinverse
inverseof
oftemperature
temperature(1/T)
(1/T)versus
versusroot
rootofofthe
thereaction
reactionrate
rateconstant
constant−-ln(k).[81].
ln(k) [81].

5.
5. Porous
Porous Graphene
Graphene andand Boron-Nitride
Boron-Nitride BasedBasedMaterials
Materials
Graphene-based materials had emerged as promising
Graphene-based materials have emerged as promising alternatives or supports
alternatives to con-
or supports to
ventional metal-based
conventional catalysts,
metal-based owing to owing
catalysts, their outstanding
to their physicochemical characteristics,
outstanding physicochemical
including high surface
characteristics, area,high
including rich surface
surface defects or functional
area, rich groups,orexcellent
surface defects mechanical
functional groups,
stability,
excellentetc. [82–84]. Such
mechanical merits
stability, etc.integrated with merits
[82–84]. Such low cost, non-toxicity
integrated withand
lowlarge-scale
cost, non-
productivity
toxicity andmade graphene-based
large-scale materials
productivity madecompetitive candidates
graphene-based for aerobic
materials oxidation
competitive
reactions [85]. On the other hand, another 2D materials, boron nitride, also
candidates for aerobic oxidation reactions [85]. On the other hand, another 2D materials, known as
“white graphite”, are recognized as an analogy to graphene. Therefore, recently
boron nitride, also known as “white graphite”, are recognized as an analogy to graphene. boron
nitride-based materials,
Therefore, recently boronsuch as hexagonal
nitride-based boron nitride
materials, such as (h-BN),
hexagonalgraphene-like
boron nitride boron ni-
(h-BN),
tride (g-BN), and
graphene-like hexagonal
boron boron carbon
nitride (g-BN), nitride (h-BCN)
and hexagonal have been
boron carbon used
nitride as low have
(h-BCN) cost
been used as low cost with excellent aerobic ODS performance in liquid fuels [86,87] The
Catalysts 2022, 12, 129 11 of 20

with excellent aerobic ODS performance in liquid fuels [86,87] The AODS performance for
porous graphene and boron-nitride-based materials were summarized in Table 5.

Table 5. Comparison on the catalytic AODS performance for porous graphene and boron-nitride-
based materials.

BET Model Reaction Reaction

Catalyst Catalyst Oil Model Sulfur Oxidant Activity Ref.
(m2 /g) Amount Solution (ppm) Temperature Time
Volume
DBT(400) 100%
BT(400) 90.5%
rGO 492 5 mg 25 mL Dodecane O2 140 ◦ C 360 min 96.1% [58]
3-MBT(400)
4,6-DMDBT(400) 97.7%

Decahydron- BT(500) 75%

POM/PIL/Gr 83.4 10 mg 20 mL DBT(500) Air 100 ◦ C 180 min 100% [88]
aphthalene 4,6-DMDBT(500) 100%
DBT(500) 480 min 99%
Cu NPs/g-BN 570 100 mg 40 mL Decalin Air 120 ◦ C 180 min 97% [89]
4,6-DMDBT(500)
BT(500) 85.9%
DBT(500) 98.3%
Pt@h-BN - 50 mg 40 mL Decalin Air 130 ◦ C 360 min 96.5% [51]
4-MDBT(500)
4,6-DMDBT(500) 93.7%
DBT(500) 180 min 100%
5-MoOxNPs/ 108 100 mg 20 mL Decalin 4-MDBT(500) Air 120 ◦ C 270 min 97% [90]
g-BN 4,6-DMDBT(500) 270 min 97%
DBT(500) 240 min 99.8%
DBT(600) 300 min 99.6%
DBT(800) 120 ◦C 300 min 96.6%
C8 V/g-BN 493 80 mg 40 mL - Air [91]
DBT(1000) 360 min 95.9%
4-MDBT(500) 300 min 99.5%
4,6-DMDBT(500) 300 min 95.3%
DBT(500) 98.2%
BN-1 - 50 mg 20 mL Decalin 4-MDBT(500) Air 130 ◦ C 480 min 97.5% [92]
4,6-DMDBT(500) 98%
DBT(500) 99.6%
V2 O5 /BNNS - 200 mg 50 mL - 4-MDBT(500) Air 120 ◦ C 240 min 97.1% [93]
4,6-DMDBT(500) 95.2%
DBT(200) 100%
BCN-20 - 70 mg 20 mL Decalin 4-MDBT(200) Air 100 ◦ C 360 min 90.5% [94]
4,6-DMDBT(200) 98.7%
DBT(500)
BCN-1 1004 50 mg 20 mL Decalin 4-MDBT(500) Air 125 ◦ C 240 min 98.4% [95]
4,6-DMDBT(500)
DBT(200)
TMAC-BCNO 838 50 mg 20 mL Dodecane 4-MDBT(200) Air 125 ◦ C 360 min 99% [96]
4,6-DMDBT(200)
DBT(200) 99.5%
B4 C-5 - 50 mg 20 mL Dodecane 4-MDBT(200) Air 130 ◦ C 480 min 91% [97]
4,6-DMDBT(200) 97.5%
20% V-IL/ DBT(200) 97.2%
46.99 10 mg 20 mL Dodecane Air 120 ◦ C 360 min
95.8% [98]
3D g-C3 N4 4,6-DMDBT(200)
Au- DBT(200) 99.7%
TiO2 @C3 N4 - - 10 mg 20 mL Dodecane 4-MDBT(200) Air 120 ◦ C 360 min 98.8% [99]
800 4,6-DMDBT(200) 99.4%

5.1. Reduced Graphene Oxide (rGO)

In 2017, Gu et al. [58] chose reduced graphene oxide (rGO) as catalysts in AODS
of model oils for the first time. The rGO material displayed 100% DBT removal with
quite low catalyst dosage (8.7 wt%) at 140 ◦ C in 2 h, which proved that the material was
superior to many other carbon-based materials. The XPS and other control experiments
indicated that the carbonyl groups, generated in situ on the chemical active defects of rGO,
Catalysts 2022, 12, x FOR PEER REVIEW 9 of 22
were efficient active sites for aerobic desulfurization of refractory sulfur compounds. The
carbonyl groups facilitated the activation of oxygen by altering the electronic structures of
the adjacent carbon atoms at the rGO surfaces. The reactive oxygen species was reported to
2 /HOO was
•− − . This
beOrGO-OO the reactive
work oxygen
inspired species in of
the application thecarbon
AODS reaction.
material intoAbout
AODS1% solvent
process.
oxidation byproducts was observed.
In the work of Ma et al. [88], monodisperse POM clusters was immobilized on
grapheneOn using
this poly
basis, Vallés-Garcí
(ionic a as
liquid) (PIL) et linker
al. [78] studied
and used a series
as AODS of The
catalyst. MIL-101(Cr)-X
monodis-
functionalized with electron withdrawing (NO2, SO3H or Cl) or electron donor (NH2 or
CH3) groups, and found that the NO2-modified MIL-101 was more efficient than the
parent MIL-101(Cr), and other isoreticular solid in promoting the AODS of DBT without
any byproduct formation. The initial reaction rate was in a good linear relationship with
the oxidation potential of the substituents on terephthalate ligands, thus MIL-101(Cr)-
Catalysts 2022, 12, 129 12 of 20

persed active sites, high specific surface area and large mesoporous size endowed the
catalyst excellent desulfurization performance. DBT could be completely converted into
DBT-sulfone at 100 ◦ C in 3 h with an air flow of 25 mL/min. Detailed tests for desulfuriza-
tion of model fuel were carried out to explore the influence of crucial parameters. Under
the optimal reaction conditions, the catalyst could remain stable at least six times without
noticeable decreases of the catalytic performance.

5.2. Boron-Nitride-Based Materials

Recently, graphene-like boron nitride (g-BN) had been developed new application as
a catalyst for aerobic catalysis due to large surface area and high chemical stability [100].
However, its insulating properties prevented it from becoming a highly active material.
In the work of Wu et al. [89], copper nanoparticles (Cu NPs) with low resistivity confined
in g-BN (Cu NPs/g-BN) showed an enhanced performance than pristine g-BN in aerobic
oxidation of aromatic sulfur compounds, with a sulfur removal of 98% at 120 ◦ C in 8 h. In
addition, the catalyst could be recycled for 10 times, and significantly reduction was not
observed, which was attributed to the enhancement of electron mobility coming from
the idiosyncratic oxidation-resisting property of Cu NPs. The existence of g-BN can
protect Cu NPs from being oxidized. This strategy enlarges the application of g-BN for
aerobic reactions.
Platinum group nanoparticles are one of the most attractive AODS catalysts due to
their high catalytic activities. However, the high surface energy of platinum nanoparticles
(Pt NPs) led to the unwanted sintering effect, deactivating the catalyst. In another work by
Wu et al. [51], strong metal-edge interactions (SMEI) between Pt NPs and non-reducible
hexagonal boron nitride (h-BN) support were established and made the Pt NPs well
dispersed, avoiding the reversible process of classic strong metal-support interactions
(SMSI) in oxygen. A DBT removal of 98.3% could be reached at 130 ◦ C with a TOF value
of 15.33 h−1 . The extraordinary AODS performance was attributed to the high dispersion
of Pt NPs and the formation of SEMI, which facilitated the electron transfer between Pt
NPs and h-BN, then improved the adsorption and activation of O2 . The sulfur removal
rates of ibenzothiophene, 4, 6-dimethyldibenzothiophene, 4-methylbenzothiophene, and
benzothiophene was 98.3%, 96.5%, 93.7% and 85.9%, respectively.
Yao et al. [90] anchored molybdenum oxide nanoparticles (MoOxNPs) on g-BN by a
simple one step method. The particle size of MoOx NPs could be controlled by the amount
of precursor, which removed the large particle size occurring in a routine high temperature
calcination method. The controlled MoOxNPs size integrated with strong metal oxide
support interaction contributed to high aerobic oxidative desulfurization activity. A high
TOF value of 37.5 h−1 could be achieved at 120 ◦ C. Moreover, 98.0% DBT sulfur removal
was still achieved after recycling 11 times, as shown in Figure 10, indicating a good stability
and recycling performance of supported catalyst.
A series of g-BN supported decavanadate ionic liquids (POM-IL) [91] was synthesized
and exhibited remarkable AODS performance owing to the inherent catalytic ability of
POM-ILs and the high surface area of g-BN. When using C8 V/g-BN as catalyst, the DBT
removal could reach 99.8% (≤1 ppm) at 120 ◦ C in 4 h with a TOF value of 42.99 h−1 ,
and it could remain stable after six cycles. On the other hand, excellent performance in
oils with different sulfide substrates, concentrations and aromatics/olefins addition was
also achieved. This facile method could reduce the dosage and enhance the stability of
pristine POM-ILs.
Wu et al. [92] developed a facile and environment-friendly liquid nitrogen gas ex-
foliation method to achieve porous monolayer nanosheets (BN-1). As Figure 11 shown,
compared with bulk BN, the sulfur removal of porous monolayer structure h-BN (BN-1)
could reach 98.2% under the same condition, achieving deep desulfurization. With the de-
crease of the layer numbers, the sulfur removal increased owing to the reduction of lateral
sizes and more exposed active sites. The results indicated that the more edge generation
through increasing exfoliation cycles, the higher catalytic activity. Moreover, the catalyst
 Catalysts 2022, 12, x FOR PEER REVIEW 14 of 22

Catalysts 2022, 12, 129 13 of 20

Figure oxide
metal 10. Recycling
supportperformance of MoOxNPs/g-BN.
interaction contributed to highReaction
aerobic conditions: V(oil) = 20 mL,
oxidative desulfurization
m(catalyst) = 0.1 g, T = 120 °C, v(air) =100 mL/min, t = 8 h [90].
activity. A high TOF value of 37.5 h could be achieved at 120 °C. Moreover, 98.0% DBT
−1

can be recycled
sulfur removaleight was times without significant
still achieved decrease
after recycling 11 in aerobic
times, as catalytic
shown inoxidation of
Figure 10,
sulfur Acompounds,
series of indicating
g-BN supportedthe decavanadate
stability of the gas ionic liquids
exfoliation 2D (POM-IL) [91] was
materials.
indicating a good stability and recycling performance of supported catalyst.
synthesized and exhibited remarkable AODS performance owing to the inherent catalytic
ability of POM-ILs and the high surface area of g-BN. When using C8V/g-BN as catalyst,
the DBT removal could reach 99.8% (≤1 ppm) at 120 °C in 4 h with a TOF value of 42.99
h−1, and it could remain stable after six cycles. On the other hand, excellent performance
in oils with different sulfide substrates, concentrations and aromatics/olefins addition was
also achieved. This facile method could reduce the dosage and enhance the stability of
pristine POM-ILs.
Wu et al. [92] developed a facile and environment-friendly liquid nitrogen gas
exfoliation method to achieve porous monolayer nanosheets (BN-1). As Figure 11 shown,
compared with bulk BN, the sulfur removal of porous monolayer structure h-BN (BN-1)
could reach 98.2% under the same condition, achieving deep desulfurization. With the
decrease of the layer numbers, the sulfur removal increased owing to the reduction of
lateral sizes and more exposed active sites. The results indicated that the more edge
generation through increasing exfoliation cycles, the higher catalytic activity. Moreover,
Figure
the
Figure 10. Recycling
catalyst
10. Recycling performance
can be recycled
performanceeightof of MoOxNPs/g-BN.
times Reactiondecrease
without significant
MoOxNPs/g-BN. Reaction conditions: V(oil) =
in aerobic
conditions: V(oil) =catalytic
20 mL,
20 mL,
m(catalyst)
oxidation =
of 0.1 g,
sulfurT = 120 °C,
◦
compounds, v(air) =100 mL/min,
indicating thet = 8 h [90].
stability
m(catalyst) = 0.1 g, T = 120 C, v(air) =100 mL/min, t = 8 h [90]. of the gas exfoliation 2D materials.

A series of g-BN supported decavanadate ionic liquids (POM-IL) [91] was

synthesized and exhibited remarkable AODS performance owing to the inherent catalytic
ability of POM-ILs and the high surface area of g-BN. When using C8V/g-BN as catalyst,
the DBT removal could reach 99.8% (≤1 ppm) at 120 °C in 4 h with a TOF value of 42.99
h−1, and it could remain stable after six cycles. On the other hand, excellent performance
in oils with different sulfide substrates, concentrations and aromatics/olefins addition was
also achieved. This facile method could reduce the dosage and enhance the stability of
pristine POM-ILs.
Wu et al. [92] developed a facile and environment-friendly liquid nitrogen gas
exfoliation method to achieve porous monolayer nanosheets (BN-1). As Figure 11 shown,
compared with bulk BN, the sulfur removal of porous monolayer structure h-BN (BN-1)
could reach 98.2% under the same condition, achieving deep desulfurization. With the
decrease of the layer numbers, the sulfur removal increased owing to the reduction of
Figure11.
lateral
Figure 11. Effect
sizes and
Effect ofexfoliation
of exfoliation
more exposedcycleson
cycles onsulfur
sulfur
active removal
sites. [92].
The[92].
removal results indicated that the more edge
generation through increasing exfoliation cycles, the higher catalytic activity. Moreover,
On the basis
the catalyst can beof the gas-exfoliated
recycled BNwithout
eight times nanosheets (BNNS),decrease
significant Wang et in
al.aerobic
[93] introduced
catalytic
2D V 2 5 of sulfur compounds, indicating the stability of the gas exfoliation a2D
O
oxidation to the BNNS carrier and constructed a 2D-2D nanocomposites via convenient
materials.
solvothermal method. The characterization results confirmed the successful introduction
of 2D V2 O5 . The catalytic aerobic oxidation performance of the 10 wt% V2 O5 /BNNS
nanocomposites was much higher than that of the BN-1, which obtained deep desulfuriza-
tion (DBT, ≤2 ppm) under 120 ◦ C in 4 h, providing an efficient fabrication strategy to design
AODS catalyst and produce ultralow S-content oils. Moreover, deep desulfurization of oils
with different substrates and distractors could also be achieved. In addition, the reaction
system could be recycled at least seven times without any appreciable. The exposed (0 0 1)
facets of V2 O5 , unsaturated V sites as well as oxygen vacancies contributed together to the
extraordinary performance of the 2D-2D nanocomposites.

5.3. Boron Carbon Nitride (BCN)-Based Materials

That electronic properties can strongly affect the performance of h-BN catalysts was
reported. Heteroatom doping was an effective way of taming electronic structure [101,102].
A carbon-doped h-BN (BCN) [94] was prepared by employing the ionic liquid (IL) as carbon
source. The
Figure 11. obtained
Effect metal-free
of exfoliation cyclesheterogeneous catalyst
on sulfur removal [92]. BCN-x showed an outstanding
catalytic performance for the AODS reaction, where a completely sulfur removal could be
achieved at 100 ◦ C and atmospheric pressure. The sulfur removal could still be remained
92% after 5 cycles. Furthermore, it was discovered that the doped carbon atoms bonded
 5.3. Boron Carbon Nitride (BCN)-Based Materials
That electronic properties can strongly affect the performance of h-BN catalysts was
reported. Heteroatom doping was an effective way of taming electronic structure
[101,102]. A carbon-doped h-BN (BCN) [94] was prepared by employing the ionic liquid
Catalysts 2022, 12, 129 (IL) as carbon source. The obtained metal-free heterogeneous catalyst BCN-x 14 of showed
20 an
outstanding catalytic performance for the AODS reaction, where a completely sulfur
removal could be achieved at 100 °C and atmospheric pressure. The sulfur removal could
with the N atoms still
andbepromoted
remained 92% after 5 cycles.
the formation of Furthermore,
π electrons, it wasimproving
thus discovered that the doped carbon
the electron
atoms bonded with the N atoms and promoted
delocalization effect of BN and facilitating the activation of molecular oxygen. the formation of π electrons, thus
improving the electron delocalization effect of BN and facilitating the activation of
The catalytic performance of BCN was closely related to the edge electronic struc-
molecular oxygen.
tures [103]. However, the carbon in BCN tended to agglomerate and form separate graphene
The catalytic performance of BCN was closely related to the edge electronic
and BN domain. structures
Therefore,[103].homogeneity
However, the wascarbon
vital for the catalytic
in BCN tended to performance
agglomerate and of BCN
form separate
materials. In the face
graphene and BN domain. Therefore, homogeneity was vital for the catalyticBCN
of this issue, Wei et al. [95] synthesized a hierarchical porous performance
catalyst using a ternary deep eutectic
of BCN materials. In thesolvent (DES)
face of this issue,asWei
theettemplate and more
al. [95] synthesized even pre- porous
a hierarchical
cursor, as shown BCNin Figure
catalyst 12. Thea as-prepared
using BCN showed
ternary deep eutectic excellent
solvent (DES) as thecatalytic
templateAODSand more even
performance withprecursor,
a sulfur as shown in
removal ofFigure
98.4%12.atThe ◦ C in 4 h. BCN
125as-prepared It canshowed excellent5 catalytic
be recycled times AODS
performance
with a little activity decrease.with Thea uniform
sulfur removal of 98.4%
dispersion ofatcarbon
125 °Cclusters
in 4 h. It improved
can be recycled
the 5 times
with a little activity decrease. The uniform dispersion of
electron delocalization effect of BCN. Combined with density functional theory (DFT), the carbon clusters improved the
electron delocalization effect of BCN. Combined with density
improved electron delocalization would increase the electron density of BCN and promote functional theory (DFT), the
improved electron delocalization would increase the electron density of BCN and
the activation of molecular oxygen, thus reducing the reaction temperature required for the
promote the activation of molecular oxygen, thus reducing the reaction temperature
AODS process. required for the AODS process.

Figureroute
Figure 12. The synthetic 12. The synthetic
diagram ofroute diagramBCN
the porous of thecatalyst
porous [95].
BCN catalyst [95].

The heteroatom-doped
The heteroatom-doped h-BN catalysts canh-BNhave
catalysts
atomiccan have atomic
disorder disorder
at the grain at the grain
bound-
boundaries. There are different configurational entropies on various atomic short-range
aries. There are different configurational entropies on various atomic short-range orderings
orderings or phase separations, leading different performance for catalytic reactions. To
or phase separations, leading different performance for catalytic reactions. To explore the
explore the effect of configurational entropies on the AODS catalytic activity, Wei et al.
effect of configurational entropies on the AODS catalytic activity, Wei et al. [97] synthesized
[97] synthesized a series of carbon and oxygen co-doped h-BN (BCNO) catalysts with
a series of carbondifferent
and oxygen
atomicco-doped h-BN DES
orderings using (BCNO) catalysts
as precursor. with
The lowdifferent atomicDES was
steric resistance
Catalysts 2022, 12, x FOR PEER REVIEW 16 of 22
orderings using DES as precursor. The low steric resistance DES was investigated
investigated as a trend of high-entropy structures (HES) in the BCNO (high as density
a of
trend of high-entropy structures (HES) in the BCNO (high density of grain boundaries).
grain boundaries). Moreover, it was found that the HES was a booster for the radical
Moreover, it was found that the HES was a booster for the radical initiation of AODS of
initiation
diesel. of AODS
Figure of diesel.
13 showed thatFigure 13 showed
TMAC-BCNO thatthe
with TMAC-BCNO
lowest stericwith theexhibited
effect lowest steric
the
effect exhibited
shortest theperiod
induction shortest
andinduction
achievedperiod
completeandsulfur
achieved complete
conversion in sulfur conversion
6 h, compared within
6 h,pure
the compared withimprovement
h-BN. The the pure h-BN. of The improvement
catalytic performanceof catalytic
of BCNO performance of BCNO
can be attributed to
the
cansufficient reactive
be attributed sites
to the in HES.reactive sites in HES.
sufficient

Figure13.
Figure 13.The
Theresults
resultsof
ofaerobic
aerobicODS
ODStests
testson
onDBT
DBTmodel
modeldiesel
dieselfor
forthe
theBCNO
BCNOcatalysts
catalysts[96].
[96].

Boron carbide
Boron carbide (B
(B44C)
C) had
has been attracted much attention
attention due
due to
to its
its extremely
extremely high
high
thermal stability,
thermal stability,low
lowdensity
densityand
andexcellent
excellent high-temperature
high-temperature thermoelectric
thermoelectric properties.
properties.
Therefore, it was good candidate to promote AODS reaction. Wu et al. [97] had
successfully prepared a metal-free B4C by mechanical ball milling exfoliation, which
induced thinner-layered structure, small size and numerous defects in B4C catalysts, as
shown in Figure 14. It was investigated that the defects functioned as catalytically active
sites. Furthermore, the exfoliated boron carbide catalyst was applied in aerobic ODS
 Figure 13. The results of aerobic ODS tests on DBT model diesel for the BCNO catalysts [96].
Catalysts 2022, 12, 129 15 of 20
Boron carbide (B4C) has been attracted much attention due to its extremely high
thermal stability, low density and excellent high-temperature thermoelectric properties.
Therefore,it it
Therefore, waswas good
good candidate
candidate to promote
to promote AODS reaction.
AODS reaction. Wu et al. Wu et al.
[97] had [97] had
successfully
successfully prepared a metal-free B C by mechanical ball milling exfoliation,
prepared a metal-free B4 C by mechanical ball milling exfoliation, which induced thinner-
4 which
inducedstructure,
layered thinner-layered
small sizestructure, small size
and numerous andinnumerous
defects defects
B4 C catalysts, in B4C in
as shown catalysts,
Figure 14.as
Itshown in Figure 14.
was investigated It was
that investigated
the defects that the
functioned defects functioned
as catalytically as catalytically
active sites. Furthermore, active
the
sites. Furthermore,
exfoliated the exfoliated
boron carbide catalyst was boron carbide
applied catalyst
in aerobic ODSwas applied
system, andin aerobic
sulfur ODS
removal
system,
reach 99.5%at 130 ◦ C
and sulfur removal reach 99.5%at
in 8 h. Moreover, the 130 °C incould
catalyst 8 h. Moreover,
be recycledthe17catalyst could be
times without a
recycled 17 times without a significant decrease in catalytic activity, indicating
significant decrease in catalytic activity, indicating their inherent robustness. In particular, their
itinherent robustness.
was found In particular,
that the current aerobicit was
ODSfound
system that the remove
could current aerobic ODS
90% sulfur system could
compounds in
remove
real diesel90%oil.sulfur compounds in real diesel oil.

Figure14.
Figure 14. Scheme
Scheme of
of exfoliated
exfoliatedmetal-free
metal-freeboron
boroncarbide
carbidefor
foraerobic
aerobicoxidative
oxidativedesulfurization
desulfurization[97].
[97].

5.4.
5.4. Porous
Porous Carbon
Carbon Nitride
Nitride
In
In 2020, Guetetal.
2020, Gu al.[98]
[98] synthesized
synthesized a three-dimensional
a three-dimensional (3D)(3D)
porousporous
g- C3g-
N4Csupported
3 N4 sup-
ported vanadium-based heterogeneous catalyst (V-IL/3D g-C N
vanadium-based heterogeneous catalyst (V-IL/3D g-C3N4) by a simple solvothermal
3 4 ) by a simple solvother-
mal method.
method. The as-prepared
The as-prepared g- C3Ng-4 carrier
C3 N4 carrier has3D
has a rich a pore
rich 3D pore structure,
structure, which was which was
beneficial
beneficial to the high dispersion of active center, while the mesoporous
to the high dispersion of active center, while the mesoporous g- C3N4 can g- C N can
3 adsorb
4 adsorb
sulfur
sulfur
compoundscompounds and enhance
and enhance the mass thetransfer
mass transfer of reaction.
of reaction. The experimental
The experimental results
results showed
showed
that small that small amount
amount (0.01 g) (0.01
of theg)catalyst
of the catalyst can activate
can activate the oxygen
the oxygen in the
in the air, andair, and
oxidize
oxidize different refractory organic sulfur compounds in the model oil to polar sulfones.
The catalyst could maintain stable catalytic activity in five cycles, indicating the excellent
cycle stability of the catalyst.
As mentioned earlier in Section 5.2, the SMEI could facilitate the dispersion of platinum
group metals with high surface energy and promote the AODS reaction [51]. However,
for supported Au NPs, the interactions between metal NPs and the support are not eas-
ily constructed due to their low surface energy and low work function. To solve this
problem, Liu et al. [99] developed a novel C3 N4 -mediated synthetic strategy to fabricate
an Au/ TiO2 nanoparticles (NPs) catalyst with SMSI between the TiO2 support and Au
NPs. The C3 N4 layer on TiO2 functioned as a sacrificial agent, mediating the formation
of a SMSI between the reducible TiO2 support and Au NPs. Compared with the catalyst
supported Au NPs without SMSI, both of the activity and stability of catalyst with SMSI
was improved. The TOF value was 40.77 h−1 for Au-TiO2 @C3 N4 -800, which was much
higher than that of Au-TiO2 -800 (28.33 h−1 ) under the same reaction conditions. After
6 h of reaction, the catalytic activity was arranged in following rank order according to
performance: DBT > 4,6-DMDBT > 4-MDBT. Moreover, sulfur removal can still remain
at 92.2% after being reused seven times, indicating the excellent stability owing to the
formation of a SMSI.

6. Conclusions and Prospects

The stringent limitation of petroleum refinery sulfur emission urged the removal of
sulfur compounds as a critical issue. As a result, AODS had received substantial consid-
eration in last decades. This reaction could be an ideal way to perform the ODS process
Catalysts 2022, 12, 129 16 of 20

because the oxidant is abundant, available everywhere and inexpensive. On the other
hand, the number of research papers related to porous materials increased significantly in
recent years, concerning the reaction of oxidation with molecular oxygen in the absence
of sacrificial compounds. Several breakthroughs were achieved in the development of an
efficient porous material catalyst for AODS. Based on the catalyst structure and catalytic
performance introduced in the current paper, the following conclusions could be drawn:
 Porous mixed metal oxides catalysts are desirable due to their tunable electronic
structure, which could facilitate the activation of molecular oxygen.
 For composites of mesoporous silica and metal oxides composites, the interaction
between carriers and active center, dispersion of metal oxides and the formation
of metal peroxides resulting in improved activity and stability of the catalysts in
AODS process.
 In MOF-based catalysts, the coordinatively unsaturated metal sites, tailorable organic
linkers, high surface area joined with unique porosity endowed MOFs with both the
ability to catalyze AODS themselves and to be supports for active centers.
 Porous graphene-based catalysts are promising catalysts due to their excellent me-
chanical stability, rich surface defects or functional groups, and high surface area.
 Boron nitride-based catalysts are the new favorite of researchers owing to their high
specific surface area, extremely high thermal stability, non-reducibility and tunable
electronic structure, which are desirable in both supported metal-containing catalysts
and metal-free catalysts.
It is envisioned that porous materials have great potential in aerobic oxidation of
organosulfur compounds. Future interest may lie in increasing exposed active sites, tunable
electronic structure and stability of porous catalysts. However, the AODS temperature is
still relatively too high, which will lead to the side reaction for oxidation of the petroleum
components and affect the octane number of the commercial gasoline or diesel products.
In the future, more attention should be devoted to designing catalysts that function at a
lower temperature. Low temperature catalysis recently occurred when using catalysts with
a reasonable electronic structure, which would find a more promising scenario in the field
of AODS catalysis. Future work should also be focused on the synthesis and in-depth
mechanism study, paving a way for the rational design of the next-generation catalysts for
AODS reactions.

Author Contributions: Writing—original draft preparation, B.Y. and X.L.; writing—review and
editing, B.Y. and X.L.; supervision, Y.S.; funding acquisition, X.L. and Y.S. All authors have read and
agreed to the published version of the manuscript.
Funding: This research was funded by Guangdong Basic and Applied Basic Research Founda-
tion, grant number 2019A1515110532, Guangdong Basic and Applied Basic Research Foundation
grant number 2021A1515011808, Post-doctoral Foundation Project of Shenzhen Polytechnic, grant
number 6021330013K0.
Data Availability Statement: The data presented in this review are available in all the references.
Conflicts of Interest: The authors declare no conflict of interest.

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