Applied Surface Science 569 (2021) 151086

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Applied Surface Science

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Full Length Article

Oxidative desulfurization of dibenzothiophene and simultaneous

adsorption of products on BiOBr-C3N4/MCM-41 visible-light-driven
core–shell nano photocatalyst
Fahime Abedini a, b, Somaiyeh Allahyari a, b, *, Nader Rahemi a, b
a
Chemical Engineering Faculty, Sahand University of Technology, P.O.Box 51335-1996, Sahand New Town, Tabriz, Iran
b
Environmental Engineering Research Centre, Sahand University of Technology, P.O.Box 51335-1996, Tabriz, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, different amounts of BiOBr (x = 0, 5, 10, 15 wt%) and 5% wt. of g-C3N4 were loaded on MCM-41 as
Photocatalyst-adsorbent core for photo oxidation of DBT and simultaneous adsorption of oxidation products. Among studied photo­
Desulfurization catalysts, the BiOBr-C3N4/MCM-41 photocatalyst with 10% wt. of BiOBr indicated the highest activity so that
Dibenzothiophene
this sample reduced DBT concentration to the lowest value of C/C0 = 0.08 after 150 min irradiation of visible
BiOBr-C3N4/MCM-41
light. The characterization of the as prepared photocatalysts by XRD, FESEM, TEM, FTIR, BET-BJH, UV–Vis DRS,
Visible light
and PL analyses revealed that this achievement was due to the highest amount of structural defects and the
strongest interaction between BiOBr-C3N4 shell and MCM-41 core in this sample. Moreover, this sample indi­
cated the lowest recombination rate of charge carriers, the narrowest band gap, and high porosity that enhanced
the photocatalytic efficiency. However, this sample lost 18% of initial activity after four successive cycles of
photo oxidation-adsorption that based on FTIR and BET-BJH was because of plugging of pores by DBT sulfones.

1. Introduction oxidative desulfurization [12–15], photocatalytic desulfurization

Although fossil fuels have been playing a dominant role in devel­
oping modern life, the combustion of sulfur compounds such as disul­
fide, thiophene, dibenzothiophene, and their derivatives in fossil fuels
releases sulfur oxides (SOx) into the atmosphere which are gradually
causing acid rain, acid fog, haze, and other environmental issues [1–3].
Therefore, essential strategies should be taken to remove the sulfur
compounds from fossil fuels.
Hydrodesulfurization (HDS) which is a conventional technique to
reduce sulfur components from liquid fuels, operates under high tem­
perature (320–380 ◦ C) and high pressures (3–7 MPa) and needs large
amounts of H2 [4,5]. Nevertheless, this technique is less effective in
removing sterically hindered compounds such as dibenzothiophene
(DBT) and its derivatives [6]. To achieve ultra-deep desulfurization,
other methods have been employed such as extractive desulfurization
(EDS) [7,8], biodesulfurization (BDS) [9,10], and adsorptive desulfur­
ization [11].
Oxidative desulfurization by a catalyst or photocatalyst is a prom­
ising strategy for degradation of sulfuric components in the liquid fuel.
While catalytic desulfurization has been indicated promising results in
because of milder operating conditions, keeping the octane number at
high level, high efficiency, and using sustainable energy of sun is suit­
able particularly in the case of in situ desulfurization of marine fuels on
board [16,17]. In this process, in the presence of a photocatalyst and an
oxidant, sulfur compounds are converted to the corresponding polar
sulfones. Dipole-dipole interactions facilitate the separation of sulfones
by solvent extraction [18,19], however, the common solvents are
expensive and harm the environment. Another alternative with
outstanding economic and environmental benefits is adsorption of
oxidation products on a porous solid. In this case, combining two stages
of oxidation and adsorption in one vessel on the same material is a new
development. As a result, the used photocatalyst should have dual
functionality both in the oxidation of sulfur compounds and in the
adsorption of oxidation products.
With regard to the photocatalytic phases, graphitic nitride carbon (g-
C3N4), as a well-known polymer, has attracted much interest due to
thermal stability, electronic characteristics, suitable band gap energy
(2.7 eV), and low cost [7,20]. g-C3N4 can be obtained through a simple
one-step polymerization of urea, thiourea, melamine, or dicyandiamide
[7,21,22]. However, this material has a high recombination rate of the

* Corresponding author.
E-mail address: allahyari@sut.ac.ir (S. Allahyari).

https://doi.org/10.1016/j.apsusc.2021.151086
Received 23 May 2021; Received in revised form 19 July 2021; Accepted 24 August 2021
Available online 27 August 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
F. Abedini et al.
electron-hole pairs [20]. Strategies such as morphological control
[23,24], element-doping [25], and creating heterojunction with other
semiconductors [26–29] have been developed so far to overcome this
drawback.
Among different semiconductors, bismuth-based ones are widely
used for building a heterojunction with g-C3N4 in order to resolve the
problem of fast recombination rate. BiOBr as a bismuth oxyholide has a
lamellar structure, visible light response, high chemical stability, and
low cost. While the heterojunction between BiOBr and g-C3N4 has been
used in the photocatalytic treatment of wastewater [30–33], to the best
of our knowledge, this heterojunction has not been used in photo­
catalytic desulfurization to date.
Porous silica, which has a good background in the adsorption of
polar sulfur compounds produced from oxidation, is a suitable choice for
our needed support of bifunctional photocatalyst-adsorbent [34].
Due to the proper performance of core–shell structures in bifunc­
tional purposes, in this study, g-C3N4-BiOBr with different BiOBr per­
centages were loaded on MCM-41 as core. The synthesized core–shell
photocatalysts were investigated in the simultaneous oxidative-
adsorptive desulfurization of DBT. X-ray Diffraction (XRD), Field
Emission Scanning Electron Microscopy (FESEM), Brunauer–Emmett–­
Teller (BET), Fourier Transform Infrared (FTIR), Energy Dispersive X-
Ray (EDX), UV–Vis Diffuse Reflectance Spectroscopy (UV–Vis DRS),
Photoluminescence (PL), and Transmission Electron Microscopy (TEM)
analyses were used to characterize the as-prepared samples.
In the following, the effect of operating parameters, such as reaction
temperature, the content of H2O2, DBT concentration, and the amount of
catalyst, were investigated on the highly active photocatalyst. The sta­
bility of this sample also was tested during successive runs.
2. Materials and methods
2.1. Materials
Dibenzothiophene (Sigma–Aldrich), hydrogen peroxide (Fisher Sci­
entific, 30% v/v.), n-hexane (Sigma–Aldrich), sodium hydroxide (Sig­
ma–Aldrich), tetraethyl orthosilicate (Sigma–Aldrich),
hexadecyltrimethylammonium bromide (CTAB, Merck), ethanol
(Merck), melamine (Merck), bismuth (III) nitrate pentahydrate (Sig­
ma–Aldrich), and potassium bromide (Merck) were used as received
without any further purification.
2.2. Sample preparation
2.2.1. Preparation of MCM-41
MCM-41 was synthesized by a sol–gel method [35]. For this, 0.28 g
of NaOH and 1 g of CTAB in 480 ml of distilled water were dissolved
under vigorous stirring at 80 ◦ C. When a clear solution was obtained, 5
ml of TEOS was added dropwise within 20 min. The solution was stirred
for 2 h. Then, white synthesized materials were separated from the so­
lution by vacuum filtration and washed several times with distilled
water. The final product was dried at room temperature for 12 h. In
order to remove remained CTAB from the solution, calcination was
performed at 550 ◦ C for 5 h.
2.2.2. Preparation of photocatalyst g-C3N4
Graphitic carbon nitride (g-C3N4) was fabricated by thermal
condensation of melamine according to [36]. 5 g melamine powder was
put into an alumina crucible and the temperature increased to 550 ◦ C
with the rate of 1 ◦ C/min and kept at this temperature for 4 h. After
calcination, a yellowish powder was obtained.
2.2.3. Preparation of BiOBr-C3N4/MCM-41
First, MCM-41 and g-C3N4 were mixed in 40 ml of distilled water and
subjected to ultrasonic irradiation with the power of 80 W for 10 min.
Then KBr was dissolved in 40 ml of ethanol and added to the above
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Applied Surface Science 569 (2021) 151086
mixture. Finally, different amounts of Bi(NO3)3⋅5H2O were gradually
added to the above solution under ultrasonic irradiations (15 min-80 W)
and then stirred for 4 h. The material was transferred to an autoclave to
stay at 140 ◦ C for 12 h. The resulting material was separated by
centrifugation, washed several times with water, and dried at 60 ◦ C for
24 h. While the percentage of BiOBr was different (0%, 5%, 10%, and
15% wt.) at samples, the amount of g-C3N4 was 5% wt.
2.3. Characterization
For the identification of crystalline phases of the as-prepared sam­
ples, X-ray diffraction (XRD, Bruker D8 ADVANCE) was performed with
Cu-Kα radiation in the 2θ range of 2-75◦ . The surface structure and
morphology of the samples were studied by Field Emission Scanning
Electron Microscope (FESEM, TESCAN vega3). Brunauer- Emmett-Teller
(BET) and Barrett-Joyner-Halenda (BJH) analyses were used to deter­
mine specific surface area and pore volume using BELSORP-mini, Japan.
Fourier Transform Infrared (FTIR, Perkin Elmer) was used to identify the
functional groups on the catalyst surface in the range of 440–4000 cm− 1.
Moreover, the ultraviolet–visible diffuse reflectance spectra (Scino
4100) were recorded to determine the optical properties of as-prepared
samples. Photoluminescence (PL) spectra were recorded using a fluo­
rescence spectrometer (Avaspec 2048 TEC) with an excitation wave­
length of 355 nm at room temperature to investigate electron-hole
recombination. The morphology of samples was obtained by trans­
mission electron microscope (Philips CM120) with a maximum voltage
of 100 kV.
2.4. Photocatalytic activity test
The model fuel was prepared by dissolving DBT into 60 ml of n-
hexane (200 ppm) and transferred into a three-neck flask. As shown in
Fig. 1S, in order to prevent evaporation of n-hexane, a condenser was
installed on top of the reaction chamber. In addition, a water bath was
used to regulate the reaction temperature. Then photocatalyst was
added to the model fuel before irradiation, the suspension was placed in
the dark for 30 min to establish an adsorption–desorption equilibrium
between the photocatalyst and DBT. To initiate the photocatalytic re­
actions, a certain amount of H2O2 was added to the reaction chamber
and a 150 W halogen-tungsten lamp with light intensity of 187 mW/cm2
as the visible light source came on. Sampling from the reactor was
performed at 30 min intervals, and samples were centrifuged to separate
the photocatalyst from the liquid. The residue concentration of DBT was
monitored using a UV–Vis spectrophotometer at λmax = 325 nm [37,38].
3. Results and discussions
3.1. Structural characteristics of BiOBr-C3N4/MCM-41 photocatalyst-
adsorbents
Fig. 1 shows X-ray diffraction patterns of as-synthesized BiOBr-C3N4/
MCM-41 photocatalyst-adsorbents with different percentages of BiOBr
(0%, 5%, 10% and 15% wt.). The diffraction peaks at 2θ of 10.9˚, 21.9˚,
25.2˚, 30.0˚, 31.2˚, 37.5˚, 44.6˚, 47.6˚, 50.6˚and 54.0˚can be well-indexed for
(0 0 1), (0 0 2), (0 1 1), (0 1 2), (1 1 0), (1 1 2), (0 0 4), (0 1 4) and (1 2 1)
planes of tetragonal BiOBr (JCPDS 96–901-1784), respectively. A shift at
2θ = 30˚toward higher 2θs could be attributed to the decrease of unit cell
parameters of BiOBr due to immobilization of BiOBr into the lattice of
MCM-41. The shift to the right is increasing with an enhanced amount of
BiOBr, which means more variations in BiOBr unit cells at higher BiOBr
percentages.
The weak diffraction peak at 2θ = 29˚, corresponding to (0 0 2) plane
of g-C3N4 (JCPDS 87–1526) [40], means that there are highly dispersed
fine crystallites of C3N4 in all samples.
Furthermore, the diffraction peak at 2θ = 22˚could be attributed to
amorphous SiO2. The decrease in peak intensity at 2θ = 22˚, particularly
F. Abedini et al.
Fig. 1. XRD patterns of BiOBr-C3N4/MCM-41 photocatalysts with different percentages of BiOBr.
in the samples with 10% wt. of BiOBr, can be attributed to the absorp­
tion of X-rays by the BiOBr/C3N4 shell and is indicative of the formation
of a good core–shell structure [39,40]. The most decrease in peak in­
tensity has been observed in the case of 10% wt. of BiOBr, which reveals
the higher amount of structural defect in this sample [41,42]. Structural
defects in a photocatalyst can extend the light absorption to the visible
region. Moreover, defects may act as a “carrier sea” and trap electrons or
holes, declining the charge carrier recombination rate [43].
As can be seen in Fig. 1, with further increasing the amount of BiOBr
to 15% wt., the intensity of SiO2 related peak increased again, probably
due to the formation of other structures like composites besides core–­
shell structures in this sample.
Low-angle X-ray diffraction patterns of the as-prepared samples have
been indicated inside Fig. 1. As can be seen, according to the emergence
of a peak at 2θ of 2.6, assigned to (1 0 0) reflection plane of MCM-41
porous structure [44,45], its formation is well-confirmed in all sam­
ples. In 10 %BiOBr-C3N4/MCM-41 sample, the intensity of this peak is
the lowest which reaffirms that a core–shell structure with SiO2 in core
and other components in shell has been produced. This also indicates
that orderliness of silica mesostructures became weaker after loading of
10% of BiOBr, leading to more defect structures [46]. A shift of peak at
2θ = 2.6 to higher degrees in the case of 10 %BiOBr-C3N4/MCM-41
photocatalyst reveals the decrease in unit cell parameters of MCM-41
due to immobilization of BiOBr [47] and thus strong interaction be­
tween photocatalytic and adsorption centers.
Table 1 shows the crystallite size of BiOBr and band gap of BiOBr-
C3N4/MCM-41 photocatalyst at different percentages of BiOBr. The
BiOBr crystallite size was calculated using Scherer equation based on the
peak at 2θ = 30.0˚. As can be seen, the crystallite size of samples
increased from 9 nm to 9.5 nm with enhancing the BiOBr amount from
5% wt. to 10% wt. The size of BiOBr crystallites slightly grew to 9.7 nm
in the case of 15 %BiOBr-C3N4/MCM-41 sample.
Fig. 2 shows FESEM images of as-prepared samples with different
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Applied Surface Science 569 (2021) 151086
Table 1
Crystallite size and band gap energy of BiOBr-C3N4/MCM-41 photocatalysts
with different percentages of BiOBr.
Bandgap (eV) BiOBr crystallite size (nm)a Photocatalyst
2.75 – 0.0 %BiOBr-C3N4/MCM-41
2.7 9 5.0 %BiOBr-C3N4/MCM-41
2.6 9.5 10 %BiOBr-C3N4/MCM-41
2.72 9.7 15 %BiOBr-C3N4/MCM-41
a. Crystallite size estimated by Scherer’s equation.
amounts of BiOBr. As can be seen, the nanoparticles of 0 %BiOBr-C3N4/
MCM-41 were spherical with a uniform distribution. g-C3N4 particles in
this sample were perfectly distributed on the surface of MCM-41 so that
no accumulation of C3N4 particles was observed. The particle size in the
5 %BiOBr-C3N4/MCM-41 sample was relatively>0 %BiOBr-C3N4/MCM-
41, and the shape of particles was elliptical. With further increasing the
amount of BiOBr to 10% wt., the distribution of spherical particles
became uniform again. No severe agglomeration and isolation of similar
particles are observed, which confirms good interaction between three
components of this sample, similar to what XRD indicated. However, by
increasing the amount of BiOBr to 15% wt., the distribution of particles
became non-uniform, and the islands of flat plates of BiOBr were
observed separated from spherical particles. Lack of strong interactions
between particles of 15 %BiOBr-C3N4/MCM-41 had been claimed earlier
using XRD as well.
Fig. 3 shows the N2 adsorption/desorption isotherms and pore size
distribution of BiOBr-C3N4/MCM-41 photocatalyst-adsorbents with
different percentages of BiOBr. It can be found that all samples have type
IV isotherm with a type H3 hysteresis loop, indicating the presence of
mesoporous structure and slit-shaped pores probably because of sheet-
like structure of BiOBr and C3N4 [48]. The mesoporous structure of
MCM-41 used in this work was confirmed previously from low-angle
F. Abedini et al.
Fig. 2. SEM pictures of BiOBr-C3N4/MCM-41 photocatalysts with different percentages of BiOBr.
XRD as well.
The textural properties of 5 %BiOBr-C3N4/MCM-41, 10 %BiOBr-
C3N4/MCM-41, and 15 %BiOBr-C3N4/MCM-41 samples are shown in
Table 2. The specific surface area of x%BiOBr-C3N4/MCM-41 that × is 5,
10, 15 wt% were 993 m2/g, 925 m2/g and 707 m2/g, respectively. It can
be found that with the addition of BiOBr, the surface area decreased, and
average pore diameter increased. This shows BiOBr particles more likely
have been immobilized into small pores of MCM-41.
Fig. 4 displays the FTIR spectra of the prepared samples with
different percentages of BiOBr (0% wt. to 15% wt.). The absorption
bands centered at 3427 and 1626 cm− 1 in all samples correspondes to
OH stretching and bending groups, respectively [49]. The bands at 962,
805, 564, and 473 cm− 1 are related to the Si-O stretching and defor­
mation frequencies. The absorption peak at 1087 cm− 1, which is a
fingerprint for the tetrahedral SiO44- structural units [44], can be
observed in all samples. This peak decays with BiOBr addition from 5%
to 10 wt%, which reveals the incorporation of BiOBr into the lattice of
MCM-41 [50]. However, with an extra addition of BiOBr to 15 wt%, the
peak intensity at 1087 cm− 1 slightly increases. It means that some
amount of BiOBr has been distributed as isolated aggregated particles
without interaction with MCM-41, consistent with XRD and FESEM. This
can disrupt the full coverage of MCM-41 with C3N4 and BiOBr as a
core–shell structure. Additionally, this peak has been shifted to lower
wavenumbers with increasing the BiOBr content, reconfirming the
interaction between BiOBr and MCM-41. Core coverage also can be
decided from the peak at 962 cm− 1, which is a characteristic peak of
surface silanol groups [51]. Among BiOBr containing samples, the
weakest peak in this region is related to 10 %BiOBr-C3N4/MCM-41,
which means the most coverage of silanol groups after adsorption of
BiOBr and thus strong interaction between silica core and BiOBr(-C3N4)
4
Applied Surface Science 569 (2021) 151086
shell. Strong interaction between species in core–shell is essential to
precede dual-functional processes like the present work.
A series of typical peaks ranging from 1300 to 1500 cm− 1 were
ascribed to the stretching modes of C-N and C = N in the g-C3N4 het­
erocycles [52]. Regardless of BiOBr content, the peaks in this region
were approximately similar. The absorption peak for pure g-C3N4 at 810
cm− 1, which is related to the stretching of the triazine units, overlapped
with symmetric Si–O–Si stretching at 805 cm− 1 [53].
For investigating the optical properties of as-prepared materials,
UV–Vis DRS analysis was performed (Fig. 5). As can be seen, all pre­
pared samples exhibit visible-light response. The absorption edge of 0 %
BiOBr-C3N4/MCM-41 is about 452 nm. Addition of BiOBr to the C3N4/
MCM-41 up to 10 wt% showed a red-shift in the absorption edge which
means improvement in photocatalytic ability under visible light
[54,55].
The photocatalytic activity is closely related to the band gap energy
(Eg) of the photocatalysts. The band gap energy of as-prepared materials
could be determined by the following equation [56]:
Eg = hc/λ0 = 1240/λ0 (1)
where c is the velocity of light, h is Plank constant, λ0 is the maximum
absorption, and Eg is the band gap energy of photocatalyst. As shown in
Table 1, the band gaps of the 0 %BiOBr-C3N4/MCM-41, 5 %BiOBr-C3N4/
MCM-41, 10 %BiOBr-C3N4/MCM-41 and 15 %BiOBr-C3N4/MCM-41
were calculated to be 2.75, 2.7, 2.6 and 2.72 eV, respectively. By
comparing the Eg of the prepared samples, it can be seen that the band
gap energy with the introduction of BiOBr up to 10 wt% became nar­
rower from 2.75 to 2.6 eV. However, extra addition of BiOBr up to 15 wt
% widens the bang gap to 2.72, probably to bigger crystallites of BiOBr
F. Abedini et al. Applied Surface Science 569 (2021) 151086

Fig. 3. Adsorption/desorption isotherms and pore size distribution of BiOBr-C3N4/MCM-41 photocatalysts with different percentages of BiOBr.

(XRD), weakening the interaction between particles (XRD, FTIR, SEM)
or lower surface area (BET).
For investigating the migration, transfer, and recombination of
electron-hole pairs, the photoluminescence (PL) spectrum was provided.
It is well acknowledged that a lower PL intensity means a lower
recombination rate of electron-hole pairs, resulting in higher
photocatalytic efficiency. Fig. 6 shows PL spectra of the synthesized
BiOBr-C3N4/MCM-41 photocatalyst-adsorbents with different percent­
ages of BiOBr from 0 to 15 wt% excited at 355 nm. PL intensity is found
to follow the sequence: 0 %BiOBr-C3N4/MCM-41 > 5 %BiOBr-C3N4/
MCM-41 > 15 %BiOBr-C3N4/MCM-41 > 10 %BiOBr-C3N4/MCM-41.
The 0 %BiOBr-C3N4/MCM-41 possesses the strongest PL emission peak

5
F. Abedini et al. Applied Surface Science 569 (2021) 151086

Table 2 uniform morphology, good interaction between particles, small parti­

BET surface area, total pore volume and average pore diameter of BiOBr-C3N4/ cles, and relatively high surface area. Furthermore, according to XRD,
MCM-41 photocatalysts with different percentages of BiOBr. this sample possesses a higher amount of structural defects that facilitate
Total pore volume Average pore BET surface area Catalyst name charge carrier separation [43].
(cm3/g) diameter (nm) (m2/g) Transmission electron microscopy (TEM) was used to investigate the
0.85 3.4 993 5.0 %BiOBr-C3N4/ morphology of the 10.0 %BiOBr-C3N4/MCM-41 core–shell structure. As
MCM-41 presented in Fig. 7, the relatively dark areas as the core are porous or­
0.94 4.0.1 925 10 %BiOBr-C3N4/ dered MCM-41 consistent with XRD observations, and the light grey
MCM-41
areas around the MCM-41 are BiOBr-C3N4. As presented, the entire
1.07 6.1 707 15 %BiOBr-C3N4/
MCM-41 surface of MCM-41 spheres with relatively 70–80 nm size is uniformly
covered with BiOBr-C3N4 shell. The thickness of the BiOBr-C3N4 shell is
about 20 nm and consists of the individual particles of BiOBr or C3N4
at around 460 nm and displays the highest recombination rate of (indistinguishable) with diameters less than 10 nm, which earlier
electron-hole pairs. After introducing BiOBr, the PL emission of BiOBr- confirmed by XRD.
C3N4/MCM-41 photocatalysts becomes lower than C3N4/MCM-41
sample, suggesting that the introduction of BiOBr is beneficial for
improving the separation of charge carriers. However, the amount of 3.2. DBT degradation using BiOBr-C3N4/MCM-41 photocatalyst-
added BiOBr is playing an important role, and more amounts of BiOBr adsorbents
necessarily do not decline the PL emission further. 10 %BiOBr-C3N4/
MCM-41 had the lowest recombination rate of electron-holes due to a In this section, BiOBr-C3N4/MCM-41 photocatalyst-adsorbents with
different BiOBr contents were evaluated in simultaneous oxidative-

0.0% BiOBr-C3N4/MCM-41
5.0% BiOBr-C3N4/MCM-41
10% BiOBr-C3N4/MCM-41
15% BiOBr-C3N4/MCM-41
Transmittance

473 564
805
1626

962
3427

C3N4
1213
1087

3940 3440 2940 2440 1940 1440 940 440

Wavenumbers (cm-1)
Fig. 4. FTIR analysis of BiOBr-C3N4/MCM-41 photocatalysts with different percentages of BiOBr.

6
F. Abedini et al. Applied Surface Science 569 (2021) 151086

0.0%BiOBr-C3N4/MCM-41

5.0%BiOBr-C3N4/MCM-41

10%BiOBr-C3N4/MCM-41
Adsorbance (a.u)

15%BiOBr-C3N4/MCM-41

Fig. 7. TEM analysis of 10 %BiOBr-C3N4/MCM-41 photocatalyst.

300 400 500 600 700 800 37% for the BiOBr containing samples of 5.0 %BiOBr-C3N4/MCM-41, 10
Wavelength(nm) %BiOBr-C3N4/MCM-41, and 15 %BiOBr-C3N4/MCM-41, respectively.
Although the BiOBr content played a key role in the photocatalytic
Fig. 5. UV–Vis DRS analysis of BiOBr-C3N4/MCM-41 photocatalysts with performance of BiOBr-C3N4/MCM-41 photocatalysts, there was no
different percentages of BiOBr. linear correlation between BiOBr content and DBT photocatalytic
degradation and 10 %BiOBr-C3N4/MCM-41 sample with a moderate
amount of BiOBr displayed the highest activity in photocatalytic
degradation of DBT. Small particle size and uniform dispersion of par­
ticles as well as high surface area enhanced the available photocatalytic
active sites in this sample, leading to more sites for light absorption.
Moreover, the band gap energy was the narrowest among studied
samples, which facilitates the production of electrons and holes. Also, PL
analysis illustrated the lowest recombination rate in 10 %BiOBr-C3N4/
MCM-41 sample, which improves the photocatalytic efficiency. There­
fore, the core–shell structure and strong interaction between them
confirmed by XRD, FTIR, and FESEM boosted the dual functionality of
10 %BiOBr-C3N4/MCM-41 sample. It means BiOBr-C3N4 in shell oxi­
dizes DBT under visible light, and MCM-41 in core adsorbs the sulfoxide
and sulfones of DBT. Passing oxidation products to the core takes the
shell sites out of the occupation and again makes them available for
adsorption and then oxidation of DBT, leading to the higher photo­
catalytic activity.

3.2.2. Effect of operating conditions on the simultaneous oxidative-

Fig. 6. PL spectra of BiOBr-C3N4/MCM-41 photocatalysts with different per­
centages of BiOBr.
adsorptive desulfurization of DBT.
3.2.1. Effect of BiOBr percentage
The activity of BiOBr-C3N4/MCM-41 photocatalyst-adsorbents with
different BiOBr loadings (0, 5, 10, and 15 wt%) was examined in DBT
desulfurization. Fig. 8 indicated that C/C0 after 30 min of dark test using
pure MCM-41 did not change, similar to [57]. The addition of g-C3N4
and BiOBr to MCM-41 slightly declined the C/C0 in the case of 5.0 %
BiOBr-C3N4/MCM-41 and 10 %BiOBr-C3N4/MCM-41. Therefore, it can
be claimed that all samples have a much low ability in DBT physical
adsorption in dark conditions. The degradation of DBT on pure MCM-41
after turning on the lamp did not change again, which reveals no pho­
tocatalytic activity of MCM-41 similar to the results in [58]. However,
BiOBr-C3N4/MCM-41 samples illustrated a significant decline in C/C0 of
DBT after visible light irradiations. The lowest fall-off was attributed to
0 %BiOBr-C3N4/MCM-41 that lessens the C/C0 to 71% after 150 min of
light irradiation. The C/C0 decreased dramatically to 46%, 31% and
adsorptive desulfurization of DBT
After finding 10 %BiOBr-C3N4/MCM-41 photocatalyst-adsorbent as
the most active sample in DBT degradation, this sample was evaluated
under different operating conditions such as different catalyst loadings,
DBT concentrations, H2O2 contents as well as reaction temperatures.
To study the effect of catalyst loading, various amounts of 10 %
BiOBr-C3N4/MCM-41 in the range of 0.15–0.3 g were used in DBT
desulfurization (Fig. 9 a). The change in C/C0 of DBT without any
photocatalyst and only in the presence of H2O2 was negligible. With
increasing the catalyst loading from 0.15 to 0.25 g, C/C0 significantly
decreased from 0.57 to 0.31, due to the increase in the number of active
sites [59,60]. When the catalyst loading further increased to 0.3 g, final
C/C0 increased probably due to the blocking of light penetration by the
excessive amount of photocatalysts and hence lower light absorption
and lower generation of electron/hole pairs [61]. Herein, the 0.25 gr of
catalyst loading was chosen as the appropriate amount of catalyst for the
next investigations.
H2O2 content is another effective parameter in DBT photocatalytic
oxidation. For investigation of this parameter, various amounts of H2O2
were poured into the reactor from 0.05 to 0.15 ml. As can be seen from
Fig. 9 b, the final C/C0 of DBT was 0.74 when no oxidant was added to
the reaction system. With increasing H2O2 contents from 0.05 to 0.1 ml,
the final C/C0 significantly decreased from 0.31 to 0.08 after 2 h irra­
diation of visible light. According to equations (2), (3), and (4), it can be

7
F. Abedini et al.
Fig. 8. Degradation of dibenzothiophene using BiOBr-C3N4/MCM-41 photocatalysts with different percentages of BiOBr. Reaction conditions: T = 60 ◦ C, catalyst
loading = 0.25 g, DBT concentration = 200 ppm, H2O2 content = 0.05 ml.
explained that electrons produced by light irradiation can react with
H2O2 or superoxides and produce hydroxyl radical (•OH). These active
species oxidize DBT to DBTO2, which can be adsorbed on MCM-41 core.
Therefore, with increasing the amount of H2O2, the removal efficiency
increases [62].
H2O2 + e → •OH + OH– (2)
H2O2 + O-•2 → OH• + OH– + O2 (3)
DBT + 4•OH → DBTO2 + 2H2O (4)
However, with a further increase of the content of H2O2 to 0.15 ml,
final C/C0 increased to 0.43 again. It can be explained from equation (5)
that in higher amounts of H2O2, the hydroxyl radical reacts with H2O2
and produces active species of HO•2 with weaker oxidizing properties,
leading to lower efficiency in DBT oxidation [62,63].
H2O2 + OH•→H2O + HO•2 (5)
As shown in Fig. 9 c, increasing the temperature from 30 C to 60 ◦ C,
◦
resulted in the decline in final C/C0 of DBT from 0.69 to 0.08. It can be
explained from a thermodynamic point of view that with increasing the
reaction temperature, the rate of H2O2 conversion to hydroxyl radicals
increased and more active species are produced to oxidize sulfur com­
pounds [64]. Moreover, with increasing temperature, the solubility of
oxidant in the fuel and also the reaction rate between DBT and oxidant is
favoured [65]. However, with further increasing of temperature to
70 ◦ C, a decrease in the ability of photocatalyst in DBT oxidation was
observed (final C/C0 = 0.21) probably due to thermal decomposition of
H2O2 [66] or enhanced recombination rate [67].
The effect of initial DBT concentration on the photocatalytic oxida­
tion of DBT using 10 %BiOBr-C3N4/MCM-41 sample is shown in Fig. 9d.
The results show that with enhancing the initial concentration of DBT
from 100 to 300 ppm, the final C/C0 of DBT decreased from 0.17 to 0.08,
8
Applied Surface Science 569 (2021) 151086
respectively. It could be attributed to the high interaction of sulfur
components with active species and also catalyst surface. However
further increasing the initial concentration of DBT to 300 ppm, increased
final C/C0 to 0.32. The decline in photocatalytic activity [68–70] at high
DBT concentrations is probably due to difficulties in light penetration.
Insufficient H2O2 content or active photocatalytic centers for this
amount of DBT could be other reasons [69,70].
3.2.3. Reusability test
Photocatalyst-adsorbent stability is one of the important steps in
developing industrial processes. To evaluate the reusability of 10 %
BiOBr-C3N4/MCM-41 sample, four successive cycles of DBT oxidation-
adsorption were carried out. After each reaction, the catalyst was
carefully separated by centrifugation from treated model fuel and
washed with acetonitrile for removing the adsorbed species. Then, it was
dried in an oven at 60 ◦ C and used for the next cycle of the reaction with
fresh H2O2 and fuel. As shown in Fig. 10, the final C/C0 of DBT after four
cycles reached to 0.25, confirming a decline in photocatalytic activity of
10 %BiOBr-C3N4/MCM-41 (18% loss of activity). This reduction in ac­
tivity could be attributed to the catalyst loss after each experiment due
to centrifugation. Furthermore, it can be seen from the BET analysis in
Fig. 2S that while the adsorption–desorption isotherms of new and used
10 %BiOBr-C3N4/MCM-41 photocatalyst are almost similar, according
to Fig. 3S, the average pore size has been shifted slightly to bigger ones.
A slight shift toward bigger pore sizes reveals the occupation of smaller
pores with guest molecules. It is absolutely accepted that DBT adsorp­
tion is not responsible for this surface reduction based on dark test in
Fig. 8. The weak affinity of MCM-41 to adsorb n-hexane is also proven in
the literature [71]. Thus, the only molecules which can reduce the
surface area are oxidation products as DBT sulfoxides and sulfones. As
shown in Table 3, a dramatic decrease in the surface area has occurred
after oxidation of DBT, which indicates a high adsorption capacity of 10
%BiOBr-C3N4/MCM-41 sample in adsorption of DBTO or DBTO2.
F. Abedini et al. Applied Surface Science 569 (2021) 151086

Fig. 9. Degradation of dibenzothiophene using 10 %BiOBr-C3N4/MCM-41 at different a) catalyst loadings, b) H2O2 content, c) temperatures, d) DBT concentrations.

Fig. 10. Degradation of dibenzothiophene using 10 %BiOBr-C3N4/MCM-41 during four successive runs. Reaction conditions: T = 60˚C, catalyst loading = 0.25 g,
content of H2O2 = 0.1 ml, DBD concentration = 200 ppm.

9
F. Abedini et al.
Table 3
BET surface area, total pore volume and average pore diameter of new and used
10 %BiOBr-C3N4/MCM-41 photocatalysts.
Total pore Average pore BET surface Catalyst name
volume (cm3/g) diameter (nm) area (m2/g)
0.94 4.0.1 925 10 %BiOBr-C3N4/
MCM-41
0.64 4 645 Used 10 %BiOBr-
C3N4/MCM-41
FTIR spectra of new and used 10 %BiOBr-C3N4/MCM-41 photo­
catalyst in Fig. 4S show all functional groups are similar except the
newly emerged peaks at 2800–2950 cm− 1 after reaction, characterizing
sulfone and sulfoxide related compounds [72]. This observation clearly
confirms the affinity of 10 %BiOBr-C3N4/MCM-41 to adsorb products of
DBT oxidation and thus the dual functionality of this sample.
3.3. Proposed mechanism for photo oxidation-adsorption of DBT using
BiOBr-C3N4/MCM-41
To investigate the mechanism of photocatalytic reaction for degra­
dation of DBT, scavenger experiments were performed with four
different quenchers, including Isopropanol (IPA, OH• radical scav­
enger), ascorbic acid (•O2– radical scavenger), ethylenediaminetetra­
acetic acid (EDTA, h+ scavenger) and silver nitrate (AgNO3, e-
scavenger). Fig. 11 shows the effect of various scavengers on the pho­
todegradation of DBT under optimum conditions. As can been seen, all
quenchers have negative impacts on the reaction, so it can be inferred
that all active species have a negative role in the DBT degradation.
However, low degradation of DBT was observed while introduction of
IPA and AgNO3 as inhibitors of the •OH and e- radicals, respectively.
Therefore, it can be concluded that •OH and e- radicals play a remark­
able role in the photocatalytic degradation of DBT. On contrary, •O2–
radicals and h+ have little effect on process performance.
Therefore, the proposed mechanism of photo oxidative-adsorptive
Fig. 11. Effect of various scavengers on the degradation of dibenzothiophene under optimum conditions.
10
Applied Surface Science 569 (2021) 151086
desulfurization of DBT using BiOBr-C3N4/MCM-41 heterojunction
based on scavenger test has been illustrated in Fig. 12. The process is
carried out in two successive sections of oxidation on the BiOBr-C3N4
shell and adsorption of oxidation products on the MCM-41 core
[34,73,74]. Both g-C3N4 and BiOBr can generate electron/hole pairs
under visible-light irradiation [75]. According to energy band theory,
the electrons in the conduction band (CB(of BiOBr can quickly transfer
to the valance band (VB) of g-C3N4 and recombine with holes. Therefore,
the electrons in the CB of g-C3N4 with high reduction potential react
with H2O2 to form OH• and OH– due to the CB potential of g-C3N4 (-1.22
eV) is more negative than the standard reduction potential of H2O2/OH•
(0.06 eV). Meantime, the VB potential of BiOBr (3.02 eV) is more pos­
itive than the standard reduction potential of H2O/OH• (2.27 eV) and
OH–/OH• (1.99 eV), so the holes in VB of BiOBr with high oxidation
potential could be also participated in the desulfurization reaction and
oxidize OH– ions and H2O (from H2O2 decomposition) to OH• [75–77].
Scavenger test correctly confirmed the major role of OH• and electrons
in DBT degrdation before. Hydroxyl radicals with strong oxidation
capability can further oxidize the DBT molecules to DBTO and then
DBTO2 [78]. These oxidized products have higher polarity than DBT and
are readily adsorbed on the MCM-41 core. Actually, the surface of MCM-
41 has a large number of hydroxyl groups that can adsorb these oxida­
tion products by Van der Waals and hydrogen bonding interactions [34].
The important point is that an excessive amount of hydrogen peroxide
would poison the catalyst. Also, the presence of water, which is pro­
duced during the decomposition in the proposed oxidation mechanism,
is only suitable in very small amounts [38]. In the proposed mechanism,
in addition to the individual functionality of core and shell, there should
be a strong interaction between them. Full coverage of core by shell
components as observed in TEM picture of 10% BiOBr-C3N4/MCM-41,
and strong interaction between core and shell as confirmed by FTIR,
SEM, and XRD, are essential in simultaneous oxidative-adsorptive
desulfurization of DBT.
F. Abedini et al. Applied Surface Science 569 (2021) 151086

•OH

•OH/OH-
-2 g-C3N4 Oxidation
H2O2
e- e- BiOBr
-1 CB=-1.22 e- e-
0 CB=-0.87
1

2 VB=1.57 h+ h+
MCM-41 core
3
h+ h+ V=3.02
•OH
H2O/OH-
•OH

Fig. 12. Proposed mechanism for simultaneous oxidative-adsorptive degradation of DBT using C3N4-BiOBr/MCM-41 photocatalyst-adsorbent.

3.4. Similar works Oxidative-adsorptive desulfurization by a photocatalyst was

Although, there are few reports on the simultaneous oxidative-
adsorptive desulfurization, this topic has received much attention
lately. A list of newly published papers about simultaneous oxidative-
adsorptive desulfurization by catalyst and photocatalyst has been indi­
cated in Table 4. As can be seen, one-pot oxidative-adsorptive desul­
furization by a solid silica core and a mesoporous shell made up of
quaternary ammonium phosphotungstate and carbon dots (C-dots) [73]
and in other work, phosphotungstic acid immobilized on amino grafted
nano-sized hierarchical hollow silica spheres (HPWNH2-HHSS) [34],
both indicated high efficiency in DBT degradation of 98.08% and
99.36%, respectively. Polar sulfone products were easily adsorbed on
the catalyst surface as well. However, to achieve high adsorption of
sulfone compounds and to prevent rapid adsorbent saturation, catalysts
with higher surface area must be designed. In another work a plasma-
assisted oxidative desulfurization was studied
[79]. The results showed that the active species produced during
plasma can reduce the sulfur content by only 3%, while in the presence
of FeCl3-SiO2 catalyst-adsorbent the removal rate reached 98.4%, which
can be attributed to the penetration of products into pores of the
adsorbent. Therefore, it seems that the selection of a suitable adsorbent
in the oxidative-absorptive desulfurization plays an important role.
considered in [74]. The core–shell Cu-benzene-1,3,5-tricarboxylic acid
(Cu-BTC)@TiO2 photocatalyst under UV light had a high performance in
oxidative-adsorptive desulfurization. TiO2-SiO2 was evaluated as
photocatalyst-adsorbent in [80] and showed 40% of DBT adsorption in
the absence of light. This value reached 100% after 1 h of UV illumi­
nation. our results were almost similar to the results of the literature. It
can be claimed that the novel core–shell structure of BiOBr-C3N4/MCM-
41 was an active and promising photocatalyst in DBT simultaneous
photo oxidation-adsorption due to high surface area, strong interactions,
performance under visible light and low-cost materials.
3.5. Conclusions
In this work, the novel core–shell structure of BiOBr-C3N4/MCM-41
nano photocatalyst-adsorbents was successfully prepared and investi­
gated in simultaneous oxidative-adsorptive desulfurization of DBT
under visible light. It was found that among studied samples the one
with 10% wt. of BiOBr indicated the highest activity in photo oxidation
of DBT due to efficient separation of charge carriers, uniform
morphology, well-defined core–shell structure and strong interaction
between particles. Characterization of spent photocatalyst also revealed
its affinity to adsorb DBT oxidation products. According to outstanding

Table 4
A list of simultaneous oxidative-adsorptive desulfurization of DBT by catalyst and/or photocatalyst in recent years.
No. Method Catalyst name Surface area Conditions DBT Ref.
(m2/g) degradation %

1 OADS* silica@C-dots/ 182.3 DBT = 250 ppm, temperature = 60˚C, H2O2/DBT = 1.75, model oil = 60 ml, catalyst = 98.08 [73]
HPW 0.2 g, time = 180 min
2 OADS HPW/NH2- 202.03 DBT = 300 ppm, temperature = 60˚C, H2O2/DBT = 2.5, ml model oil = 10 ml, catalyst 99.36 [34]
HHSS = 0.06 g, time = 1 h
3 Plasma FeCl3-SiO2 74.4 DBT = 200 ppm, DBT Plasma, oxygen = 60 ml/min, 600 Hz, time = 30 min 98.4 [79]
OADS
4 Photo Cu-BTC@TiO2 901 DBT = 250 ppm, 300 W high-pressure mercury lamp, temperature = 80˚C, air = 60 l/h, 86 [74]
OADS model oil = 10 ml, catalyst = 0.01 g, time = 180 min
5 Photo TiO2-SiO2 691 DBT = 50 ppm, 300 W xenon lamp, temperature = 25˚C, air = 40 ml/min, model oil = 100 [80]
OADS 10 ml, catalyst = 0.5 g, time = 1 h
6 Photo C3N4-BiOBr/ 925 DBT = 200 ppm, temperature = 60˚C, H2O2/DBT = 7.5, model oil = 60 ml, catalyst = 92 this
OADS MCM-41 0.25 g, time = 120 min, light intensity = 187 mW/cm2 work
*
Oxidative-adsorptive desulfurization

11
F. Abedini et al.
results in this paper, the proposed combined system of photo oxidative-
adsorptive desulfurization can be applied for deep desulfurization of
liquid fuels. This system due to using visible-light-driven photocatalysts
can take advantage of solar energy as well. Moreover, it is not deniable
that combination of oxidation and adsorption in one vessel can signifi­
cantly reduce the costs. Although stability test confirmed the ability of
BiOBr-C3N4/MCM-41 photocatalyst-adsorbent in long-term use but the
methods of regeneration and also enhancing the affinity to adsorb more
of oxidation products from fuel should be considered in future works to
approach industrial standards.
CRediT authorship contribution statement
Fahime Abedini: Conceptualization, Methodology, Data curation,
Validation, Writing – original draft. Somaiyeh Allahyari: Supervision,
Writing – review & editing, Funding acquisition, Project administration.
: . Nader Rahemi: Supervision, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors gratefully acknowledge financial support from Sahand
University of Technology.
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