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Article(SpecialIssueonEnvironmentalCatalysisandMaterials)
Fabrication and characterization of tungstencontaining
mesoporous silica for heterogeneous oxidative desulfurization
Ming Zhang a, Wenshuai Zhu b,*, Hongping Li b, Suhang Xun b, Meng Li b, Yanan Li b, Yanchen Wei b,
Huaming Li a,b,#
a Institute for Energy Research , Jiangsu University, Zhenjiang 212013, Jiangsu, China
b School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China

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

Article history: A series of functional, tungstencontaining mesoporous silica materials (WSiO2) have been fabri
Received 29 January 2016 cated directly from an ionic liquid that contained imidazole and polyoxometalate, which acted as
Accepted 7 April 2016 mesoporous template and metal source respectively. These materials were then characterized
Published 5 June 2016 through Xray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy,
Fourier transform infrared spectra (FTIR), diffuse reflectance spectra (DRS), and N2 adsorp
Keywords: tiondesorption, which were found to contain tungsten species that were effectively dispersed
Heterogeneous oxidative throughout the structure. The asprepared materials WSiO2 were also found to possess a mesopo
desulfurization rous structure. The pore diameters of the respective sample WSiO220 determined from the TEM
Tungsten species images ranged from 2 to 4 nm, which was close to the average pore size determined from the nitro
Mesoporous silica gen desorption isotherm (2.9 nm). The materials were evaluated as catalysts for the heterogeneous
Onepot synthesis oxidative desulfurization of dibenzothiophene (DBT), which is able to achieve deep desulfurization
Organosulfur within 40 min under the optimal conditions (Catalyst (WSiO220) = 0.01 g, temperature = 60 C,
oxidant (H2O2) = 20 L). For the removal of different organic sulfur compounds within oil, the ability
of the catalyst (WSiO220) under the same conditions to remove sulfur compounds decreased in
the order: 4,6dimethyldibenzothiophene > Dibenzothiophene > Benzothiophene > 1dodecanethi

ol. Additionally, they did not require organic solvents as an extractant in the heterogeneous oxida
tive desulfurization process. After seven separate catalytic cycles, the desulfurization efficiency was
still as high as 90.3%. From the gas chromatographymass spectrometer analysis, DBT was entirely
oxidized to its corresponding sulfone DBTO2 after reaction. A mechanism for the heterogeneous
desulfurization reaction was proposed.
2016, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.

1. Introduction Hydrodesulfurization (HDS) is a mature technology and ef

ficiently removes aliphatic and acyclic sulfur compounds (e.g.
As the worldwide demand for fuel continues to increase thiols, sulfides, and disulfides) [35] but not thiophene sulfides,
rapidly, the industrial desulfurization of diesel fuel faces in such as dibenzothiophene and its derivatives [68]. Addition
creasing technological challenges to comply with environmen ally, further improvements to the HDS process for deep desul
tal concerns and legal requirements [1,2]. furization are limited to increasingly harsh operating condi

* Corresponding author. Tel: +8651188791800; Fax: +8651188791708; Email: zhuws@ujs.edu.cn

# Corresponding author. Tel: +8651188791800; Fax: +8651188791708; Email: lhm@ujs.edu.cn

This work was supported by the National Nature Science Foundation of China (21276117, 21376111, 21406092).
DOI: 10.1016/S18722067(15)611032 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 37, No. 6, June 2016
972 Ming Zhang et al. / Chinese Journal of Catalysis 37 (2016) 971978

tions with high associated costs [9,10]. Hence, it is critical to 2. Experimental

develop supplementary strategies for deep desulfurization,
including extraction [1114], adsorption [15,16], oxidation 2.1. Materials
[1722], and biodesulfurization [23]. Oxidative desulfurization
(ODS) can remove aromatic organosulfur compounds under H2O2 (aqueous solution, 30 wt%), H3PW12O4014H2O (AR
mild conditions. As such, it is considered as a promising tech grade), WO3 (AR grade), noctane (AR grade), NH3H2O (aque
nique for deep desulfurization. ous solution, 25 wt%), acetonitrile (AR grade), tetraethyl or
Ionic liquids (ILs) are organic salts with low melting points thosilicate (TEOS, AR grade) and tetradecane (AR grade) were
and vapor pressures, and have attracted wide attention owing purchased from Sinopharm Chemical Reagent Co., Ltd. Ben
to their unique physicochemical properties, including negligible zothiophene (BT, 99%), dibenzothiophene (DBT, 98%)
volatility, low toxicity, excellent thermal stability, good solubil 1dodecanethiol (DT, 99%), and 4,6dimethyldibenzothiophene
ity characteristics, and the variety of available structures [24]. (4,6DMDBT,99%) were purchased from SigmaAldrich.
Taskspecific IL anions that are tethered to functional groups [C16mim]Br was purchased from Shanghai Chengjie Chemical
(e.g. polyoxometalates) show great potential for the modifica Co., Ltd. All the materials are used without further purification.
tion and control of different chemical and physical functions in
a material [2527]. Polyoxometalates (POMs) are a vast class of 2.2. Sample preparation
welldefined, early transition metal oxyanion clusters that ex
hibit distinctive physicochemical properties, including adjusta The POMbased IL [C16mim]3PW12O40 was prepared ac
bility of composition, size, shape, acidbase properties, and cording to a literature procedure [47]. The mesoporous hybrid
redox potential [2832]. As such, POMs are extensively used as material (WSiO2) was prepared using a onepot method from
green catalysts, particularly in oxidation reactions [33,34]. A an initial gel that consisted of TEOS:[C16mim]3PW12O40:H2O:

number of studies have demonstrated that POMbased ILs ex NH3H2O = 1:x:160:1.5 (x = 0.002, 0.004, 0.008). In a typical
hibited efficient catalytic ODS [3537]. However, the wide synthesis, [C16mim]3PW12O40 (0.14 g) was added into acetoni
spread use of these materials for homogeneous desulfurization trile (4 mL) with constant stirring. Subsequently, TEOS (2 mL)
in an industrial setting has been hindered because of their in and NH3H2O (0.52 mL) were added into the mixture and
trinsic liquid nature and high viscosity, which leads to difficul stirred for 3 h. The resulting gel was filtered, washed with wa
ties in separation and recovery, recyclability, cost, and the large ter (200 mL), dried overnight at 120 C, and then calcined at
amounts of ILs that are required [38]. 550 C with a heating rate of 5 C/min for 6 h. The samples
To overcome some of these problems, considerable efforts were named based on the Si/W molar ratio used in the gel
have been made to introduce active POMbased species into (WSiO2y, where y = Si/W = 10, 20 and 40).
heterogeneous desulfurization systems, where materials such
as zeolites, porous carbon, clays, siliceous materials, and met 2.3. Characterization and methods
alorganic frameworks were employed as a support [3944].
Among these supports, mesoporous silica possesses a number The samples were ground into a fine powder for character
of desirable properties, including a stable mesoporous struc ization. Fourier transform infrared (FTIR) spectra were rec
ture, a large surface area and pore volume, wellordered pore orded with a Nicolet Nexus 470 FTIR instrument using KBr
structure, and narrow poresize distributions. Moreover, silica pellets. Raman spectroscopy was recorded at ambient temper
has no inherent catalytic property and can be used as a support ature using a DXR Raman microscope with an excitation wave
that can be functionalized by framework substitution or length of 532 nm from a laser source. Diffuse reflectance spec
postsynthesis surface modification. As such, POMbased tra (DRS) were measured between 200 and 800 nm with BaSO4
ILsupported mesoporous silica has been fabricated for ODS, used as the reflectance standard using a UVvisible spectrome
but required relatively excessive oxidants. Additionally, the ter (UV2450, Shimadzu). The surface area of the samples was
requirement for organic solvents (e.g. acetonitrile and dime calculated using the BrunauerEmmettTeller (BET) method,
thylformamide) may limit future applications of these materials while the poresize distribution was obtained from the adsorp
[45,46]. tion branches of the isotherms using the BarrettJoyner

In this work, active tungsten species were introduced di Halenda (BJH) method. Transmission electron microscopy
rectly into mesoporous silica from a POMbased IL (TEM) was recorded using a JEOLJEM2010 (JEOL, Japan) op
([C16mim]3PW12O40), where the imidazole cation and polyoxo erated at 200 kV. The crystalline phases within the samples
metalate anion acted as template and metal source, respective were analyzed using Xray diffraction (XRD) spectroscopy with
ly. The hybrid materials (WSiO2) were highly effective on re a Bruker D8 diffractometer with Cu K radiation ( = 0.154 nm).
moving organosulfur compounds under mild conditions and
were separated easily for recycling. Additionally, organic sol 2.4. Catalytic activity test
vents were not required for the heterogeneous desulfurization.
All samples were characterized using Xray diffraction, Trans A model oil sample was prepared by dissolving DBT, BT, DT
mission electron microscopy, Raman spectroscopy, Fourier and 4,6DMDBT in noctane with a corresponding sulfur con
transform infrared spectra, Diffuse reflectance spectra, and tent of 500, 250, 250 and 250 ppm, respectively. Desulfuriza
BrunauerEmmettTeller analysis. tion was performed in a flask equipped with a magnetic stirrer
 Ming Zhang et al. / Chinese Journal of Catalysis 37 (2016) 971978 973

and condenser. In a typical run, a water bath was initially

heated to 60 C then allowed to stabilize. WSiO2 (0.01 g) and
H2O2 (20 L) were added to the reactor and then the oil (5 mL)
was injected.
(1)

Absorbance
2.5. Analysis method of products

The sulfur contents in the oil after the desulfurization test

were analyzed using gas chromatographyflame ionization (3) (2)
detector (GCFID) with tetradecane as the internal standard
(Agilent 7890A; HP5, 30 m 0.32 mm 0.25 m; FID: Agilent). (4)
The conversion of the sulfur compounds in the oil was used to (5)
calculate the removal of sulfur compounds. 200 300 400 500 600 700 800
The oxidized sulfur compounds were characterized using Wavelength (nm)
gas chromatographymass spectrometer (GCMS, Agilent 7890/
Fig. 2. UVvis diffuse reflectance spectra of (1) WO3, (2)
5975CGC/MSD; HP5 MS column, 30 m 250 m 0.25 m; [C16mim]3PW12O40, (3) WSiO210, (4) WSiO220, and (5) WSiO240.
temperature program: 100 C temperature rising 15 C/min
200 C for 10 min).
The electronic behavior of the materials was examined us
3. Results and discussion ing UVvis DRS, as shown in Fig. 2. The spectrum of
[C16mim]3PW12O40 exhibited an absorption band at approxi
3.1. Characterization of the catalysts mately 212 nm that was assigned to an OP transition, while
the absorption peak located at 260 nm was ascribed to a charge
FTIR spectra of WSiO2y, WO3 and [C16mim]3PW12O40 are transfer transition within the Keggin units. Bulk WO3 exhibited
shown in Fig. 1. The spectrum of bulk WO3 (Fig. 1(1)) exhibited a strong absorption near 430 nm that was assigned to a lig
a strong and broad peak at approximately 820 cm1 that was andtometal charge transfer (O2W6+) [52]. After the intro
caused by the stretching vibrations of WOW. In addition to duction of the tungsten species into the silica matrix, two lig
the CH stretching vibrations of the alkyl chain (2950 to 2850 andtometal charge transfer bands were observed near 202
cm1), [C16mim]3PW12O40 (Fig. 1(2)) exhibited four bands that and 267 nm (O2sW5dO2p). The absorption onset of the
were characteristic of Keggin units (as(POa) = 1080 cm1, WSiO2y materials was shifted to a lower wavelength by ap
as(W=Ot) = 978 cm1, as(WOcW) = 898 cm1 and proximately 100 nm when compared with bulk WO3, which
as(WOeW) = 808 cm1). The WSiO2y materials (Fig. indicated that the tungsten species were incorporated into the
1(3)(5)) exhibited a broad peak near 3500 cm1 that was at silica matrix [53].
tributed to surface silanols and adsorbed water molecules [48]. To examine the structure of the tungsten species that were
The three peaks located at 1086, 812, and 460 cm1 were incorporated into the hybrid materials, Raman scattering spec
caused by asymmetric asym(SiOSi), symmetric sym(SiOSi) troscopy was used (Fig. 3). Bulk WO3 (Fig. 3(1)) exhibited a
and bending modes of the SiO4 tetrahedra vibrations within the series of characteristic peaks in the regions 1000600 cm1 and
silica, respectively [49,50]. The band near 954 cm1 in the 600150 cm1 that were assigned to WO stretching and
WSiO2y materials was characteristic of SiOW bonds, which bending vibrations, respectively [54]. These bands were also
indicated that tungsten species were incorporated into the observed in the WSiO2y materials (Fig. 3(2)(4)) and as the
framework of the mesoporous silica matrix [51].

(5)
(4)
(3)
Transmittance

Intensity

(2)

(1) (1)
(2)
(3)
(4)

4000 3500 3000 2500 2000 1500 1000 500 1000 900 800 700 600 500 400 300 200
1 1
Wavenumber (cm ) Raman shift (cm )

Fig. 1. FTIR spectra of (1) WO3, (2) [C16mim]3PW12O40, (3) WSiO210, Fig. 3. Raman spectra of (1) WO3, (2) WSiO210, (3) WSiO220, and (4)
(4) WSiO220, and (5) WSiO240. WSiO240.
974 Ming Zhang et al. / Chinese Journal of Catalysis 37 (2016) 971978

tungsten content increased, the bands became more intense cm3/g, and a pore size of 3.20 nm. As the tungsten content
and well defined. These results indicated that the tungsten spe within the samples increased, the BET surface area, pore vol
cies in the hybrid materials were tungsten oxide. ume and pore size decreased. This effect has been reported to
XRD pattern was performed to analyze the composition and be caused by the anchoring of tungsten species in the pore
phase structure of the WSiO2y materials (Fig. 4). Small angle walls [55], which was confirmed by the results of the lowangle
XRD patterns of the samples exhibited a broad diffraction peak XRD analysis.
that was located at approximately 2 = 2.2, which is a feature TEM was used to investigate the structural features of the
of mesoporous materials (Fig. 4(a)). However, the wideangle representative sample. TEM images of WSiO220 exhibited
XRD patterns exhibited a broad peak that was consistent with numerous interconnected wormlike mesoporous structures
amorphous silica walls (Fig. 4(b)). The diffraction peaks of with a disordered arrangement (Fig. 6). The pore diameters
crystalline WO3 were not obvious, even in the WSiO2 sample determined from the TEM images ranged from 2 to 4 nm, which
that had a relatively high tungsten content (Si/W = 10), which was close to the average pore size determined from the nitro
indicated that the tungsten species were effectively dispersed gen desorption isotherm (2.9 nm). The TEM images also con
throughout the silica matrix. firmed the lowangle XRD results and textural properties listed
Nitrogen adsorptiondesorption isotherms and the BJH in Table 1.
poresize distribution curves are shown in Fig. 5. The nitrogen
adsorptiondesorption isotherms of all samples were assigned 3.2. Catalytic performance of the samples
according to the IUPAC classification as Type IV, which is char
acteristic of a mesostructure in WSiO2 materials (Fig. 5(a)). The removal of DBT from the sample oil by the WSiO2y
Typical unimodal poresize distribution curves with pore di materials under identical conditions is shown in Fig. 7. Both
ameters that ranged between 2 and 5 nm indicated the uniform WSiO210 and WSiO220 achieved deep desulfurization within
mesoporosity of the hybrid materials (Fig. 5(b)). The textural 40 min. Importantly, WSiO220 catalyzed the complete remov
properties of the samples are listed in Table 1. The WSiO240 al of DBT in 30 min, which was higher than either WSiO210 or
sample had a surface area of 743 m2/g, a pore volume of 0.50 WSiO240 (97.7% and 69.4%, respectively). This may have

(a)
(b)
Intensity

Intensity

(1)

(2)
(1)
(2)
(3)
(3)
2 4 6 8 10 20 30 40 50 60 70
2 /( ) 2 /( o )
o

Fig. 4. (a) Lowangle and (b) wideangle XRD patterns of (1) WSiO210, (2) WSiO220, and (3) WSiO240.

0.50
(a) (b)
320 0.45
0.40
280 (3) (2)
Volume adsorbed (cm /g)

dV/dD (cm /(gnm))

0.35
3

240 (2) 0.30

(3)
3

(1) 0.25
200
0.20 (1)
160 0.15
120 0.10
0.05
80
0.00
0.0 0.2 0.4 0.6 0.8 1.0 2 3 4 5 6 7 8 9 10
Relative pressure (p/p0) Diameter (nm)
Fig. 5. (a) Nitrogen adsorptiondesorption isotherms and (b) poresize distribution of (1) WSiO210, (2) WSiO220, and (3) WSiO240.
 Ming Zhang et al. / Chinese Journal of Catalysis 37 (2016) 971978 975

DBT BT 4,6-DMDBT DT
100

Sulfur removal (%)

80

60

40
Fig. 6. TEM images of the WSiO220 sample.
20
Table 1
Textural properties of WSiO210, WSiO220, and WSiO240.
0
W/Si molar BET area Pore volume Pore size 10 20 30 40 50 60
Sample Time (min)
ratio * (m2/g) (cm3/g) (nm)
WSiO210 1:46 513 0.37 2.91 Fig. 8. Removal of various sulfurcontaining compounds during desul
WSiO220 1:88 612 0.42 2.98 furization. Reaction conditions: catalyst (WSiO220) = 0.01 g, O/S = 2.5,
WSiO240 1:107 743 0.50 3.20 T = 60 C.
* Measured by ICP.
> BT (5.739)) [56]. However, the sulfur removal of DT was the
been because WSiO220 possessed a larger BET surface area lowest, which was attributed to the strong steric hindrance of
and pore volume compared with WSiO210, and more active the long carbon chains.
sites (tungsten species) compared with WSiO240. The adsorp The ability of the catalyst to be recycled was investigated.
tion desulfurization of DBT was also investigated without the After the first reaction, the upper oil phase was separated by
presence of H2O2 (catalyst = 0.01 g, T = 60 C, t = 40 min). This decanting from the reactor. The remaining catalyst within the
experiment yielded adsorption desulfurization values of 6.9%, reactor was dried at 60 C overnight, and then fresh H2O2 and
5.6%, and 4.7%, which corresponded to calculated adsorptive model oil were added to the reactor for the next cycle. The abil
capacities of 17.2, 14.0, and 11.7 mg/g for WSiO240, ity of the catalyst to remove sulfur from the reaction system
WSiO220, and WSiO210, respectively. was able to reach 90.3% after recycling seven times, as shown
The identity of a sulfurcontaining compound can influence in Fig. 9.
the ability of a catalyst to remove sulfur. The effectiveness of The oxidation products of DBT were determined using
WSiO220 for the removal of a series of organosulfur com GCMS analysis after reaction (Fig. 10). The upper oil layer was
pounds was studied. In addition to DBT, the compounds BT, decanted, and the used catalyst was extracted using carbon
4,6DMDBT and DT were examined (Fig. 8). The removal of tetrachloride for the GCMS analysis. A single, intense peak at
sulfur reached equilibrium after approximately 30 min except 3.4 min was ascribed to ntetradecane, which indicated that
for 4,6DMDBT, which took 20 min. The levels of sulfur removal DBT was completely removed from the oil phase (Fig. 10(a)).
from the oil after 20 min for BT, DBT, DT and 4,6DMDBT were The GC trace for the extracted catalyst only exhibited an obvi
84.4%, 90.4%, 75.0% and 100.0% , respectively. Thus, the abil ous peak at 9.8 min, which corresponded to DBTO2 (Fig. 10(b),
ity of WSiO220 to remove sulfur decreased in the order inset). The fact that a peak for DBT was not detected demon
4,6DMDBT > DBT > BT > DT. This decrease in ability to remove strated that it was entirely oxidized to DBTO2 in the desulfuri
sulfur corresponded to the decrease in sulfur electron density zation process.
of the aromatic compounds (4,6DMDBT (5.760) > DBT (5.758)

100
100
(2)
Sulfur removal (%)

80 80
Sulfur removal (%)

60 60
(1)
40
40
(3)
20
20
0
10 20 30 40 50 60 0
Time (min) 1 2 3 4 5 6 7
Recycle time
Fig. 7. Removal of DBT from the sample oil using (1) WSiO210, (2)
WSiO220, and (3) WSiO240. Reaction conditions: catalyst = 0.01 g, Fig. 9. Recycling ability of the catalyst. Reaction conditions: catalyst
O/S = 2.5, T = 60 C. (WSiO220) = 0.01 g, O/S = 2.5, T = 60 C, t = 40 min.
976 Ming Zhang et al. / Chinese Journal of Catalysis 37 (2016) 971978

(a) (b)
n-tetradecane

Abundance
Intensity

DBTO2

6 8 10 12 14
Time (min)
216.0

2 4 6 8 10 12 14 16 50 100 150 200 250

Time (min) m/z

Fig. 10. (a) GC analysis of the upper oil after reaction and (b) GCMS analysis of sulfur compounds in the catalyst after reaction.

organic solvents as an extractant. The ability of the catalysts to

remove sulfur compounds decreased in the order: 4,6DMDBT
> DBT > BT > DT. Importantly, the catalyst could be recycled up
to seven times without any significant decrease in activity.

Acknowledgments

The authors wish to acknowledge the financial support pro

vided by Advanced Talents of Jiangsu University (13JDG080),
Postdoctoral Foundation of China (2014M551516), and A Pro
ject Funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD).

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Graphical Abstract
Chin. J. Catal., 2016, 37: 971978 doi: 10.1016/S18722067(15)611032
Fabrication and characterization of tungstencontaining
mesoporous silica for heterogeneous oxidative desulfurization
Ming Zhang, Wenshuai Zhu *, Hongping Li, Suhang Xun, Meng Li,
Yanan Li, Yanchen Wei, Huaming Li *
Jiangsu University
In the desulfurization process, the organic sulfur compounds were
firstly absorbed by the mesoporous material and then oxidized into
the corresponding sulfones by the active peroxo species, which
were formed by reaction of tungsten species and H2O2.

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