Microporous and Mesoporous Materials 212 (2015) 137e145

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Enhanced adsorption selectivity of dibenzothiophene on ordered

mesoporous carbon-silica nanocomposites via copper modication
Jieling Cheng, Shuangling Jin*, Rui Zhang, Xia Shao, Minglin Jin*
School of Materials Science and Engineering, Shanghai Institute of Technology, Shanghai 201418, China

a r t i c l e i n f o a b s t r a c t

Article history: In this study, copper-modied ordered mesoporous carbon-silica nanocomposites (MCSs) were syn-
Received 15 November 2014 thesized by incipient wetness impregnation of copper nitrate. The desulfurization performance of the as-
Received in revised form prepared adsorbents was evaluated by the selective adsorption of dibenzothiophene (DBT) as model
18 February 2015
sulfur compound from model fuels at ambient conditions. For comparison, the adsorptive desulfurization
Accepted 17 March 2015
capacity for copper species supported on pure silica SBA-15 and pure carbonaceous CMK-3 was also
Available online 27 March 2015
investigated, respectively. The results indicate that MCS with 10wt.% of copper performed highest
selectivity for DBT in competition with benzene. The signicantly enhanced desulfurization performance
Keywords:
Carbon-silica nanocomposite
of MCS could be attributed to its hybrid mesoporous carbon-silica nature which is favorable for high
Copper modication dispersion extent of copper and synergistic effect between the carbon substrate and the supported
Dibenzothiophene copper species.
Selective adsorption 2015 Elsevier Inc. All rights reserved.
Desulfurization

1. Introduction is a conventional technology to produce low-sulfur fuels under high

Fossil fuels as the largest source of energy are rened into
various petroleum products such as gasoline, diesel and jet fuel
widely applied in many areas. The sulfur compounds in the fuel are
converted to SOx during combustion, which not only results in acid
rain, but also poisons catalysts in catalytic converters for reducing
CO and NOx [1e3]. Many countries have implemented more strin-
gent regulations for reneries to produce diesel or gasoline with
low sulfur content. On the other hand, liquid hydrocarbon fuels are
candidate fuels for producing H2 for use in automotive and portable
fuel cells due to their higher energy density and safety for trans-
portation and storage. However, the sulfur compounds in the fuel
and H2S produced from them within hydrocarbon reforming pro-
cess are poisons to reforming and shift catalysts and the electrode
catalysts. Thus, sulfur concentration in the fuel needs to be reduced
to less than 1 ppmw for proton exchange membrane fuel cell
(PEMFC) and less than 10 ppmw for solid oxide fuel cell (SOFC)
[4,5].
Current approaches for desulfurization mainly include hydro-
desulfurization (HDS), oxydesulfurization (ODS), biodesulfurization
(BDS), and adsorptive desulfurization (ADS) [3e6]. At present, HDS
* Corresponding authors. Tel.: 86 021 60873070; fax: 86 021 60873407.
E-mail addresses: jinshuangling@gmail.com (S. Jin), jinml@sh163.net (M. Jin).
temperature and high pressure using hydrogen gas. Besides the
severe conditions of operation, HDS is not effective for removing
heterocyclic sulfur compounds such as DBT and its derivatives due
to steric hindrance, which makes HDS more complicated and
difficult, not suitable for deep desulfurization. In comparison with
the HDS process, the selective adsorption for removing sulfur
(SARS) considered to be a more promising technology owing to
such advantages as they react at atmospheric pressure, ambient
temperature and without hydrogen consumption. Various types of
adsorbents such as zeolites [7,8], activated carbons [9e11], metal
oxides [12e17], metal-organic frameworks (MOFs) [18e20] have
been investigated during the past decade. For efcient removal, not
only adequate porosity/pore size but also specic adsorption sites
are required. In particular, adsorption of thiophenic sulfur com-
pounds using the adsorbent modied with transition metal like Cu,
Ag, Pd and Pt which employ the function of p-complexation has
attracted more attention [8e11]. Because only those active species
dispersed on the outermost layer are accessible to interact with
adsorbate molecules, the adsorption efciency is strongly depen-
dent on the dispersion degree of active species.
Because of the high surface areas and large pore volumes,
mesoporous silicas such as SBA-15 and MCM-48 used as adsorbent
supports have received much attention. To disperse guest species
on those mesoporous silicas, several interesting approaches have
been developed, which include adjusting the properties of SBA-15

http://dx.doi.org/10.1016/j.micromeso.2015.03.016
1387-1811/ 2015 Elsevier Inc. All rights reserved.
138 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145
or MCM-48 by incorporating alumina [12], and using as-
synthesized mesoporous silica SBA-15 as support that own
conned space between template and silica walls [13e17]. How-
ever, most of commercial fuels consist of 70e80 wt.% aliphatics
components and 20e30 wt.% aromatics. The aromatics can strongly
compete with thiophenic sulfur compounds, due to their similar
adsorption mode as sulfur compounds toward active sites via p
electronic interaction. Therefore, the enhancement of the selec-
tivity of mesoporous silica for sulfur compounds is still limited.
Compared with other adsorbents, activated carbon is proposed to
be better support for p-complexation adsorbents to remove sulfur-
containing compounds, due to the geometric effect between the
carbon substrate and the supported p-complexation species [7].
Nevertheless, the extremely inert and hydrophobic carbon surface
is unfavorable for introducing the guest species by impregnation
method and subsequent heattreatment can lead to aggregation and
pore blockage. Hence, the sulfur-adsorption capacity and selectivity
of adsorbents need to be further improved by modifying the
properties of the hosts.
In this study, copper species supported on MCS adsorbents were
prepared by incipient wetness impregnation of copper nitrate. The
desulfurization performance of the as-prepared adsorbents was
evaluated by the selective adsorption of dibenzothiophene (DBT) as
model sulfur compound from model fuels at ambient conditions. To
understand the effect of pore wall compositions on the copper
distribution and hence the desulfurization performance, the
introduction of copper species into the pure silica SBA-15 and pure
carbonaceous CMK-3 and their desulfurization performance are
also investigated. Among the tested materials, the carbon-silica
nanocomposites with 10wt.% copper performed highest selec-
tivity ability for DBT in competition with benzene. The signicantly
enhanced sulfur selectivity could be attributed to its highly ordered
hybrid mesoporous carbon-silica nature which is favorable for high
dispersion extent of copper and synergistic effect between the
carbon substrate and the supported copper species.
2. Experimental section
2.1. Material synthesis
The MCS is prepared by a direct tri-constituent co-assembly
method with soluble phenolic resins as carbon precursor, triblock-
copolymer F127 as the soft template and tetraethoxysilane (TEOS)
as silica precursor according to the procedure reported by the Zhao
group [21]. Resols preparation: 5 g of phenol was melted at 42 " C,
and then 1.06 g of 20 wt.% NaOH aqueous solution was added. After
stirring for 10 min, 8.85 g of 37 wt.% formaldehyde aqueous solu-
tion was added, and the mixture was stirred at 70 " C for 1 h. The
mixture was further neutralized by 2 M HCl solution after naturally
cooling down to room temperature. Water was removed under
"
vacuum at 45 C. Then the mixture was made up of 20 wt.% resols
ethanolic solution. MCS was prepared as following. 1.6 g of F127
"
was dissolved in 7 g of ethanol at 40 C, followed by the addition of
1 g of 0.2 M HCl solution. Next, 2.08 g of TEOS and 5 g of 20 wt.%
resols ethanolic solution were added in sequence and stirred for
2 h. Then the mixture was transferred to several Petri dishes and
evaporated at room temperature for 8 h, followed by thermal
"
polymerization at 100 C for 24 h. The as-made product was
calcined at 900 " C for 4 h under N2 ow to obtain sample MCS, with
the heating rate of 1 " C/min below 600 " C and 5 " C/min above
600 " C.
The preparation of the SBA-15 silica is based on the synthesis
procedure rst reported by Zhao et al. [22]. The typical synthetic
process is as follows. First, 4 g of P123 was dissolved in 30 g of
"
deionized water and 120 g of 2 M HCl with stirring at 38 C. Then,
8.5 g of TEOS was added and the resulting mixture was stirred at
"
38 C for 20 h. The milky mixture was transferred into an auto-
"
clave and aged at 100 C for 48 h. The solid was harvested by
ltration, washed with deionized water, dried at room tempera-
ture, and calcined in air at 550 " C for 6 h to obtain the SBA-15
sample.
The synthesis of the host structure CMK-3 was carried out using
SBA-15 silica as the hard template and sucrose as the carbon source
following the synthesis procedure described by Jun et al. [23].
Briey, 1 g of SBA-15 was impregnated with an aqueous solution
obtained by dissolving 1.25 g of sucrose and 0.14 g of H2SO4 in 5.0 g
of deionized water. The mixture was then dried at 100 " C for 6 h,
and subsequently at 160 " C for 6 h. The silica sample, containing
partially polymerized and carbonized sucrose, was treated again at
100 " C and 160 " C after the addition of 0.8 g of sucrose, 90 mg of
H2SO4 and 5.0 g of deionized water. The sucrose/silica composite
"
was then heated at 900 C for 6 h under nitrogen to complete the
carbonization. The silica template was dissolved with 1 M NaOH
"
(50% vol ethanol and 50% vol H2O) at 80 C. The template-free
carbon product thus obtained was ltered, washed with deion-
ized water and ethanol, and dried.
A denite quantity of Cu(NO3)2 was incorporated into as-
prepared MCS powder by incipient wetness impregnation
method for 24 h. Then the mixture was placed inside a quartz
reactor and heated to 400 " C at a rate of 1 " C/min and maintained at
this temperature for 2 h in pure Ar atmosphere. Then the reactor
was cooled in the pure Ar atmosphere to room temperature, and
the complex adsorbent nCu/MCS was obtained, where the n rep-
resents the mass percentage of copper in the samples. In contrast to
the previous series, pure mesoporous carbons CMK-3 and pure
mesoporous silicate SBA-15 were used as supports. 10Cu/CMK-3,
10Cu/SBA-15 samples were prepared by the same procedures as
descripted above.
2.2. Characterization
Thermogravimetric (TG) measurement was carried out on a
SDT Q600 thermal analyzer in the temperature range from 25 to
800 " C at a heating rate of 10 " C/min in air. X-ray diffraction
(XRD) patterns were recorded on a Rigaku-DMAX2200PC
diffractometer using Cu Ka (l 0.1506 ) radiation over the
range 0.5 to 5" (low angle) and 10 to 80" (wide angle). Trans-
mission electron microscopy (TEM) was performed on a JEOL
JEM-2100F eld emission source transmission electron micro-
scope operated at 200 kV. Energy dispersive X-ray spectroscopy
(EDX) was performed on a Philips EDAX instrument. TEM sam-
ples were ultrasonically treated in a solution of ethanol and then
deposited on molybdenum grids coated with carbon. N2
adsorptionedesorption isotherms were measured at 77 K with
an ASAP 2020 instrument. The samples were separately degassed
at 200 " C in a vacuum environment for a period of at least 4 h
prior to measurements. Experimental adsorption data in the
relative pressure (P/P0) range of 0.05e0.2 was used to calculate
surface area values using the Brunauer-Emmett-Teller (BET)
equation. The pore size distribution was determined by applying
density functional theory (DFT) model, assuming slit-pore ge-
ometry for the pores less than 2 nm and cylindrical pore ge-
ometry for the pores in the range of 2e30 nm.
2.3. Adsorptive test
DBT was used as the representative of sulfur contaminants.
The model fuel with different sulfur concentrations from 32 to
960 ppmw was prepared by mixing DBT and n-octane. For
competitive adsorption experiments, an extra 20 wt.% of benzene
 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145
was added to the model fuel above. The desulfurization perfor-
mance of adsorbents was evaluated by static saturation tests.
About 0.1 g of tested adsorbent and 10 g of model were added
into a glass tube. The tube was capped and placed in a shaking
"
bath at 30 C for 48 h. Then the mixture was ltered, and the
treated model fuel samples were analyzed to estimate the sulfur
adsorption capacity of the adsorbents. The amount of sulfur
adsorbed on per gram of adsorbent, qe (mg/g), was calculated
with the following equation:
C0 % Ce m'
qe
m CMK-3 samples before and after loading copper species. The MCS
where C0 and Ce are the initial and equilibrium sulfur concentra-
tions in the model fuel (mg/g), respectively, m* is the weight of
model fuel (g) and m is the mass of the adsorbent (g).
In order to facilitate the quantitative discussion of the adsorp-
tive selectivity, a selectivity factor K was used in the present study,
which is dened as:
q1e % q2e
K (2)
q1e
where q1e is the sulfur adsorptive capacity for the model fuel
without benzene (mg/g) and q2e is the sulfur adsorptive capacity for
the model fuel with benzene (mg/g). K represents the percentage of
reduced adsorption capacity in the presence of benzene. Note that
the larger K value, the lower selectivity.
The adsorption equilibrium data were tted using the Langmuir
equation:
Ce 1 Ce
(3)
qe Kl qm qm
where qm is the maximum adsorption capacity (mg/g), Kl is the
adsorption equilibrium constant (g/mg), characteristic of the af-
nity between the adsorbent and adsorbate. Kl and qm can be ob-
tained by linear regression of (Ce/qe) vs. Ce data.
The adsorption data were also tted using the Freundlich iso-
therms. The Freundlich isotherm is an empirical model that can be
applied for non-ideal adsorption on heterogeneous surfaces as well
as for multilayer adsorption. The Freundlich isotherm is expressed
by the following empirical equation:
1=n
qe Kf Ce
where Kf is the Freundlich adsorption constant ((g/mg)1/n), which is
an indicator of the adsorption capacity, while n refers to the
adsorption tendency. In all cases, a double-log plot of qe vs. Ce data
resulted in a good linear relationship, allowing for the estimation of
the model parameters Kf and n by linear regression.
The sulfur content of the treated model fuels was determined
using a gas chromatograph (Shimadzu 2014C) equipped with a
ame ionization detector (FID), a capillary column (MXT-5, Restek,
60 m length, 0.25 mm inner diameter, 0.25 mm lm thickness) and a
split mode injector (ration: 100:1). Ultrahigh purity helium was
used as a carrier gas. The column temperature was set at 140 " C for
" "
5 min, 10 C/min from 140 to 220 C, hold for 7 min. The temper-
"
ature of both injector and detector was 280 C. The injection volume
of sample was 1 mL. In this analysis, phenyl sulde was used as an
internal standard.
139
3. Results and discussion
3.1. Mesostructure and chemical compositions of copper-modied
hosts
TG measurement was used to reveal the precise chemical
composition of the as-obtained MCS. The TG curve (Fig. 1) shows a
signicant weight loss of 40 wt.% in the temperature range from
400 to 600 " C in air, and the weight residue is 60 wt.%, implying that
MCS is composed of silica and carbon with the weight ratio of about
1.5:1.
Fig. 2a displays the low-angle XRD patterns of MCS, SBA-15,
(1)
sample exhibits an intense diffraction peak at 2q of 0.95" indexed as
(100) reection, and a weak peak at 2q of 1.85" indexed as (110),
corresponding to a two-dimensional hexagonal pore regularity of a
p6mm space group. The SBA-15 sample also shows three well-
resolved peaks at 2q of 0.95" , 1.6" and 1.8" that can be indexed as
(100), (110), and (200) reections associated with hexagonal sym-
metry. Compared with SBA-15, the diffraction peaks of the
carbonization material CMK-3 in the low-angle range shift some-
what to higher angles with three peaks at 2q of 1.0" , 1.8" and 2.0"
assigned to (100), (110), and (200), and the width of peak (100)
increased slightly, which should be due to structural defects and
shrinkage happened in the carbonization and the silica removal
steps. In contrast with the XRD patterns of pristine samples, after
copper incorporation, the characteristic peaks of the samples shift
to higher angles and the intensity decreased, indicating copper
modication results in the contraction of frameworks and the
decrease of the mesostructural ordering. The shrinkage of meso-
porous frameworks is caused by the calcination during the incor-
poration of copper species, and the declined intensity of diffraction
lines is attributed to the pore-lling effects that can reduce the
scattering contrast between pore walls and space. Similar results
have been reported previously [13,24e26]. These changes in the
diffraction patterns suggest that the copper species was success-
fully introduced into the mesochannels of the hosts. And the in-
tensity of peak (100) of sample 15Cu/MCS and 10Cu/CMK-3
decreases sharply compared with their parent hosts, implying the
introduced copper species is blocking the pore or the ordered
mesostructure is somewhat destroyed. Wide-angle XRD patterns of
different samples were also obtained, as shown in Fig. 2b. All MCS
samples possess a broad diffraction peak centered at 22.5" , which
(4)
Fig. 1. TG analysis curves of sample MCS in air.
140 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145
Fig. 2. Low-angle (a) and wide-angle (b) XRD patterns of MCS, SBA-15, CMK-3 samples before and after loading copper species.
can be assigned to amorphous carbon and silica walls [14,24]. The
diffraction peaks of MCS samples with different copper content
locate at 2q of 43.2" , 50.4" and 74.0" match well with those of the
metallic Cu (JCPDS No. 04-0836), and the peaks become stronger
when copper amount is enhanced. For the sample 15Cu/MCS, be-
sides prominent peaks for elemental Cu, a weak peak at 2q of 36.5"
originated from Cu2O (JCPDS No. 65-3288) is also detected,
implying the copper species begin to aggregate and is difcult to be
reduced with the increasing of loading amount. During heat
treatment in inert atmosphere, copper nitrate decomposed to CuO
and then was reduced to Cu by the carbon wall. And if the generated
CuO particles aggregated severely, they are difcult to be reduced.
For the sample 10Cu/CMK-3, the presence of the apparent diffrac-
tion peak of Cu2O also suggests that some large copper-derived
agglomerates on the exterior of CMK-3 cannot be fully reduced
due to their poor contact with carbon framework. The sample 10Cu/
SBA-15 shows intense diffraction peaks originated from CuO (JCPDS
No. 44-0706). It has been reported that the CuO supported on SiO2
can be partially autoreduced to Cu2O under inert condition
[12,14,16], which function as active species in desulfurization and
can capture organo-sulfur compounds by p-complexation adsorp-
tion. These results suggest that the support and copper loading
degree have a signicant effect on the existence state of copper
species. Corresponding crystallite sizes of copper species estimated
by using the Scherrer formula are listed in Table 1. It should be
noted that the calculated crystallite size is the average value, and
incipient wetness impregnation method usually results in the some
extra species which may exist in the spaces of the bulk particles of
the supports [27].
TEM was used to directly observe the periodic ordering of the
mesostructure and the existing state of the copper species. The
images of different samples are shown in Fig. 3. For all of the
samples, the ordered hexagonal arrays of mesopores can be judged
from the white dark contrast, as shown in Fig. 3a, f and h, which is
consistent with the low-angle XRD patterns. The difference of
copper content leads to the different dispersion state of copper
particles inside the pore channels of MCS adsorbents. The dispersed
small copper particles inside mesochannels of 5Cu/MCS sample can
be seen in Fig. 3b. In the low-magnication TEM image of 10Cu/MCS
(Fig. 3c), no bulk particles are observable, while the EDAX probe
reveals the presence of copper (Fig. 3e). From the enlarged image
(Inset of Fig. 3c), we can see that the copper nanoparticles are
dispersed in the mesochannels of host MCS. Further increasing the
copper loading level to 15wt.%, the copper particles begin to
aggregate in the pore channels, as shown in Fig. 3d. On the contrary,
bulk aggregated particles can be easily found on the external sur-
face of CMK-3 (Fig. 3g). In addition, the TEM image of 10Cu/SBA-15
in Fig. 3i shows that the aggregation of CuO nanoparticles occurs in
some regions of the mesochannels. These results reveal that the
guest tends to aggregate in pure SBA-15, and the hydrophobic
carbon surface of CMK-3 restricts the impregnation of copper ni-
trate aqueous solution, while the nanocomposite MCS favors the
introduction of guest solution and promotes the dispersions of
copper nanoparticles.
N2 adsorptionedesorption isotherms and the corresponding
pore size distributions obtained using a DFT model of different
samples are shown in Fig. 4. The pore parameters are listed in
Table 1. All samples display a typical IV isotherm with two sharp
inections and an H1-type hysteresis loop [28]. The capillary
condensation between the two inections indicates the preserva-
tion of ordered mesoporous channels after introduction of copper,
which can be conrmed by the pore size distributions. As presented
in Table 1, the surface area is found to decrease gradually from
333 m2/g for MCS to 327 m2/g for 5Cu/MCS, 291 m2/g for 10Cu/MCS,
and 276 m2/g for 15Cu/MCS. Similarly, the pore volume of pores in
the range of 2e30 nm (V2e30nm) decreases also in this order, and
the pore size distribution curve of 10Cu/MCS in the range of
6e8 nm shift toward the smaller pores. All these results suggest
that the successful introduction of copper species to the meso-
channels of the MCS hosts. It is worth noting that the sample 15Cu/
MCS exhibits similar V2e30nm as 10Cu/MCS, indicating incorpora-
tion of copper by high concentration of copper nitrate solution via
 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145
Table 1
Microstructure parameters of MCS, SBA-15 and CMK-3 samples before and after loading copper species.
Samples SBET (m2/g) V<2nm (cm3/g)
MCS 333 0.060
5Cu/MCS 327 0.051
10Cu/MCS 291 0.055
15Cu/MCS 276 0.050
SBA-15 595 0.053
10Cu/SBA-15 345 0.030
CMK-3 1000 0.171
10Cu/CMK-3 928 0.171
SBET: BET surface area.
V<2nm: pore volume of pores less than 2 nm.
V2e30nm: pore volume of the pores in the range of 2e30 nm.
dCu, dCu2O and dCuO: Cu, Cu2O and CuO crystallite sizes calculated by the Scherrer formula.
incipient wetness impregnation make copper difcult to enter into
the mesopores. For CMK-3, the surface area decreases from
1000 m2/g to 928 m2/g, and V2e30nm decreases from 1.011 cm3/g to
0.832 cm3/g after incorporation of copper, however, the micopore
volume is unchanged, implying some copper species is introduced
into the mesochannel not in the micopore. And the incorporation of
copper also leads to the diminution of surface areas and pore vol-
umes of SBA-15. All these results are in good agreement with above
XRD and TEM results.
For clarity, a comparison mechanism for the incorporation of
copper species on different supports is given in Fig. 5. The silanol
groups on the surface of SBA-15 can interact with the copper so-
lution, which favors the mass transfer of copper solution inside
mesochannels. However, when the nucleation of copper oxides
occurs at some domains in the conned mesochannels, the pre-
cursors in other areas transfer and nucleate together. In contrast,
the inert and hydrophobic carbon surface of CMK-3 makes it
difcult to introduce the aqueous solution of copper nitrate into the
mesopores. And the copper ions/nanoparticles in the mesopores
easily aggregate due to their weak interaction with carbon surface.
The MCS clearly demonstrates great advantages over its single-
component counterparts when acting as the support. The intro-
duction of silica in the framework favors the introduction of the
aqueous solution of copper nitrate. Moreover, copper ions may
have strong afnity with the hydrophilic surface of silica, while the
inert, hydrophobic component carbon possibly plays a role in
separating them. The synergistic effect of hybrid silica and the
carbon nature of the hosts lead to the formation of relatively
dispersed copper nanoparticles after annealing.
3.2. Adsorptive desulfurization performance
The MCS samples with different copper loading levels were
screened for their adsorptive desulfurization ability for DBT from
the model oil with the sulfur concentrations of 320 ppmw. The
results of adsorptive desulfurization experiments are displayed in
Fig. 6. Cu/MCS adsorbents adsorb more DBT than pristine MCS, but
the uptake amounts are not proportional to the loading amount of
copper. This nonlinear response could be a consequence of varia-
tions in the structure and composition of domains on the Cu/MCS
surface or inaccessibility to the active copper sites for some do-
mains. It is found that after loading 5wt.% copper, the sulfur uptake
capacity of 5Cu/MCS is increased compared with that of MCS,
which is due to p-complexation between DBT and copper. Further
increasing the copper loading level increases the amount of the
active copper sites, which results in the better desulfurization ca-
pacity of 10Cu/MCS than that of 5Cu/MCS in the presence of ben-
zene, indicating there are more active copper sites in 10Cu/MCS
than 5Cu/MCS. However, with more copper species introduced into
141
V2e30nm (cm3/g) dCu(nm) dCu2O (nm) dCuO (nm)
0.329 e e e
0.307 26.0 e e
0.291 35.2 e e
0.292 23.0 8.0 e
1.341 e e e
0.818 e e 29.8
1.011 e e e
0.832 24.7 24.5 e
the support, the copper particles begin to aggregate and subse-
quently block the mesopores, leading to the decreased amount of
accessible active copper sites to form the p-complexation with DBT.
Thus, the adsorbent with higher copper loading (15Cu/MCS) shows
a smaller sulfur uptake capacity than that with lower copper
loading (10Cu/MCS). Therefore, among all the samples, 10Cu/MCS
shows the highest desulfurization capacity. In addition, it has been
proved that the particle size and dispersion state of metallic copper
have important effect on the utilization of p-complexation [29],
and the aggregated copper particles are not effective for the
adsorption of thiophenic sulfur compounds.
To compare the desulfur function of copper species on supports
with different properties, desulfurization by 10Cu/CMK-3 and
10Cu/SBA-15 were also tested under the same desulfurization
conditions. DBT adsorption capacities of different substrates before
and after loading of copper are shown in Fig. 7. It is shown that the
adsorption capacities of the substrates decrease in the following
sequence, CMK-3>MCS > SBA-15. Moreover, the selectivity factor K
of the samples, which represents the decreased magnitude of
adsorption capacity in the presence of benzene is listed in Table 2.
For the MCS samples, K is decreased with the increase of copper
content until 10 wt.%, indicating the introduction of copper
enhanced the selectivity of MCS with its p-complexation effect.
However, for the CMK-3, K has no change after incorporation of
copper. Previous results reported by other groups show that the K
value is in the range of 40e75% by introducing of aromatics. He
et al. [14] reported the adsorption of thiophene with the CuCl-
modied SBA-15 and Alumina-incorporated SBA-15, and the K
value ranged from 47% to 68% after introducing 8 wt.% of toluene.
The results of Dai et al. [30] suggested the introduction of 20 wt.%
benzene can lead to a 75% decrease of capacity for thiophene by
using Cu(I)/SBA-15. Yang et al. [8] studied the desulfurization per-
formance of zeolite CuY by adsorption of thiophene, and the
saturation adsorption capacity was reduced by 65% after intro-
ducing 20 wt.% benzene. Khan et al. [31] found that the presence of
25 wt.% toluene can decrease the adsorption amount by 70% for the
adsorption of benzothiophene by using Cu/activated carbon. Dai
et al. [18] also reported the sulfur adsorption capacity of DBT of
Cu(I)/MOF was reduced by 38% due to the introduction of 20 wt.%
benzene. Those results indicate that aromatics can reduce sulfur
compounds adsorption seriously. It is worth noting that the Cu/
MCS adsorbents are superior to those of copper species supported
on SBA-15, zeolites, activated carbons and MOFs reported
previously.
The sample 10Cu/MCS exhibits the highest adsorption capacity
per unit of surface area among all samples, as shown in Table 2. For
the pure carbon substrate CMK-3, the excellent sulfur capacity is
due to its larger BET surface area and higher micropore volume
ratio. The adsorption driving force of DBT on carbon is mainly due
142 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145
Fig. 3. TEM images of MCS (a), 5Cu/MCS (b), 10Cu/MCS (c), 15Cu/MCS (d), CMK-3 (f),
10Cu/CMK-3(g), SBA-15(h) and 10Cu/SBA-15 (i) and the EDAX pattern of 10Cu/MCS (e).
Insets in (a) and (c) are the enlarged images.
to the pep dispersion interactions between the aromatic ring of
DBT and the aromatic structure of the graphene layers [32], and the
DBT adsorption capacity governed by micropore volume of carbon
has been observed in previous study [33e36]. After copper species
are loaded onto CMK-3, the agglomeration of copper-derived par-
ticles may block pores, and they are not effective for the adsorption
of DBT due to their low activity, resulting in the decline of
adsorption capacity. And it is found that although SBA-15 has a
relatively high surface area of 595 m2/g, it could not x DBT due to
the weak interaction (probably by van der Waals forces) between
DBT and silica surface [30,37]. Compared with SBA-15, the
adsorption capacity of the 10Cu/SBA-15 increase to 0.6 mg/g, but it
can only capture 0.2 mg/g in the presence of benzene. This may be
because the CuO can be partially autoreduced to Cu2O, and the
Cu2O can form p-complexation with DBT, but benzene with the
similar adsorption mode can reduce the DBT adsorption capacity.
Moreover, the aggregated CuO in the pores is more difcult to be
reduced to cuprous species which function as active species and
thus the enhancement of the adsorption capacity is limited.
3.3. Adsorption isotherms of DBT
Adsorption isotherm models have been widely adopted to assess
the relationship between adsorbate and adsorbent at equilibrium.
The tting parameters obtained by different models can help to
explain the adsorption mechanism, heterogeneity of the adsorbent
surface and afnities of the adsorbents which are important to
optimize the design of an adsorption system to remove the adsor-
bate [38,39]. In the present investigation, the experimental data of
adsorbing DBT were t by the Langmuir and Freundlich models to
study the adsorption characteristics and mechanism. Fig. 8 shows
the experimental data points along with Langmuir and Freundlich
tting cures of sample MCS and 10Cu/MCS. The higher adsorption
capacities of DBT on the 10Cu/MCS than on their original counter-
parts MCS with and without benzene are obviously seen. Since the
surface area and pore volume all decrease after loading of copper,
the increased adsorption on the 10Cu/MCS adsorbent suggests
favorable p-complexation between copper and DBT. The tting
parameters of the experimental adsorption equilibrium data are
given in Table 3. The data calculated from the Langmuir equation
reveal an increase of qm and Kl upon the sample after incorporation
of copper, which is an indication of the enhanced afnity between
DBT and adsorbent surface. Moreover, Kl and qm are all decreased in
the presence of benzene, maybe owing to the benzene with the
similar adsorption mode toward the adsorbent as DBT occupy the
active site. The same tendency of copper modication facilitating
the adsorption process is also observed from the tting of
Freundlich models. It shows that after loading of 10wt.% copper, Kf
and n increased, indicating that the adsorption potential between
adsorbent and DBT enhanced with the incorporation of copper. In
any cases, when considering the value of correlation coefcient
square (R2), it seems that the experimental data of 10Cu/MCS is
better tted to Freundlich model than Langmuir model, possibly
implying that the introduction of copper had resulted in a more
heterogeneous surface of the adsorbents.
3.4. Mechanism of selective adsorption for copper-modied MCS
The signicantly enhanced sulfur selectivity of MCS compared
with that of SBA-15 after copper incorporation is attributed to its
synergistic effect between the carbon substrate and the supported
copper species. There are a large number of peripheral sites on the
edges of the supported copper which are dispersed on the MCS
substrates [10], and the edge sites provide an ideal combination of
sites for the DBT molecule, as illustrated in Fig. 9. The thiophene
 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145 143

Fig. 4. N2 adsorptionedesorption isotherms (a,c,e) and the corresponding DFT pore size distributions (b, d, f) of MCS, SBA-15 and CMK-3 samples before and after loading copper
species.

Fig. 5. Schematic illustration of the preparation strategy.

144 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145

Table 3
Isotherm model parameters for DBT on MCS and 10Cu/MCS under different
adsorption conditions.

Samples Langmuir Freundlich

qm Kl R2 n Kf R2

With benzene MCS(B) 10.739 0.861 0.986 1.465 4.923 0.999

10Cu/MCS(B) 11.143 1.147 0.980 1.592 5.975 0.990
Without benzene MCS 13.190 1.276 0.992 1.636 7.446 0.982
10Cu/MCS 13.954 1.915 0.970 1.929 9.259 0.988

Fig. 6. Adsorption capacities of MCS samples with different copper loading levels.

Fig. 9. Depiction of synergistic effect in adsorption of DBT on copper-modied MCS

samples.

ring of DBT molecule adsorbs strongly at well-dispersed copper

active sites on the substrate, while benzene rings of DBT molecule
are bonded to the surface of carbon by the pep dispersive inter-
action between the aromatic rings and the graphene layers of
carbon. By binding cooperatively in this manner, stronger adsorp-
tion and hence higher adsorbed amounts were achieved. Based on
above edge sites theory, after incorporation of copper, CMK-3
should have superior adsorption performance, but the copper ag-
gregation and pore blockage restrict the mentioned synergistic
effect. The hybrid carbon-silica nature of the MCS support may play
Fig. 7. Adsorption capacities of SBA-15 and CMK-3 samples before and after loading a role in generating relatively dispersed copper nanoparticles. Thus,
copper species. it is shown in this work that MCS is a relatively effective support for
p-complexation adsorbent.
Table 2
The selectivity factor K and sulfur capacities based on per unit of surface area of
samples. 4. Conclusion
2 3
Samples K(%) Sulfur capacity (mg/m ( 10 )
Copper species supported on MCS adsorbents were prepared by
Without benzene With benzene
an incipient wetness impregnation method and the desulfurization
MCS 38.8 14.7 9.0 properties for model fuels were evaluated under ambient condi-
5Cu/MCS 36.8 17.4 11.0
tions. It is shown that the pore wall nature has great inuence on
10Cu/MCS 27.6 19.9 14.4
15Cu/MCS 28.0 18.1 13.0 the dispersion of copper species and the interaction between
SBA-15 e 0.0 0.0 adsorbate and substrate, in turn, the desulfurization performance.
10Cu/SBA-15 69.0 1.7 0.5 The selectivity and sulfur capacity based on per unit of surface area
CMK-3 32.7 15.3 10.3 for MCS with 10wt. % copper are higher than that of SBA-15 and
10Cu/CMK-3 32.6 14.5 9.8
CMK-3 with same copper loading amount. The signicantly

Fig. 8. Langmuir (a) and Freundlich (b) isotherms for DBT on MCS and 10Cu/MCS under different adsorption conditions. (symbols: experimental data points, solid lines: tting
curves).
 J. Cheng et al. / Microporous and Mesoporous Materials 212 (2015) 137e145
enhanced desulfurization performance of MCS could be ascribed to
its highly ordered hybrid mesoporous carbon-silica nature which is
favorable for high dispersion extent of copper and synergistic effect
between the carbon substrate and the supported copper species.
The application of hybrid silica-carbon as metal carriers would
open up an avenue for the design and fabrication of efcient ad-
sorbents for fuel desulfurization as well as other applications.
Acknowledgments
This work was supported by the Capacity Building Program of
Shanghai Local Universities (No. 12160503600), Youth Innovation
Fund from Shanghai Institute of Technology (No. YJ2013-35), the
First-class Discipline Construction Fund of Shanghai Municipal
Education Commission (No. J201212), Nature Science Foundation of
China (No. U1332107) and Key Discipline Construction Fund of
Composite Materials of Shanghai Institute of Technology (No.
10210Q140001).
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