Chemical Engineering Journal 302 (2016) 239–248

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Chemical Engineering Journal

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

Facile fabrication of Ni-based KIT-6 for adsorptive desulfurization

Sobia Aslam a,b, Fazle Subhan a,b,⇑, Zifeng Yan a,⇑, Peng Peng a, Ke Qiao a, Wei Xing a, Peng Bai a,
Rooh Ullah a, U.J. Etim a, Jingbin Zeng a, Muhammad Ikram b
a
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, China
b
Department of Chemistry, Abdul Wali Khan University Mardan, Pakistan

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Nickel was fabricated on as-

synthesized-KIT-6 for the first time by
one-step reduction strategy.

Silanols and confined space between
template and silica walls promoted
Ni-dispersion.

Shielding effect of capping anions of
nickel precursors affect nickel
dispersion and sulfur removal.

One-step-reduction strategy save
time and energy for fabricating Ni-
based mesoporous silica.

The present work may open an
avenue of research by use of such
confined spaces.

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

Article history: In the present contribution, a single step H2-reduction strategy was developed for the first time to fabri-
Received 20 March 2016 cate nickel-based KIT-6 (Ni-KIT-6) for adsorptive desulfurization of fuels. As-synthesized KIT-6 was used
Received in revised form 7 May 2016 as a support and nickel nitrate, nickel chloride and nickel acetate as a nickel precursor was directly intro-
Accepted 9 May 2016
duced into as-synthesized KIT-6. Ni0-based KIT-6 was obtained by single-step H2-reduction strategy
Available online 10 May 2016
which not only remove template and decompose nickel precursors to NiO but also reduce NiO to Ni0.
This strategy is much more convenient and facile than reported strategies for Ni-based mesoporous silica
Keywords:
KIT-6. Characterization results show that Ni-KIT-6 with nickel content up to 30 wt.% was highly dispersed
One-step H2-reduction strategy
Nickel precursors
due to silanols and confined space in as-synthesized KIT-6. The percentage content (54%) of Ni0 in the as-
KIT-6 synthesized KIT-6 is higher than Ni-based calcined KIT-6 (38%). Interestingly, Ni-based as-synthesized
Adsorption KIT-6 prepared using nickel nitrate as a precursor exhibited stronger nickel-KIT-6 interaction, higher
Fuels Ni0 content and dispersion than those prepared with nickel chloride and nickel acetate precursors. We
also demonstrate here that the shielding effect of capping anions and hydration degree of different nickel
precursors significantly affect the dispersion of nickel species even using as-prepared KIT-6 as a support.
As a result, Ni-KIT-6(NO3 ) captured 0.195 and 0.12 mmol g
1
of sulfur from model fuel and FCC gasoline,
respectively. Thus, single step H2-reduction strategy may have potential applications to be applied for
fabrication of other nickel based mesoporous silicas for adsorptive desulfurization technology.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction
⇑ Corresponding authors at: State Key Laboratory of Heavy Oil Processing, China
University of Petroleum, Qingdao 266580, China (F. Subhan).
In the last few years, deep desulfurization of transportation
E-mail addresses: [email protected] (F. Subhan), [email protected]
fuels in a petroleum refining industry received great importance
(Z. Yan).

http://dx.doi.org/10.1016/j.cej.2016.05.041
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
240 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248

because of stringent environmental regulations imposed by gov- on the effective role of silanols and microenvironment for nickel
ernments around the globe to lower down the existing sulfur levels dispersion in as-synthesized mesoporous silica KIT-6 via single-
[1–3]. The existence of sulfur species in commercial fuels not only step H2-reduction strategy are very scarce, if any.
harm environment but also dangerous for other utilities [4–7]. Herein, we report for the first time single-step H2-reduction
Among different alternatives, hydrodesulfurization (HDS) is one strategy to fabricate nickel based KIT-6 adsorbents (Scheme 1B).
of a major process employed in refineries worldwide for desulfur- Three different nickel precursors were loaded into as-prepared
ization of transportations fuels to make it environmental friendly. KIT-6, and Ni0-based KIT-6 was prepared through single-step H2-
However, HDS need elevated temperature (>300 °C) along with reduction strategy which not only remove template of mesoporous
high hydrogen pressure (>4 MPa) for capturing thiols and sulfides support and decompose nickel precursors to NiO but also reduces
instead of thiophene derivatives than other process for sulfur NiO to Ni0. Our results show that the shielding effect of capping
removal employed elsewhere [3,8–11]. Therefore, adsorptive anions along with hydration degree of nickel precursors highly
desulfurization (ADS) emerged as a best industrial option to pro- affect the dispersion degree of nickel species even using as-
duce sulfur free fuels under mild operation conditions and over- prepared KIT-6 as a support and adsorption capacities were
come the deficiencies of the existing HDS. strongly correlated with nickel dispersion from different nickel
Adsorbents/materials play a crucial role in adsorptive desulfur- precursors. Thus, one-step H2-reduction strategy synthesized
ization, and hence many attempts by different research groups highly active nickel based materials for desulfurization of fuels
have been made towards the development of particularly high with minimum consumption of time and energy and with the
performance nickel based adsorbents based on various supports effective use of the confined spaces and silanols in mesoporous
[12–16]. However, two factors are considered crucial for high silicas.
activity of such materials i.e., support with high surface area
because it accommodate maximum amount of nickel species and 2. Experimental
appropriate method disperse well the nickel species on supports.
Thus, there is a great need of appropriate method and a support 2.1. Materials
for nickel dispersion to increase the sulfur removal capacity from
fuels. Other than various supports reported in literature, meso- Thiophene with percentage purity of 99% was obtained from
porous silica with different pore structures are promising and Aladdin Reagent Limited Company (Shanghai, China). Ni(NO3)2-
has attracted considerable attention for different fields including 6H2O (98%) was purchased from Shanghai Hengxin Chemical
sulfur adsorption [3,17,18]. Reagent Co., Ltd. NiCl26H2O (98%), Ni(CH3COO)24H2O (98%), n-
KIT-6, mesoporous silica, has received great interest since it dis- Octane (98%) and TEOS (28.4%) were supplied by Sinopharm Chem-
covery for metal/guest species dispersion. The excellent properties ical Reagent Co., Ltd (Shanghai China). Pluronic P123
for metal dispersion and sulfur removal were obtained due to its (EO20PO70EO20, Aldrich) was purchased from Germany.
three-dimensional structure [19]. Park et al. reported Ni based
KIT-6, which presented larger total sulfur adsorption capacity 2.2. Preparation of as-prepared KIT-6
(3.3 mg/g) than (2.3 mg/g) of Ni/SBA-15 for diesel fuel [12]. The
higher adsorption in the case of Ni based KIT-6 was attributed to KIT-6 was synthesized hydrothermally as reported in literature
the structure of mesoporous silica support. However, in those pre- [21]. In this procedure, 4 g of Pluronic P123 as a template was first
vious fabrication strategies, calcined mesoporous KIT-6 were dissolved in 144 mL distilled water. Then, 144 mL of HCl (35%) was
employed as support instead of as-synthesized and the loading added by continuous stirring at temperature of 35 °C for 4 h, fol-
process were consisted of KIT-6 calcination to remove template, lowed by dropwise addition of n-butanol (4.95 mL) and continued
dispersion of nickel by IWI impregnation, followed by second cal- stirring for an additional 1 h. Finally, TEOS (9 mL) was introduced
cination to convert Ni (NO3)2 to NiO and finally reduction of NiO and stirred at 35 °C for one day. The hydrothermal treatment at
to Ni0 by high temperature H2-reduction treatment to generate 100 °C for 24 h was performed in Teflon lined SS autoclave. The
Ni0-based mesoporous silicas for sulfur removal as shown in Sche- as-synthesized white material named as KIT-6 was recovered by
me 1A. These 4 steps approaches are rather complicated and con- filtration and subsequently dry at 100 °C for 12 h. Calcination of
sume a lot of time, energy and hard to be industrialized. Thus, as-prepared KIT-6 was carried out in air at 550 for 8 h.
the demand for a facile and single step strategy for nickel disper-
sion over KIT-6 with maximum Ni0 active sites is highly required. 2.3. Preparation of Ni-KIT-6 and Ni/KIT-6 samples
Using as-synthesized mesoporous silica SBA-15 as a support,
Liu and his co-workers introduced high amount of copper precur- In fabrication process before one step H2-reduction strategy,
sor for adsorptive desulfurization of fuel [20]. High amount disper- three different nickel precursors as a nickel source were incorpo-
sion of copper and sulfur adsorption capacity of Cu-SBA-15 was rated into as-synthesized KIT-6 via solid-state grinding at room
correlated with the confined space and silanol groups in template temperature for 0.5 h, followed by drying overnight at 100 °C.
possessing SBA-15. However, to the best of our knowledge, reports The as-synthesized samples using Ni (NO3)26H2O, NiCl26H2O

Scheme 1. Synthesis of Ni-based KIT-6 via (A) Conventional method and (B) One-step H2-reduction strategy.
 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248 241

Table 1
3-MT FCC gasoline: 510 ppmw
Specifications of FCC gasoline used in the present study T10, T50
5000 T
and T90 are 10, 50 and 90% vol. evaporated temperatures,
respectively.
4000 2-MT
Aromatics 20 vol.%
Olefins 30 vol.%
3000 2,4-DMT

mV
Total sulfur content 510 ppmw BT
T10 50 °C
T50 89 °C 2000
T90 176 °C
End point 199 °C
1000 2-MBT
Density 7.5 g/cm3

0 2 4 6 8 10 12 14 16 18 20 22
and Ni (CH3COO)24H2O as a precursor were denoted as Ni-KIT-6 Retension time, min
(NO  
3 ), Ni-KIT-6(Cl ), and Ni-KIT-6(Ac ), respectively. Whereas,
the mass ratios of each Ni (NO3)26H2O, NiCl26H2O and Ni (CH3- Fig. 1. GC-SCD chromatogram of fluidized catalytic cracking (FCC) gasoline used in
the study.
COO)24H2O precursor per g of KIT-6 were 1.48, 1.25 and 1.27,
respectively. All samples have identical nickel content irrespective
of nickel precursors (30 wt.% of Ni per g of KIT-6) because of com- column was 7.5 cm. Before adsorption tests, the samples were
plete recovery of nickel content in the final material, as confirmed reduced at 650 °C in hydrogen flow at a flow rate of 50–60 mL/
by ICP-OES analysis (Table 2). Template-free/calcined mesoporous min for 4 h. After cooling the column to 30 °C, the model or com-
silica KIT-6 was used to synthesize Ni/KIT-6(NO 3 ) with exactly the mercial gasoline fuels at flow rate of 2 mL/h were introduced.
same nickel content (30 wt.%) using nickel nitrate as a precursor as The treated commercial/model fuel after column adsorptive desul-
stated above. The samples were pressed into small shape particles furization was taken periodically and checked for sulfur content by
and sieved through 80–100 mesh prior to evaluation for adsorptive Hewlett Packard 6890 chromatograph having SCD. Breakthrough
desulfurization. adsorption curves were plotted according to our previous studies
[23]. The sulfur adsorption capacity was obtained using Eq. (1):
2.4. Fuel samples used in evaluation

Z t  
00
v qfuel X i CðtÞ
QðbreakthroughÞ ¼ 1 dt ð1Þ
Fluidized catalytic cracking (FCC) gasoline was used as a real
madsorbent MW sulfur 0 Ci
feed stock and obtained from Qingdao, China. The specifications where Q is the breakthrough capacity of nickel based sample
are summarized in Table 1. The total sulfur content was analyzed (mmolg1),00 v is the column fuel flow rate, madsorbent is mass in the
by using Multi ea3100 total sulfur analyzer. For composition of adsorption column (g), qfuel denote density of fuel used (g/cm3), X i
gasoline, a GC-SCD chromatogram with major peaks related to is the total sulfur fraction (by weight) in fuels, MW sulfur is sulfur
thiophene, 3-methylthiophene (3-MT), 2-methylthiophene (2- molecular weight (g/mol), C i represent the total sulfur content of
MT), 2,4-dimethylthiophene (2,4-DMT), and Benzothiophene fuel (ppmw S) and CðtÞ is sulfur content (ppmw S) of treated fuel
(BTh) are presented as Fig. 1. Standard model compound solutions at different time t (min) interval.
were employed to differentiate different sulfur species in chro-
matogram using similar procedure already reported in literature 2.6. Characterization
[22]. T10, T50 and T50 listed in Table 1 were estimated through
American standard test method for distillation (ASTM D86). The Physical adsorption of N2 was carried out using Micromeritics
model thiophene fuel with sulfur content of 517 ppmw was pre- Tristar 3000 at 196 °C [24] for N2-adsorption-desoption iso-
pared by mixing thiophene with n-octane. therms and pore size distribution of samples. Wide (5–75°) and
small angle (0.7–5°) X-ray diffraction (XRD) were collected on
2.5. Breakthrough evaluation PAN analytical X’Pert PRO MPD diffractometer with Cu Ka radia-
tion at 40 kV and 100 mA. High resolution transmission electron
Breakthrough experiments/tests were carried out in a steel microscopy micrographs were taken using JEOL JEM-2100UHR
made column. For each adsorptive desulfurization test over syn- transmission electron microscope. KBr wafer technique and Nicolet
thesized material, exactly 1 g of sample was packed along with Fourier spectrophotometer was used to collect the FT-IR spectra.
quartz sand. The length occupied by one gram of sample in the For chemical composition of samples, X-ray photoelectron

Table 2
Physiochemical properties of different samples.

Sorbents SBET (m2/g)a VT (cm3/g)b Ni (wt.%)f dp (nm)c d211 (nm)d a0 (nm)e

KIT-6 847 1.13 8.9 9.4 23

Ni-KIT-6(NO 3) 390 0.39 30 8.4 9.9 24.4
Ni-KIT-6(Cl) 490 0.58 29.7 8.3 9.5 23.3

Ni-KIT-6(Ac ) 391 0.48 30 8.3 9.7 23.8
Ni/KIT-6(NO3) 342 0.34 29.5 5.5 9.41 23
Reg. Ni-KIT-6(NO
3) 250 0.29 – 6.5 – –
a
SBET = BET method was used to calculate specific surface area.
b
VT = BHJ method at p/po = 0.98 was employed to calculate total pore volume.
c
dp = For pore diameter BHJ method was used.
d
d211 = (2 1 1)
pffiffiffiplane reflection was taken for calculating spacing.
e
a0 ¼ a0 ¼ 6d211 was used to calculate unit cell constant.
f
Ni = Nickel contents measured by ICP-OES.
242 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248

spectroscopy (XPS) characterization was under taken by PHI-500 degree of different nickel precursors [28,29]. As reported in litera-
Versa Probe spectrometer with an Al-Ka X-rays source ture, the size of an acetate anion (0.159 nm) is larger than nitrate
(1486.6 eV) and operating at 15 kV and 15 mA. H2-Temperature (0.11 nm) [28] and chloride anions (0.11 nm) [29]. Similarly, the
programmed reduction (H2-TPR) of samples to get the reduction water of hydration of acetate precursor (32%) is also higher than
temperature was performed on Auto Chem 2910 (Micromeritics, nitrate (13%) and chloride (25%) precursor. Thus, larger anion size
USA) [1]. TG-DTG analysis of materials was carried out by employ- and higher hydration value result in the poor mixing of nickel acet-
ing thermobalance (STA-499C, NETZSCH). During TG analysis, the ate with as-synthesized support during grinding process and lead
sample was heated from 50 to 700 °C in the presence of air at to the aggregation of nickel species. While, high dispersion in case
25 mL/min. The nickel content of all samples was determined by of nitrate precursor can be attributed to the smaller anion size and
J-A1100 inductively coupled plasma optical emission spectrometry comparatively lower hydration extent. In addition, low melting
(ICP-OES). The water of hydration or hydration degree of nickel point of Ni(NO3)26H2O also increases the mobility of ions on the
precursors was determined by heating it at 100 °C for 12 h in an surface of support and increases the dispersion. The slightly lower
oven to remove water. Weight losses were divided by total weight dispersion of chloride than nitrate precursor can be ascribed to the
of hydrate and finally multiply with 100 to obtain the percent water of hydration of nickel chloride and/or volatility of nickel
water of hydration. chloride precursor at high reduction temperature [30]. High reduc-
tion temperature tends to vaporize extremely small nickel parti-
cles on the support to combine and form larger particles. In
3. Results and discussion addition, the diffraction peaks of metallic nickel in Ni/KIT-6(NO 3)
sample are stronger than that in Ni-KIT-6(NO 3 ) counterpart, which
3.1. Structural and surface analyses of nickel based samples implies the agglomeration of nickel particles into large particle
sizes in the channel of calcined KIT-6. The particle size of nickel
Fig. 2 depicts the low and wide angle XRD patterns of as- estimated according to the XRD peaks analyzed using Scherrer
prepared KIT-6, Ni-KIT-6(NO  
3 ), Ni-KIT-6(Cl ), Ni-KIT-6(Ac ) and equation was about 3 nm for the Ni-KIT-6(NO 3 ) and more than
Ni/KIT-6(NO 3 ) samples. As-prepared KIT-6 exhibited one strong 50 nm for Ni-KIT-6(Ac) and Ni/KIT-6(NO 3 ) samples. This is possi-
intense diffraction peak with two minor diffraction peaks corre- bly due to the confined space in as-prepared KIT-6. Thus, XRD anal-
sponding to the (2 1 1), (2 2 0), and (3 3 2) reflections, (Fig. 2A) ysis suggests that the confined spaces in as-synthesized KIT-6 and
respectively. This is suggesting highly ordered mesoporous KIT-6 anion size in nickel precursors along with hydration degree affect
silica structure [25]. After loading different nickel precursors into the size and dispersion of nickel species greatly over as-
as-prepared KIT-6, a decrease in the peak intensity corresponds synthesized KIT-6.
to (2 1 1) reflection was observed (Fig. 2A), indicating that the Textural properties of samples were determined by N2 adsorp-
nickel species were successfully entered into KIT-6 channels and tion–desorption isotherms and pore size distributions. As shown in
structure of support remained intact [26,27]. However, there is Fig. 3A, Ni-KIT-6(NO  
3 ), Ni-KIT-6(Cl ) and Ni-KIT-6(Ac ) samples
no diffraction peak corresponding to (2 1 1) reflection in case of display type IV isotherms along with an H1 hysteresis loop similar
Ni/KIT-6(NO 3 ) was noticed, confirming that parent structure of to pure as-prepared KIT-6. This is attributed to the well distribu-
calcined KIT-6 were collapsed completely during fabrication pro- tion of nanosize metallic nickel particles throughout the pores of
cess (Fig. 2A). Ni-containing samples [31]. The pore size distribution for Ni-KIT-
The XRD patterns of the samples at wide-angle after one step 6(NO  
3 ), Ni-KIT-6(Cl ) and Ni-KIT-6(Ac ) samples (Fig. 3B) become
H2-reduction treatment is also illustrated in Fig. 2B. A single broad broader and slightly shifted to small pore diameters as compared
diffraction peak at 2h of 44.5° with weak intensity correspond to with as-prepared KIT-6 (8.9 nm). However, the pore diameter of
(1 1 1) diffraction plane of metallic Ni0 was observed in Ni-KIT-6 Ni/KIT-6 is very much lower (5.5 nm). Similarly, an apparent
(NO 3 ) synthesized using as-prepared KIT-6 as support and nickel decrease in surface area of all Ni-containing samples was also
nitrate as a precursor. In the case of Ni-KIT-6(Ac), the diffraction observed (Table 2). This phenomenon is due to well distribution
peaks at 2h of 44.5° and 51.5° Correspond to (1 1 1) and (2 0 0) of nickel particles inside the pores of as-prepared KIT-6 support
diffraction planes of Ni0 are relatively stronger than that in Ni- along with outer surface which prevents the shrinkage of meso-
KIT-6(Cl) and Ni-KIT-6(NO 
3 ), which implies that Ni-KIT-6(NO3 ) porous frameworks during one step H2-reduction treatment pro-

and Ni-KIT-6(Cl ) samples possess higher dispersion degree of cess. Suck kind of investigations are in good agreement with
Ni0 as compared with Ni-KIT-6(Ac) sample. Such trend can be foregoing XRD analysis (Fig. 2). The lack of hysteresis loop and very
ascribed to the shielding effect of the capping anions and hydration weak pore size diameter of Ni/KIT-6(NO 3 ) were caused by the

(211)
(A) (B) (111)
(200)
(220) -
Ni/KIT-6(NO3 )
Intensity (a.u)
Intensity (a.u)

(332)
KIT-6
-
Ni-KIT-6(NO3 )
-
Ni-KIT-6(Cl )
- Ni-KIT-6(Ac )
- -
Ni-KIT-6(Ac ) Ni-KIT-6(Cl )
- -
Ni/KIT-6(NO3 ) Ni-KIT-6(NO3 )

1 2 3 4 5 20 30 40 50 60 70
2 Theta (degree) 2 Theta (degree)
Fig. 2. (A) Low-angle and (B) wide-angle XRD patterns of KIT-6 and nickel based KIT-6 samples after one step H2-reduction strategy.
 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248 243

(A) (B)

Fig. 3. (A) N2 adsorption–desorption isotherms and (B) BJH pore size distributions of KIT-6 and nickel based KIT-6 samples after one step H2- reduction strategy.

0.25 Besides, Ni/KIT-6(NO 3 ) material synthesized by using template

(320) free/calcined KIT-6 exhibited H2 consumption peak at 320 °C
0.20 (Fig. 4D). Thus, TPR results reveal that small and highly interacted
(402) nickel particles with the support KIT-6 required high reduction
TCD signal (a.u.)

(D)
0.15 (380) temperature than bulky isolated particles.
HRTEM images of all samples are presented in Fig. 5. It can be
0.10
(428)
(C) seen that sample Ni-KIT-6(NO 
3 ), Ni-KIT-6(Cl ) and Ni-KIT-6(Ac )


after one step H2-reduction treatment still maintained the ordered

(320)
0.05 mesoporous structure of KIT-6 in accord with XRD and N2 adsorp-
(490) (B) tion isotherms analysis (Figs. 2 and 3). Fig. 5 shows that metallic Ni
0.00 (340) (520) particles with a small average particle size of about 3.8 nm are well
(A)
dispersed and confined into the channels of KIT-6, and large metal-
100 200 300 400 500 600 700 800 lic Ni particles are not observed on the Ni-KIT-6(NO 3 ). On the other
hand, nickel particles with an average particle size larger than
Temperature (oC)
50 nm can be easily observed in Ni/KIT-6(NO 3 ) and Ni-KIT-6
Fig. 4. H2-TPR profile of Ni-KIT-6(NO  
3 ) (A), Ni-KIT-6(Cl ) (B), Ni-KIT-6(Ac ) (C) and (Ac). These HRTEM results are demonstrating the aggregation of
Ni/KIT-6(NO 3 ) (D) samples before H2- reduction strategy. nickel particles over KIT-6, result in the formation of large nickel
particles as shown in Fig. 5 and similar to XRD analysis. In addition,
Ni-KIT-6(Cl) contained small nickel particles but relatively larger
nickel particles aggregation and the use of calcined KIT-6. On the in size compared with Ni-KIT-6(NO 3 ). Thus, HRTEM analysis con-
ground of these N2-adsorption-desoption evaluations, we can say cludes that both as-prepared KIT-6 and nickel precursors highly
that Ni species were located both deep inside the channels and affect the dispersion of nickel species and follow the same order
outside surface in as-synthesized KIT-6 samples, while only on as that of foregoing XRD.
the surface in Ni/KIT-6(NO 3 ). Furthermore, a decrease in N2 FTIR spectra of KIT-6 and Ni-containing KIT-6 samples before
adsorption isotherm intensity (Fig. 3A) and a shift of pore size dis- and after one step reduction process consisted of IR bands at
tribution (Fig. 3B) were observed in Ni-KIT-6(NO 3 ) after regenera- 1080, 800 and 650 cm1, indicating the characteristic symmetric
tion. Similarly, the specific surface area and pore volume (Table 2) and asymmetric vibrations in Si–O–Si bonds in silica
were also reduced to 250 m2/g and 0.29 cm3/g, respectively, indi- Fig. 6A and B [33]. The bands in all synthesized samples at 440
cating partial structural collapse or blockage of channels of meso- and 1625 cm1 can be respectively attributed to the bending vibra-
porous silica KIT-6. tion of O–H and physiosorbed water [33]. The presence of vibration
H2-TPR profiles of synthesized samples before H2-reduction bands at 2850 corresponds to symmetric and at 2975 cm1 to
strategy are displayed in Fig. 4. It can be seen that all Ni- asymmetric stretching vibrations of -CH2 in case of as-prepared
containing unreduced samples can be reduced at a reduction tem- KIT-6 indicating that pores of as-prepared KIT-6 were occluded
perature up to 650 °C. For Ni-KIT-6(NO 3 ), there are two broad and with P123 template (Fig. 6A) [27,34]. The bending vibration of
low intensity reduction peaks at 340 and 520 °C are observed, the template of the same as-synthesized KIT-6 can be observed
which are associated with the reduction of Ni2+ to Ni0 (Fig. 4A). at 1380 cm1. The silanol groups (Si-OH) gave their corresponding
However, the first reduction peak is assigned to the reduction of stretching vibration band at 960 [20]. For sample Ni-KIT-6(NO 3 ),
bulky isolated Ni oxide particles while the second peak is attribu- the band at 1380 cm1 ascribed to N-O of nitrate was observed
ted to the hardly reducible nickel oxide strongly interacted with [20]. After one step H2 reduction process, the band at 960 cm1
framework of KIT-6 [32]. In comparison with Ni(NO3)26H2O syn- become weak in case of as-prepared KIT-6 while the bands at
thesized Ni-KIT-6(NO 
3 ) sample, Ni-KIT-6(Cl ) and Ni-KIT-6(Ac )

2850 and 2975 cm1 corresponds to template disappear. This phe-
samples showed a relatively high intensity reduction peaks at nomenon can be attributed to the decomposition of template and
380 and 320 °C, together with small shoulders (Fig. 4B and C). condensation of silanol groups (Fig. 6B) during one step H2
244 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248

3.8 nm
15 nm
10 nm

3.8 nm 15 nm
3.8 nm
7 nm

3.7 nm 3.8 nm 7.5 nm

3.6 nm
(A) (B)

41 nm 50 nm
58 nm

50 nm
33 nm

70 nm
53 nm
50 nm 55 nm
(C) 41 nm (D)

Fig. 5. HRTEM images of Ni-KIT-6(NO   

3 ) (A), Ni-KIT-6(Cl ) (B), Ni-KIT-6(Ac ) (C) and Ni/KIT-6(NO3 ) (D) samples after H2-reduction strategy.

reduction process. Similarly, the bands derived from nitrate disap- of P123 can be ascribed to absence of catalyzing effect of silica wall
pear in case of Ni-KIT-6(NO 3 ). This is further suggesting that both due to existence of Ni(NO3)26H2O in between P123 and silica wall
removal of template and decomposition of nickel precursor com- of as-prepared KIT-6. No change in Ni(NO3)26H2O weight loss over
pleted in a one-step H2-reduction process instead of repeated as-prepared KIT-6 was observed at a temperature above 500 °C.
one in conventional modification process for nickel based materi- While an opposite trend was observed in KIT-6 (Fig. 7A), indicating
als reported earlier. Moreover, IR spectra shown in Fig. 6B revealed the relationship of silanols consumption with Ni(NO3)26H2O
that the silanols peak intensity in Ni-KIT-6(NO 3 ) obtained from as- conversion similar to that of FT-IR analysis (Fig. 6). Different
prepared KIT-6 is very lower compared with Ni/KIT-6(NO 3 ). Simi- from Ni-KIT-6(NO 
3 ), in case of Ni-KIT-6(Cl ), decomposition of
larly, the peak intensity of silanols of other samples derived from NiCl26H2O and P123 starts simultaneously at 50 °C after desoption
Ni(NO3)26H2O, NiCl26H2O and Ni(CH3COO)24H2O increases in of water which gives a constant weight loss till the temperature
the order Ni-KIT-6(NO  
3 ) < Ni-KIT-6(Cl ) < Ni-KIT-6(Ac ) as shown reaches to 655 °C accompanied with a DTG peak at 155 °C
in Fig. 6B. These FT-IR results concluded that even using as- (Fig. 7A and B). This can be assigned to the early decomposition
synthesized KIT-6; the nickel precursor still has a substantial influ- of the template P123 than NiCl26H2O along with silanols.
ence on silanols consumption in the KIT-6, and hence establishing Similarly, the conversion of both Ni(CH3COO)24H2O and template
a strong and favorable relation in term of nickel dispersion P123 in as-prepared KIT-6 occurred simultaneously and completed
between nickel precursors with KIT-6. in the range of 100–450 °C (Fig. 7A and B). The different tempera-
TG analyses of different samples before one step H2-reduction ture range compared with Ni(NO3)26H2O and NiCl26H2O in
strategy are displayed in Fig. 7. Pure as-prepared KIT-6 gave a as-prepared KIT-6 can be ascribed to the strong interaction of
slight weight loss below 115 °C with a DTG peak at 140 °C due to Ni(CH3COO)24H2O with template P123.
loss of physiosorbed water (Fig. 7A and B) [34]. Weight loss of Thus, TG-DTG analyses indicate that both as-prepared KIT-6
about 23% in the temperature range from 140 to 550 °C and 550 and nickel precursors are crucial factors for nickel dispersion over
to 650 °C was observed giving DTG/DSC profile at 290 °C attributed mesoporous silica KIT-6. As-prepared KIT-6 provides confined
to template P123 removal and dehydroxylation of silanols spaces while nickel precursors interact with mesoporous silica
(Fig. 7A). For Ni(NO3)26H2O in as-prepared KIT-6 in the case of KIT-6. For sample Ni-KIT-6(NO 3 ), decomposition of Ni(NO3)26H2O
Ni-KIT-6(NO 3 ), 33% of weight loss occurred because of the earlier occurred before P123 as stated above which provide evidence for
decomposition of Ni(NO3)26H2O to NiO than template P123 in the location of nickel species in the confined space of KIT-6 [20].
the temperature range of 50–500 °C gave three peaks in the DTG While, there is no such evidence of nickel species in the confined
and DSC profiles as shown in Fig. 7B and C. As can be seen that spaces both in the case of Ni-KIT-6(Cl) and Ni-KIT-6(Ac) [20].
Ni-KIT-6(NO 3 ) exhibited a greater weight loss than pure as- In addition, the same happened with calcined KIT-6 in Ni/KIT-6
prepared KIT-6, indicating the presence of Ni(NO3)26H2O in the (NO 3 ) and result in the absence of those spaces and least
structure of as-prepared KIT-6 [20]. Higher removal temperature dispersion of nickel species. On the other hand, P123 and
 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248 245

- oxidized nickel particles on the surface and only determined the

Ni/KIT-6(NO3 )
bulk while XPS mainly investigate the surface of the samples
- [38,39]. Furthermore, the percentage content of Ni0 and NiO spe-
Ni-KIT-6(Cl )
cies of different nickel precursors in different samples were calcu-
Ni-KIT-6(Ac )
- lated and presented in Table 3 in order to correlate the dispersion
Intensity (a.u.)

extent of nickel precursor with the production of metallic nickel

Ni-KIT-6(NO3 )
- during one step H2-reduction strategy. As listed in Table 3, the
quantity (54%) of reduced nickel in the case of Ni-KIT-6(NO 3 ) is
higher than (38%) Ni/KIT-6(NO 3 ) and the percentage of active/
KIT-6 reduced Ni0 in samples synthesized via using different nickel pre-
960
2850 cursors decreases in the order Ni-KIT-6(NO 
3 ) > Ni-KIT-6(Cl ) > Ni-
1625 650  
1380 800 KIT-6(Ac ) Ni/KIT-6(NO3 ). Thus, these XPS results also revealed the
3440 2975 (A)
1080 effectiveness of both as-synthesized KIT-6 and nickel precursors
4000 3500 3000 2500 2000 1500 1000 for production of more Ni0 species during one step H2-reduction
strategy.
Wavenumber (cm-1) One step H2-reduction strategy for fabrication of nickel-based
mesoporous silica KIT-6 was compared with other nickel based
-
mesoporous silicas reported by Song, Park and Yang groups
Ni/KIT-6(NO3 ) [12,14,25]. Interestingly, it was found that the present strategy
1080 avoid the use of multiple calcinations in their works by directly
- obtaining Ni0-based KIT-6 in H2 atmosphere. Those researchers
Ni-KIT-6(Ac )
provided novel and interesting strategies for nickel dispersions
Intensity (a.u.)

- and synthesis of nickel based materials, but the dispersion

Ni-KIT-6(Cl )
amount was relatively lower than the present investigations even
- with the consumption of a lot of energy and time. Thus, single
Ni-KIT-6(NO3 )
step H2-reduction strategy is a facile, energy and time saving
for well distribution of large amount of nickel species over
KIT-6
KIT-6 support.
1625 800
3440 (B) 960 650 3.2. Adsorptive desulfurization performance for FCC and model fuel
3500 3000 2500 2000 1500 1000 500
Breakthrough curves of different samples for thiophene adsorp-
Wavenumber (cm-1)
tion at temperature of 30 °C are shown in Fig. 9. The least adsorp-
Fig. 6. FT-IR spectra of synthesized samples (A) before and (B) after H2-reduction tion of 0.0336 mmol g1 thiophene (Figs. 9 and 10) over KIT-6 was
strategy. observed, possibly due to absence of active sites for adsorption. As
shown in Fig. 9, the adsorption capacity of KIT-6 was increased
after loading of nickel precursors due to the provision of active
Ni(CH3COO)24H2O in the case of Ni-KIT-6(Ac) decomposes at a sites. The breakthrough adsorption capacity of Ni/KIT-6(NO 3)
higher temperature than that of Ni(NO3)26H2O and NiCl26H2O shown in Fig. 10 is about 0.057 mmol g1 only at a breakthrough
respectively in Ni-KIT-6(NO 3) and Ni-KIT-6(Cl) samples, level of 0 ppmw (Figs. 9 and 10). Comparing with Ni/KIT-6(NO 3 ),
suggesting that Ni(CH3COO)24H2O has a strong interaction with Ni-KIT-6(NO 3 ) captured 0.195 mmol g
1
thiophene at break-
template rather than silica made walls of as-prepared KIT-6. In through volume of 17 mL/g. In addition, adsorption capacity of
contrast, a strong interaction of Ni(NO3)26H2O and NiCl26H2O Ni-KIT-6(NO 
3 ) is much better than Ni-KIT-6(Cl ) (0.115 mmol g
1
)
with silica wall of as-synthesized KIT-6 are responsible for and Ni-KIT-6(Ac) (0.0896 mmol g1) (Figs. 9 and 10). The larger
excellent dispersion of large amount nickel particles in Ni-KIT-6 adsorption capacity might be attributed to the higher amount of
(NO 
3 ) and Ni-KIT-6(Cl ) [20]. However, such kind of interaction reduced/active Ni0 in Ni-KIT-6(NO 3 ) and three-dimensional
of each Ni(NO3)26H2O and NiCl26H2O with silica of branched networks of KIT-6 which provide an easy access for the
as-synthesized KIT-6 is because of silanols as already revealed by diffusion of thiophene molecules to Ni species located deep inside
FTIR characterization. Similar to FT-IR, TG-DTG results also proved the channels during adsorptive desulfurization reaction. Obviously,
the interaction of nickel species with KIT-6 due to silanols. Thus, nickel species in adsorbents function as active species in desulfur-
TG-DTG analysis provides solid proof for the higher nickel ization and can capture thiophene by Ni0-S or Ni-p⁄ bonding inter-
dispersion in the case of Ni-KIT-6(NO 
3 ) and Ni-KIT-6(Cl ) than action [37]. Moreover, the sulfur adsorption capacities of all these

Ni-KIT-6(Ac ). synthesized samples are strongly correlated with the dispersion of
The quantitative analysis of nickel in the as-prepared KIT-6 and nickel species, which has also been verified from XRD, TEM, and
or calcined KIT-6 samples after one step H2-reduction treatment XPS characterizations.
were carried out by XPS for the purpose of relationship of disper- The best Ni-KIT-6(NO 3 ) sample among all in model fuel was
sion of metal precursor with production of metallic nickel species. also employed for deep desulfurization of FCC gasoline (Fig. 11)
As shown in Fig. 8A–D, all the synthesized samples exhibited dif- to test its activity for real fuel analysis. The activity results revealed
ferent Ni 2p3/2 emission lines, indicating the existence of different that the breakthrough volume for sulfur removal in FCC gasoline
oxidation states of nickel. The main Ni 2p3/2 peak appears from 850 was 4 mL g1 and the calculated adsorption capacity of
to 858 eV along with a satellite occurred at 861.5 eV (Fig. 8A–D). As 0.05 mmol g1. At 10 mL breakthrough volume of fuel, the sulfur
shown in Fig. 8, the Ni 2p3/2 XPS spectra fitted by the XPS peak soft- content in fuel reached to 25 ppmw, which is in accord with the
ware give two peaks at 852.9 and 855.5 eV, which are derived from standards of U.S. Environmental Protection Agency (EPA) for
Ni 2P03/2 and Ni 2P2+
3/2, respectively (Table 3) [35–37]. In comparison commercial gasoline [40]. It was observed that in the case of
with XPS, no such evidence for the existence of NiO along with Ni0 model fuel (Fig. 10), the adsorption capacity of FCC gasoline at
species were observed because XRD cannot measure small breakthrough level over Ni-KIT-6(NO 3 ) is much lower, which
246 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248

(A) (B)

(C)

Fig. 7. TG (A), DTG (B) and DSC (C) curves of as-synthesized KIT-6 with and without nickel before one step H2-reduction strategy.

may be attributed to the existence aromatics, olefins and light

sulfur species exist in FCC gasoline (Table 1). The spent Ni-KIT-6
(NO 3 ) adsorbent was regenerated [1] and applied again for adsorp-
(D) tive desulfurization test after reduction to test its stability for sul-
fur removal efficiencies in real fuels. As shown in Fig. 11, the sulfur
concentration was reduced from 510 to 25 ppmw at 6 mL flow of
real gasoline and the corresponding capacity was 0.07 mmol g1,
which is lower than that over fresh Ni-KIT-6(NO 3 ). The decline in
(C) surface area or the partial collapse of KIT-6 framework structure
may be responsible for such decrease (Table 2). Previously, Ni
based MCM-41 was synthesized and reported to adsorb
0.05 mmol g1 of sulfur from model fuel containing 243 ppmw sul-
fur. The lower sulfur adsorption capacity than the present material
(B) may be attributed to the low loading amount of nickel precursor
[37]. 55% Ni supported over SiO2–Al2O3 was also employed for
adsorptive desulfurization of commercial fuels [14,41] and
reported to adsorb 0.01 mmol g1 sulfur both from gasoline and
ULS-diesel much lower than the present work attributed to low
surface area of SiO2-Al2O3 compared with as-synthesized KIT-6.
(A)
In addition, the sulfur adsorption capacity (0.12 mmol g1) over
Ni-KIT-6(NO 3 ) (Fig. 11) is also higher than that (0.08 mmol S/g)
over 16%Ni/c-Al2O3 adsorbent [42] at the 10 mL treated/effluent
volume of FCC gasoline. La-Zeolite (NaY) reported to capture
0.004 mmol g1 of sulfur from FCC gasoline [43], which is signifi-
cantly lower than the present work. These comparative results
Fig. 8. XPS peak fitting of Ni 2p spectra of Ni-KIT-6(NO 
3 ) (A), Ni-KIT-6(Cl ) (B), Ni-
with the present study indicate that Ni based KIT-6 samples are
KIT-6(Ac) (C) and Ni/KIT-6(NO 3 ) (D) samples after H2-reduction strategy. highly promising for adsorptive desulfurization of fuels.
 S. Aslam et al. / Chemical Engineering Journal 302 (2016) 239–248 247

Table 3
XPS Fitting data of Ni 2p3/2 and surface composition of (at.%) after reduction treatment.
2+
Sorbent Ni 2p3/2 Ni 2p03/2 Surface composition (at.%)
Eb (eV) ri (%) Eb (eV) ri (%) Ni Si C O
Ni-KIT-6(NO3) 955.5 46 952.9 54 3.26 26.67 6.81 63.25
Ni-KIT-6(Cl) 955.5 54 952.9 46 1.53 27.88 4.05 66.54

Ni-KIT-6(Ac ) 955.5 60 952.9 40 1.32 28.14 8.06 62.48
Ni/KIT-6(NO3) 955.5 62 952.9 38 2.62 27.36 6.19 63.83

Initial Sulfur Concenteration: 510 ppmw

500
ppm total Sulfur eluted

ppm Sulfur eluted

400

300

200 KIT-6
-
Ni-KIT-6(NO3 )
-
100 Ni-KIT-6(Cl )
-
Ni-KIT-6(Ac )
-
Ni/KIT-6(NO3 )
0
5 10 15 20 25 30
mL Thiophene feed/g sorbent
Fig. 9. Breakthrough curves of thiophene fuel over KIT-6, Ni-KIT-6 and Ni/KIT-6
Fig. 11. A breakthrough curve of FFC gasoline fuel over fresh and regenerated Ni-
samples collected at 30 °C.
KIT-6(NO 3 ) sample.

0.20
Breakthrough Sulfur Adsorption Capacity

interactions with support. Characterization results revealed that

0.18 KIT-6
- well dispersed NiO form more Ni0 via single step H2-reduction pro-
Ni-KIT-6(NO3 )
0.16 -
cess and adsorb more sulfur compounds via Ni0-S or Ni–p⁄ interac-
Ni-KIT-6(Cl )
- tions. Breakthrough tests showed that Ni-KIT-6(NO 3 ) can capture
0.14 Ni-KIT-6(Ac )
Ni/KIT-6(NO3 )
- 0.195 and 0.12 mmol g1 of sulfur from model fuel and FCC gaso-
(mmol.g )

0.12 line, respectively. Thus, nickel precursors, synthesis strategy, and

-1

state of supports play an active role for the improved sulfur

0.10
adsorption capacity of adsorbents.
0.08
0.06 Acknowledgements
0.04
We are thankful to the joint financial support of China Univer-
0.02 sity of Petroleum (East China), Qingdao, P.R. China and Abdul Wali
0.00 Khan University Mardan Pakistan for this work.
1 2 3 4 5
Adsorbents
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