Applied Catalysis A: General 467 (2013) 224234

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Applied Catalysis A: General

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

Metathesis of 2-butene to propylene over W-mesoporous molecular

sieves: A comparative study between tungsten containing MCM-41
and SBA-15
Tazul Islam Bhuiyan a , Palani Arudra a , Muhammad Naseem Akhtar a , Abdullah M. Aitani a ,
Raed H. Abudawoud b , Mohammed A. Al-Yami a , Sulaiman S. Al-Khattaf a,
a
b

Center of Research Excellence in Petroleum Rening and Petrochemicals, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
Research & Development Center, Saudi Aramco, Dhahran 31311, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 12 February 2013
Received in revised form 8 July 2013
Accepted 19 July 2013
Available online 29 July 2013
Keywords:
Mesoporous silica
Metathesis
MCM-41
SBA-15
2-Butene
Propylene
Tungsten oxide

a b s t r a c t
Mesoporous silica (MCM-41 and SBA-15) having tungsten oxide in the framework was synthesized by
hydrothermal crystallization process using CTAB and P123 as structure directing agents, respectively.
Tungsten oxide was supported on the MCM-41 and SBA-15 by wet impregnation method for a comparative study. The synthesized materials were characterized by XRD, N2 adsorptiondesorption, NH3 -TPD,
pyridine-FT-IR, UVvis DRS and Raman spectroscopy techniques. The catalysts were used to perform
metathesis reaction of 2-butene in a xed-bed reactor at different temperatures and under atmospheric
pressure. It was observed that catalysts having tungsten oxide in the framework of mesoporous silica
exhibited higher activity as compared to tungsten oxide impregnated catalysts. The results revealed that
WO3 -MCM-41(30) catalyst has much higher activity at a low temperature (450 C) as compared to WO3 SBA-15(30). At 550 C, WO3 -MCM-41(30) and WO3 -SBA-15(30) showed comparable activity with highest
propylene yield of 39 mol% and 37 mol%, respectively. The higher metathesis activity of WO3 -MCM-41
catalysts can be related to the well-dispersed active tetrahedral tungsten oxide species as evidenced from
XRD, UVvis DRS and Raman spectroscopy results.
2013 Published by Elsevier B.V.

1. Introduction
The demand for propylene is increasing for downstream
applications such as polypropylene, acrylonitrile, cumene, oxoalchohols, propylene oxide, acrylic acid and isopropyl alcohol and
polygas chemicals [1]. Several on-purpose propylene production
technologies are being developed to meet the high demand for
propylene which is usually produced from naphtha steam cracking
and renery uid catalytic cracking (FCC) units [2]. Olen metathesis is an important organic reaction that transforms less desired
olens to higher desired ones through rearrangement of a pair of
C C bonds and currently it is widely used for the production of
propylene from low-value C4 olens [3,4]. Currently, the Olens
Conversion Technology (OCT) process licensed by Lummus Technology is the only commercial olen metathesis technology in the
petrochemical industry [5]. The key step in olen metathesis is
the intermediacy of metal carbene active species and consequently
the formation of unstable metallocyclobutane. Both homogeneous

Corresponding author. Tel.: +966 3 860 1429; fax: +966 3 860 4234.
E-mail address: skhattaf@kfupm.edu.sa (S.S. Al-Khattaf).
0926-860X/$ see front matter 2013 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.apcata.2013.07.034

and heterogeneous catalysts are used in the metathesis reaction.

However, heterogeneous catalysts are widely accepted due to the
advantage of higher thermal stability, easy separation from the
reaction products and regeneration [6]. The most successful heterogeneous catalysts for olen metathesis are supported rhenium,
molybdenum and tungsten oxides [7].
Rhenium oxide catalysts supported on alumina or
silicaalumina are the most active and selective under mild
conditions [8]. However, the cost of rhenium compounds are high
[5], the catalyst activity with low Re loading (<10 wt%) is poor [9]
and the catalysts are easily deactivated [10]. At the same time,
molybdenum oxide catalysts supported on alumina [11], siliceous
material [12] and silicaalumina [13] have received much attention
because of their relatively low price, and their high activity under
mild conditions. On the other hand, tungsten oxide supported
on SiO2 [2,14,15], -Al2 O3 [16] and -Al2 O3 -HY [1,17,18] require
much higher temperature (250500 C) to achieve acceptable
metathesis activity. Nevertheless, due to long online lifetime,
considerable resistance to poisons and continuous regeneration
without negative effect on catalyst structure, tungsten based catalysts remain the most attractive for commercial use [19]. Catalytic
activity of tungsten oxide catalysts depends on the oxidation

T.I. Bhuiyan et al. / Applied Catalysis A: General 467 (2013) 224234

state of tungsten species [19], the content of tungsten oxide

[2,19,20], the properties of support and the pretreatment condition
[21].
Mesoporous molecular materials with their large surface
area and large void volume, exhibit high catalytic activity after
introducing of heteroatoms into the framework [22]. SBA-15 is a
mesoporous silica having large pores (520 nm), hexagonal structure, large channel diameter and it is thermally, hydro-thermally
robust due to its thick framework walls (36 nm) [23]. Deposition of
tungsten into SBA-15 activated the support which allowed higher
diffusion rate [24]. Chen et al. reported that, tungsten oxide was
effectively incorporated into the framework of SBA-15 for C4 olen
metathesis exhibiting 92.6% conversion of 1-butene and 27.0%
propylene yield [25]. Direct tungsten incorporation using hydrothermal method has advantages such as high tungsten species
dispersibility and strong interaction between tungsten species and
silica compared to conventional impregnation method [14,25,26].
Mesoporous silica, MCM-41, shows a highly ordered hexagonal
array of one-dimensional channel with a very narrow pore size
distribution [5]. To the best of our knowledge, few publications
reported tungsten distribution in MCM-41 and none were tested
for 2-butene metathesis [27]. MCM-41 has been used as a support for Mo and Ru-based metathesis catalysts for 1-heptene cross
metathesis [28].
In this study, we have focused on three main effects on 2-butene
metathesis over tungsten supported SBA-15 and MCM-41; (i) the
synthesis method and support architecture of tungsten oxide catalyst, (ii) the concentration of active WO3 species on the support,
and (iii) effect of reaction temperature.
2. Experimental
2.1. Materials
Pluronic 123(EO20 PO70 EO20 ), tetraethylorthosilicate (98%,
TEOS), sodium tungstate (99.99%, NaWO4 2H2 O), hydrochloric
acid (36%), sodium metasilicate (98%, Na2 SiO3 ), cetyltrimethylammonium bromide (98%, CTAB), anhydrous ethyl acetate (99.8%)
and ammonium metatungstate [99%, (NH4 )6 H2 W12 O40 xH2 O]
were purchased form SigmaAldrich and used without any further
purication. 2-Butene with 99.9% purity (50% cis-2-butene and
50% trans-2-butene) was purchased from Saudi Industrial Gas
Company, Saudi Arabia.
2.2. Support synthesis
Two types of mesoporous supports, SBA-15 and MCM-41 were
synthesized using the hydrothermal method.
2.2.1. Mesoporous SBA-15
Hexagonally ordered mesoporous SBA-15 was synthesized
using triblock co-polymer P123 (EO20 PO70 EO20 ) as structure directing agent and tetraethylorthosilicate (TEOS) as silica precursor.
Synthesis of SBA-15 was performed according to the procedure
reported in literature [25]. In a typical synthesis, 6 g of Pluronic 123
was dissolved to 210 ml of 2 M HCl and stirred at 40 C to achieve
a transparent solution. After 34 h, 12.8 g TEOS was quickly added
into the solution. The solution was stirred at 95 C for 2 days. The
solid products obtained were washed with water and dried at 80 C
overnight. The template was removed by calcination in air at 550 C
for 5 h. The molar ratio of the gel composition is 1 SiO2 :0.0167
P123:5.82 HCl:190 H2 O.
2.2.2. Mesoporous MCM-41
Mesoporous support MCM-41 was synthesized by using the
sodium metasilicate (Na2 SiO3 ) and cetyltrimethyl-ammonium

225

bromide (CTAB) as a source of silica and structure directing agent,

respectively. Synthesis was performed according to the method
described in literature [29]. 9.96 g of sodium metasilicate with
150 ml H2 O was stirred at 85 C for 30 min. Then, 9.8 g of CTAB was
added to the solution and stirred for 10 min. 30 ml ethyl acetate
was rapidly added into the solution under vigorous stirring. The
stirring was continued for 24 h at 85 C. The solid products were
recovered by ltration. After washing with deionized water several times, the solid was air-dried and then calcined in air at 600 C
for 4 h to remove the template. In this procedure, cheap and convenient sodium silicate was used as an inorganic silica precursor
instead of expensive organic TEOS and ethyl acetate was employed
as the acid producing precursor instead of a conventional strong
acid, such as HCl or H2 SO4 . The synthesis gel molar composition is
1 SiO2 :0.335 CTAB:3.8 EtOAc:120H2 O.

2.3. Catalyst synthesis

Several catalysts were synthesized by supporting tungsten on
mesoporous silica SBA-15 & MCM-41 using hydrothermal crystallization and wet impregnation procedures (Table 1). The details of
the synthesis procedure are given below.

2.3.1. W containing SBA-15 by direct hydrothermal method

(WO3 -SBA-15)
Sodium tungstate (NaWO4 2H2 O) was used as the source of
tungsten ion for the synthesis of WO3 -SBA-15 by direct hydrothermal method. In a typical synthesis of WO3 -SBA-15, tungsten
was incorporated into the framework of mesoporous support
SBA-15 depending upon the Si/W molar ratio. Pluronic 123 was
dissolved in HCl and TEOS was added with vigorous stirring. Then,
calculated amount of sodium tungstate solution was added to
the solution and stirred at 95 C for 3 days under hydrothermal
conditions. The resultant solid was ltered, dried and calcined at
550 C for 5 h. The catalysts obtained in this way were identied
as WO3 -SBA-15(x), where x represented the molar ratio of silicon to tungsten (Si/W). The molar ratio of the gel composition is
1 SiO2 :0.30.6 WO3 :0.0167 P123:5.82 HCl:190 H2 O.

2.3.2. W containing MCM-41 by direct hydrothermal method

(WO3 -MCM-41)
In a typical synthesis of WO3 -MCM-41, the solution of sodium
tungstate was added into the solution of sodium metasilicate and
CTAB, depending upon the Si/W molar ratio. Then ethyl acetate
was added as an acid producing precursor and the solution was
stirred for 24 h at 85 C under hydrothermal conditions. After ltration, the solid was air-dried and calcined at 600 C for 4 h. The
catalysts obtained in this way were identied as WO3 -MCM41(x),
where x represents the molar ratio of silicon to tungsten (Si/W).
The synthesis gel molar composition is 1 SiO2 :0.30.6 WO3 :0.335
CTAB:3.8 EtOAc:120 H2 O.

2.3.3. Impregnation method (WO3 /SBA-15 and WO3 /MCM-41)

WO3 /SBA-15 and WO3 /MCM-41 catalysts with different tungsten loading in the range of 5 and 10 wt% of WO3 were prepared
by wet impregnation method. Aqueous solution of ammonium
metatungstate [(NH4 )6 H2 W12 O40 xH2 O] and the siliceous support
SBA-15 or MCM-41 were mixed together and stirred for 3 h. Then
the impregnated product was dried in an oven at 80 C for 12 h and
calcined at 550 C for 5 h. The catalysts obtained in this way were
identied as WO3 /SBA-15(x) and WO3 /MCM-41(x) where x is the
molar ratio of silicon to tungsten (Si/W).

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Table 1
Physico-chemical properties of synthesized catalysts.
Samples
a

MCM-41
WO3 /MCM-41(35)b
WO3 -MCM-41(30)a
WO3 -MCM-41(50)a
SBA-15a
WO3 /SBA-15(35)b
WO3 -SBA-15(30)a
WO3 -SBA-15(60)a

dspacing (nm)

% of WO3 (ICP-AES)

Surface area (m2 /g)

Pore diameter (nm)

Total pore volume (cc/g)

3.75
3.61
4.32
4.07
5.53
5.69
5.58
5.97

10
7.43
4.91

10
9.19
4.92

1056
419
680
714
833
468
501
571

4.4
4.2
4.9
4.7
4.4
4.3
6.9
6.2

1.169
0.453
0.785
0.82
0.939
0.636
0.777
0.988

Si/W molar ratio for each catalyst shown in the parenthesis; the d spacing for MCM-41 and SBA-15 catalyst was calculated using [1 0 0] reection and [1 1 0] reection
respectively.
a
Synthesized by hydrothermal method.
b
Synthesized by impregnation method.

2.4. Catalyst characterization

2.4.1. X-ray powder diffraction
The samples were characterized by the X-ray powder diffraction (XRD) method, using a Rigaku Mini-ex II system using nickel
at a scanning rate of 1 min1
ltered CuK radiation ( = 1.5406 A)
in the 2 range of 1.350 . The X-ray tube was operated at 40 kV
and 30 mA. The amounts of WO3 present in the nal samples were
analyzed using ICP-AES (Ultima 2, Horiba Scientic).
2.4.2. N2 adsorptiondesorption
The surface areas of the samples were measured by nitrogen adsorption at 196 C using AUTOSORB-1 (Quanta Chrome).
Before adsorption measurements, samples (ca. 0.1 g) were heated
at 220 C for 2 h under nitrogen ow. The nitrogen adsorption
isotherms of calcined materials were measured at liquid nitrogen
temperature (196 C). The surface areas and pore diameters were
calculated by the BrunauerEmmettTeller (BET) method and the
BarrettJoynerHalenda (BJH) method, respectively.
2.4.3. Temperature programmed desorption of ammonia
Temperature-programmed desorption of ammonia (TPD) was
performed with BEL-CAT-A-200, chemisorption apparatus. This
apparatus consists of a gas mixing unit, quartz micro reactor and a
thermal conductivity detector (TCD). Samples were pretreated in a
stream of He (50 ml/min) at 500 C for 1 h. Then, NH3 was adsorbed
at 100 C for 25 min. In order to remove loosely bounded ammonia,
samples were purged with He stream for 1 h at 100 C. Then, the
samples were heated again from 100 to 700 C at a heating rate of
10 C/min in a ow of He (25 ml/min) and the desorbed NH3 was
monitored by a TCD detector.
2.4.4. Pyridine adsorption by FT-IR
The acidity of synthesized material was analyzed by pyridine
adsorption followed by FT-IR study. The catalyst sample was nely
ground and pressed into a self-supporting wafer. The wafers were
calcined under vacuum at 400 C for 1 h, followed by exposure of
pyridine vapor. The adsorbed pyridine was desorbed at various
temperatures (150350 C). The thin wafer was placed in the FT-IR
cell and the spectrum was recorded on a Nicolet FT-IR spectrometer
(Magna 500 model). The difference between the spectra of pyridine
adsorbed on the samples and that of reference was obtained by
subtraction. The amount of Brnsted acid sites (B) and Lewis acid
sites (L) were calculated using the following equation as reported
in literature [30].
C(pyridine on B sites) = 1.88 IA(B)R2 /W.
C(pyridine on L sites) = 1.42 IA(L)R2 /W.

where C = concentration (mmol g1 catalyst); IA(B, L) = integrated

absorbance of B or L band (cm1 ); R = radius of catalyst disk (cm);
W = weight of disk (mg).
2.4.5. Raman spectroscopy
Raman spectra were recorded at room temperature on Horiba
Jobin Yvon in situ Raman, iHR 320 with synapse CCD detector (excitation line, 532.5 nm of an Ar+ ion laser; source power, 4060 mW;
resolution, 4 cm1 ).
2.4.6. UVvis DRS
UVvis DR spectra were recorded on a JASCO V-670 spectrophotometer at 200 nm/min scan rate with BaSO4 as reference.
2.5. Catalysts evaluation
The metathesis reaction of 2-butene (1:1 mixture of trans2-butene & cis-2-butene) was performed in a xed-bed tubular
reactor (stainless steel tube grade 316 material, 0.312 inch
ID 0.562 inch OD 8 inch length). In a typical experiment, the
reactor was charged with 2 ml of catalyst previously sieved to a
particle size of 0.51.0 mm diameter. The catalyst sample was rst
activated in a nitrogen stream at 550 C for 1 h. The ow rates of feed
(2-butene) and N2 were maintained at 5.0 ml/min and 25 ml/min,
respectively, during the reaction. The metathesis reaction was carried out at different temperatures, ranging between 450 and 550 C,
GHSV (gas hourly space velocity) of 900 h1 , 5 h time-on-stream
(TOS) and atmospheric pressure. The quantitative analysis of the
reaction products was carried out on line using Varian GC with FID
(Varian 450-GC), equipped with a CP-Al2 O3 /Na2 SO4 column (50 m
length 0.32 mm I.D. df = 5 m). The GC was programmed from
50 to 90 C at a heating rate of 8 C/min (hold it for 10 min at 90 C)
and 90 to 190 C at a heating rate of 10 C/min (hold it for 5 min
at 190 C). Helium was used as carrier gas with a constant ow of
30 ml/min.
3. Results and discussion
3.1. Catalyst characterization
3.1.1. X-ray powder diffraction
The results of low angle powder X-ray diffraction (XRD) patterns for all samples based on MCM-41 are presented in Fig. 1.
The peak at 2 ranging from 1.5 to 2.5 is indicative of MCM41 structure. The intense peak at 1.8 is due to [1 0 0] reection
and the weak broad signals between 2.5 and 4 (2) are due
to [1 1 0], [2 0 0] and [2 1 0] reections. The d-spacing values of
these samples are presented in Table 1. These peaks were indexed
by Beck et al. [31] for the hexagonal unit. These XRD patterns
coincide with the data already reported in the literature [32].

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227

Fig. 1. XRD patterns of different samples (a) MCM-41, (b) WO3 -MCM-41(50), (c) WO3 -MCM-41(30), (d) WO3 /MCM-41(73), (e) WO3 /MCM-41(35) at (A) low angle and (B)
wide angle.

Incorporation of tungsten into the MCM-41 framework resulted in

reduction of [1 0 0] reection intensity for WO3 -MCM-41(30) and
WO3 -MCM-41(50) samples due to the change in electron density
of the tungsten incorporated materials [33]. In the case of impregnated samples, apart from the reduction in peak intensity, a small
shift in the [1 0 0] reection was also observed. The intensity of the
[1 0 0] reection decreased drastically and the [1 1 0] and [2 0 0]
reections are disappeared completely due to the impregnation
of WO3 oxide. The d spacing values of 4.32 nm and 4.07 nm were
observed for WO3 -MCM-41(30) and WO3 -MCM-41(50), respectively. In the case of the WO3 /MCM-41(35), d spacing value was
smaller than parent material. Very small peaks at 2230 (2) corresponding to the crystalline phase of WO3 were observed for
the WO3 -MCM-41(30), whereas no peak was observed for WO3 MCM-41(50). In the case of impregnated samples, strong peaks of
crystalline WO3 were observed in the range 25 to 35 (2). The
intensity of crystalline WO3 peaks was increased with an increase
in W loading.
The X-ray diffraction patterns of SBA-15, WO3 -SBA-15 and
WO3 /SBA-15 samples are shown in Fig. 2 and d spacing values are
given in Table 1. Two diffraction peaks in the region of 2 = 1.52 ,
which can be indexed to the [1 1 0] and [2 0 0] reections characteristic of the p6mm hexagonal symmetry, were observed for the
SBA-15 catalysts [34]. In all cases, [1 0 0] reection (2 < 1.5 ) was
not observed due to limitation of XRD instrument. The d spacing
values for all the catalysts were calculated using [1 1 0] reection
as shown in Table 1. There is no signicant difference in [1 1 0]
and [2 0 0] reections for WO3 -SBA-15 catalyst samples, whereas in

case of WO3 /SBA-15 catalysts the peak intensities were decreased

with increase in amount of WO3 due to poor dispersion. There were
small peaks assigned to the crystalline phase of WO3 as observed
for WO3 -SBA-15 (30 and 60) samples. However, WO3 impregnated
on SBA-15 has strong crystalline WO3 peaks compared with hydrothermal synthesized WO3 -SBA-15 materials. The amount of WO3
present in the catalysts was analyzed by ICP-AES and is presented
in Table 1.
3.1.2. N2 adsorptiondesorption
Table 1 summarizes the textural properties of the supports
and catalysts calculated from nitrogen adsorption studies. The
isotherms of nitrogen adsorption for the calcined MCM-41 materials are shown in Fig. 3A. The isotherm shows three well-dened
stages and they coincide with those already reported in the literature [27]. All MCM-41 samples show a typical type IV adsorption
isotherm with steps of capillary condensation in the primary mesopores. It is evident from these isotherms that high mesostructural
ordering and narrow pore size distribution were attained. The
surface areas of the catalysts decreased in the order; WO3 /MCM41(35) < WO3 -MCM-41(30) < WO3 -MCM-41(50) < Si-MCM-41. The
pore volumes also decreased in the same order due to the presence
of textural mesoporosity. The surface area of WO3 /MCM-41(35) is
lower than that of other catalysts probably due to the sintering of
tungsten metal itself and/or tungsten metal and silica support [15].
The isotherms of SBA-15 samples are presented in Fig. 3B.
These materials exhibit type IV classication, characteristic of
mesoporous materials. According to the IUPAC classication, the

Fig. 2. XRD patterns of different samples (a) SBA-15, (b) WO3 -SBA-15(60), (c) WO3 -SBA-15(30), (d) WO3 /SBA-15(73), (e) WO3 /SBA-15(35) at (A) low angle and (B) wide
angle.

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Fig. 3. N2 adsorption isotherm of different samples, (A) MCM-41 based samples (a) MCM-41, (b) WO3 -MCM-41(50), (c) WO3 -MCM-41(30), (d) WO3 /MCM-41(35), and (B)
SBA-15 based samples (e) SBA-15, (f) WO3 -SBA-15(60), (g) WO3 -SBA-15(30), (h) WO3 /SBA-15(35).

hysteresis loops of the WO3 -SBA-15 can be classied as the H1

type [26]. H1 is associated with a more uniform pore distribution.
A sharp increase in adsorbed volume at P/P0 of approximately 0.70
arising from capillary condensation of nitrogen within the uniform mesoporous structures. The surface area and pore volume
both shows a monotonic decrease with increasing concentration
of tungsten (Table 1). According to Table 1, WO3 -SBA-15(30) and
WO3 -SBA-15(60) materials have high surface area compared to
impregnated WO3 /SBA-15(35) due to the presence of well dispersed WO3 in the framework.
3.1.3. Temperature programmed desorption of ammonia
NH3 -TPD proles for the supports and catalysts are shown in
Fig. 4 and the total acidity (combination of weak and medium acid
sites) results are presented in Table 2. After Gaussian deconvolution, two peaks corresponding to weak (100300 C) and medium
(300500 C) sites were obtained. As shown in Fig. 4, a week
ammonia desorption peak was observed at 140 C for MCM-41
and 180 C for SBA-15. With increasing tungsten amount in the
framework, the intensity of ammonia desorption peak at 180 C
was increased along with some medium acid site peaks observed
above 350400 C. The total acidity of WO3 -SBA-15(30) was slightly
higher than that of WO3 -MCM-41(30). In the case of impregnated
samples, the presence of WO3 on the external surface of the catalyst was observed and it creates Lewis acid centers of bulky WO3
as reported in literature [4,14]. Impregnated samples have very
small amount of tungsten species deposited on the inner surface
of the pores and most of them are incorporated into the walls of

the material and therefore not accessible for ammonia molecules.

These results were in accordance with results of XRD. Higher acidity of WO3 -SBA-15(30) and WO3 -MCM-41(30) exists due to the
presence of more Si-O-W bonds, which are predominately formed
during hydrothermal process.
3.1.4. Raman spectroscopy
Raman spectra of the supports and catalysts are shown in
Fig. 5. Three intense strong peaks were observed at 265, 707 and
797 cm1 for all the catalyst corresponding to crystalline WO3
species. These peaks have been assigned to the symmetric stretching mode of W O, bending mode of W O and the deformation
mode of W O W, respectively [26]. It is obvious that pure silica
does not have WO3 species, therefore no peaks were observed. A
small peak at 970 cm1 was assigned to the symmetric stretching
mode of the terminal W O bond of the tetrahedrally coordinated
tungsten oxide species [3638], which are considered as active
sites for metathesis reactions [39]. Another peak at about 900 cm1
could be related to the incorporation of the transition metal ions
in the silica framework [37]. It is also a typical evidence for the
isomorphous substitution of silicon by tungsten in the WO3 -SBA15 catalysts. High intensity crystalline peaks were observed for
the impregnated samples with 10% WO3 loadings compared to
WO3 -MCM-41 or WO3 -SBA-15 framework catalysts. This clearly
indicates that more octahedral tungsten species are present in
impregnated samples due to poor dispersion of tungsten oxides. On
the other hand, WO3 -MCM-41 or WO3 -SBA-15 materials show less
intense crystalline peaks with tetrahedrally coordinated tungsten

Fig. 4. NH3 -TPD proles of different samples, (A) MCM-41 based samples (a) MCM-41, (b) WO3 -MCM-41(50), (c) WO3 -MCM-41(30), (d) WO3 /MCM-41(35), and (B) SBA-15
based samples (e) SBA-15, (f) WO3 -SBA-15(60), (g) WO3 -SBA-15(30), (h) WO3 /SBA-15(35).

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229

pyridine and subsequent evacuation at 150 C. The Py-FT-IR spectrum recorded after adsorption of pyridine at room temperature on
the pure MCM-41 or pure SBA-15 shows two major peaks at 1595
and 1445 cm1 , ascribed to pyridine coordinately bonded to weak
surface Lewis acid sites. These peaks disappeared after outgassing
at 350 C. In case of WO3 -MCM-41 and WO3 -SBA-15 samples three
additional peaks at 1545 and 1635 cm1 were also observed due
to protonated pyridine bonded to surface Brnsted acid sites, indicating the presence of tungsten-incorporated species [35,36]. The
peak at 1485 cm1 has been identied as combination of both Lewis
and Brsted acid sites [30]. The intensities of all of these bands
were decreased after outgassing at 350 C (see supporting information Fig. S1 for SBA-15). Similar spectra are recorded for tungsten
impregnated samples of SBA-15 and MCM-41, the number of the
Lewis and Brnsted acid sites decreased after outgassing at 350 C.
The IR bands near 1445 cm1 and 1545 cm1 were used for calculation of Lewis and Brnsted acid sites respectively. The amount of
Lewis and Brnsted acid sites was higher for WO3 -MCM-41(30) as
compared to WO3 -MCM-41(50) due to increase in the tetrahedrally
co-ordinated tungsten oxide species (Table 2). This observation is
a good evidence for better catalytic activity of WO3 -MCM-41(30)
compared to WO3 -MCM-41(50). It can be concluded that the presence of Brnsted acid sites in the tungsten containing SBA-15 or
MCM-41 samples are related to the presence of tetrahedrally coordinated tungsten oxide species.

Fig. 5. Raman spectra of different samples (A) MCM-41 based samples (a) MCM41, (b) WO3 /MCM-41(35), (c) WO3 -MCM-41(30) and (B) SBA-15 based samples (d)
SBA-15, (e) WO3 /SBA-15(35) (f) WO3 -SBA-15(30).

species. The less intensity of crystalline WO3 peaks in WO3 -MCM41(30) compared to WO3 -SBA-15(60) indicates high dispersion of
WO3 in the framework.
3.1.5. Pyridine adsorption by FT-IR
Pyridine adsorption measured by IR spectroscopy was carried
out to evaluate the strength and types of acid sites present in the
tungsten impregnated and framework samples. Fig. 6 shows the FTIR spectra of the all the catalysts recorded after the adsorption of

3.1.6. UVvis DRS

Diffuse reectance spectra of tungsten supported samples in
the region of 200600 nm are shown in Fig. 7. This method is
very sensitive for distinguishing the species between incorporated
metal and extra-framework metal oxides in different heteroatomic
mesostructures. The spectrum of sodium tungstate presents a
spinel structure at 230 nm which mainly implies the presence
of ligand to metal charge transfer involving isolated transition
metal sites and is considered a direct proof for the presence of
framework tungsten oxide species in tetrahedral co-ordination
[27,40]. This band was not observed in case of pure SBA-15 and
MCM-41. The WO3 -SBA-15(30) and WO3 -MCM-41(30) catalysts
exhibited a similar band at 230 nm, which could be attributed to
the presence of isolated [WO4 ]2 tetrahedral species in the catalysts. On the other hand, the spectra of impregnated samples,
WO3 /SBA-15(35) and WO3 /MCM-41(35) have a less intense band at
230 nm, indicating small concentration tetrahedral tungsten oxide
species. The second band at 263 nm may be attributed to isolated tungsten species or low-condensed oligomeric tungsten oxide

Fig. 6. FT-IR spectra of pyridine adsorbed on different samples at 150 C, (A) MCM-41 based samples (a) MCM-41, (b) WO3 -MCM-41(50), (c) WO3 -MCM-41(30), (d) WO3 /MCM41(35), (B) SBA-15 based samples (e) SBA-15, (f) WO3 -SBA-15(60), (g) WO3 -SBA-15(30) and (h) WO3 /SBA-15(35). B = Bronsted acidity; L = Lewis acidity.

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Table 2
Acid sites characteristics of tungsten incorporated and impregnated SBA-15 and MCM-41 catalysts.
Samples

MCM-41
WO3 /MCM-41(35)
WO3 -MCM-41(30)
WO3 -MCM-41(50)
SBA-15
WO3 /SBA-15(35)
WO3 -SBA-15(30)
WO3 -SBA-15(60)

NH3 TPD (mmol g1 )a

FT-IR chemisorbed pyridine (mmol g1 )

TA

L.T.
<300 C

H.T.
300550 C

B
150 C

L
150 C

B
250 C

L
250 C

0.039
0.160
0.391
0.325
0.035
0.108
0.458
0.357

0.039
0.080
0.210
0.140
0.035
0.096
0.270
0.180

0.00
0.080
0.181
0.185
0.00
0.013
0.188
0.177

0.0233
0.0318
0.1527
0.0608
0.0265
0.0347
0.1086
0.0433

0.3611
0.1889
0.2581
0.2410
0.3818
0.1715
0.3521
0.1979

0.0033
0.0205
0.0484
0.0241
0.0056
0.0152
0.0539
0.0208

0.1155
0.0709
0.1685
0.1036
0.1397
0.0667
0.1555
0.0952

TA = total acidity; L.T. = low temperature; H.T. = high temperature; B = Bronsted acidity (peaks at 1545 cm1 ); L = Lewis acidity (peaks at 1445 cm1 ).
a
Calculated from the areas of Gaussian deconvolution bands.

species. A broad band at 350400 nm was observed for ammonium metatungstate having mainly octahedral tungsten species.
The peak at 375 nm was observed for WO3 /SBA-15(35), WO3 /MCM41(35) and WO3 -SBA-15(30) catalysts indicated the presence of
octahedral tungsten oxide species. This band was not observed in
case of WO3 -MCM-41(30) catalyst indicating the presence of more
tetrahedral tungsten oxide species present in the catalyst.

3.2. Reaction studies

A systematic study of metathesis reactions of 2-butene over
tungsten oxide supported mesoporous molecular sieves (SBA-15
and MCM-41) was performed. 2-Butene can undergo a series
of different reactions e.g. isomerization, metathesis, oligomerization, cracking etc. All possible reactions of 2-butene are presented

Scheme 1. Possible reaction pathways for 2-butene metathesis over W-based heterogeneous catalyst.

T.I. Bhuiyan et al. / Applied Catalysis A: General 467 (2013) 224234

231

Fig. 7. UVvis diffuse reectance spectra of various samples (a) Na2 WO4 2H2 O,
(b) WO3 -SBA-15(30), (c) WO3 -MCM-41(30), (d) WO3 /SBA-15(35), (e) WO3 /MCM41(35), (f) ammonium metatungstate.

in Scheme 1 [41]. Metathesis reaction between 2-butene and

1-butene to produce propylene and 2-pentene is termed as
Metathesis I. Apart from Metathesis I, propylene can also be produced by metathesis between 2-butene and ethylene (Metathesis
II), as well as 2-butene with isobutylene (Metathesis III). Metathesis IV is a reaction between isomerized products 1-butene and
isobutylene to produce ethylene with hexene. 1-Butene can also
undergo self metathesis to produce ethylene and hexene, presented
as metathesis V.
Fig. 9. Results of metathesis reaction of 2-butene over (a) MCM-41, (b) WO3 /MCM41(73), (c) WO3 /MCM-41(35), (d) WO3 -MCM-41(50), (e) WO3 -MCM-41(30)
catalysts at 2 h (A) conversion of 2-butene, propylene yield (mol%), ethylene yield
(mol%) and (B) ratio of propylene to pentene (reaction temperature: 550 C, pressure: 1 atm, GHSV: 900 h1 ).

Fig. 8. Results of metathesis reaction of 2-butene over (a) SBA-15, (b) WO3 /SBA15(73), (c) WO3 /SBA-15(35), (d) WO3 -SBA-15(60), (e) WO3 -SBA-15(30) catalysts at
2 h (A) conversion of 2-butene, propylene yield (mol%), ethylene yield (mol%) and
(B) ratio of propylene to pentene (reaction temperature: 550 C, pressure: 1 atm,
GHSV: 900 h1 ).

3.2.1. Catalysts based on SBA-15

The tungsten oxide supported SBA-15 catalysts were prepared
following two different methods. In the rst method, two catalysts having tungsten oxide with Si/W ratio of 35 and 73 were
prepared following wet incipient impregnation method while in
the second method two catalysts having Si/W ratio of 30 and 60
were synthesized following hydrothermal crystallization procedure. The results of the metathesis reaction of 2-butene at 550 C
over tungsten oxide supported SBA-15 catalysts are presented in
Fig. 8 and Table S1. A signicant increase in conversion of 2-butene
was observed after incorporation of tungsten oxide. The catalytic
conversion of 2-butene increased with an increase in the amount
of tungsten oxide in both types of catalysts. The WO3 -SBA-15 with
Si/W ratio of 30 resulted in high 2-butene conversion of 86.7%.
Similarly propylene and ethylene yields were observed to increase
with an increase in the amount of tungsten oxide. Pure SBA-15
exhibited 1 mol% of propylene yield and 0 mol% of ethylene yield.
The WO3 -SBA-15(30) depicted the highest yield of 37.1 mol%, and
16.7 mol% of propylene and ethylene, respectively. It was noticed
that C3= /C5= ratio also increased with an increase in the amount
of tungsten oxide. The WO3 /SBA-15(73) resulted in a low ratio
of C3= /C5= (1.3) indicating metathesis I reaction was taking place
predominately, whereas in the case of WO3 -SBA-15(30), C3= /C5=
ratio was 2.3 indicating the possibility of other reactions apart from
metathesis I.
It was noticed that catalysts based on hydrothermal synthesis
exhibited higher conversion and propylene yield as compared to
that of impregnated ones, indicating the vital role of framework
tungsten oxide sites in the metathesis reaction. The total acidity

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T.I. Bhuiyan et al. / Applied Catalysis A: General 467 (2013) 224234

Fig. 10. Results of metathesis reaction of 2-butene at different temperatures over (a) WO3 /MCM-41(35), (b) WO3 /SBA-15(35), (c) WO3 -MCM-41(30), and (d) WO3 -SBA15(30) catalysts at 2 h (A) conversion of 2-butene, (B) propylene yield (mol%), (C) ethylene yield (mol%) and (D) ratio of propylene to pentene (reaction temperature: 550 C,
pressure: 1 atm, GHSV: 900 h1 ).

(Table 2) of WO3 -SBA-15(30) was higher than WO3 /SBA-15(35).

Higher acidity of WO3 -SBA-15(30) enhanced the isomerization of
2-butene to 1-butene and thus provided more availability of 1butene for metathesis reaction with 2-butene. The higher acidity
and availability of more tetrahedrally coordinated tungsten species
were responsible for superior metathesis activity of WO3 -SBA15(30) as compared to that of WO3 /SBA-15(35). The reproducibility
of results was test by performing three different runs at 550 C using
WO3 -SBA-15(30) as catalyst. The standard deviation of 2-butene
conversion, propylene yield and ethylene yield was found to be
0.96, 0.69 and 1.17 respectively (see supporting information Fig.
S2).

3.2.2. Catalysts based on MCM-41

The MCM-41 supported tungsten oxide catalysts were also prepared following two different methods. In rst case, tungsten was
impregnated using wet incipient impregnation method, whereas
in second case, tungsten was incorporated into the framework of
mesoporous MCM-41 support using hydrothermal crystallization
procedure. The catalytic activity of MCM-41 supported tungsten
oxide catalysts for 2-butene metathesis at 550 C are presented
in Fig. 9 and Table S2. A signicant increase in conversion of

2-butene was observed after incorporation of tungsten oxide into

MCM-41. The catalytic conversion of butene was increased with
an increase in the amount of tungsten oxide in both types of catalysts. The WO3 -MCM-41(30) exhibited the highest conversion of
86.7%. Pure MCM-41 exhibited 5 and 2 mol% yield of propylene
and ethylene, respectively, whereas WO3 -MCM-41(30) depicted
highest yield of 36.3 and 16.5 mol% of propylene and ethylene,
respectively. It was noticed that C3= /C5= ratio was greater than
1.5 over all four catalysts. The higher activity of WO3 -MCM41(30) compared to other catalysts could be related to its higher
acidity as well as larger amount of tetrahedrally co-ordinated tungsten species as observed from pyridine-FT-IR, XRD and Raman
spectroscopy. The lower activity of impregnated MCM-41 samples was probably due to less availability of tetrahedral tungsten
species and higher intensity of extra framework octahedral WO3
species.

3.2.3. Effect of reaction temperature

Metathesis reaction of 2-butenes over WO3 /MCM-41(35),
WO3 /SBA-15(35), WO3 -MCM-41(30) and WO3 -SBA-15(30) catalysts at three different temperatures from 450, 500 and 550 C
was carried out and the results are shown in Fig. 10. It was

T.I. Bhuiyan et al. / Applied Catalysis A: General 467 (2013) 224234

observed that conversion of 2-butene increased with increase in

temperature for all four catalysts. It was also noticed that at low
temperature, catalysts based on MCM-41 shows higher activity
as compared to that of SBA-15 based catalysts. The activity of
all four catalysts at 450 C was: WO3 -MCM-41(30) > WO3 /MCM41(35) WO3 -SBA-15(30) > WO3 /SBA-15(35). Higher activity of
WO3 -SBA-15(30) could be correlated to the presence more number of tetrahedrally co-ordinated WO3 species than other catalysts
(evidenced from pyridine-FT-IR and UVvis DRS). However, at
higher temperature i.e. 550 C the catalytic activity of WO3 MCM-41(30) and WO3 -SBA-15(30) were comparable with highest
propylene yield of 39 mol% and 37 mol%, respectively.
A summary of various catalysts used so far in butene metathesis is presented in Table S3. Harmse et al. [16] have reported
highest yield (33 mol%) of propylene over WO3 /Siralox-40 catalyst for 1-butene metathesis reaction. However, in our present
investigation propylene yield of 39 mol% was achieved. The highest yield of propylene could be linked to the moderate acidity
of WO3 -MCM-41 and WO3 -SBA-15 catalysts. This moderate acidity was sufcient for isomerization of 2-butene to 1-butene and
then metathesis reaction. Higher yield of ethylene at 550 C
could be related to metathesis reactions of 2-butene and isobutylene as well as 1-butene auto-metathesis (Scheme 1) as these
reactions occur at higher temperature with moderate acidity.
At high temperature, C1 and C2 alkanes were not observed
which are considered to be the main products of cracking
reactions. This clearly indicated that metathesis I was predominately taking place at 550 C. The activity of all four catalysts at
550 C was: WO3 -SBA-15(30) WO3 -MCM-41(30) > WO3 /MCM41(35) > WO3 /SBA-15(35). The WO3 /MCM-41(35) and WO3 /SBA15(35) catalysts resulted into C3= /C5= ratio 1 at 450 C indicating
only metathesis I reaction taking place at lower temperature.
4. Conclusions
The conclusions of this study can be summarized as below:
Catalysts having tungsten oxide in the framework of mesoporous
silica exhibited the higher metathesis activity as compared to
tungsten oxide impregnated catalysts.
The lower activity of impregnated catalysts is due to abundance of
crystalline WO3 , which are shown to be non-active for metathesis
reactions.
WO3 -MCM-41(30) and WO3 -SBA-15(30) catalyst showed comparable activity with highest propylene yield of 39 mol% and
37 mol%, respectively at 550 C.
The activity order of all catalysts at 450 C was: WO3 -MCM41(30) > WO3 /MCM-41(35) WO3 -SBA-15(30) > WO3 /SBA15(35), whereas at 550 C the order was: WO3 -SBA-15(30)
WO3 -MCM-41(30) > WO3 /MCM-41(35) > WO3 /SBA-15(35).
WO3 -MCM-41 catalysts exhibited much higher activity at low
temperature (450 C) as compared to that of WO3 -SBA-15.
The higher activity of WO3 -MCM-41 could be related to the presence of more number of tetrahedrally co-ordinated tungsten
oxide species as evident from UVvis DRS and pyridine-FT-IR
spectroscopy.
WO3 -MCM-41 is a better choice from industrial point of view due
to lower cost of structure directing agent as compared to that of
WO3 -SBA-15.
Acknowledgments
The authors would like to acknowledge the support provided
by Saudi Aramco for funding project# CRP02252. The support from
the Ministry of Higher Education, Saudi Arabia, in establishment

233

of the Center of Research Excellence in Petroleum Rening &

Petrochemicals at King Fahd University of Petroleum & Minerals (KFUPM) is appreciated. The support of KFUPM is also highly
appreciated.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.apcata.
2013.07.034.
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