Microporous and Mesoporous Materials 126 (2009) 234244

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Microporous and Mesoporous Materials

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Incorporation of tin in different types of pores in SBA-15:

Synthesis, characterization and catalytic activity
M. Sasidharan a, Y. Kiyozumi a, N.K. Mal b, M. Paul c, P.R. Rajamohanan d, A. Bhaumik c,*
a
Laboratory for Membrane Chemistry, AIST Tohoku, 4-2-1 Nigatake, Miyagino-ku, Sendai 983-8551, Japan
b
Tata Chemicals Limited Innovation Centre, Anmol Pride, Baner Road, Pune 411 045, India
c
Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India
d
Central NMR Facility, National Chemical Laboratory, Pune 411 008, India

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

Article history: Mesoporous Sn-SBA-15 has been synthesized by three different methods such as conventional hydrother-
Received 29 October 2008 mal route, using cocatalyst NH4F and in the presence of organosilane precursor. All the materials are thor-
Received in revised form 13 May 2009 oughly characterized by powder X-ray diffraction (XRD), SEM, TEM, N2 sorption and surface area
Accepted 13 May 2009
measurements, diffuse-reectance UVvisible and FTIR spectroscopy, TGDTA and elemental analysis
Available online 18 June 2009
through ICP. Nitrogen adsorption data, XRD patterns, and TEM observations suggests that the textural
properties are retained during the isomorphous substitution of silicon by tin. ICP chemical analysis indi-
Keywords:
cates that tin can be substituted in the range of Si/Sn = 69162. UVvisible spectra of samples synthe-
BaeyerVilliger oxidation
Catalysis
sized by the cocatalytic approach exhibit unique absorption band at 213 nm characteristics of tin atom
Functionalization of mesopores substituted in the smaller pores (23 nm) located inside the walls of mesopores. Further, an additional
MeerwinPondorfVerly reduction band at 224 nm can be assigned to Sn atoms located in the distorted tetrahedral position along the pri-
Sn-SBA-15 mary mesopores. In contrary, only one absorption band centered at 224 nm is observed for all the sam-
ples synthesized by conventional hydrothermal as well as in the presence of organosilane precursor. 19F
NMR spectra conrmed (no signal) the absence of occluded F ions in the samples made with NH4F.
Observed high catalytic activity in BaeyerVilliger oxidation and MeerwinPondorfVerly reduction
under the liquid-phase conditions suggest the incorporation of a portion of tin in the smaller pores for
the Sn-SBA-15 materials synthesized through cocatalyst method.
2009 Elsevier Inc. All rights reserved.

1. Introduction
The substitution of aluminum by tin in the faujasites, and
mordenites through postsynthesis [14] or direct substitution of
silicon in high-silica zeolites such as ZSM-5 and ZSM-11 has been
an area of major research interest over the years [58]. Since then,
much effort has been directed toward preparing Sn-silicates with
outstanding catalytic properties. The utility of these tin-containing
molecular sieves has received great attention in recent times due
to their applications in the elds of both redox and acid catalytic
reactions. Hydroxylation of phenol and oxidation of various func-
tional groups [7,8] have been investigated over medium-pore tin-
silicates such as Sn-silicalite-1 and Sn-silicalite-2. More recently,
Corma et al. [9,10] have demonstrated the superiority of Sn-beta
as a chemoselective Lewis acid catalyst together with selective
activation of carbonyl compounds under the liquid-phase condi-
tions. In addition, the performance of Sn-silicates also differs sig-
nicantly over other metallo-silicates such as Ti, V, Cr, and Fe in
a way that the latter promote the oxidation reactions mainly by
* Corresponding author.
E-mail address: msab@iacs.res.in (A. Bhaumik).
activating H2O2 [11] unlike the former, which directly activates
the organic functional groups.
Mesoporous molecular sieves, such as MCM-41 [12] and FSM-
16 [13] have attracted much attention as adsorbents and catalysts
due to their wide pore dimensions compared to related micropo-
rous materials. In this context, Ti, Zr, V, Mn and Sn incorporated
2D-hexagonal MCM-41 materials have been investigated in detail
for various oxidation reactions using peroxides under mild condi-
tions [1416]. In spite of these developments, the utility of these
mesoporous materials as a potential candidate in the area of ne
chemical synthesis is, however, lacks far behind mainly because
of their poor intrinsic activity as well as hydrothermal stability.
However, attempts are being made continuously to solve the above
problems using various direct and postsynthesis modications.
These efforts resulted in a successful synthesis of hydrothermally
stable SBA-15 mesoporous silica with uniform hexagonal channels
ranging from 5 to 30 nm [17,18]. Following these remarkable
achievements, the introduction of different heteroelements in the
siliceous SBA-15 has been explored both by direct hydrothermal
as well as postsynthesis methods [1927]. It is worth to note that
in all the aforementioned synthesis procedures, however, the
metal atoms are mainly grafted or substituted along the primary

1387-1811/$ - see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2009.05.038
 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244
mesopores of ordered meosporous silica, and consequently exhibit
lower activity compared to microporous metallo-silicates. There-
fore, design of a suitable catalyst having active sites located in
the micropores of the primary mesopores would be of great inter-
est in the eld of ne chemical synthesis.
Moreover, based on extensive nitrogen adsorption studies, the
presence of disordered micropores and different pore connectiv-
itys have been established in the siliceous SBA-15 in addition to
2-dimensional ordered primary mesopores [2830]. Ryoo and co-
workers have developed a method to inltrate pores of SBA-15
with carbon or platinum, in order to synthesize negatives of mes-
oporous system and these negatives retained the 2-D hexagonal
structures, which exhibited very similar XRD patterns to that of
SBA-15 even after complete dissolution of the silica frameworks
with dilute HF [31]. This result indicated that the main channels
in SBA-15 were interconnected randomly through smaller pores lo-
cated in the channel walls [32]. Furthermore, investigation through
high-resolution electron microscope (HREM) of platinum wires
that were produced within SBA-15 revealed that, the channels
are corrugated and interconnected to each other through microp-
ores that penetrate the silica walls in a disordered way. Thus,
although various research groups have proved the existence of
micropores in SBA-15 unambiguously, the introduction of active
sites in the micropores remains a great challenge despite an enor-
mous development in the material synthesis. Also the generation
of microporosity within the amorphous pore walls of mesoporous
materials is a promising strategy for endowing with a specic func-
tionality. Such material possessing catalytically active sites in
micropores within the walls of mesopores would be ideal catalysts,
because organic molecules are rst freely diffused through the
main channels and then strongly interact with the active sites lo-
cated in the micropores for better reactivity. Inspired by the above
developments in terms of pores and channels connectivity of ther-
mally stable SBA-15 and its applications in the areas of advanced
materials design and catalysis, we have pursued to incorporate
tin in mesoporous SBA-15 sillica, since the presence of tin in the
silicate frameworks affords good Lewis acidity.
In the beginning of this research, however, our aim was to
achieve the maximum incorporation of tin in SBA-15 structure
and therefore, we have carried out extensive syntheses by different
synthesis procedures such as conventional hydrothermal route,
using mixture of TEOS along with organosilane and in presence
of cocatalyst NH4F as well as by changing the synthesis parameters
like concentration of surfactant and aging temperature. But de-
tailed characterization of the above synthesized materials revealed
a notable difference among the samples made by cocatalytic route
and that obtained with conventional method. Moreover, Sn-MCM-
41 materials showed remarkable catalytic activity in the liquid
phase selective oxidation [8,24], hydroxylation [7] and BaeyerVil-
liger oxidation reactions [9,10]. Herein, we have carried out the
catalytic BaeyerVilliger oxidation of cyclohexanone [33] and
MeerwinPondorfVerley reduction [34] of 4-tert-butylcyclohexa-
none to understand the catalytic performance of Sn-SBA-15
materials synthesized through different routes. The activity of
Sn-SBA-15 has also been compared with other tin-containing
materials having different pore-structures such as Sn-MCM-41
and microporous Sn-beta.
2. Experimental
2.1. Synthesis of Sn-SBA-15 by direct hydrothermal method
Syntheses were performed using triblock copolymer, poly(eth-
ylene glycol)-block-poly(propylene glycol)-block-poly(ethylene
glycol) (PEGPPGPEG; average molecular weight 5800, Aldrich)
235
and anhydrous SnCl4 (99%, Aldrich) as source of tin. Typically, 8 g
of triblock copolymer was dissolved in distilled water followed
by the addition of hydrochloric acid (36 wt%, Wako) and SnCl4. Fi-
nally, tetraethyl orthosilicate (TEOS; TCI) was added to get the
clear homogeneous solution with molar gel composition of SiO2:
0.012 PEGPPGPEG: 6.5 HCl: xSnCl4: 169 H2O (where x = 0,
0.011, 0.022, 0.033, and 0.05; for Si/Sn = 1, 90, 45, 30, and 20,
respectively). The resultant solution was stirred constantly at
313 K for 20 h and further aged at 353 K for 48 h. The white solid
product (Sn-SBA-15) was ltered, washed with deionized water,
dried at 343 K, and then calcined in a mufe furnace at 773 K for
5 h.
2.2. Synthesis of Sn-SBA-15 in the presence of organosilane precursors
Various functionalized Sn-SBA-15 were synthesized using
different organosilanes such as 3-(triethoxysilyl)-butyronitrile
(Aldrich, 98%), 3-(triethoxysilyl)propyl chloride (TCI, 96%), tri-
ethoxyvinylsilane (TCI, 96%), and triethoxymethylsilane (TCI,
96%) along with tetraethyl orthosilicate. In a typical procedure,
8 g of triblock copolymer was dissolved in distilled water followed
by the addition of HCl (36%, Wako) and SnCl4. Then the calculated
amount of TEOS was added into the above solution and the mix-
ture was stirred for a period of 2 h before the addition of 8%
organosiliane to get the molar gel composition: 0.926 SiO2: 0.08
RSi(OR)3: 0.012 PEGPPGPEG: 6.5 HCl: xSnCl4: 169 H2O, where
x = 0.0330.015. The simultaneous addition of organosilane and
TEOS was avoided since the former undergoes faster hydrolysis
than the latter [35,36]. The gel was further stirred for 20 h at
313 K and then aged at 353 K for 48 h. The product after crystalli-
zation was washed thoroughly with deionized water, dried at room
temperature. The surfactant was removed by extraction in a boil-
ing ethanol (1 g solid/100 ml ethanol) at 353 K for 12 h and this
procedure was repeated three times to achieve more than 80% re-
moval of surfactant.
2.3. Synthesis in the presence of cocatalyst NH4F
In this method, catalytic amount of NH4F was added prior to the
hydrolysis of TEOS. The homogeneous mixture was prepared as de-
scribed in the case of conventional hydrothermal synthesis with
the molar gel composition of SiO2: 0.012 PEGPPGPEG: 6.5 HCl:
xSnCl4: 169 H2O, (where x = 0, 0.011, 0.022, 0.033, and 0.05; for
Si/Sn = 1, 90, 45, 30, and 20, respectively). Addition of catalytic
amount of NH4F to the clear solution (F/Si = 0.030.15) causes pre-
cipitation in a period of 1060 min, and the resultant solution was
stirred for 12 h at 313 K before aging at 353 K for 48 h. The resul-
tant white solid was ltered off, washed with deionized water,
and calcined at 773 K in a ow of air for 5 h. It is pertinent to men-
tion here that in all the above-described syntheses, relatively lower
amount of surfactants and aging temperature were employed than
the original reported procedures [17,18].
2.4. Characterizations
Powder X-ray diffraction patterns were recorded using a MAC
Science powder diffractrometer with CuKa radiation (50 kV,
200 mA) with 0.02 step size and 2 s step time over the range
0.76 of 2h. The textural properties such as BET surface area,
mesopore-size distribution, total pore volume, and micropore vol-
ume of the calcined samples were evaluated using nitrogen
adsorption/desorption isotherms with a Bel Japan Inc. BELSORP
Mini instrument. The morphology and phase purity of the samples
were conrmed from eld emission SEM (Hitachi S-800) and TEM
(JEOL-2000EX II, 200KV) observations. FTIR spectra were recorded
on a Shimadzu FTIR-8100 spectrometer using a KBr pellet tech-
236 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244

nique. Pellets are prepared after diluting the sample in KBr (8 wt%).
The spectra were recorded after evacuating at 373773 K in a
quartz cell sealed with KBr windows. Diffuse-reectance UVvis
spectra of different calcined samples were collected in the region
of 200400 nm on a JASCO V-550 spectrometer using BaSO4 as a
reference. TG and DTA (MAC Science TG-DTA 2100), and 13C CP
MAS NMR (Bruker MSL500 instrument, 200 MHz) were used to
characterize organic tethering. The 13C CP/MAS NMR spectra were
recorded on a Bruker AMX-400 spectrometer equipped with an
MAS unit. The spectra were recorded at 100.6 MHz referenced to
an external glycine standard (176.4 ppm) with a contact time of
2 ms, a delay time of 2 s and spinning rate of 5 KHz. 19F NMR (Var-
ian INOVA-500) was used to characterize to locate the presence of
F ions and NaF was used as reference compound. Elemental anal-
ysis was performed with a Perkin Elmer Plasma 400 ICP-OES.

2.5. Catalytic experiments

Both BaeyerVilliger oxidation and MeerwinPondorfVerley

reduction were carried out in the liquid-phase conditions. In a typ-
ical reaction of BaeyerVilliger oxidation, 10 mmol of cyclohexa-
none was mixed with 10 mmol of tert-butylhydroperoxide in a
round bottom ask followed by addition of 100 mg of Sn-SBA-15
and 5 mL of dioxane. Cycloheptanone was used as an internal stan-
dard. The ask was tted with a water condenser and the mixture
was vigorously stirred using magnetic stirrer at 363 K while circu-
lating cold water through the condenser. The progress of the reac-
tion was made by analyzing the products with a capillary gas
chromatograph (Shimadzu 14A, OV-1 columns with ame ioniza-
tion detectors). The quantication of products has been performed
with special care using internal standard and response factor of
reactants and products. The products were identied using authen-
tic samples. Similarly, the MeerwinPondorfVerley reduction was
carried out by using 10 mmol of 4-tert-butylcyclohexanone and
30 mmol of 2-butanol and 100 mg of Sn-SBA-15. In this reaction,
2-butanol acts as hydrogenating agent for the reduction of 4-tert-
butylcyclohexanone catalyzed by Sn-SBA-15. The MPV reaction
products were also identied using authentic samples and quanti-
ed as mentioned above.
3. Results and discussion
3.1. X-ray diffraction analysis
Fig. 1A shows the XRD patterns of siliceous SBA-15 and Sn-SBA-
15 with different tin contents synthesized by conventional hydro-
thermal method. All the Sn-SBA-15 samples before and after
calcinations exhibited a well-resolved diffraction pattern with a
prominent peak at 0.9 degree and two weak peaks at 1.65 and
1.85 of 2h, as is the case in the synthesis of purely siliceous
SBA-15 [18]. The estimated unit-cell parameters (ao = 2d(100)/(3)1/2)
for the calcined samples as well as bulk (ICP) and surface (EDS)
Si/Sn mole ratios are given in Table 1. Relatively higher loading
of Sn is observed at the surfaces. The calcinations of Sn-SBA-15
caused appreciable decrease in the unit-cell size in comparison
to that of uncalcined sample. The unit-cell parameters of the
samples having Si/Sn ratio of 74.3 and 71.5 are found to be higher
than that of siliceous SBA-15.
XRD patterns of extracted Sn-SBA-15 synthesized using mixed
organosilanes as precursor are shown in Fig. 1B. From the gure
it is clear that all samples retained their 2D-hexagonal periodicity
after the removal of the templates. Furthermore, the Sn-SBA-15
prepared by using different organosilanes with TEOS (mixed orga-
nosilane method) show higher unit-cell parameters than those of
siliceous SBA-15 and/or Sn-containing samples synthesized by
Fig. 1A. XRD patterns of calcined Sn-SBA-15 synthesized by conventional hydro-
thermal method.
conventional hydrothermal method; this effect is attributed to
the presence of a certain amount of the copolymer in the etha-
nol-extracted (about 20% still remains in the framework as veried
by TGA) samples. Thus, the residual template present in the etha-
nol-extracted samples prevent the structural shrinkage to some
extent and eventually leads to higher unit-cell parameters unlike
the calcined samples. In addition, Sn-SBA-15 synthesized in pres-
ence of different organosilanes exhibit a very low amount of tin
substitution and no relationship is found with the unit-cell param-
eters. Similar to the conventional hydrothermal method, samples
synthesized by cocatalytic approach using NH4F also featured three
well-resolved (1 0 0), (1 1 0), and (2 0 0) reections and exhibited
unit-cell parameters, which increase monotonically with increas-
ing Si/Sn ratio (Fig. 1C). Such expansion of unit-cell parameters
both in the case of conventional hydrothermal as well as cocatalyst
approach may presumably indicate the incorporation of heavy
atoms in the framework. However, making such conclusion would
be difcult for samples made by mixed organosilane method, since
they contain residual templates and organic moiety. A similar
observation in the unit-cell parameters has also been made for
the substitution of zirconium and titanium in SBA-15 by micro-
wave-hydrothermal synthesis [20]. In Fig. 2 wide-angle powder
diffraction patterns of Sn-SBA-15 materials synthesized through
hydrothermal and cocatalyst methods are shown. No noticeable
wide-angle diffraction is observed in either of our samples. Powder
diffraction pattern of crystalline nonporous SnO2 is shown (Fig. 2a)
for comparison. These XRD patterns suggest that there is no oc-
cluded nano-SnO2 particle in our Sn-SBA-15 samples and their
pore walls are amorphous in nature.
3.2. SEM and TEM studies
Fig. 3 shows the scanning electron micrographs of Sn-SBA-15
made by different methods. The morphology of Sn-SBA-15 changes
slightly with the gel constituents and the hydrolysis products asso-
ciated with the silica source. In the case of conventional hydrother-
mal method, wheat like particles with rather random size of <1 lm
was observed (Fig. 3A). Nevertheless, these particles are joined to-
gether to form a kind of chain with 45 lm in length or agglomer-
 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244 237

Table 1
Structural parameters for the various template-free Sn-SBA-15 samples prepared through different routes.

Sample Si/Sn ratio (gel) Si/Sn ratio (product) d100 () aa () SBET (m2/g) Vt (cm3/g) Vmi (cm3/g)
ICP EDS
1b 1 1 1 93.87 108.3 847.6 0.83 0.07
2b 90 155 130 95.91 110.7 795.3 0.91 0.04
3b 45 108 101 96.02 110.9 768.9 0.89 0.05
4b 30 74.3 57 97.2 112.2 865.7 0.93 0.06
5b 20 71.5 46 97.45 112.5 789.0 0.91 0.07
6c 30 162 137 105.4 121.3 702.1 0.48 0.02
7d 30 133 121 102.6 118.5 635.0 0.51 0.01
8e 30 101 77 104.0 120.0 693.5 0.45 0.02
9f 30 114 92 99.8 115.2 654.0 0.55 0.03
10g 90 131 119 98.5 113.7 798.0 0.98 0.06
11g 45 103.5 87 98.4 113.6 749.0 1.03 0.08
12g 30 83 72 99.3 114.6 805.7 1.07 0.07
13g 20 69 65 99.8 115.2 788.0 1.02 0.07
14h 20 70.1 61 99.8 115.2 810.0 1.05 0.06
a
a = 2d100/(3)2 ; SBET = BET specic surface area; Vt = total pore volume; Vmi = micropore volume evaluated using the as-plot method.
b
Sn-SBA-15 synthesized by conventional hydrothermal method.
c
8% 4-(triethoxysilyl)-butyronitrile was used.
d
8 % triethoxyvinylsilane was used.
e
8% 3-chloropropyltriethoxysilane was used.
f
Methyltriethoxysilane was used.
g
Syntheses are performed with cocatalyst NH4F.
h
F/Si ratio was 0.015.

Fig. 1B. XRD patterns of extracted Sn-SBA-15 synthesized using mixed organosi-
lanes: (a) 8% 4-(triethoxysilyl)-butyronitrile; (b) 8% triethoxyvinylsilane; (c) 8% 3-
chloropropyltriethoxysilane; (d) 8% methyltriethoxysilane.
Fig. 1C. XRD patterns of calcined Sn-SBA-15 synthesized by using NH4F cocatalyst
method.

ated to form macrostructure. TEM image of this sample (Fig. 4, A

Si/Sn = 71.5) further show typical well-dened hexagonal symme-
try (p6 mm) viewed along the channel direction. However, when
TEOS is cocondensed in the presence of 3-chloropropyltriethoxysi-
lane (Si/Sn = 101), rope or sticklike particles with approximately
3040 lm size are formed (Fig. 3B). These sticks are usually com-
prised of smaller particles of about 1 lm in length. Fig. 4B exhibits
the corresponding TEM image of this sample, where hexagonal
honeycomb like arrangement of the pores are quite clear. Further-
more, Sn-SBA-15 synthesized with cocatalyst NH4F exhibits uni-
form gyroidlike particles (Fig. 3C) with 0.51 lm in length.
Similar morphology of mesoporous SBA-15 has also been reported
by Stucky et al. through the addition of highly concentrated or
charged inorganic electrolytes such as MgSO4 and Na2SO4
[37,38]. Also, these gyroidlike crystals are some times agglomer-
ated to form a macrostructure as seen from the scanning electron
micrograph. The samples synthesized by F route also show hexag-
onal array of uniform channels with the typical honeycomb
appearance of SBA-15 materials [17] (Fig. 4B, Si/Sn = 69). The above
study clearly indicates that the texture of SBA-15 is maintained by
the incorporation of tin in the mesoporous silicate.
238 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244

110
101
211
Intensity (arb. unit)

10 20 30 40 50 60
2 in degrees

Fig. 2. Wide angle powder XRD patterns of SnO2 (a) and calcined Sn-SBA-15
synthesized through hydrothermal (b) and cocatalyst (c) methods.

3.3. Nitrogen adsorption

Nitrogen adsorption isotherms for various calcined Sn-SBA-15

samples are similar to those reported earlier [17,18] and character-
istic of good-quality SBA-15 material. Fig. 5 shows a few represen-
tative adsorption/desorption isotherms for samples synthesized by
conventional hydrothermal, cocatalyst, and mixed organosilanes
methods. All the nitrogen adsorption/desorption isotherms are
found to be of Type IV in nature as per the IUPAC classication
and exhibited a H1 hysteresis loop, which is typical of mesoporous
solids consisting of very large mesopores [39]. The sample synthe-
sized by conventional hydrothermal method (Fig. 5A) showed a
sharp inection at a relative pressure value of about 0.72 and this
position is relatively unchanged with Si/Sn ratios (not shown in the
gure). This is characteristic of capillary condensation within uni-
form mesopores [40]. For samples synthesized by cocatalyst and
mixed organosilanes methods (Figs. 5B and 5C, respectively), how-
ever, the positions of adsorption branches are shifted toward lower
relative pressure of 0.71 and 0.66, respectively. Furthermore, the
adsorption branches changes between 0.63 and 0.67 when differ-
ent organic moieties such as chloropropyl, butyronitrile, vinyl,
and methyl (not shown in the gure) are present in the silica lat-
tices. In addition, the lower total pore volume, surface area, and
mesopores size of all the Sn-SBA-15 hybrid samples (Table 1) are
attributable to the presence of a certain amount of copolymer
and organic tethering. This is further conrmed from thermo gravi- Fig. 3. Scanning electron micrographs of Sn-SBA-15: conventional method (A);
metric analysis (TGA) of copolymer-extracted samples, which mixed organosilanes method (B) and cocatalyst method (C).
showed about 18% residual polymeric templates normally decom-
posed below 473 K in air; whereas the organic functionalities from as-plots method [41] given in Table 1 is signicantly lower for
decompose between 483 and 613 K. samples containing organic groups. This may presumably be due to
A good match between the points of inection on the adsorp- the partial blockage of micropores by the organic groups as re-
tion branch and mesopore-size distribution has also been noticed. ported by Jaroniec et al. [28].
The pore diameter of the representative samples discussed above
13
varies from 6.2 to 7.7 nm for different Sn-SBA-15 samples 3.4. C MAS NMR
(Fig. 6). For the sample synthesized by conventional hydrothermal
method exhibits an average mesopore diameter of 7.7 nm (Fig. 6A) The presence of various organic groups is also conrmed by 13C
and no signicant change in pore diameters is observed with dif- CP MAS NMR analysis and Fig. 7 exhibits the typical spectrum of
ferent Si/Sn ratios. The samples prepared by cocatalyst method Sn-SBA-15 containing chloropropyl group covalently bonded to
exhibited slightly lower pore diameter (7.2 nm, Fig. 6B) consistent the silica surface. In the 13C NMR spectrum, a band of peaks at
with its inection point in the nitrogen absorption branch. How- about 5670 ppm is assigned to ether groups of the EOPOEO sur-
ever, samples with organic groups exhibit relatively narrow pores factant residue [42] and peaks at ca. 8.9 ppm (CH3) and ca.
and Sn-SBA-15 containing chlorpropyl group shows 6.2 nm 51.6 ppm (CH2OH) are from ethanol, either formed during
(Fig. 6C). Furthermore, the amount of micropore volume evaluated hydrolysis of ethoxysilane or as the solvent residue. A peak at
 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244
Fig. 4. TEM images of calcined Sn-SBA-15: (A) conventional hydrothermal method;
(B) 8% of 3-chloropropyltriethoxysilane was used; and (C) cocatalyst method.
1.52.0 ppm is ascribed to the methylene carbons bonded to sili-
con atoms (CH2Si) and a peak at 18.1 ppm to the second carbon
on the propyl chloride. The third carbon, adjacent to the chloride
functional groups, is observed at 39.1 ppm. Thus, the combination
of various results discussed above by different characterization
techniques indicates that the textural properties of all the Sn-
SBA-15 are intact in all the aforementioned synthesis routes; how-
ever the incorporation of tin is quite low as estimated through the
ICP analysis and the nature of tin species in the mesopores and
complementary micropores (23 nm) also differs signicantly
and is discussed in the following section.
29
3.5. Si MAS NMR
29
Si chemical shifts of metallo-silicates are often utilized as
a sensitive tool to characterize the local environment of the
239
Fig. 5. Nitrogen adsorptiondesorption isotherms of Sn-SBA-15: (A) conventional
hydrothermal method (Si/Sn = 71.5); (B) cocatalyst method (Si/Sn = 69); and (C)
with 8% chloropropyltriethoxy silane (Si/Sn = 101). Adsorption points are marked
by empty symbols whereas the desorption points by lled symbols. Y-axes of B and
C are enhanced by 400 and 800, respectively.
Fig. 6. Pore size distribution of Sn-SBA-15 evaluated by DH method: (A) conven-
tional hydrothermal method; (B) cocatalyst method; and (C) with 8% chloro-
propyltriethoxy silane.
T-atoms connected with a SiO4 tetrahedral unit [43]. 29Si MAS
NMR spectrum of hydrothermally synthesized Sn-SBA-15 (Si/
Sn = 71.5) is shown in Fig. 8. From the gure it is clear that there
are two major species corresponding to chemical shifts at ca.
108.3 and 101.9 ppm, and a minor one at 90.3 ppm. These
could be attributed to the Sn substitution in Si(OSi)4 (Q4), Si(O-
H)(OSi)3 (Q3) and Si(OH)2(OSi)2 (Q2) environments, respectively
[24]. Considerable downeld chemical shifts for all these peak
maximas vis--vis Sn-free pure silica SBA-15 [44] suggested Sn
incorporation adjacent to the SiO4 tetrahedral units. High Q4/Q3 ra-
tio (Q1: Q2: Q3: Q4 = 1.52: 22.57: 19.60: 56.31) in this hydrother-
mally prepared Sn-SBA-15 material shows increased
condensation between silanol groups during the formation of Sn-
SBA-15 and more cross-linked framework. The presence of Sn
atoms in the SBA-15 network may also create Si (3Si, Sn) and Si
(2Si, 2Sn) like local environments, which contribute to the reso-
nance peaks at 101.9 and 90.3 ppm, respectively [24]. Thus this
240 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244

80 60 40 20 0
Chemical Shift (PPM)

Fig. 7. 13C solid state MAS NMR for Sn-SBA-15 synthesized in presence of 8% 3-
Chloropropyltriethoxysilane.

Fig. 9. FTIR spectra in the 1500400 region for samples evacuated at 373 K: (A) Si-
SBA-15; (B) Sn-SBA-15 (Si/Sn = 71.5, conventional hydrothermal method); (c) Sn-
SBA-15 (Si/Sn = 69, cocatalyst method).

Experimental

Deconvoluted

Q1

Q2

Q3

Q4

-50 -100 -150 -200

Chemical Shift (ppm)

Fig. 8. 29Si solid state MAS NMR for hydrothermally synthesized Sn-SBA-15 (Si/ Fig. 10. FTIR spectra of Si-SBA-15 in the 1500400 region recorded at different
Sn = 71.5). The spectrum has been deconvoluted into respective Q1, Q2, Q3 and Q4 temperatures: (a) 298 K; (b) 373 K; (c) 473 K; (d) 573 K; (e) 673 K; and (f) 773 K.
spectra.

problem has recently solved by measuring the IR spectra after

29
Si MAS NMR study revealed the incorporation of Sn inside the
mesoporous SBA-15 network.
3.6. Fourier transform infrared spectroscopy
Figs. 911 show the FTIR spectra of siliceous as well as Sn-SBA-
15 samples using KBr pellet technique. Fig. 7 compares the spectra
of siliceous SBA-15 with that of Sn-SBA-15 synthesized by conven-
tional hydrothermal method and cocatalyst method. All the sam-
ples show characteristic absorption bands at ca. 460, 798, and
956 cm1 and assigned to d(SiOSi), cs(SiOSi), and cs(SiOM),
respectively [45]. The appearance of band at ca. 956 cm1 is often
attributed to the presence of metal in the lattice position. However,
in the present case, Si-SBA-15 also exhibits a similar band even in
the absence of metal atoms and suggests that, this band can also be
due to SiOH groups, adsorbed water, etc. [46]. However, this
evacuating the samples in situ at elevated temperatures [47].
Fig. 10 shows the IR spectra of siliceous SBA-15 recorded after
evacuation at different temperatures. The sample was diluted in
KBr and pressed into pellets to obtain well-resolved bands in the
lower region. The pellet was heated in the IR cell for 2 h at the re-
quired temperature under vacuum and then recorded the spec-
trum. Pure silica SBA-15 showed a band at 956 cm1 at room
temperature before evacuation. However, the intensity of this
absorption band gradually decreased with increasing temperature,
and was hardly observed after evacuation at 773 K. This is attrib-
uted to removal of adsorbed water and dehydroxylation of silanol
groups. Furthermore, in the case of Sn-SBA-15 synthesized by NH4F
route (Fig. 9, Si/Sn = 69), the band at 956 cm1 gradually decreases
and after 573 K the band splits into two different bands. Subse-
quent evacuation at 773 K showed a new band at 943 cm1 with
relatively weak intensity. Thus the appearance of new band at
 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244 241

1082 260 nm. The absorption band at 224 nm is attributed to ligand-

to-metal charge transfer from an O2 to an isolated Sn4+ ion in tet-
rahedral conguration [48]. In the case of microporous Sn-MFI, [8]
four coordinated tin species are observed at 210 nm; whereas
Absorbance (arb. unit)

extraframework species and bulk SnO2 showed a broad band at

1221 460 255 and 300 nm, respectively. However, the substitution of Ti
and Zr in mesoporous SBA-15 exhibited a broad band around
943 798 200230 nm due to the presence of metals in a distorted environ-
f
ment as a consequence of amorphous nature of the pore walls of
e mesoporous solids [20,49,50]. Moreover, the intensity of the band
d centered at 224 nm increases monotonically with increase in Si/Sn
c 956
b
a

1400 1200 1000 800 600 400

Wavenumber (cm-1)

Fig. 11. FTIR spectra of Sn-SBA-15 (Si/Sn = 69, synthesized by cocatalyst method) in
the 1500400 region recorded at different temperatures: (a) 298 K; (b) 373 K; (c)
473 K; (d) 573 K; (e) 673 K; and (f) 773 K.

943 cm1 and its absence in siliceous SBA-15 suggests that tin
atoms are presumably be substituted in the framework position.

3.7. Diffuse UVvis reectance spectroscopy

UVvisible spectroscopy is a sensitive tool, which is widely used

to detect the presence of framework and extraframework species
particularly in the case of titanium, tin, and zirconium. Figs. 12
14 exhibit the spectra of various Sn-SBA-15 synthesized by differ-
ent methods. Fig. 12 shows the spectra of samples with different
Si/Sn ratios synthesized by conventional hydrothermal method.
The appearance of a strong absorption band at 224 nm is charac- Fig. 13. Diffuse reectance UVvis spectra of extracted Sn-SBA-15 synthesized
teristic of tin substituted in the framework positions in addition using mixed organosilanes (a) 8% 4-(triethoxysilyl)-butyronitrile; (b) 8% triethoxy-
to a small amount of extraframework species observed around vinyl silane; (c) 8% methyltriethoxysilane and (D) 8% 3-chloropropyltriethoxysilane.

Fig. 12. Diffuse reectance UVvis spectra of calcined Sn-SBA-15 synthesized by Fig. 14. Diffuse reectance UVvis spectra of SnO2 (a), Sn-MCM-41 (b), Sn-MFI (c)
conventional hydrothermal method: (a) Si/Sn = 1; (b) Si/Sn = 155; (c) Si/Sn = 108; and calcined Sn-SBA-15 synthesized by cocatalyst method: Si/Sn = 69 (d); Si/Sn = 83
(d) Si/Sn = 74.3, and Si/Sn = 71.5. (e); Si/Sn = 103.5 (f) and Si/Sn = 131 (g).
242 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244
ratio (Fig. 12BE). Similar absorption band (at 224 nm) was also
observed for the samples synthesized by mixed organosilane
method (Fig. 13) and neither shift in the absorption position nor
octahedral species were noticed with the use of different organic
tethering. Nonetheless, the amount of tin incorporation is invari-
ably quite low and no relationship has been found between the
amount of Sn incorporation and length and/or bulkiness of organic
functionalities. Thus, butyronitrile and vinyl functionalities real-
ized very low incorporation, whereas chloropropyl (Si/Sn = 101)
and methyl groups (Si/Sn = 114) showed an appreciable amount
of incorporation. The above results suggest that the incorporation
of tin is signicantly hindered by the presence of organic function-
alities under the present investigation in acidic-medium unlike
MCM-related materials, where it improves the incorporation of
titanium in basic-medium in the preparation of Ti-MCM-41 [51].
In contrast to the results obtained by conventional hydrother-
mal and mixed organosilane methods, Sn-SBA-15 synthesized with
NH4F cocatalyst exhibits (Fig. 14) a unique absorption bands that
differs signicantly from the rest of the samples. A well-resolved
two absorption bands below 225 nm were observed for all samples
with different Si/Sn ratio. Similar to microporous Sn-silicate [8]
and Sn-MCM-41 [43], the appearance of the relatively sharp
absorption band at 213 nm is attributed to the presence of tin in
the smaller pores of 23 nm within the walls of primary mesopore;
whereas the band at 224 nm, commonly observed for all the Sn-
SBA-15 samples regardless of different synthesis procedure, is
characterized by the Sn located in the distorted tetrahedral envi-
ronment along the primary mesopores as discussed earlier. Fur-
thermore, the relative intensity of the band at 213 nm varies
with Si/Sn ratio and suggests that the distribution of tin atoms uc-
tuates among the complementary micropores and primary mesop-
ores of SBA-15. It is also worth to note that even the samples
obtained in the absence of NH4F appears to have the band at
213 nm but the intensity is very small compared to that made with
NH4F. In addition, when the F/Si ratio is reduced from 0.03 to
0.015, the Si/Sn ratio is almost unchanged as seen from the Table
1 (Si/Sn = 70.1) suggesting that the amount of Sn incorporation is
not related to the F content of the gel. The above results clearly
enunciate that NH4F cocatalyst promotes the incorporation of tin
at least in part in the smaller complementary pores than the other
methods described under the present investigation.
3.8. Plausible mechanism for incorporation of tin in the micropores
The utility of uoride ions for tailoring the silica pore size as
well as to facilitate the synthesis in more dilute solutions has al-
ready been reported [52,53]. Inagaki et al [30] have modied the
texture of mesoporous silica SBA-15 by judicious choice of temper-
ature and surfactant concentration. It is well-known that EOmPO-
nEOm triblock copolymers in water form micelles, in which the
core and mantle are composed of PO blocks and EO blocks, respec-
tively [5456]. Furthermore, the amphiphilic property of the
copolymer is strongly controlled by temperature; that is the PO
block is strongly hydrophobic, whereas the hydrophobicity of the
EO block increases as temperature increases [5456]. In the pres-
ent investigation, the syntheses were carried out at relatively low-
er temperature and surfactant concentration than the original
reported procedures [17,18]. Thus, at the temperature used in this
study, that is 353 K, the PO block is not appreciably hydrated,
whereas the poly (ethylene oxide) chains are surrounded by water
molecules [56] and this EO block may be penetrated into the silica
walls to give micropores and/or voids. Hence, all the Sn-SBA-15
samples exhibit micropore volumes in the range of 0.01
0.07 cm3/g; the decreased micropore volume of the samples syn-
thesized by mixed organosilanes could be due to partial blockage
of micropores by the organic groups as reported by Jaroniec et al.
[28]. In addition, the lower surfactant concentration also induces
the formation of micropores possibly by changing the siloxane net-
work structure in the pore walls, and thereby results in changes of
microporosity as reported by Inagaki et al [30]. Under these condi-
tions, the addition of cocatlyst NH4F (F/Si = 0.030.015) to TEOS
during the synthesis produces a white gel in very short period.
For example, without uoride, the time required for hydrolysis is
about 4 h compare to only about 5 min in the presence of NH4F.
Thus, the faster hydrolysis rate traps some of the tin ions likely
in the micropores during the mesostructure formation as revealed
from the UVvis spectral data. However, no such observation was
made for the samples synthesized by either conventional hydro-
thermal or mixed organosilane methods. Thus optimum aging
temperature and surfactant concentration favors the formation of
micropores, whereas the NH4F promotes the incorporation of tin
atom in smaller pores located in the mesopore walls in addition
to the substitution at the mesopore itself. This observation is fur-
ther corroborated with catalytic performance of these materials
described in the following section.
3.9. Catalytic activity
Schematic representations of the BaeyerVilliger oxidation of
cyclohexanone and MeerwinPondorfVerly reduction of tert-
butylcyclohexanone are shown in Schemes 1 and 2, respectively.
It is a well-established fact that the catalytic activity of a partic-
ular active site in mesoporous materials exhibits lower activity
than that observed for the microporous materials. In order to get
more precise information on the nature of active sites vis--vis
possible location of tin atoms in pores of different size, we have
performed two different catalytic reactions namely, BaeyerVilliger
oxidation and MeerwinPondorfVerley reduction under liquid-
phase conditions. At rst, the activity of various Sn-SBA-15
catalysts (synthesized by different methods) towards the Bayer
Villiger oxidation cyclohexanone (Table 2) in presence of tert-butyl-
hydroperoxide (70% solution) is discussed. As demonstrated in
entries 14, the activity as well as turn-over-number increases with
increasing tin content for the catalysts made by conventional
hydrothermal method. Although the conversion varies with Si/Sn
ratio, the selectivity is not changed signicantly suggesting the
chemoselective transformation of cyclohexanone to the corre-
sponding lactones. Sn-SBA-15 synthesized in presence of various
organic functionalities displayed lower activity (entries 58) in
accordance with their tin content and thus the reactivity is mainly
Scheme 1. BaeyerVilliger oxidation of cyclohexanone over Sn-SBA-15.
Scheme 2. MeerwinPondorfVerly reduction of tert-butylcyclohexanone over Sn-
SBA-15.
 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244 243

Table 2
BaeyerVilliger oxidation of cyclohexanonea and MeerwinPondorfVerley (MPV) reduction of 4-tert-butylcyclohexanoneb over Sn-SBA-15 synthesized by different routes.

Entry Si/Sn ratio (bulk) BaeyerVilliger oxidation MPV reduction

c
Conversion (mole %) Selectivity (%) TON Conversion (mole %) Selectivity (%) TONc
d
1 155 3.1 99.0 1.1 1.3 100 0.5
2d 108 5.5 99.0 2.7 3.5 100 1.8
3d 74.3 11.6 98.7 8.5 9.1 100 6.3
4d 71.5 12.5 98.8 8.9 11.2 100 8.2
5e 162 3.7 99.0 1.2 1.5 100 0.5
6e 133 3.5 99.0 1.4 1.3 100 0.55
7e 101 4.2 99.0 2.3 4.8 100 2.6
8e 114 4.6 99.0 2.1 2.8 100 1.4
9f 131 4.9 98.6 2.0 3.6 100 1.5
10f 103.5 6.2 98.6 3.3 7.3 100 3.9
11f 83.0 27.9 98.4 18.3 18.8 100 13.5
12f 69.0 34.1 98.3 26.9 22.7 100 18.6
13g 69.0 33.8 98.5 26.8 22.5 100 18.6
14h 131 68.9 99.0 103 78.0 100 121.3
15i 73.3 38.7 99.0 32.2 26.0 100 23.7
a
Reaction conditions: 10 mmol cyclohexanone, 10 mmol tert-butyl hydroperoxide (70% solution), 10 ml dioxane, 100 mg catalyst, temperature 363 K, time 8 h.
b
Reaction conditions: 10 mmol tert-butyl cyclohexanone, 20 mL 2-butanol, 100 mg catalyst, temperature 363 K, time 12 h.
c
Turn-over-number in mole mole-1Sn h-1.
d
Sn-SBA-15 samples are made by conventional hydrothermal method.
e
Sn-SBA-15 was synthesized using different organotrialkoxysilanes with TEOS.
f
Sn-SBA-15 samples are made in presence of cocatalyst NH4F.
g
The catalyst was pretreated with pyridine to remove any of the occluded F? ions.
h
Sn-beta was used as catalyst.
i
Sn-MCM-41 was used as catalyst.

dependent on tin loading rather than the hydrophobicity, which is
expected to be higher for catalyst containing hydrophobic organic
groups. In contrast to the above catalysts, the Sn-SBA-15 synthe-
sized by using NH4F method exhibits better activity (entries 9
12) and turn-over-number without altering the lactones selectiv-
ity. The increased activity is attributed to the existence of apprecia-
ble number of active sites (framework substituted tin atom) in the
smaller complementary pores and easy accessibility of organic
molecules to the active sites via diffusion through primary mesop-
ores. However, it is important to clarify the role of occluded F ions
if any at this juncture. Therefore, in order to remove the F ions if
at all any, the catalyst was pretreated with pyridine at 333 K for 6 h
and activated at 773 K for 5 h. Thus obtained catalyst (entry 13)
exhibited a similar activity as that of untreated catalysts conrm-
ing that the reaction is indeed catalyzed by framework Sn atoms.
Furthermore 19F NMR spectra of sample with Si/Sn of 69 (Table
2, entry 12) before and after pretreatment with pyridine also con-
rm the absence of either free F ions resonance signal or its com-
plex with metal. Therefore, the observed catalytic activity is solely
attributed to the isomorphously substituted Sn atom in the solid.
In addition, we have also compared the activity of Sn-SBA-15 made
by cocatalytic route with microporous Sn-beta and Sn-MCM-41.
The observed activity over Sn-beta (Si/Sn = 131, entry 14) is 3
times higher than that of Sn-SBA-15 (entry 12) for BaeyerVilliger
oxidation. Therefore, we arrive at a conclusion that it is quite unli-
kely that Sn atoms are substituted in perfect micropores of size
1 nm. Moreover, for the BaeyerVilliger (BV) oxidation of cyclohex-
anone and MeerwinPondorfVerley (MPV) reduction of 4-tert-bu-
tyl cyclohexanone strength of the acid site Sn(IV), plays a crucial
role in the catalytic activity. In Sn-Beta because of the crystalline
pore structure, Sn(IV) sites have much stronger acidity. This could
be responsible for its high activity. On the other hand amorphous
nature of the pore wall for Sn-SBA-15 and Sn-MCM-41, could be
responsible for low acidity and hence relatively lower catalytic
activity. Interestingly, turn-over-number for Sn-MCM-41 (entry
15) matches closely with that of Sn-SBA-15 (entry 12), although
the former has been synthesized under basic-medium. Hence, this
experimental result suggests that a portion of active sites in Sn-
SBA-15 made by F route would be similar to that of Sn-MCM-
41. Thus, the increased TON by a factor of 3 for the sample with
Si/Sn = 69 (entry 12) compared to that synthesized by conventional
hydrothermal method (entry 4, Si/Sn = 71.5) is attributed to the
presence of tin atoms in the smaller pores (23 nm) which greatly
enhances the activity.
In order to prove unambiguously, the catalysts were also evalu-
ated over MeerwinPondorfVerley (MPV) reduction. In MPV
reduction, tert-butylcyclohexanone is selectively reduced to the
corresponding alcohols using 2-butanol as transfer hydrogenation
agent under liquid-phase conditions, as reported in the case of
microporous Sn-beta [10]. Similar to BayerVilliger oxidation, the
turn-over-numbers decreases with increasing Si/Sn ratios for all
the catalysts; however the activity of the catalysts synthesized
by NH4F again exhibits two fold increase than that made by con-
ventional hydrothermal method (compare entries 4 and 12 in Ta-
ble 2). Furthermore in the MPV reduction, the Sn-MCM-41 and
Sn-beta exhibit similar pattern of reactivity as that of BaeyerVil-
liger oxidation. The above results unambiguously lead to a conclu-
sion that a portion of tin atom is substituted in the smaller pores,
which in turn accounts for the higher activity than the catalysts
made by either conventional hydrothermal or mixed organosilane
methods.
In some published literature it has been mentioned that the
activity of V- and Ag-containing molecular sieves [57,58] in liquid
phase oxidation reactions is due to minor amounts of metal leach-
ing out of the solid catalyst and being present in the reaction med-
ium. A leaching experiment has been carried out to check for any
hypothetically leached Sn species under similar reaction condi-
tions. We found no increase in activity for the liquid phase alone
after ltering out the catalyst from the reaction media and contin-
uing the reaction for another 4 h. It is evident that no hypothetical
Sn species leached out of the catalyst and the BV and MPV reac-
tions are stopped after the removal of the respective catalysts. Thus
it is concluded that the activity of the catalyst can be only due to
the Sn atoms substituted in the framework of the mesoporous
materials. The reusability of the catalyst was also checked after
reactivation of the used Sn-SBA-15 (Si/Sn = 69) with highest tin
content under the present investigation. The catalyst has been acti-
vated at 673 K for 5 h under air-ow and reused for MPV reduction.
244 M. Sasidharan et al. / Microporous and Mesoporous Materials 126 (2009) 234244
Almost equal activity (11.0% vis--vis 11.2% conversion at the rst
cycle, Table 1, entry 4) has been noticed after three successive uses
with reactivation. This result suggests that Sn-SBA-15 materials
synthesized herein can be repeatedly used for carrying out BV
and MPV reactions.
4. Conclusions
From the above experimental results we can conclude that Sn-
substituted SBA-15 materials can be synthesized by different direct
synthesis methods; both conventional and cocatalyst methods pro-
duced an appreciable amount of incorporation, whereas the mixed
organosilanes method led to very little substitution of tin. The
incorporation of tin in the SBA-15 silica did not change the overall
textural properties of SBA-15 silica as revealed from small angle
XRD, SEM, TEM, TGA, 13C NMR, and nitrogen adsorption/desorption
studies. 19F NMR conrmed the absence of occluded F ions in the
samples made with NH4F. FTIR spectra of Sn-SBA-15 after evacua-
tion at different temperature showed a band at 943 cm1, which is
absent for Si-SBA-15 conrming the presence of Si-O-Sn network.
Sn-SBA-15 synthesized by direct hydrothermal method revealed
the presence of band at 224 nm characteristics of distorted tetrahe-
dral Sn species in the primary mesopores in addition to a small
amount of six-coordinated species; however materials made by
mixed organosilanes did not show any octahedral species. The
Sn-SBA-15 made with NH4F cocatalyst showed unique UVvisible
spectra containing two different absorption bands at 213 and
224 nm. The band at 213 nm is assigned to the tin atoms in the
smaller pores within the mesopore walls and 224 nm for that lo-
cated in the distorted tetrahedral position along the primary mes-
opores. The difference in activity between the catalyst synthesized
by NH4F route and conventional hydrothermal method over the
BayerVilliger oxidation and MPV reduction, suggesting the exis-
tence of active sites in the pores of size with 23 nm and this could
open up new opportunities for the heteroelement incorporated
SBA-15 materials in liquid phase catalytic reactions.
Acknowledgments
The authors kindly thank Dr. Peng Wu, Yokohama National Uni-
versity for the help regarding UVvis spectra during the initial
phase of this project. AB wishes to thank DST, New Delhi, for a
Ramanna Fellowship grant.
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