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Microporous and Mesoporous Materials 108 (2008) 2940

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Bridging the gap between micropores and mesopores by the controlled

transformation of bifunctional periodic mesoporous silicas
S. Shylesh a, Ch. Srilakshmi b, A.P. Singh a,*
, B.G. Anderson b

a
Inorganic and Catalysis Division, National Chemical Laboratory, Pune 411 008, India
b
Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600MB, Eindhoven, The Netherlands

Received 7 July 2006; received in revised form 17 March 2007; accepted 19 March 2007
Available online 4 April 2007

Abstract

Novel bifunctional periodic mesoporous silicas having high content of organic groups in the pore channels and chromium in the frame
wall has been synthesized by direct co-condensation method, using organo trialkoxysilanes (chloro propyl, vinyl, methyl), chromium
nitrate and tetraethyl orthosilicate, in presence of cetyltrimethyl ammonium surfactants. The obtained materials show one main peak
in the XRD patterns up to a molar ratio of 1:1 between TEOS and organosilane in the synthesis gel and N2 adsorptiondesorption anal-
ysis shows that the mesopore structure remains intact after the surfactant removal process. Among the organosilanes, chloro propyl and
vinyl pendant chromium samples shows a shift in the main peak to higher 2-theta values with a corresponding decrease in pore volume
and pore diameter, with the percentage of organosilane functionalization. Small-pore silicas and chromium silicas can be prepared from
the large pore mesoporous MCM-41, by eectively removing the organic groups by calcination. By this method, the pore size of the
material can be tailored into the super-microporous region, without changing the chain length of the surfactant used in the assembly
process. The shrinkage in pore size is dependent on the nature and percentage of the organic pendant groups that the chloro propyl
and vinyl pendant mesoporous materials show the maximum pore size shrinkage than the small chain length methyl units. Because
of the tailorable pore size and with better textural characteristics, chromium-silica materials nd applications in the eld of shape selec-
tive heterogeneous catalysis, as demonstrated in the oxidation reaction of cyclohexane, than the conventional metal-containing mesopor-
ous materials.
 2007 Elsevier Inc. All rights reserved.

Keywords: Bifunctional silicas; MCM-41; Chromium; Cyclohexane; Oxidation

1. Introduction the content of organic groups determine the specic prop-

Soon after the discovery of mesoporous materials of the
M41S family by Mobil researchers, ordered mesoporous
materials possessing high content of organic groups consti-
tute an active research area [16]. These organicinorganic
hybrid materials with reactive groups are unique as they
oer potential advantages than the pristine silica analog
for various surface modications, and are widely explored
in the eld of catalysis, separation science, adsorption,
sensing and so forth [712]. Importantly, the nature and
*
Corresponding author. Tel.: +91 20 2589376; fax: +91 20 25893761.
E-mail addresses: ap.singh@ncl.res.in (A.P. Singh), B.G.Anderson@
tue.nl (B.G. Anderson).
erties of these nanocomposites like the surface hydropho-
bicity, hydrothermal, thermal and mechanical properties.
However, the uniformity of the organic groups inside the
pore channels aects the surface properties, functionalized
organic group reactivity and the accessibility of the porous
network for further modications.
There are two methods by which organic groups of
desired functionality can be loaded on mesoporous support
surfaces; viz. direct co-condensation method or post-syn-
thesis grafting method [79]. Generally, post-synthesis
method is the commonly and routinely used procedure
for the synthesis of organicinorganic hybrid mesoporous
materials. In this process, a surface reaction of the silanol
groups of mesoporous materials (surfactant-free) with the

1387-1811/$ - see front matter  2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.03.039
30 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940
desired organic coupling groups is eectively utilized. How-
ever, the time-consuming two-step synthesis procedure,
instability of the inorganic framework at higher loadings
and the inhomogeneous distribution of organic groups
make the process less demanding [8,13]. On the other hand,
the direct co-condensation method helps to modify the sur-
face of mesoporous materials in a single step with control-
lable as well as homogenous distribution of organic species.
Moreover, following this method, organic-rich mesoporous
materials can be prepared and on an average 4050% sili-
con atoms carrying organic groups can be eectively
synthesized [1416]. However, many of the synthesis
methods reported in the literature shows that at higher
loadings, materials with very low channel ordering as well
as inhomogenity in the functionalized groups are obtained.
Hence, careful and judicious synthesis procedures are
needed in the synthesis of organicinorganic hybrid
mesoporous materials, unless results in the disordering of
the mesoporous material with concomitant phase separa-
tions, viz. organosilica rich and silica rich phases.
One of the well-studied and widely used mesoporous
catalyst support is the one-dimensional channel oriented,
MCM-41 due to their unique high surface area, hexagonal
channels arrays as well as simple synthesis protocols [1,17].
Although numerous synthesis procedures are present in lit-
erature for the single site functionalization on MCM
related materials, very few reports and limited success are
obtained over bifunctional groups [15,16,1820]. Bifunc-
tional mesoporous materials containing organic groups
and transition metals are versatile that their applications
can be tuned in diverse areas, where the organic groups
play the role of providing improved hydrophobicity and
the presence of metals provide the catalytic property
[21,22]. Thus the current state-of-art method has to be
improved so that one can design a periodic mesoporous sil-
ica material having bifunctional sites of tunable pore sizes.
For the past decade, the design and synthesis of porous
materials having pore size >3 nm have been the main area
of research, utilizing the chain length of the surfactant
groups, micelle expanders, and using various polymeric
surfactants [23,24]. However, solid materials having pore
sizes in between that of zeolites and mesoporous materials
(super microporous region, 1622 A) received less attention
and hence ordered silicas that eectively bridge the gap
between the conventional microporous zeolites and the
mesoporous materials is overwhelming [2528]. Earlier
such materials are synthesized by using surfactants of short
alkyl chain length like the hexyltrimethylammonium sur-
factant or octyltrimethylammonium surfactants or short
chain neutral templates. Unfortunately, these materials
show poorly ordered structure, reveal the tendency to col-
lapse the pore structures upon storage and the reproduc-
ibility of synthesis procedures are not promising [2933].
Therefore, one of the major goals in the synthesis of porous
materials was the development of materials having pores in
the borderline between microporous and mesoporous
materials with catalytic properties. Such a material further
allows shape selective catalytic transformations, which are
not possible with the zeolite catalysts. Very recently, Bag-
shaw and Hayman showed the synthesis of microporous
materials using x-hydroxy-bolaform surfactants while
Sun and Wang had shown that using adamantamine as a
surfactant one can prepare porous materials in the super-
microporous region [26,30]. In an another way, small-pore
silicas with lower unit cell dimensions can be prepared from
alkyl trimethylammonium surfactants, due to the excep-
tionally large degree of shrinkage upon surfactant removal
by calcination process [25,3436]. Kruk et al. had shown
that vinyl-functionalized mesoporous organosilicas can be
transformed via calcination into ordered microporous sili-
cas with pore diameters tailorable from 2.5 to 1.4 nm by
using an appropriate loading of the vinyl-functionalized
precursor [28]. Thus, by increasing the calcination temper-
ature one can tailor the d spacing and pore size of mesopor-
ous materials, but disordered materials are usually
obtained. Hence, new synthesis methods for ordered por-
ous silicas having pore sizes in the super microporous
region is alluring and we had achieved this target by eec-
tively introducing organic and inorganic groups in to the
periodic mesoporous structures.
Herein, we suggest an alternative route towards the syn-
thesis of materials having tailorable pore sizes, typically in
the super-microporous region, and more importantly with
a catalytic functionality. The novelty of the current synthe-
sis procedure is that metal-containing porous materials,
with tailorable pore sizes, can be fabricated by simply vary-
ing the nature or percentage of the organic groups. These
organic groups can be further sacriced so that that the
pore size of the materials can be eectively tailored from
the mesoporous region to the super-microporous region.
Further, compared to the earlier literature reports where
the property of single silylating agents was studied, the
present study probed in detail the shrinkage eect by taking
three dierent silylating agents having varying carbon
numbers like methyl (1C), vinyl (2C) and propyl (3C). A
hallmark of the present synthesis protocols is that the prep-
aration of bifunctional mesoporous materials that have
functional groups inside the mesoporous matrix can be
designed according to the requirement and hence a variety
of materials can be prepared using the synthesis procedure
reported herewith.
2. Experimental
2.1. Materials
Tetraethylorthosilicate (TEOS) and cetyltrimethylam-
monium bromide (CTMABr) was obtained from Aldrich
chemicals, chromium nitrate (Cr(NO3)3 6H2O) was
obtained from Loba Chemie. 3-Chloropropyltriethoxy
silane (Cl-ES), triethoxyvinyl silane (Vi-ES), trimethoxym-
ethyl silane (Me-MS) and all other reagents were procured
from Lancaster.
 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940
2.2. Synthesis of organo-functionalized silicas
Organic-functionalized mesoporous silica samples were
synthesized using the following gel composition:
(1  x)TEOS:xX-ES:0.25CTMABr:0.25Na2O:60H2O. The
amount of organosilane was varied from x = 1560 in case
of all organosilanes. The synthesis procedure for chloro
propyl functionalized mesoporous silica was typically fol-
lowed as follows. In a 250 ml plastic bottle, a solution of
CTMABr (2.6 g, 7.1 mmol), NaOH (0.57 g, 14.2 mmol) in
water (30 g) was prepared under room conditions and
was stirred for 15 min. To this mixture, a solution of TEOS
silica source (5 g, 24 mmol) as well as Cl-ES (0.90 g,
4.5 mmol, x = 15%) was added slowly with vigorous stir-
ring for approximately 30 min. The mixture was stirred
for 6 h under room conditions and then aged at a higher
temperature of 100 C for 48 h. The product obtained
was then ltered, washed with copious amounts of water
and dried under ambient conditions for 5 h to obtain a
white ne powder. A similar procedure was carried out
for the other organosilanes, that instead of Cl-ES, Vi-ES
and Me-MS was added with the TEOS silica source. The
Me-MS samples prepared with 30% and above loadings
as well as Cl-ES and Vi-ES samples prepared with 50%
and 60% loadings remain as a thick gel after aging. For
these samples the solvent was removed by simple evapora-
tion and the thick, jelly, solid material was crushed in a
mortar to obtain a pale yellowish powder. The surfactant
occluded inside the pores of the hybrid samples was
removed by stirring the as-synthesized sample with an
HClEtOH mixture (0.5 g/100 ml) at 60 C for 6 h. The
product was then ltered, washed well with ethanol and
dried in vacuum. The surfactant-extracted samples
obtained from chloro propyl sample is denoted as ClEx,
vinyl silane is denoted as ViEx, methyl silane is denoted
as MeEx, where x stands for the amount of organosilane
added. Porous silica samples were also prepared from the
as synthesized samples by calcination at 540 C for 12 h,
under air atmospheres, at a heating ramp of 1/min. The
calcined samples obtained from chloro propyl containing
sample was denoted as ClCx, vinyl silane is denoted as
ViCx, methyl silane is denoted as MeCx.
2.3. Synthesis of chromium-containing organosilicas
Organic-functionalized chromium-containing mesopor-
ous silica samples were synthesized using the following
gel composition: (1  x)TEOS:xX-ES:0.25CTMABr:0.25-
Na2O:yCr2O3:60H2O. The amount of organosilane was
varied from x = 1560 in case of all organosilanes and y
is 0.018, Si/Cr = 27. A typical synthesis procedure for
chromium-containing chloro propyl functionalized meso-
porous silica was as follows. In a 250 ml plastic bottle, a
solution of CTMABr (2.6 g, 7.1 mmol), NaOH (0.57 g,
14.2 mmol) in water (30 g) was prepared under room con-
ditions and was stirred for 15 min. To this mixture, a solu-
tion of TEOS silica source (5 g, 24 mmol) and Cl-ES
31
(0.90 g, 4.5 mmol, x = 15%) was added slowly with vigor-
ous stirring for approximately 30 min. An aqueous solution
of chromium nitrate (0.34 g, 0.8 mmol, y = 0.018) was then
added to the above mixture with vigorous stirring. The
mixture was stirred for 6 h under room conditions and then
aged at a temperature of 100 C for 48 h. The product
obtained was then ltered, washed with copious amounts
of water and dried under ambient conditions for 5 h to
obtain a green ne powder. A similar procedure was car-
ried out for the other chromium-containing organosilane
samples, that instead of Cl-ES, Vi-ES and Me-ES was
added with the TEOS silica source. Chromium-containing
Me-ES, Vi-ES samples prepared with 30% and above
organic loadings as well as Cl-ES samples prepared with
50% and above loadings remain as a thick gel after aging.
For these samples the solvent was removed by simple evap-
oration and the thick, jelly, solid material was crushed in a
mortar to obtain a green powder. For comparison, chro-
mium-containing MCM-41 sample was also prepared
under the present synthesis conditions, but without the
addition of any organosilane source. The surfactant
occluded inside the pores of the hybrid samples was
removed by stirring the as-synthesized sample with an
HClEtOH mixture (0.5 g/100 ml) at 60 C for 6 h. The
product was then ltered, washed well with ethanol and
dried in vacuum. The surfactant-extracted, chromium-con-
taining chloro propyl sample is denoted as CyClEx, vinyl
silane is denoted as CyViEx, methyl silane is denoted as
CyMeEx, where x stands for the amount of organosilane
added and y stands for Si/Cr ratio. Chromium-containing
small-pore silica samples were also prepared from the as-
synthesized samples by calcination at 540 C for 12 h,
under air atmospheres, at a heating ramp of 1/min. The
calcined samples obtained from chloro propyl sample was
denoted as CyClCx, vinyl silane is denoted as CyViCx,
methyl silane is denoted as CyMeCx. The surfactant-
extracted Cr-MCM-41 sample prepared without any
organosilanes is denoted as CRE while the calcined sample
is denoted as CRC.
2.4. Sample characterization
PXRD patterns of the samples were recorded on a Rig-
aku D MAX III VC instrument using Ni-ltered Cu Ka
radiation (k = 1.5404 A), with a step size of 0.02. N2
adsorptiondesorption isotherms, pore size distributions
as well as the textural properties of the hybrid materials
were determined at 196 C by a NOVA 1200 (Quanta
chrome) instrument. Before analysis, the samples were acti-
vated at 200 C for 6 h under vacuum and then the adsorp-
tiondesorption was conducted by passing nitrogen into
the sample, which was kept under liquid nitrogen. The
average pore size of the samples was deduced from the den-
sity functional theory (DFT) method and was also esti-
mated using a geometrical equation derived under the
assumption of a 2-D hexagonal honeycomb porous
structure.
32 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940

0:5
wd cd 100 qV p =1 qV p 1 (activated at 200 C/2 h) and was heated at a constant tem-
perature of 70 C under magnetic stirring (ca. 800 rpm).
where c is a constant equal to 1.213 for cylindrical pore After reactions, the reaction mixture was cooled to room
geometry, q is the pore wall density equal to 2.2 g cm3 conditions and the catalysts were separated from the reac-
for silicas, Vp is the primary pore volume and d100 is the tion mixture by centrifugation. The oxidized products were
(1 0 0) XRD interplanar spacing. analyzed on a gas chromatograph (HP 6890) equipped with
Solid-state 13C CP MAS NMR and 29Si MAS NMR a ame ionization detector (FID) and a capillary column
spectra were recorded on a Bruker MSL 300 NMR spec- (5 lm cross linked methyl silicone gum, 0.2 mm 50 m).
trometer with a resonance frequency of 75.5 MHz and The formation of carboxylic acid side products was deter-
59.6 MHz for 13C and 29Si using 4 mm zirconia rotors mined by performing the GC analysis after conversion in
and a sample spinning frequency of 3 kHz. 13C spectra to the respective methyl esters.
were collected with 70 rf pulses, 5 s delay while 29Si spectra
were collected with 70 rf pulses, 30 s delay and in both
3. Results
cases with 6000 scans. The chemical shifts were refer-
enced to glycine and TMS, respectively, for 13C and 29Si.
3.1. Powder X-ray diraction and N2 adsorption isotherms
Raman spectra were measured using a Bruker RFS 100/S
spectrometer equipped with a Nd:YAG laser (1064 nm)
XRD patterns of surfactant-extracted organic-function-
and an InGaAs detector. A laser power of 75 mW was
alized mesoporous silica samples with dierent percentage
used. Spectra were acquired from 4000 to 25 cm1 at a res-
of organic groups are shown in Fig. 1. The surfactant-
olution of 4 cm1. In order to increase the signal-to-noise
extracted samples shows larger peak intensities than the
ratio 2000 scans were coadded. Temperature studies were
as-made samples and these dierences arise due to the
performed by placing the powdered sample into a Specac
enhanced contrast in electron density after the removal of
Environmental ChamberTM DRIFTS cell modied with a
the surfactant from the pore channels than the surfac-
near-infrared-transparent quartz window. In order to
tant-silicate samples [37]. Regardless of organosilane, the
enable quantitative measurement of intensity changes
intensity of the d100 peak as well as higher ordered reec-
boron nitride powder was physically mixed (1 wt%) with
tions decreased with an increase in the percentage of
the powdered sample. Boron nitride is stable to high tem-
organosilica loading up to 50%, where after no reections
peratures and its Raman spectrum contains a single,
are observed. With methylsilanes no XRD peaks are
intense band at 1365 cm1 (no band overlap with the sam-
observed at a high loading of 50%, while the chloro propyl
ples measured here). After measuring the Raman spectrum
and vinyl-pendant silica samples retains the structure.
at room temperature the sample was heated in situ in ow-
Notably, a decrease in d100 spacing or an increase in 2h
ing articial air (20 ml/min) to 100 C, held for 60 min, and
value is observed with the organosilane loading. The reduc-
then cooled to room temperature where the Raman spec-
tion in unit cell size with the percentage of organic pendant
trum was remeasured. This process was then repeated at
groups indicate that the organic groups gets loaded in the
200 C, 300 C and 400 C for each sample. Diuse reec-
frame wall positions and it is interesting that with respect
tance UVVis spectra were recorded in the range 200600
to the nature of organosilane, the unit cell shrinkage varies
nm with a Shimadzu UV-2101 PC spectrometer equipped
(Fig. S1, Table 1).
with a diuse reectance attachment, using BaSO4 as the
Elemental analyses of the hybrid samples were also car-
reference. The as-synthesized samples were kept at 100 C
ried out for a better understanding about the percentage of
for 5 h while the calcined samples were treated in dry air
organic group functionalization. The mole percentage of
atmosphere at 550 C for 5 h and ushed with an inert
atmosphere, repeatedly, before the spectra was taken.
A B C
2.5. Oxidation of cyclohexane
c c c
Cyclohexane oxidation reactions were carried out in a
Intensity / a.u.

10 ml round bottom ask tted with a water-cooled con-

denser using non-aqueous tert-butyl hydroperoxide, b
b
TBHP, as an oxidant. For that, stock solutions of tert- 100 b
100 100
butyl hydroperoxide in cyclohexane were prepared by
extraction of TBHP (70%) in cyclohexane. Phase separa- a
tion was promoted by the addition of NaCl in the aqueous a a

layer and nally the organic layer was dried over MgSO4.
The reactant mixtures of cyclohexane (10 mmol, E-Merck, 2 3 4 2 3 4 2 3 4
2 / degree
99%, dried over 4 A molecular sieves), oxidant (10 mmol,
E-Merck) and acetone solvent (5 ml, E-Merck, 99%, dried Fig. 1. XRD patterns of organosilica samples (A) ClEx, (B) ViEx and (C)
over 4 A molecular sieves) was added to 0.1 g of catalyst MeEx; (a) 15% loading, (b) 30% loading and (c) 50% loading.
 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940 33

Table 1
Structural properties of organo-functionalized chromium samplesa
Sample d100 (nm) SBET (m2 g1) SEX (m2 g1) Vt (cm3g1) Vp (cm3 g1) Dp (nm)
wd DFT
C27ClE15 3.5 581 41 0.52 0.47 3.0 2.9
C27ClE30 3.4 583 119 0.48 0.44 2.8 2.7
C27ClE50 3.2 441 204 0.45 0.37 2.6 2.5
C27ViE15 3.1 320 33 0.41 0.37 2.5 2.6
C27ViE15-(P) 3.6 535 38 0.45 0.41 2.9 3.0
C27MeE15 3.4 412 58 0.36 0.31 2.6 2.7
CRE 3.8 455 63 0.39 0.37 3.0 2.9
a
d100, XRD (1 0 0) interplanar spacing; SBET, specic surface area; SEX, external surface area; Vt, total pore volume; Vp, primary pore volume; Dp, pore
diameter determined using Eq. (1) (wd); DFT, pore size determined using density functional theory method.

organosilanes loaded versus the input concentration of
organosilanes is shown in Fig. S1 (Supporting Informa-
tion). Despite the high amounts in the synthesis gel, the
nal products contain fewer organosilanes and at higher
loadings the percentage of incorporation is very less. In
addition, the percentage of organic functionalization varied
with respect to the nature of the organosilane and it was
found that the methyl-groups show less functionalization
while the vinyl- and chloro propyl-terminated samples
show an almost similar loading. The higher organic func-
tionalization of chloro propyl and vinyl groups shows the
uniform organization of the trialkoxy silyl groups at the
Gouy-Chapman region of the surface of micelles and their
increased chain lengths may helps in the rapid cross-link-
ing/condensation of the micelle-oriented trialkoxy organo-
silanes [38]. Hence, the increased unit cell shrinkage
observed with the percentage of vinyl- and chloro propyl
organic groups may arise due to the increased condensa-
tion reactions between the silicate species and organosili-
cate species. It is anticipated that the high temperature
employed in the synthesis provides a better hydrolysis rate
of the alkoxy silanes, which may enhance the condensation
rate between the silicates and the organosilicates. Hence, in
an attempt to understand the eect of temperature in the
hydrolysis and condensation of organosilanes, the syn-
thesis of organo-modied mesoporous materials are also
carried out under room temperatures. However, after sur-
factant removal by solvent extraction or calcination the
XRD patterns are featureless, even for the ClE15 sample,
Thus the dierence in the percentage of functional groups
incorporated depends on the intrinsic properties of the
organosilanes itself. Hence, in order to increase the surface
coverage of organic groups in hybrid mesoporous materials
and to enhance the condensation between the organosil-
anes and TEOS, the current synthesis was done at higher
temperature viz. 100 C.
Observing the eect of reduction in d100 values with the
percentage of organo functionalization, the unit cell
shrinkage eect in presence of an inorganic cation was fur-
ther probed. Since chromium is presumed to anchor on the
defect sites of porous materials and thereby reduce the pore
size of the material, chromium nitrate was considered as
an ideal precursor, so that we can prepare mesoporous
material with tailorable pore sizes and with a catalytic
functionality. The XRD patterns of chromium-containing
organosilica materials, prepared using organosilanes and
chromium are shown in Fig. 2A. All the as-synthesized
samples show the characteristic reections of mesoporous
materials having 2D hexagonal arrangement of pore chan-
nels. This result shows that in presence of organic modiers
(15%) and chromium (2%), no phase separation had
100 A B
Intensity / a.u.

e
which shows that the stability of the materials was less 110
for the samples synthesized under room temperatures. 200 210 e d
Elemental analysis results show that 6% of chloro propyl
groups get loaded over the mesoporous support. The d c
decreased stability as well as the lower loading of organic c
groups, under room temperature, may arise due to the dif- b
b
ference in the hydrolysis/condensation rates of both silica a
species. It is known that the hydrolysis rate of trialkoxy a
organosilanes are generally slower than the rate of TEOS 2 4 6 8 10 20 40 60
due to the electron donating ability of the alkyl groups 2 / degree
bonded to the silicon of the SiR species [1416]. For
Fig. 2. XRD patterns of (A) surfactant-extracted hybrid chromium-
instance, the hydrolysis rate of SiCH3 proceeds much containing samples and (B) calcined samples, where (a) Si-MCM-41, (b)
slower than the other SiR species used, supported by the Cr-MCM-41, (c) methyl chromium silica, (d) vinyl chromium silica and (e)
lower loading of methyl-groups, from elemental analysis. chloro propyl chromium silica.
34 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940

Table 2
Structural properties of small-pore chromium silicasa
Sample d100 (nm) SBET (m2 g1) Sex (m2 g1) Vt (cm3 g1) Vp (cm3 g1) Dp (nm)
wd DFT
C27ClC15 2.8 719 50 0.46 0.42 2.3 2.5
C27ViC15 2.6 672 70 0.34 0.30 1.9 2.0
C27MeC15 2.8 808 72 0.39 0.38 2.2 2.0
CRC 3.0 711 83 0.36 0.35 2.4 2.3
a
Notations are similar as in Table 1.

occurred. However, XRD patterns are featureless for struc- N2 adsorptiondesorption analysis of surfactant-
tural interpretation for chromium-containing mesoporous extracted chromium-containing samples having 15% chloro
samples synthesized with greater than 15% organic groups, propyl groups shows type IV isotherms with a capillary
except the chloro propyl-terminated chromium sample. condensation step in the low-pressure region (P/Po  0.2
Thus a high concentration of vinyl or methyl silanes 0.3) and an almost constant adsorption in the high-pressure
(>15%) and chromium in the synthesis gel restrict the con- region (Fig. 3A). Increasing the content of chloro propyl
densation of the silicate species to form stable inorganic groups in the pore channels resulted in a shift in the type
framework while the chloro propyl mesoporous sample of isotherm and at >15% chloro propyl loading the iso-
retains one reection up to a loading of 50%. therm changed from type IV to type I. According to
Compared to surfactant-extracted samples, chromium- IUPAC classication, type IV isotherms relates to capillary
containing organosilicas shows a pronounced contraction condensation steps, characteristics of the mesoporous
after calcination (Table 2, Fig. 2B). The enhanced pore size materials (250 nm), while type I isotherms are characteris-
shrinkages may arise due to the low degree of silica conden- tic of microporous or super microporous materials (<2 nm)
sation or due to the strong interactions between the sur- [32]. The change in type of isotherm with the percentage of
factants and the inorganic salts. So after calcination organic group loading is accompanied by a concomitant
treatments chromium-containing materials with d spacing decrease in the textural qualities of the samples. The BET
as low as 2.6 nm can be prepared. Notably, it was also surface area, pore volume and the pore size observed for
observed that compared to the non-modied chromium all the surfactant-extracted samples are given in Table 1.
sample, the organo-modied chromium samples shows In particular, the external surface area as well as the dier-
the absence of Cr2O3 in the wide-angle XRD patterns ence between the total pore volume and primary pore vol-
(denoted by arrows in Fig. 2B). Thus the presence of larger ume increases after 15% loading of organic groups in case
organo spacers introduced into the synthesis gel, like the of chloro propyl pendant samples. Such changes may pos-
chloro propyl, reduces the formation of Cr2O3 and its for- sibly relate to the development of secondary porosity. Since
mation gets decreased with the chain length of the organo- secondary porosity was not observed for materials pre-
silanes. These results demonstrate that by a judicious pared with 15% organosilanes, the additional porosity fea-
choice of the SiR groups, chromium-containing mesopor- tures of the materials observed at higher organosilane
ous materials without any crystalline Cr2O3 species can be loadings may probably results from the phase separations,
synthesized with Si/Cr ratios as low as 27. viz. silica rich and organosilica rich phases, and are

CRE, C27CE15 A 500 C 27CC 15 B

C27CE50, C27CE 30 C27 MC 15
1000 C27VE15, C ME15
27 C 27VC 15
C27VE15-(P), Si-MCM-41
-1

CRC
Adsorbed volume / ccg
-1

400
Adsorbed volume / ccg

800

+200
+200
600 300
+150

+100

400
200

200
100

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0
P/Po P/P o

Fig. 3. (A) Nitrogen adsorptiondesorption isotherms of surfactant-extracted chromium-containing mesoporous organosilicas and (B) calcined samples.
 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940
supported by the distinct hysterisis loop observed in the
high-pressure regions of C27ClE50 sample [14]. Interest-
ingly, among the chromium-containing hybrid samples,
the C27ViE15 sample shows an unusual sharp decrease in
the textural qualities. A possible reason for this result can
be due to the uncontrolled polymerization of the vinyl
groups in presence of chromium in the synthesis gel. In
order to conrm this pore blockening, an additional exper-
iment was carried out that to an alcoholic solution of
Si-MCM-41, vinyl silane and chromium was added at dif-
ferent time intervals. The N2 adsorptiondesorption of this
sample [C27ViE15-(P)] is shown in Fig. 3A. Contrary to the
direct synthesized C27ViE15 catalyst, this sample retains the
capillary condensation step with improved textual qualities
showing that the vinyl groups had undergone polymeriza-
tion but in a controlled manner (see Section 3.2). Since
the vinyl silane is added 1 h before the addition of chro-
mium salts, it is possible that the vinyl source gets xed
over the support samples and in presence of chromium
salts they may undergo controlled polymerization and
eectively cover the inner wall surface of the mesoporous
material, with better wall thickness.
The formation of ordered super micropores in the sam-
ples, after calcination, was further deduced from the N2
sorption isotherms. Nitrogen adsorptiondesorption iso-
therms of calcined chromium-containing materials having
15% organosilanes are shown in Fig. 3B. The adsorption
isotherms are of type I and are similar to the isotherms
observed with the short chain templated materials [26
29]. The isotherms shows a condensation in the low-pres-
sure region, somewhere around P/Po = 0.150.2, indicating
the formation of pores less than 2 nm diameter, typically in
the super microporous region. Since the position of capil-
lary condensation step correlates to the pore diameter of
the material, the observed dierences before and after cal-
cination shows that the pore size of the material can be tai-
lored by the choice of organic species in the synthesis gel.
However, we nd it dicult to compare our samples with
the pore diameters reported in literatures for small-pore
materials. Since the pore sizes are mainly examined by
gas adsorption studies, where the calculation methods are
highly inecient, dierences up to 1 nm can be obtained
and thus produces material with larger unit sell size but
with low pore sizes [14,39]. The textural properties of all
calcined porous chromium-silica samples are given in Table
2. Thus, a combination of the XRD results and adsorption
studies suggest that chromium-containing mesoporous sili-
cas having smaller d spacing, higher surface areas and pore
sizes in the border line between mesoporous and micropo-
rous materials, around 2 nm (Eq. (1) and DFT), can be pre-
pared by a judicious choice of organosilanes.
3.2. Spectroscopic studies
29
Si MAS NMR of surfactant-extracted, chromium-
containing mesoporous organosilicas exhibit peaks at
110, 100, 91 (sh), 65 and 57 ppm which are usually
35
assigned to Q4 [Si(OSi)4, siloxane], Q3 [Si(OH)(OSi)3, single
silanol], Q2 [Si(OH)(OSi)3, geminal silanol], T3 [SiR(OSi)3]
and T2 [Si(OH)R(OSi)2] sites, respectively [1416]. The
unmodied Si-MCM-41 sample shows the presence of
broad resonance peaks from 95 to 110 ppm, indicative
for a range of SiOSi bond angles, and it is noteworthy
that the sample contains large amounts of Q3 sites showing
a reduced framework cross-linking (Fig. S2). Compared to
Si-MCM-41, chromium and organic pendant group con-
taining samples shows a decrease in the Q3 + Q2 sites show-
ing that the material posses few residual silanols, resulting
in siliceous pore wall structure with higher degree of silica
condensation (Table S1). The decrease in the Q3 and Q2
signals after organo functionalization suggests that the
functionalization proceeds by the simultaneous cooperative
assembly or co-condensation of the TEOS and the organo-
silanes at the structure-orienting micelle interface. Presence
of Q3 sites, even after high organic group loading, suggest
that the decreased structural regularity observed for vinyl
and methyl silanes (>15%) does not arise from the lack
of charge balancing silanols and hence further modica-
tions in the current synthesis protocols can incorporate
more organosilanes. However, such a possibility can be
utilized for the synthesis of multi-functional organic
inorganic hybrid mesoporous materials, by various
post-synthesis modications. In particular, it can be noted
that the Q3/Q4 ratio is lower for the chloro propyl contain-
ing samples. This observation supports the results observed
from the XRD analysis that an increase in the chain length
of the organic pendant groups, helps to intercalate with the
surfactant groups in the self assembly process leading to a
better incorporation with better framework cross-linking.
In addition, the chloro propyl pendant mesoporous
organosilica sample showed an increased surface coverage
of organic groups than the vinyl- and methyl-pendant
organosilica samples. All these results suggest that more
hydrophobic organosilanes can better orient themselves
around the watermicelle interface and can intercalate into
the hydrophobic region of the surfactant species in co-con-
densation reactions.
13
C CP MAS NMR shows the presence of functional-
ized organic groups inside the MCM-41 pore channels
and the absence of surfactant species, after the solvent
extraction process. Absence of signals at 15 and 58 ppm,
assigned to the SiOCH2CH3 species, and in the range
5070 ppm, for surfactant groups, indicates that the hydro-
lysis of the organosilane monomers is complete and the
surfactant had removed from the pore channels of
the MCM-41 framework. These results are supported by
the negligibly low amounts of nitrogen (from surfactant)
from the CHN elemental analysis. The 13C CP MAS
NMR spectra of chloro propyl pendant mesoporous sam-
ple shows three peaks at 9, 26 and 45 ppm corresponding
to the carbon atoms of the propyl chain while the methyl
pendant organosilica sample shows the presence of a sharp
peak at 7 ppm, for the methyl carbon atoms [40]. These
results conrm that the chloro propyl and methyl-groups
36 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940

C1 C2 C3

d
C3 C1
O
O Si Cl
C1 C2 O
C2

c Cl-ES
C2
O
Si C1
O
b
O Vi-ES

O C1
C1 O Si CH3
O Me-MS
a

-40 0 40 80 120 160

ppm

Fig. 4. Solid-state 13C CP MAS NMR plots of surfactant-extracted mesoporous chromium samples; (a) C27MeE15, (b) C27ViE15, (c) C27ViE15-(P) and (d)
C27ClE15.

are functionalized in the developed samples and the
organic groups are not decomposed during the synthesis
conditions (Fig. 4a and d). In synthesis of organic
inorganic hybrid mesoporous materials, a particularly
interesting organic pendant group is the vinyl silane, since
the double bond is stable under the synthesis conditions
and is suciently reactive to follow further post-synthesis
modications. Generally, in carbon NMR, the vinyl car-
bon atoms show peaks at 129 ppm and at 138 ppm [3].
However, it is of interest to note that the vinyl terminated
mesoporous chromium sample shows an ill-dened NMR
spectrum. Such a result amply suggests that the vinyl
groups had undergone some kind of coupling or oligomer-
ization reaction and the presence of chromium salts may
promotes such reactions (Fig. 4b). For comparison, the
13
C CP MAS NMR of the C27ViE15-(P) is also shown in
Fig. 4c. The post-synthesis modied sample also shows
ill-dened peaks, but less intense peaks are observed
at 129 ppm and at 138 ppm. These results support the
ndings from nitrogen adsorption studies that the polymer-
ization of vinyl silanes is dierent in the two synthesis
methods.
Raman spectra were recorded for all mesoporous mate-
rials with and without Cr-loading. The peaks assignments
lapped by the water deformation mode. Samples contain-
ing chloro propyl pendants (ClE15, C27ClE15, C27ClE30,
C27ClE50) all contained a weak band at 1275 cm1, which
is assigned to the CH2Cl stretching mode. This mode
was observed at 1280 cm1 by infrared spectroscopy by
Kunko et al. [48]. Measurements made after calcinations
at temperatures up to and including 400 C showed no sig-
nicant decrease in the intensity of these bands (except
dH2O, which decreased). For samples containing methyl-
pendant groups (MeE15, C27MeE15) unique bands due to
vs and vas (CH3) (2923 and 2970 cm1, respectively) were
observed only following calcination at 400 C, once all
traces of surfactant were removed.
Raman spectra of chromium-containing samples did not
show any distinct peaks due to chromium oxide species
indicating that the transition metal is very well dispersed.
Close inspection often showed a shoulder at 980 cm1
when chromium was in the sample. This could be due to
A B
d
d
Absorbance / a.u.

are listed in Table S2. The bands at 1000 and 795 cm1
are similar in position to those previously reported in these
c
mesoporous siliceous materials and are assigned to the c

stretching modes of surface silanols (vO3SiOH) and silox- b

ane bridges (SiOSi) [4144]. The band at 1600 cm1 has b
also been observed and assigned to the deformation mode
of water (dH2O). The vinyl pendant samples (ViE15 and a a
C27ViE15) showed a peak at 2984 cm1, which we assign
to the symmetric stretching mode of CH2. This band was 400 600 800 200 400 600
previously observed by Li et al. at 2988 cm1 in solgels Wavelength / nm
containing vinyl triethoxysilane [47]. The weak asymmetri-
Fig. 5. UVVis spectra of (A) as-synthesized chromium-containing
cal stretching mode seen by these authors at 3072 cm1 was mesoporous materials and (B) calcined chromium-containing mesoporous
not observable in our spectra. Similarly the C@C stretching materials; (a) Cr-MCM-41, (b) methyl chromium silica, (c) vinyl
mode observed at 1608 cm1 was not resolved; it was over- chromium silica and (d) chloro propyl chromium silica.
 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940
the asymmetric stretching mode of dehydrated monochro-
mate CrO2 4 however spectra were not conclusive. For
comparison, a sample of the siliceous mesoporous material
was impregnated with the same amount of chromium
(2 wt%) and calcined at 500 C. A weak but discernible
peak at circa 870 cm1 appeared (assigned to either
hydrated monochromate or hydrated polychromate spe-
cies) [42,45,46]. Thus chromium added during synthesis
was clearly stabilized in a manner absent in post-synthesis
impregnation.
Diuse reectance UVVis analysis of the as-synthe-
sized and calcined chromium samples is shown in Fig. 5a
and b. All the as-synthesized chromium samples were pale
green colored and following calcination changed to an
intense yellow color. The green color of the materials
implies the presence of trivalent chromium ions in octahe-
dral geometry while the yellow color would imply the pres-
ence of high-valent chromium ions in tetrahedral
coordination. UVVis spectra of as-synthesized samples
show two sharp absorption bands at 440 nm and 610 nm
typical of dd transitions corresponding to the 4A2g(F) to
4
T1g(P) and 4A2g(F) to 4T2g(F) transitions, for the trivalent
chromium ions (Cr3+) in octahedral coordination (Fig. 5a).
The spectra of calcined chromium samples show bands at
270, 340 and 450 nm. The sharp bands observed at
270 nm and 340 nm are assigned to the OCr(VI) charge
transfer transitions of chromate species while the weak
band centered at 450 nm is assigned to the charge transfer
bands associated with dichromate- or polychromate-type
species. These results indicate that the major species
formed over the chromium catalysts be the monochromate
species [46]. However, closer analysis of the peaks shows
that, except C27CC15, all other chromium samples show a
distinct tailing of the band to higher wavelengths. This
may possibly arise due to the presence of Cr2O3 species,
as observed from the XRD analysis.
4. Discussion
As mentioned in Section 1, the synthesis of ordered mes-
oporous materials having pore sizes in the borderline
between mesoporous and microporous silicas constitutes
an active research area during the last decade. This target
is generally achieved by using short chain templates like
the octyl ammonium surfactants or the hexylamine surfac-
tants in the assembly process, so that porous materials
below 2 nm can be synthesized [2327,32]. However, many
of the surfactants used for this purpose are not commer-
cially available and hence have to synthesize before it get
utilized in the assembly process. An alternative method
used in the synthesis of small-pore silicas is based on the
extensive structural shrinkage upon surfactant removal
during high temperature calcinations. This shrinkage dri-
ven small unit cell formation allow one to prepare small-
pore silicas having tailorable pore sizes, depending on the
nature of the structure orientor as well as its formation
mechanism. Kruk et al. showed that more than three out
37
of ve silicon atoms bearing organic groups (vinyl-) can
be prepared by the direct co-condensation method and they
demonstrated that calcination of high percentage vinyl-
loaded samples produces small-pore silicas, having pore
sizes in the micropore region [28]. In an another method,
Aguado et al. showed that by varying the concentration
of aluminium in the synthesis of micelle templated silicas
(Al-MTS), small-pore silicas having pore size below 2 nm
can be prepared [14,25]. Herein, we propose an alternate
method for the syntheses of organicinorganic hybrid
materials of tailorable pore sizes and the objective of this
approach is three fold: (a) to synthesize metal-containing
organicinorganic hybrid mesoporous materials, (b) to
bridge the gap between the mesoporous and microporous
materials from the mesopore region and, (c) to observe
the eect of organosilanes in the dispersion of the catalytic
active sites and its catalytic performance than the conven-
tional metal-containing mesoporous materials.
In the syntheses of organicinorganic hybrid mesopor-
ous materials, it was observed that with the percentage of
organic group functionalization, the d100 XRD peak gets
shifted to higher 2h angle. Among the organosilanes used,
the chloro propyl and vinyl pendant samples show the
highest shrinkage in d100 spacing, with the percentage of
loading, than the short chain methyl silane groups. This
result shows that the intrinsic nature of the organo silanes
decides the percentage of organo functionalization as well
as the lattice shrinkages. Thus the interactions between
the organosilanes and the surfactant molecules are very
important in the formation of ordered mesoporous materi-
als with high organic loadings and these in turn depends on
the nature of the organic groups present on the organosil-
anes and synthesis procedures. In the current synthesis,
hydrophobic organosilanes are taken deliberately, due to
the consideration that organoalkoxy silanes having hydro-
phobic ends can orient more eectively around the water
micelle interface and can intercalate in to the hydrophobic
regions of the surfactant micelles, during co-condensation
reactions. Thus the primary reason for the dierences in
the percentage of organic group functionalization may
arise from the dierent hydrolysis and condensation of
the TEOS and organosilanes and with respect to the size,
hydrophilichydrophobic property, as well as inductive
eects, the percentage incorporation of organosilanes var-
ied. As a result, if the rate of hydrolysis of the organosil-
anes will not match with TEOS, its percentage will be
less and hence for a better co-condensation reaction
between TEOS and alkoxy silanes, well tuning in synthesis
procedures are usually needed.
Our experimental results suggest that, because of the
inductive eects of the methyl-groups in the methyl alkoxy
silanes, its hydrolysis/condensation with TEOS will be less,
leading to low methyl-loadings. Hence, at a higher percent-
age of methyl loading (typically >30%), the gel mixture
becomes viscous and lead to distinct phase separations.
Moreover, the homocoupling of the hydrolyzed organosil-
anes rather than the co-condensation between TEOS and
38 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940

Cr R Cr
R
540 oC
Cr R= -CH3, -CH=CH2, -(CH2)3-Cl
Cr

R
Cr R Cr

Dp=>25 Dp=20

Scheme 1.

organosilanes may also enhance phase separation and the 5. Catalytic activity
formation of more viscous solids at higher organosilane
loadings. Thus if the organic groups are not condensed Selective oxidation of cyclohexane to a mixture of cyclo-
with the inorganic chain of TEOS it will disturb the surfac- hexanone and cyclohexanol (the so-called KA oil), under
tant-silicate assembly, leading to materials having poor mild conditions, is of industrial relevance due to its impor-
channel structures [49,50]. Hence, even though the input tance in the production of Nylon 6 and Nylon 66 [51].
amount of organosilanes is high, after reux and washing Hence, the present small-pore chromium samples are
steps it gets easily removed and thereby reduces the per- applied as catalysts in the oxidative transformation of
centage of organic loading. Elemental analysis results show cyclohexane and the catalytic activity was compared with
that with respect to the nature of organosilanes the percent- a Cr-MCM-41 catalyst synthesized without any organic
age of organic functionalization varied, and the incorpora- spacers (Table 3). The main products obtained are cyclo-
tion is found minimum for the Me-MS samples. Thus it is hexanol (A) and cyclohexanone (K) with trace amounts of
likely that the methyl alkoxy silanes are not suciently cyclohexyl hydroperoxide (CHHP) as well as cyclohexyl-
hydrophobic to get entrapped with the micelle groups to tert-butylperether (CHTB). The samples prepared using
produce a rigid framework. Perhaps this reason may also organic spacers showed higher conversion than the conven-
accounts for the structural collapse of higher methyl con- tional Cr-MCM-41 catalyst and among them, the C27ClC15
tent samples, after template removal. Thus the systematic catalyst shows the maximum conversion followed by
dierences observed with dierent organosilanes shows C27ViC15, C27MeC15 and Cr-MCM-41, after 5 h run. The
that, if the chain length is long, it can be intercalated with enhanced activity of the C27ClC15 catalysts is assumed to:
the surfactant groups in the condensation process while if (i) the wormhole-like channel morphology obtained (from
the chain length is small it may disturb the surfactantsili- TEM images), which may facilitate an enhanced access
cate assembly leading to organicinorganic hybrid materi- for the cyclohexane molecules to the active chromium sites,
als having poorly ordered mesoporous structures, with (ii) the better hydrophobicity relations between the oxidant
low organic loadings. and catalyst and (iii) the absence of Cr2O3 clusters, which
Due to the extensive structural shrinkage, upon calcina- create all the active chromium sites available for the sub-
tion, small-pore chromium silicas can be adequately strate molecules. Thus, the better conversion results
prepared from the developed chromium-containing obtained with the C27ClC15 catalyst reasonably suggest that
organicinorganic hybrid mesoporous materials (Scheme
1). A sharp decrease in unit cell size is observed for all
Table 3
the calcined samples and N2 adsorption results show type
Cyclohexane oxidation reaction over various chromium catalystsa
I isotherms with pore sizes in the super-microporous region
Sample Cr (%) Cyclohexane K/A TON Meta
(1.82.2 nm). These results show a calcination driven
conv. (mol.%) leaching
shrinkage of the pore size and the presence of chromium
C27ClC15 2.3 9.5 5.5 2.0 13
and organosilanes enhance the shrinkage so that materials
C27ClC30 1.9 10.3 5.7 2.7 n.d.
with tailorable pore size in the super microporous region C27ClC50 1.7 9.6 4.8 2.8 n.d.
can be developed. Thus mesoporous materials with tailor- C27ViC15 2.4 7.3 6.1 1.4 8
able pore sizes and good ordering can be systematically C27MeC15 2.4 6.6 5.5 1.3 22
synthesized with a combination of organic and inorganic CRC 2.5 4.0 6.8 0.8 26
Si-MCM-41
species and materials, preferentially in the upper micropo-
rous region can be readily obtained after calcinations. The Reaction conditions: catalysts (mg), 100; T (C), 70; cyclohexane:TBHP
(mol/mol), 1; solvent (5 ml), (CH3)2CO; time (h), 5.
present synthesis routes explained herein demonstrate that a
K/A, cyclohexanone/cyclohexanol ratio; TON, Turn over number,
if surfactants of shorter alkyl chain length are used for the moles of cyclohexane converted per mole of chromium; percentage of
assembly process, chromium (or any metal) silica samples chromium and chromium leaching was determined by ICP-OES analysis;
having still lower pore sizes can be adequately prepared. n.d., not determined.
 S. Shylesh et al. / Microporous and Mesoporous Materials 108 (2008) 2940
isolated, well-dispersed chromium (metal) species are highly
active in the oxidation of cyclohexane. Moreover, it is
attractive to note the major formation of oxidized product
cyclohexanone and the K/A ratios reached a value of >6,
after 5 h reaction time. Since CHHP is also formed as a
product, it is reasonable that the peroxide species formed
can also enhance the conversion of cyclohexane. However,
kinetic measurements showed that its percentage gets
increased with the percentage of cyclohexane conversion
in the initial stages of the reaction. This indicates that
CHHP does not act as an oxidizing agent. Thus, the
increased formation of cyclohexanone may possibly arise
from the mixed Russell termination [52].
To conrm that the catalysts are heterogeneous and
chromium was not leached out during reactions, ICP anal-
ysis of the reaction mixture was done. Results show that
the catalysts are heterogeneous and shows limited leaching
than the chromium-containing catalysts prepared without
the addition of any organosilanes (Table 3). These results
suggest that the organic groups introduced not only helps
to tailor the pore sizes but also helps to disperse the active
catalytic sites and the hydrophobic features are maintained
akin to the recently reported periodic mesoporous organo-
silicas [53]. Remarkably, the leaching of chromium was
found least for the C27ViC15 catalyst than the other chro-
mium-containing catalysts. We attribute this eect to the
better wall thickness of the C27ViC15 sample, due to the
polymerization of the vinyl groups, which may helps in
the better stabilization of chromium than the other chro-
mium catalysts.
6. Conclusions
Bifunctional periodic mesoporous organosilicas having
chromium in the frame wall positions and organic groups,
such as chloro propyl, vinyl and methyl, in the pore chan-
nels are prepared by a one-pot synthesis procedure. The
extent of structural ordering and the percentage of organic
group loading depend on the intrinsic properties of the
organic groups as well as the mode of preparation proce-
dures. The concept of introducing chromium in the frame
wall position, organic silanes like the chloropropyl silane
in the pore channels lead to a low degree of framework
cross-linking which nally lead to the development of chro-
mium-containing silicas having pore size in the super
microporous region, after calcinations. The new materials
show promising catalytic activity, selectivity and stability
in the liquid phase oxidation reaction of cyclohexane than
the Cr-MCM-41 catalyst. We anticipate that even small-
pore materials can be prepared by using surfactants of
smaller alkyl chain lengths or by systematically increasing
the calcination temperatures.
Acknowledgments
We gratefully acknowledge our reviewers for the con-
structive suggestions. S.S. thanks Council of Scientic
39
and Industrial Research (CSIR), India, for a research fel-
lowship. The authors are thankful to Dr. Nalini Jacob
and Mr. R.K. Jha for the adsorption measurements and
Mr. Prinson P. Samuel for the experimental assistance.
This research was also nancially supported by the CSIR
task project, under the scheme, Catalysts and Catalysis
(P23-CMM0005B).
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.micromeso.
2007.03.039.
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