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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Selective oxidation of cyclic olens over framework Ti-substituted,

three-dimensional, mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves
Anuj Kumar, Darbha Srinivas
Catalysis Division, 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: Framework Ti-substituted, three-dimensional, mesoporous titanosilicates, Ti-SBA-12 and Ti-SBA-16,
Received 9 December 2011 were prepared by direct hydrothermal synthesis method. These catalysts showed catalytic activity higher
Received in revised form 23 January 2012 than the hitherto known titanosilicates for the oxidation of cyclic olens (cyclohexene and cyclooctene)
Accepted 28 January 2012
with tert.-butyl hydroperoxide. An epoxide selectivity of 100% and olen conversion greater than 92%
Available online xxx
were obtained. Cubic Ti-SBA-16 with interconnected cage-like mesopore structure was more active
than hexagonal Ti-SBA-12. X-ray diffraction and diffuse reectance UVvis, Fourier transform infrared,
Keywords:
Raman and electron paramagnetic resonance spectroscopies provided evidence for the substitution
Titanosilicates
Mesoporous materials
of Ti4+ (for Si4+ ) in the framework locations. The catalytic activity correlated with the concentration
Ti-SBA-12 of framework-substituted, tetrahedral Ti4+ ions. Easy accessibility of the active sites and the three-
Ti-SBA-16 dimensional mesoporous structure are the possible causes for the superior activity of these titanosilicate
Molecular sieves catalysts.
Selective oxidation 2012 Elsevier B.V. All rights reserved.
Epoxidation of cyclic olens

1. Introduction heteroatoms in SBA-15, a material with two-dimensional hexago-

Titanosilicate molecular sieves (especially TS-1) have been
widely investigated due to their remarkable catalytic activity for
oxidation reactions at mild conditions using aqueous hydrogen
peroxide as oxidant [1,2]. Their application is, however, limited
to molecules with smaller dimensions due to inherent constraints
on pore size of the catalysts. Mesoporous M41S-type titanosili-
cates are not only less stable but show a lower intrinsic catalytic
activity and selectivity toward the use of hydrogen peroxide in
epoxidation reactions than the microporous TS-1 owing to their
high hydrophilicity [3,4]. Silylation of the surface of Ti-MCM-41
and removal of water from the reaction media improve the cat-
alytic activity of these materials [4,5]. However, there is a need to
develop more efcient ordered, mesoporous silica materials with Ti
substituted in their framework for transformation of bulky organic
molecules of pharmaceutical interest. Among several, SBA-12 and
SBA-16 attract attention due to their outstanding stability and
three-dimensional mesopore structure [6,7]. Incorporation of Ti in
their framework is difcult because under the conventional, high
acidic conditions of their synthesis, Ti exists only in the cationic
form rather as oxy/hydroxy species. The former cannot be intro-
duced easily into the framework via condensation processes with
silica species [911]. While there are reports of incorporation of
nal structure [1214], such reports in the case of three-dimensional,
mesoporous materials are scarce. In a recent communication [15],
we have reported that Ti can be substituted in the framework of
SBA-12 by a controlled adjustment of the HCl concentration used
in the synthesis gel. HCl solution of 2 M concentration is usually
used in the synthesis of SBA-12. We have systematically varied the
concentration of HCl from 0.052 M and found that Ti can be substi-
tuted to a greater extent in the framework when a 0.1 M solution of
HCl is used in the synthesis gel. Ti-SBA-12 thus prepared shows high
catalytic activity and selectivity for the epoxidation of cyclic olens.
In the case of Ti-SBA-16, a 2 M HCl solution was found appropriate
for the synthesis. However, it may be noted that apart from HCl
concentration, several other parameters including Ti source, mode
of addition of the Ti source, ionic strength of the medium, synthesis
temperature and amount of water could also inuence the incor-
poration of Ti in ordered mesoporous silica during their synthesis
under acidic conditions [16]. We report here a comparative study of
the structural characteristics and oxidation properties of Ti-SBA-12
and Ti-SBA-16 prepared by direct hydrothermal synthesis.
2. Experimental
2.1. Catalyst preparation

Brij 76 [C18 H37 (OCH2 CH2 )10 OH, mol. wt 711, Aldrich Co.] and
Corresponding author. Tel.: +91 20 2590 2018; fax: +91 20 2590 2633. Pluronic F127 block-copolymer (EO106 PO70 EO106 ; mol. wt 12600,
E-mail address: d.srinivas@ncl.res.in (D. Srinivas). Aldrich Co.) were used as structure directing agents in the synthesis

0920-5861/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2012.01.035

Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035
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of SBA-12 and SBA-16, respectively. Tetraethyl orthosilicate (TEOS,
Aldrich Co., 98%) was used as a Si source and titanium iso-propoxide
(Spectrochem. Pvt. Ltd., India, 98%) was used as a Ti source. All the
solvents (A.R. grade) were procured from Thomas Baker and the
reagents were purchased from Aldrich Co.
2.1.1. SBA-12
SBA-12 was prepared by a modied procedure of Zhao et al. [6],
wherein, 8 g of Brij 76 was dissolved in 40 g of distilled water and
160 g of 0.1 M HCl taken in a polypropylene beaker. The mixture was
stirred at 313 K for 2 h till a homogeneous solution was obtained.
To it, 17.6 g of TEOS was added over 30 min. Stirring was contin-
ued for 20 h. The gel formed was transferred into a Teon-lined
stainless steel autoclave and heated at 373 K for 24 h while placing
in an electric oven. The solid (as-synthesized SBA-12) formed was
ltered, washed thoroughly with distilled water (23 L) and dried
at 373 K for 12 h. It was calcined at 823 K for 8 h to remove all the
organic matter in it. The calcined SBA-12 was white in color. Yield:
94%.
2.1.2. Ti-SBA-12
In a typical preparation of Ti-SBA-12 with Si/Ti (input) molar
ratio of 30 [15], 8 g of Brij 76 was dissolved in 40 g of distilled water
and 160 g of 0.1 M HCl. The mixture was stirred at 313 K for 2 h and
17.6 g of TEOS was added to it over 30 min. Then, 0.8 g of titanium
iso-propoxide dissolved in 10 mL of iso-propanol was added and
stirring was continued for 20 h. The gel formed was transferred
into a Teon-lined stainless steel autoclave and heated at 373 K
for 24 h. The solid [as-synthesized Ti-SBA-12 (Si/Ti = 30)] formed
was recovered by ltration, washed thoroughly with distilled water
(23 L), dried at 373 K for 12 h and calcined at 823 K for 8 h. The
calcined material (Ti-SBA-12) was white in color. Yield 94%. Ti-
SBA-12 with Si/Ti input ratio = 80, 50, 40 and 20 were also prepared
in a similar manner using appropriate amounts of the Si and Ti
sources.
2.1.3. SBA-16
Pluronic F127 block-copolymer (7.4 g) was dissolved in 384.3 g
of 2 M HCl solution at 313 K while stirring for 2 h. To it, 28.34 g of
TEOS was added drop-wise over 30 min. The stirring was contin-
ued for 24 h. The gel formed was transferred into a Teon-lined
stainless steel autoclave. It was crystallized at 353 K for 48 h. The
solid formed was ltered out, washed with distilled water (23 L),
dried at 373 K overnight and calcined at 823 K for 8 h. The calcined
SBA-16 [6,17] was white in color. Yield: 96%.
2.1.4. Ti-SBA-16
In a typical synthesis of Ti-SBA-16 (Si/Ti input molar ratio = 30),
7.4 g of Pluronic F127 was dissolved in 384.3 g of 2 M HCl solu-
tion at 313 K. After 2 h of stirring, 28.34 g of TEOS was added
drop-wise over 30 min and stirred for 4 h. Then 1.28 g of tita-
nium iso-propoxide dissolved in 10 mL of iso-propanol was added
slowly. The stirring was continued for another 20 h. The gel formed
was transferred into a Teon-lined stainless steel autoclave. It was
heated at 353 K for 48 h. The solid formed was separated by ltra-
tion, washed with distilled water (23 L), dried at 373 K overnight
and calcined in air at 823 K for 8 h. The calcined Ti-SBA-16 was white
in color. Yield: 95%.
Ti-SBA-16 with Si/Ti input ratio = 80, 50, 40 and 20 were also
prepared in a similar manner taking appropriate amounts of the Si
and Ti sources.
2.2. Characterization techniques
The Ti content in titanosilicate samples was determined using
an Inductively Coupled Plasma-Optical Emission Spectrometer
Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035
(Spectro Arcos ICP-OES). A known quantity of the sample was dis-
solved in a minimum amount of HF and made up to the required
volume. Powder X-ray diffraction (XRD) patterns were recorded on
a PANalytical (Xpert Pro) diffractometer operated with a Ni-ltered
Cu-K radiation ( = 0.15418 nm, 40 kV and 30 mA) and a propor-
tional counter detector. The diffraction patterns in the low 2 angle
region (0.55 ) were recorded at a scan rate of 0.2 /min and those
in the high 2 region (1080 ) at a rate of 4 /min. The step size
in the measurements was 0.02 . The N2 adsorption and desorp-
tion measurements at 77 K were carried out on a Quantachrome
USA (Autosorb-1 C) equipment. Prior to N2 adsorption, the sam-
ples were evacuated at 573 K for 5 h. The specic surface area of
the samples was determined by the Brunauer, Emmett and Teller
(BET) method using the data points in the relative pressure (P/P0 )
region of 0.050.3. The total pore volume was determined from the
uptake of adsorbate at a relative pressure (P/P0 ) of 0.99. A refer-
ence alumina sample (supplied by Quantachrome, USA) was used
for calibrating the instrument. The average pore diameter was esti-
mated from the desorption-branch of the isotherms by using the
BarretJoynerHalenda (BJH) model. High resolution transmission
electron micrograph (HRTEM) images of the samples were collected
on a FEI Technai-F30 instrument with a 300 kV eld emission gun.
For this, the samples were prepared by dispersing the calcined
materials in iso-propanol, placing them on a carbon coated Cu grid
(200 mesh, type B) and drying at 298 K.
Fourier transform infrared (FTIR) spectra were recorded on a
Shimadzu 8300 spectrophotomer in the region 4004000 cm1
(spectral resolution = 4 cm1 ; number of scans = 300). Samples
were prepared in the form of KBr pellets (1 wt%). FT-Raman spec-
tra were recorded with a Horiba JY LabRaman HR 800 MicroRaman
spectrometer using a wavelength of 630 nm generated by a HeNe
laser operating at 20 mV. Diffuse reectance UVvis (DRUVvis)
spectral measurements were conducted using a Shimadzu UV-
2550 spectrophotometer equipped with an integrating sphere
attachment (ISR 2200). Spectral grade BaSO4 was used as a ref-
erence material. Electron paramagnetic resonance (EPR) spectra of
titanosilicates were recorded on a Bruker EMX X-band spectrom-
eter ( = 9.42 GHz) operating with a 100 kHz eld modulation. The
microwave frequency was calibrated using a frequency counter t-
ted in a microwave bridge (ER 041 XG-D). The EPR spectra were
recorded taking the samples in suprasil quartz tubes. Prior to mea-
surements, the samples were activated at 373 K in air. Then, 0.1 mL
of 30% aqueous H2 O2 was added to 45 mg of the titanosilicate sam-
ple. It was ensured that the whole sample was completely soaked
in the oxidant medium. The catalyst changed its color from white to
pale yellow, an indication of the formation of reactive oxo-titanium
species. 29 Si magic-angle spinning nuclear magnetic resonance
(MAS NMR) spectra were recorded at 59.63 MHz on a Bruker AV300
NMR spectrometer with 4 mm sample rotors. Samples were spun at
a frequency of 10 kHz. A single pulse sequence was applied and the
measurements were performed at 293 K. Thermogravimetric and
differential thermal analyses (TG-DTA) of the samples were done
under nitrogen (50 mL/min) on a PerkinElmer Diamond TG/DTA
instrument at a ramp rate of 10 K/min in the temperature range
of 2981273 K.
2.3. Reaction procedure: oxidation of cyclic olens
In a typical reaction, known quantities of substrate (cyclohex-
ene or cyclooctene), solvent, catalyst and oxidant were taken in a
50 mL double-necked round-bottom ask placed in a temperature-
controlled oil bath and tted with a water-cooled condenser. The
reactions were conducted at a specied temperature for a desired
period of time. After completion of the reaction, the catalyst was
separated by centrifugation and the liquid products were iden-
tied by GCMS (Shimadzu GCMS-QP5050A, HP-5 column: 30
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A. Kumar, D. Srinivas / Catalysis Today xxx (2012) xxxxxx 3

m-long 0.25 mm i.d. 0.25 m thickness) and quantied by gas

Wall thickness
chromatography (Varian 3400, CP-SIL8CB column: 30 m-long and
0.53 mm i.d.).

4.6 (4.3)

8.4 (7.7)
8.8 (8.8)
5.3 (5.0)
(nm)
3. Results and discussion

Wall thickness = c average pore diameter (for SBA-12 and Ti-SBA-12) and 3/2 aaverage pore diameter (for SBA-16 and Ti-SBA-16). Values in parentheses are those obtained from HRTEM measurements.
3.1. Catalyst characterization

3.1.1. X-ray diffraction

Pore volume
Fig. 1 shows the XRD patterns of SBA-12, Ti-SBA-12 (Si/Ti = 30),

(cm3 /g)
SBA-16 and Ti-SBA-16 (Si/Ti = 30) in the low and wide-angle (inset)
regions. SBA-12 showed an intense peak at 1.76 corresponding to

1.49
0.67
0.67
1.10
the (0 0 2) reection and two less intense, resolved peaks (at 3.0
and 3.5 ) due to (1 1 2) and (3 0 0) reections, respectively. A shoul-
der (to the main peak) at 1.27 due to (1 0 0) reection was also

diameter (nm)
observed. SBA-16 showed an intense peak at 0.92 attributable to

Average pore
the (1 1 0) reection and two poorly resolved weak peaks at 1.2 and

5.4 (5.4)
5.9 (5.8)
3.4 (3.6)
3.5 (3.4)
1.9 due to (2 0 0) and (2 1 1) reections, respectively. These diffrac-
tion patterns are typical of mesoporous materials with long-range
ordering. While the XRD patterns of SBA-12 can be indexed to a

N2 physisorption
hexagonal symmetry (p63 /mmc), those of SBA-16 can be described
by a cubic symmetry (Im3m) [68]. In the case of Ti-containing

SBET (m2 /g)

materials these peaks had shifted to lower 2 values. This shift in
peak position is more in the case of Ti-SBA-12 than in Ti-SBA-16

819
1015
800
765
(Fig. 1). Ti incorporation did not alter the integrity of the frame-
work structure. But then, the unit cell parameters (a and c for the

Unit cell parameter

hexagonal Ti-SBA-12 and a for the cubic Ti-SBA-16) and unit cell

11.2
10.0
volume (V) had increased (Table 1). Note that the ionic radii of Ti

c
(0.0606 nm) is larger than that of Si (0.04 nm). With increasing Ti
content, the unit cell parameters and unit cell volume (V) of Ti-SBA-

Unit cell parameter a = 2d1 0 0 / 3 and c = 2d0 0 2 (for SBA-12 and Ti-SBA-12) and a = 2 d1 1 0 (for SBA-16 and Ti-SBA-16).
(nm)
12 and Ti-SBA-16 increased linearly up to a Ti/(Si + Ti) molar ratio of

8.7
13.6
14.2
8.0
a
0.033 and 0.025, respectively (Fig. 2). These observations provide
a clear evidence for the substitution of Ti (for Si) in the framework
of mesoporous Ti-SBA-12 and Ti-SBA-16. Earlier, such correlations

d1 1 0

9.6
10.0
were shown as evidence for Ti substitution in the framework of

microporous TS-1 and large pore Ti- molecular sieves [1820].
Interplanar spacing (nm)

We report here, for the rst time, an extension of this relationship

to three-dimensional mesoporous materials. The weak peak at 23
d0 0 2

5.6
5.0
in the wide-angle region (Fig. 1, inset) is attributed to silica with


microporous structure. No separate peaks due to extra-framework
anatase/rutile TiO2 were detected. However, their presence, based

Chemical composition, structure and textural properties of Ti-SBA-12 and Ti-SBA-16.

on this evidence alone, cannot be completely excluded as the main

d1 0 0

6.9
7.5

peak of TiO2 can overlap with the peak of microporous SiO2.

3.1.2. N2 physisorption
Hexagonal (p63 /mmc)
Hexagonal (p63 /mmc)

SBA-12 and Ti-SBA-12 showed typical type-IV N2

adsorptiondesorption isotherms with H1 hysteresis loop which
X-ray diffraction

is characteristic of a hexagonal mesoporous material (Fig. 3)

Cubic (Im3m)
Cubic (Im3m)

[6,7,15]. SBA-16 and Ti-SBA-16 showed isotherms with a broad

Structure

H2 hysteresis loop representative of a cubic, interconnected,

cage-like mesopore structure (Fig. 3) [8,21,22]. All these materials
showed a narrow pore size distribution curve. Ti incorporation
altered the textural properties (Table 1). The BET surface area
increased considerably on Ti substitution. Such an increase was
Output

not observed in the case of Ti-SBA-16, neither in surface area nor

39.1

53.8
Si/Ti molar ratio

in pore volume. While the actual reason for this is not clear at this

point of time, we feel that it could be due to differences in surface

structure (hydrophilic/hydrophobic nature and silanol groups
concentration) of these two silica materials.
Input

30

30

3.1.3. High resolution transmission electron microscopy

HRTEM images (Fig. 4) have reconrmed the long-range
mesoporous ordering in these materials. The textural parame-
Ti-SBA-12

Ti-SBA-16
Catalyst

SBA-12

SBA-16

ters determined from HRTEM agree well with those obtained

Table 1

from the N2 physisorption studies (Table 1). The SBA-12 mate-

rials have a three-dimensional, hexagonal, closed-packed (hcp)

Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035
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Fig. 1. XRD proles: (a) SBA-12 and Ti-SBA-12, and (b) SBA-16 and Ti-SBA-16. Si/Ti molar ratio (input) in Ti-containing sample = 30. Inset shows the patterns at higher 2
values.

15.5
7.6 Ti-SBA-12
7.4 Ti-SBA-16
Unit cell parameter

7.2 15.0

a (nm)
7.0
6.8 a (nm)
6.6
14.5
11.8
11.6 14.0
11.4 3600
11.2 c (nm)
11.0
V (nm )

3400
3

600
550 3200
V (nm )
3

500
450 3000
400
0.00 0.01 0.02 0.03 0.04 0.00 0.01 0.02 0.03 0.04
Ti/(Si + Ti) mol ratio Ti/(Si + Ti) mol ratio

Fig. 2. Correlation of unit cell parameters (a/c) and unit cell volume (V) with the Ti content in Ti-SBA-12 (left panel) and Ti-SBA-16 (right panel).

Fig. 3. N2 adsorptiondesorption isotherms and pore size distribution of SBA-12, Ti-SBA-12, SBA-16 and Ti-SBA-16. Si/Ti molar ratio (input) in Ti-samples is 30.

Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035
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Fig. 4. High resolution transmission electron micrographs. Top: SBA-12 and Ti-SBA-12 (Si/Ti = 30) and bottom: SBA-16 and Ti-SBA-16 (Si/Ti = 30).

Q3 = -101.7 ppm Q4 = -108.8 ppm

Q2 = -92.3 ppm
Q4 = -110.7 ppm
Q3 = -98.3 ppm
Ti-SBA-12 (30) Ti-SBA-16 (30)

SBA-12 SBA-16

-60 -75 -90 -105 -120 -135 -150 -60 -75 -90 -105 -120 -135 -150
Chemical shift, / ppm Chemical shift, / ppm
29
Fig. 5. Si MAS NMR spectra. Left: SBA-12 and Ti-SBA-12 (Si/Ti = 30), and right: SBA-16 and Ti-SBA-16 (Si/Ti = 30).

mesopore structure [7] whereas the SBA-16 materials have a three- 100
SBA-12
dimensional, body-centered cubic (bcc), cage-like interconnected 98 SBA-16
mesopore structure [8].
96
Weight loss (%)

94
3.1.4. 29 Si MAS NMR 92
Ordered silica materials show 29 Si MAS NMR signals at around 90
91, 101, and 110 ppm which are attributed to three chem-
88
ically and magnetically distinct tetracoordinated Si species viz.,
86
Si(OSi)x (OH)4x , where x = 2 (Q2 ), 3 (Q3 ), and 4 (Q4 ), respec-
tively [23,24]. SBA-12 and Ti-SBA-12 showed these peaks at 84
92.3, 101.7 and 110.7 ppm, respectively. SBA-16 and Ti-SBA- 82
16 showed only two peaks at 98.3 and 108.8 ppm attributable to 400 600 800 1000 1200
Q3 and Q4 species, respectively (Fig. 5). While the intensity of Q3 sig- Temperature (K)
nal is higher than that of Q4 in SBA-12 materials, the reverse is true
Fig. 6. Thermogravimetric analysis of SBA-12 and SBA-16.
for SBA-16 materials. This indicates that SBA-16 is relatively more

Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035
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gzz = 2.024

gyy= 2.008
Ti-SBA-12
Ti-SBA-16

Intensity (a.u.)
Intensity (a.u.)
955 A B

SBA-12 Ti-SBA-12
981 gzz = 2.038

gxx= 2.002

3275 3300 3325 3350 3375 3400 3425

200 400 600 800 1000 Magnetic Field (G)
Raman shift (cm -1)
Fig. 9. EPR spectra (at 77 K) of superoxo-Ti species generated on Ti-SBA-12 and
Fig. 7. Representative FT-Raman spectra of SBA-12 and Ti-SBA-12. Ti-SBA-16 contacted with 30% aqueous H2 O2 .

hydrophobic than SBA-12. Ti substitution did not alter markedly expected, the all-silica samples, SBA-12 and SBA-16 did now show
the intensity ratio of Q4 to Q3 signals. It may be noticed that at any absorption bands in the UVvis region. Ti-SBA-12 and Ti-SBA-
similar Ti loading, Ti-SBA-16 showed downeld chemical shift for 16 (Fig. 8) showed an absorption band maximum at 206 nm and
Q3 and Q4 species. This deshielding effect on the position of 29 Si a shoulder band at 217220 nm which have been attributed to
MAS NMR signals is possibly due to differences in the structures of mono-atomically dispersed Ti4+ ions in tetracoordination geome-
Ti-SBA-12 and Ti-SBA-16. In the past, experimental and theoretical try. While the band at 206 nm has been corresponded to tetrapodal
studies on zeolites evidenced correlations between chemical shifts Ti with Ti(OSi)4 structure that at 217220 nm has been attributed
and Si O Si bond angles [2527]. to tripodal Ti with Ti(OH)(OSi)3 structure [28]. Additionally, a weak
To validate the conclusions drawn on the hydrophobicity of SBA- absorption band at 315 nm was observed in Ti-SBA-12 which is
16, we have conducted, additionally, thermal analysis studies on attributed to anatase-like titania (this species present in small
water exposed SBA-12 and SBA-16 samples. The amount of water quantity could not be detected by FT-Raman due to its lower sen-
desorbed from SBA-16 (up to 473 K) was found to be 10 times lower sitivity compared to UVvis spectroscopy). The anatase pahse is
(1.5 wt%) than from SBA-12 samples (11.2 wt%) (Fig. 6). absent in the samples of Ti-SBA-16. From the band shape it could
be clearly understood that the relative concentration of framework
3.1.5. FTIR and FT-Raman spectroscopies substituted tetrapodal Ti [Ti(OSi)4 ] is higher in Ti-SBA-16 than in
Ti-SBA-12 and Ti-SBA-16 showed overlapping vibrational bands Ti-SBA-12. It is this, which is the selective Ti site.
in FTIR spectrum at 948 and 969 cm1 . While the former was
attributed to SiOTi vibrations of framework substituted Ti, the 3.1.7. Electron paramagnetic resonance spectroscopy
latter band was assigned to SiOSi vibrations [1820,28,29]. Ti-SBA-12 and Ti-SBA-16 were EPR-silent consistent with the
SBA-12 and SBA-16 showed only the latter band. Ti framework- +4 oxidation state of titanium in these catalysts. Reactive oxygen
substitution was conrmed also from FT-Raman spectroscopy species viz., hydroperoxo-, peroxo- and superoxo-Ti were gener-
wherein a new band at 955 cm1 was observed in Ti-containing ated on contact with aq. H2 O2 (30%). While the former two types
materials (Fig. 7). TiO2 anatase shows characteristic FT-Raman of oxo-Ti species are diamagnetic, the superoxo-titanium Ti(O2 )
bands at 397, 515 and 639 cm1 [30]. However, these bands were are paramagnetic and detectable by EPR spectroscopy [31]. We
absent in the spectra of our samples pointing out that Ti in Ti-SBA- showed earlier in the experiments with microporous TS-1 and
12 and Ti-SBA-16 is isolated and no anatase-like titania phase is mesoporous Ti-MCM-41 that these reactive oxo-Ti species are in
present. equilibrium and one gets converted to the other as the temperature
is varied. The spectrum of superoxo-titanium Ti(O2 ) generated
3.1.6. Diffuse reectance UVvis spectroscopy on Ti-SBA-12 and Ti-SBA-16 are shown in Fig. 9. From the spectral
The nature and coordination of titanium in Ti-SBA-12 and Ti- features, the presence of two types of Ti(O2 ) species, A and B,
SBA-16 was investigated by DRUVvis spectroscopy (Fig. 8). As arising from tetrapodal, and tripodal titanium sites (Ti(OSi)4 and

(a) (b)
206
206
Kubelka-Munk units (a.u.)

Kubelka-Munk units (a.u.)

217 220

315 Ti-SBA-16

Ti-SBA-12
SBA-12 SBA-16
200 300 400 500 200 300 400 500
Wavelength (nm) Wavelength (nm)

Fig. 8. Diffuse reectance UVvis spectra of (a) Ti-SBA-12 and (b) Ti-SBA-16.

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Table 2
Effect of solvent, oxidant and silica structure on the oxidation of cyclohexene.a

Solvent Ti-SBA-12 Ti-SBA-16

TBHP (70%, aqueous) TBHP (5.5 M, decane) TBHP (70%, aqueous) TBHP (5.5 M, decane)
1 1 1
Conversion (wt%) TOF (h ) Conversion (wt%) TOF (h ) Conversion (wt%) TOF (h ) Conversion (wt%) TOF (h1 )

Dichloromethane 80.4 16 90.6 18 92.1 25 92.7 25

Chloroform 74.1 15 88.2 18 90.0 25 91.6 25
1,2-Dichloroethane 60.5 12 84.7 17 85.0 23 90.0 25
Toluene 49.6 10 78.0 15 70.5 19 82.4 23
Acetone 46.0 9 72.4 14 33.8 9 76.0 21
Acetonitrile 27.3 5 44.8 9 30.6 8 62.2 17
Methanol 5.0 1 7.1 1 6.5 2 8.1 2
a
Reaction conditions: catalyst (Ti-SBA-12 or Ti-SBA-16; input Si/Ti = 30) = 0.1 g, cyclohexene = 0.82 g, cyclohexene: oxidant (molar ratio) = 2: 1, solvent = 5 mL, reaction
time = 12 h, reaction temperature = 313 K (for dichloromethane) and 333 K (rest of the solvents). Conversion = theoretical conversion of cyclohexene. Epoxide selectivity = 100%.
Turnover frequency (TOF) = moles of cyclohexene converted per mole of Ti in the catalyst per hour.

Table 3
Effect of the amount of solvent on the oxidation of cyclohexene with TBHP (in decane, 5.5 M).a

Catalyst (Si/Ti, output) Amount of solvent Conversion (%) TOF (h1 ) TBHP efciency (%) Products selectivity (%)
(dichloromethane; mL)
Cyclohexene TBHP epoxide -diol -ol -one

Ti-SBA-12 (39.1) 5 90.6 96 18 94.4 100

3 93.8 97 19 96.7 100
1 94.7 98 19 96.6 100
0 100 100 20 100 100

Ti-SBA-16 (53.8) 5 92.7 97 25 95.6 100

3 94.1 98 26 96.0 100
1 98.7 100 27 98.7 100
0 100 100 27 100 100

Ti-MCM-41 (33) 5 87.6 94.0 15 93.2 95.0 3.0 2.0

3 90.3 96.0 15 94.1 93.2 2.9 3.9
1 92.4 98.0 16 94.3 92.6 2.7 4.7
0 95.0 100.0 16 95.0 91.0 2.5 6.5
a
Reaction conditions: catalyst = 0.1 g, cyclohexene = 0.82 g, cyclohexene: oxidant (molar ratio) = 2: 1, reaction time = 12 h, reaction temperature = 313 K, reaction time = 12 h.
TBHP conversion was determined by iodometric titrations. Cyclohexene conversion (theoretical value). Turnover frequency (TOF) = moles of cyclohexene converted per mole
of Ti in the catalyst per hour. TBHP efciency = (moles of oxidation products of cyclohexene formed/moles of TBHP consumed) 100.

Ti(OH)(OSi)3 , respectively) can be discerned [28]. They are char- When both these sites co-exist, all the four oxidation products of
acterized by a rhombic EPR spectrum and differed in their gzz cyclic olens will be formed (Scheme 1).
value (species A: gzz = 2.038, gyy = 2.008 and gxx = 2.002; species B:
gzz = 2.024, gyy = 2.008 and gxx = 2.002). From spectral deconvolu- 3.2.1. Oxidation of cyclohexene
tion, the relative concentration of the A-type species was found Microporous TS-1 [Si/Ti (output molar ratio) = 33] was less
higher in the case of Ti-SBA-16 than in Ti-SBA-12. It may be noted active for the oxidation of cyclohexene with 70% aq. TBHP [cyclo-
that neat SBA-12, SBA-16 and bulk TiO2 could not generate such hexene conversion and turnover frequency (TOF) = 14% and 2 h1
reactive oxo-Ti species. Solvent inuences the relative concentra- (in chloroform), 34% and 6 h1 (in dichloromethane) and 0% and
tion of A and B species. We found earlier, in the case of TS-1 samples, 0 h1 (in acetonitrile, acetone and methanol)]. Mesoporous, two-
a direct correlation of oxidation activity and epoxide selectivity dimensional Ti-MCM-41 [Si/Ti (output molar ratio) = 33] gave
with the concentration of the A-type species [3133]. Even in the good conversion but allylic oxidation products had also formed
present systems (Ti-SBA-12 and Ti-SBA-16), these differences in along with epoxide and -diol [conversion and TOF in chloroform
A and B species concentrations are expected to reect on their with 70% aq. TBHP = 74% and 12 h1 , respectively, product selec-
catalytic activity performances (see Section 3.2). tivity = 92.8% (epoxide), 3.0% (diol) and 4.2% (-one); conversion
and TOF (in chloroform) with TBHP (5.5 M in decane) = 86% and
14 h1 , respectively, product selectivity = 94% (epoxide) and 6% (-
3.2. Catalytic activity one)]. Ti-SBA-12 and Ti-SBA-16 were more active than TS-1 and
Ti-MCM-41 (Tables 2 and 3). Interestingly, epoxide was the only
Oxidation of carbon-carbon double bond of cyclic olens (cyclo-
hexene and cyclooctene, for example) with peroxides yields the Secondary OH
corresponding epoxide which upon further reaction with water, Epoxidation reaction
O
produces diols (Scheme 1). Oxidation of the allylic C H bond results Heterolytic
OH
O-O cleavage Epoxide -diol
in alcohol (-ol) which can get further oxidized to a ketone prod- products
Titanosilicate
uct (-one) [34]. Selective epoxidation over titanosilicates occur via + aq. H2O2/TBHP
heterolytic cleavage of the O O bond of hydroperoxo/superoxo- OH O
Ti species. Allylic C H bond oxidations proceed via homolytic Allylic oxidation
O O bond cleavage (Scheme 1) [28,30,33]. Due to differences in Homolytic +
electronic structure, tetrapodal Ti in titanosilicates [Ti(OSi)4 ] facil- O-O cleavage
products -ol -one
itate heterolytic O O bond cleavage while the tripodal Ti sites
[Ti(OH)(OSi)3 ] facilitate homolytic cleavage of the O O bond [34]. Scheme 1. Oxidation products of cyclohexene.

Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
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100 Ti-SBA-12. It may be recalled (29 Si MASNMR and thermogravimet-

Ti-SBA-12
Conversion of cyclohexene (%) Ti-SBA-16
80
60
40
20
0 surface structure arrested the secondary reactions of epoxides to
0 2
Reaction time (h)
Fig. 10. Comparative catalytic activities of Ti-SBA-12 (Si/Ti = 30) and Ti-SBA-
16 (Si/Ti = 30) in the oxidation of cyclohexene with TBHP (5.5 M in decane).
Reaction conditions: catalyst = 0.1 g, cyclohexene = 0.82 g, cyclohexene: oxidant
(molar ratio) = 2: 1, reaction time = 12 h, reaction temperature = 313 K, solvent
(dichloromethane) = 5 mL and oxidant = 0.90 g.
product over three-dimensional, mesoporous titanosilicates. Easy
accessibility of Ti sites and their framework substitution are the
possible attributes for the superior performance of Ti-SBA-12 and
Ti-SBA-16.
Fig. 10 shows effect of reaction time on the conversion of cyclo-
hexene over Ti-SBA-12 and Ti-SBA-16. The reaction was conducted
at 313 K and using dichloromethane as solvent and TBHP (5.5 M in
decane) as oxidizing agent. Conversion of cyclohexene increased
gradually with reaction time. Ti-SBA-16 was more active than
ric studies) that Ti-SBA-16 is relatively more hydrophobic than Ti-
SBA-12. The pore structure (Ti-SBA-16 with cubic interconnected
cage-like pore arrangement and Ti-SBA-12 with hexagonal pore
arrangement) which controls the diffusion of reactant and product
molecules and surface hydrophobicity which facilitates adsorption
of non-polar olens and desorption of polar products play impor-
tant roles on the oxidation activity of titanosilicates. At the end of
12 h (at 313 K), cyclohexene conversions of 92.7% and 88.6% were
achieved over Ti-SBA-16 and Ti-SBA-12 catalysts, respectively. The
epoxide selectivity was 100% in both the cases. The hydrophobic
4 6 8 10 12 diols and thereby formed epoxide as the selective product.
The inuence of reaction parameters on the oxidation of cyclo-
hexene is depicted in Fig. 11. With increasing Ti/(Si + Ti) ratio, the
activity of the catalyst increased and this increase was more sig-
nicant for a change in molar ratio from 0.01 to 0.033 than beyond
that. When the TBHP to substrate ratio was increased from 1/4 to
1, a decrease in conversion from near 94 to 90% was observed.
Some part of TBHP got decomposed when it was taken in stoi-
chiometric ratio than in the oxidant-lean conditions. Temperature
has a major effect on the reaction. While it took more than 12 h
at 333 K, a shorter period of time (3 h) itself was enough to
get complete conversion of cyclohexene to its epoxide when the
reaction was carried out at 353 K. Such high conversions and epox-
ide selectivities have not been reported so far over the known
titanosilicate catalysts. A linear correlation was observed between
catalytic activity and the content of framework, tetrahedral Ti ions
[15].

(A) (B)
100 100
Conversion of cyclohexene (%)

90 353 K 90
343 K
Conv. of cyclohexene (%)

80 80
70 70
323 K 333 K
60 60
333 K
50 343 K 50
40 353 K 40
30 30
20 20
10 323 K 10
0 0
0 2 4 6 8 10 12 0.00 0.01 0.02 0.03 0.04 0.05
Reaction time (h) Ti/(Si+Ti)

(C) 100

90
Conv. of cyclohexene (%)

80
70
60
50
40
30
20

1/4 1/3 1/2 1

Molar ratio (oxidant/substrate)

Fig. 11. Inuence of reaction parameters on the oxidation of cyclohexene over Ti-SBA-16 (Si/Ti = 30). Reaction conditions for A: catalyst = 0.1 g, cyclohexene = 0.82 g, cyclohex-
ene: oxidant (molar ratio) = 2: 1, solvent (dichloroethane) = 5 mL and oxidant (70% aq. TBHP) = 0.64 g. Reaction conditions for B: same as for A except that reaction time = 12 h,
reaction temperature = 313 K, solvent (dichloromethane) = 5 mL and oxidant (TBHP, 5.5 M in decane) = 0.90 g. Reaction conditions for C: same as for A except that oxidant:
cyclohexene (molar ratio) = 0.251, reaction time = 12 h, reaction temperature = 313 K, solvent (dichloromethane) = 5 mL, oxidant (TBHP, 5.5 M in decane) = 0.451.80 g.

Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035
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Table 4
Oxidation of cyclooctene: Inuence of reaction conditions.a

Solvent Ti-SBA-12 Ti-SBA-16

TBHP (70%, aqueous) TBHP (70%, aqueous) TBHP (5.5 M, decane)

1 1
Conversion (wt%) TOF (h ) Conversion (wt%) TOF (h ) Conversion (wt%) TOF (h1 )

Dichloromethane 44.0 (2.6) 4 45.0 6 92.0 13

Chloroform 43.1 (2.1) 4 43.3 6 87.0 12
1,2-Dichloroethane 39.0 (5.4) 4 33.7 5 79.5 11
Toluene 36.5 4 29.3 4 66.7 9
Acetone 42.9 4 32.0 4 40.8 6
Acetonitrile 39.4 (7.8) 4 27.7 3 33.2 4
Methanol 5.5 1 5.0 1 13.7 2
a
Reaction conditions: catalyst (Ti-SBA-12 or Ti-SBA-16; input Si/Ti = 30) = 0.1 g, cyclooctene = 1.1 g, cyclooctene: oxidant (molar ratio) = 2: 1, solvent = 10 mL, reaction
time = 24 h, reaction temp.= 313 K (for dichloromethane) and 333 K (rest of solvents). Values in parentheses are conversions obtained with 30% aq. H2 O2 under similar
conditions. Conversion = theoretical conversion of cyclooctene. Epoxide selectivity = 100%. Turnover frequency (TOF) = moles of cyclooctene converted per mole of Ti in the
catalyst per hour.

Solvent and the nature of oxidant (70% aq. TBHP verses 5.5 M
TBHP in decane) showed a remarkable effect on the oxidation
reactions over Ti-SBA-12 and Ti-SBA-16 (Table 2). The oxidation
reactions did not occur in the absence of a catalyst. Conversions
were higher while using 5.5 M TBHP than with 70% aq. TBHP. This
difference is more apparent in the case of Ti-SBA-12 than with
hydrophobic Ti-SBA-16 catalyst (Table 2). The relative ordering
of catalytic activity in different solvents decreased in the order:
CH2 Cl2 > CHCl3 > (CH2 )2 Cl2 > C6 H5 CH3 > CH3 COCH3 > CH3 CN > CH3 OH.
The lower activity in acetonitrile and methanol solvents is perhaps
due to higher competitive adsorption of these solvents (than the
other solvents) on the catalyst surface. The conversion of cyclo-
hexene increased with decreasing amount solvent in the reaction
medium. Cyclohexene conversion and epoxide selectivity were
100% when the reaction was conducted in the absence of solvent
(Table 3). Reactions over Ti-MCM-41 had showed a similar trend
in cyclohexene conversion. But, in terms of intrinsic activity (TOF)
and TBHP efciency, Ti-SBA-16 was found superior to Ti-SBA-12
and Ti-MCM-41 (Table 3).
3.2.2. Oxidation of cyclooctene
Even bulkier olens like cyclooctene could be converted into
their epoxides with high efciency (Table 4). Solvent and the nature
of oxidant (70% aq. TBHP versus 5.5 M TBHP in decane) inu-
enced the oxidation reaction. The reaction goes more effectively
when TBHP in decane (than in water) was used as oxidant. Such
effect was hardly observed in cyclohexene oxidation reactions.
Dichloromethane was found to be the best solvent. Cyclooctene
oxide formed with 100% selectivity. The conversion of cyclooctene
was 92% in CH2 Cl2 when using 5.5 M TBHP as oxidant. Reactions
with 30% aqueous H2 O2 showed poor results (2.6%).
Solvents are used to keep both reactants and products in a single
phase. Apart from enabling proper mixing of the reactants, sol-
vents are known to affect conversions and product selectivities
through interaction with the active sites and the transition state.
Atoguchi and Yao [35] investigated the effect of solvents (various
mixtures of H2 O and CH3 OH) on the oxidation of phenol catalyzed
by TS-1 both experimentally and by DFT calculations. Water addi-
tion to methanol increased the dielectric constant of the reaction
medium and accelerated the catalytic oxidation of phenol. Solvents
can inuence the reactivity of the hydroperoxo-Ti species. In sol-
vents with high dielectric constants, the heterolytic cleavage of the
O O bond is probably dominant when the partially or totally ionic
intermediates are stabilized by the solvent. Wu and Tatsumi [36]
reported the inuence of solvents of varying polarity on the epox-
idation of allyl alcohol catalyzed by TS-1, Ti-beta and Ti-MWW. In
the present case the reactions did go well in the presence of sol-
vents with low polarity and low to moderate dielectric constant.
The surface structure and the pore architecture of Ti-SBA-12 and
-16 and the relative adsorption capacity of reactant as against the
solvent play a dominant role on the oxidation of cyclic olens over
the present catalysts.
4. Conclusions
Three-dimensional, mesoprous titanosilicates, Ti-SBA-12 and
Ti-SBA-16, with varying Ti contents (Si/Ti = 20, 30, 40, 50 and 80)
were prepared by direct hydrothermal synthesis methods and
characterized. Unit cell parameters and unit cell volume of the
catalysts increased with increasing Ti content in the lattice and
provided an unequivocal evidence for the location of Ti in the meso-
porous silica framework structure. DRUVvis studies pointed out
that Ti is isolated and possesses tetracoordinated geometry. The
presence of both tetrapodal and tripodal type Ti species [Ti(OSi)4
and TiOH(OSi)3 , respectively] was inferred. These catalysts showed
higher catalytic activities for the epoxidation of cyclic olens
(cyclohexene and cyclooctene) than the hitherto known titanosil-
icate catalyst. Epoxide selectivity was 100%. This discovery opens
up an avenue for the application of these oxidation catalysts for
the transformation of bulkier organic molecules of pharmaceutical
interest.
Acknowledgment
Anuj Kumar acknowledges the Council of Scientic and Indus-
trial Research (CSIR), New Delhi for the Research Fellowship.
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mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035
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Please cite this article in press as: A. Kumar, D. Srinivas, Selective oxidation of cyclic olens over framework Ti-substituted, three-dimensional,
mesoporous Ti-SBA-12 and Ti-SBA-16 molecular sieves, Catal. Today (2012), doi:10.1016/j.cattod.2012.01.035