ChemCatChem
10.1002/cctc.201700162
FULL PAPER
(
Aldrich) . The mixtures were stirred at 65°C for 24 h. Then, the mixtures
from adsorption data in the range of a relative pressure from P/P
0
= 0.05
[
30]
were centrifuged and the solid materials were dried for 48 h at room
temperature. Individual samples were hydrolyzed in water with 5% of
ethanol (100 ml/1 g) at ambient temperature for 24 h under vigorous
stirring. Finally, the materials were centrifuged again, dried at 65°C and
calcined in air, at 550° C for 10 h, using the temperature ramp of 2°
C/min.
to P/P
(Sext) were determined by t-plot method.
was determined from nitrogen amount adsorbed at relative pressure
P/P = 0.95.
0
=0.20.
The micropore volume (Vmic) and external surface area
[
31]
Total adsorption volume (Vtot
)
0
Diffuse reflectance ultraviolet-visible (DR-UV/Vis) spectra were obtained
using Perkin-Elmer Lambda 950 Spectrometer with a 2 mm quartz tube
and a 8 x 8 mm slit. Spectra were collected in a wavelength range of
IPC-1-SnPI material was prepared from parent UTL zeolite. Synthesis
procedure of the B-UTL, procedure for the B-UTL disassembly into IPC-
4
190-500 nm with a 100% reflectance standard (BaSO ), and converted to
1
P lamellar precursor and swelling procedure forming IPC-1SW material
an absorption spectrum using the Kubelka-Munk function.
[
13-14, 17]
were the same as in ref.
Swollen IPC-1SW (consisting of silica
IPC-1 layers with intercalated cetyltrimethylammonium hydroxide
surfactant) was tin-silica pillared with a mixture of TEOS and Sn(IV)
butoxide using the above procedure for MFI-SnPI-a. Final hydrolyzed
material was calcined with a temperature program of 200°C for 2 h, then
The content of Sn was determined using an ICP-OES ThermoScientific
iCAP 7000 instrument. The samples (50mg) were dissolved in a mixture
of 4 ml of HCl (36 %), 4 ml of HNO
solution was treated in the microwave irradiation and subsequently 15ml
of H BO was added to complex the HF excess. Finally the solutions
3
(67 %) and 2 ml of HF (48 %). The
350°C for 4 h and finally 550°C for 8h, using a temperature ramp of
°C/min.
3
3
2
were diluted by ultrapure water.
Impregnation of the pure silica supports with Sn(IV) chloride (SnCl
4
,
Morphological characterization was carried out by scanning electron
microscopy technique (SEM) on a JEOL, JSM-5500LV microscope. The
images were collected with an acceleration voltage of 20 kV.
Aldrich, 98%) was performed using the following procedure. SnCl was
4
dissolved in dry toluene. The parent support (pure silica layered MFI,
SBA-15, SBA-16 or MCM-41) was activated at 450°C for 60 min, cooled
down in a desiccator and added to the SnCl
stirred at room temperature for 16 h in a glass round bottom flask under
nitrogen atmosphere. In particular, 217 mg of SnCl and 15 ml of toluene
were used per 0.5 g of the parent material. After the given time, the
mixture was centrifuged, washed out with fresh dry toluene and the
impregnated zeolite was dried at 65°C. At the end, the material was
calcined at 550°C for 6 h with the temperature ramp of 2°C/min.
4
solution. The mixture was
The Baeyer-Villiger oxidation was investigated in a 25 ml magnetically
stirred glass two-necked round bottom flask equipped with a reflux
condenser at 80°C. Prior to the catalytic experiment catalyst was
activated in air at 450°C for 90 min and let to cool down in a desiccator.
In a typical experiment, catalyst powder 50 mg, was added to a solution
4
consisting of
2 mmol of the ketone (cyclopentanone (Aldrich),
norcamphor (Aldrich) or 2-adamantanone (Aldrich)), 1.08 mmol
mesitylene (internal standard) and 6 ml of 1,4-dioxane. The reaction was
Impregnation of the supports with Sn(IV) butoxide was carried out using
a similar procedure. Sn(IV) butoxide was dissolved in 1-butanol and the
activated parent material (pure silica layered MFI) was introduced into
the mixture. The mixture was stirred and heated at 50°C for 16 h in a
glass round bottom flask under nitrogen atmosphere. In particular, 35 mg
of Sn(IV) butoxide and 15 ml of 1-butanol were used per 0.5 g of the
parent material. After the given time, the mixture was centrifuged, two
times washed out with fresh 1-butanol and the impregnated zeolite was
dried at 65°C and calcined at 550°C for 6 h with the temperature ramp of
started by addition of 2 mmol of H
1
1
equivalents) was used. Samples of the reaction mixture were taken in
regular interval, centrifuged to remove the catalyst and analyzed using an
Agilent 6850 gas chromatograph with a 50 m long DB-5 column an
autosampler and FID detector.
2
O
2
(Aldrich, 35 wt% aqueous solution,
molar equivalent). Therefore, maximum theoretical conversion was
00%. In case of cyclopentanone, mmol of (0.5 molar
1
2 2
H O
2°C/min.
Acknowledgements
The Sn-MS material was synthesized from 2 mmol of SnCl
00 mmol of TEOS using 35 mmol of SDA C18-6-6OH (vide supra). The
SnCl .5 H O was dissolved in a solution of SDA in 4 mol of distilled water.
4 2
.5 H O and
1
2
The authors acknowledge the Czech Science Foundation
(P106/12/G015) for the financial support of this research.
4
2
Then, the TEOS was added and the mixture was homogenized at room
temperature for 1 h. Final gel was hydrothermally treated for 260 h at
Keywords: Heterogeneous catalysis • Ketones • Layered zeolite
160°C. After the given time, the product was filtered off, washed with
•
Oxidation • Tin-silicate
water, dried at 65°C and calcined at 550°C for 8 h with a temperature
ramp of 2°C/min.
[
[
[
[
1]
2]
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The structure and crystallinity of the samples were determined by X-ray
powder diffraction using a Bruker AXS D8 Advance diffractometer
equipped with a graphite monochromator and position-sensitive detector
Våntec-1 using Cu Kα radiation in Bragg–Brentano geometry. The
crystalline samples (lamellar and pillared) were measured in 2θ range 1-
3]
4]
R. A. Michelin, P. Sgarbossa, A. Scarso, G. Strukul, Coord. Chem. Rev.
2010, 254, 646-660.
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40°. XRD patterns of mesoporous sieves were recorded using 2θ range
1
04, 4105-4124.
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23-425; b) M. Renz, T. Blasco, A. Corma, V. Fornés, R. Jensen, L.
0
.75-10°.
[
7]
4
Textural properties were determined from nitrogen adsorption/desorption
isotherms recorded on a Micromeritics ASAP2020 volumetric instrument
at -196°C. Prior to the measurement, individual samples were degassed
in a stream of helium at 300°C for 3 h. The BET area was determined
Nemeth, Chem. Eur. J. 2002, 8, 4708-4717; c) A. Corma, M. a. T.
Navarro, M. Renz, J. Catal. 2003, 219, 242-246; d) I. Nowak, A.
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This article is protected by copyright. All rights reserved.
P?ech, Jan
