02438nas a2200241 4500008004100000022001400041245017000055210006900225260009500294300001200389490000800401520147800409653001401887653003201901653002101933653001301954100001901967700001301986700002201999700001702021700002802038856013002066 2005 eng d a0021-951700aFormation of nanosized zirconia-supported 12-tungstophosphoric acid in mesoporous silica SBA-15: a stable and versatile solid acid catalyst for benzylation of phenol0 aFormation of nanosized zirconiasupported 12tungstophosphoric aci a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcOCT a341-3520 v2353 a

A nanosized zirconia-supported 12-tungstophosphoric acid (TPA) in SBA-15 composite was prepared by wet impregnation of TPA/ZrO2 nanoparticles inside the mesoporous channels of SBA-15. The resulting composite material was calcined at 1123 K and characterized by elemental analysis, powder X-ray diffraction, nitrogen adsorption isotherms, transmission electron microscopy (TEM), scanning electron microscopy (SEM), solid-state P-31 CP-MAS NMR, Si-29 MAS NMR, UV-vis diffuse reflectance spectra, FTIR, TPD of ammonia, FTIR pyridine adsorption, and thermogravimetric analysis (TG-DTG). The synthesized TPA/ZrO2/SBA-15 showed a well-ordered hexagonal inesoporous structure and mesoporous support SBA-15 stabilized ZrO2-t (tetragonal) phase with crystal size in the range of 3-4 nm. SBA-15 was a better support than MCM-41 and MCM-48 because it retained its mesostructure even after high TPA loading and high calcination temperatures. Mesoporous silica support plays an important role in stabilizing the catalytically active tetragonal phase of zirconia, which gave the most active catalysts. The catalysts were examined for their catalytic activities in the liquid phase benzylation of phenol with benzyl alcohol and the catalyst 15 wt% TPA/ 22.4 wt% ZrO2/SBA-15 calcined at 1123 K was found to have high acidity and to be 10 times more active than neat TPA/ZrO2 Under the reaction conditions studied in benzylation of phenol. (c) 2005 Elsevier Inc. All rights reserved.

10ananosized10aphenol benzylation reaction10aterragonal phase10aTPA/ZrO21 aSawant, D., P.1 aVinu, A.1 aJacob, Nalini, E.1 aLefebvre, F.1 aHalligudi, Shivappa, B. uhttp://library.ncl.res.in/content/formation-nanosized-zirconia-supported-12-tungstophosphoric-acid-mesoporous-silica-sba-15-001721nas a2200229 4500008004100000022001400041245014100055210006900196260007300265300001200338490000800350520085900358653001601217653001101233653001301244653001401257653002101271100002601292700002101318700002801339856012401367 2007 eng d a1387-181100aEffect of pretreatment conditions on the catalytic activity of nano-sized TPA/ZrO2 dispersed in SBA-15 channels in acetylation reactions0 aEffect of pretreatment conditions on the catalytic activity of n aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcMAY a223-2330 v1023 a

Acetylation of an aromatic compounds such as veratrole (1,2-dimethoxybenzene), anisole, thioanisole, isobutyl benzene and 2-methoxynaphthalene with acetic anhydride has been investigated over a nano-sized 12-tungstophosphoric acid (TPA)/22.4 wt.%ZrO2/SBA- 15 catalysts in the liquid phase conditions. Catalysts with different (%) TPA and zirconia loadings calcined at different temperatures were prepared by wet-impregnation and characterized by XRD, N-2 adsorption-desorption, FT-Rarnan, X-ray photoelectron spectroscopy (XPS). The acidic behavior of the catalyst was studied by TPD of ammonia and FT-IR pyridine adsorption. Among the catalysts, 15 wt.%TPA/22.4 wt.%ZrO2/SBA- 15 calcined at 1123 K had the highest acidity and was the most active catalyst in veratrole acetylation with acetic anhydride. (C) 2007 Elsevier Inc. All rights reserved.

10aacetylation10aSBA-1510aTPA/ZrO210averatrole10awet-impregnation1 aSawant, Dhanashri, P.1 aHartmann, Martin1 aHalligudi, Shivaraj, B. uhttp://library.ncl.res.in/content/effect-pretreatment-conditions-catalytic-activity-nano-sized-tpazro2-dispersed-sba-1502437nas a2200241 4500008004100000022001400041245012100055210006900176260007300245300001100318490000800329520157000337653001901907653001601926653001101942653001301953653001401966100002601980700001302006700001702019700002802036856013102064 2007 eng d a1381-116900aTungstophosphoric acid supported over zirconia in mesoporous channels of MCM-41 as catalyst in veratrole acetylation0 aTungstophosphoric acid supported over zirconia in mesoporous cha aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcFEB a98-1080 v2623 a

Tungstophosphoric acid (TPA) over zirconia dispersed uniformly in mesoporous silica (MS) channels of MCM-41 and MCM-48 were synthesized and tested for their catalytic activity in veratrole acetylation. Catalysts with different TPA loadings (5-50 wt.%) on 22.4 wt.%ZrO2/MCM-41 and 15 wt.%TPA on different zirconia loadings (10-70 wt.%)/MCM-41 were prepared and calcined at 1123 K. The physico-chemical characterization of the supported catalysts was done by powder X-ray diffraction (XRD), surface area measurement (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transformed-infrared (FT-IR) spectroscopy, UV-vis diffuse reflectance spectra, Temperature programmed desorption (TPD) of ammonia, FT-IR pyridine adsorption and (31) P cross polarization-magic angle spinning (CP-MAS) NMR spectroscopy. The mesoporous silica supports play an important role in stabilizing catalytically active TPA along with tetragonal phase of zirconia. Among the catalysts, 15 wt.%TPA/22.4 wt.%ZrO2/MCM-41 calcined at 1123 K was found to have highest acidity and at least four times more active than neat 15 wt.%TPA/ZrO2 in veratrole acetylation to acetoveratrone by acetic anhydride. Reaction conditions were evaluated with 15 wt.%TPA/22.4 wt:%ZrO2/MCM-41 calcined at 1123 K to get higher conversion of acetic anhydride to acetoveratrone. The reaction was found to be heterogeneously catalyzed and no contribution from homogeneous (leached) TPA into the medium under the reaction conditions. (c) 2006 Elsevier B.V. All rights reserved.

10aacetoveratrone10aacetylation10aMCM-4110aTPA/ZrO210averatrole1 aSawant, Dhanashri, P.1 aVinu, A.1 aLefebvre, F.1 aHalligudi, Shivaraj, B. uhttp://library.ncl.res.in/content/tungstophosphoric-acid-supported-over-zirconia-mesoporous-channels-mcm-41-catalyst-veratrole