Font Size: a A A

Pt Nanoparticles Entrapped In OMC And Pt-containing MA For Enantioselective Catalytic Hydrogenation

Posted on:2012-10-04Degree:MasterType:Thesis
Country:ChinaCandidate:K X LiFull Text:PDF
GTID:2131330335465701Subject:Physical chemistry
Abstract/Summary:PDF Full Text Request
The well-ordered carbon materials are a class of advanced non-silicon materials, which possess the textural porosities of mesoporous materials with uniform pore size, well-ordered mesopores and high specific surface area, and simultaneously possess the merits of carbons with high hydrophobicity, easy functionalization and high mechanical stability. MP-C-type mesoporous carbon materials, derived from ordered mesoporous polymer-silica which is calcined under N2 flow and and then removed silica by HF etching, are a class of newly-developed advanced materials, with two-dimensional hexagonal p6mm symmetry, large pore volumes (1.22 cm3/g) and high surface areas (1600 m2/g). They have been successfully synthesized via one pot synthesis of solvent evaporation self-assembly (EISA), wherein soluble resol polymer is used as an organic precursor; TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. The application of MP-C-type OMCs supported Pt nanoparticles in heterogeneous asymmetric hydrogenation ofα-functionalized ketones has been rarely reported up to now.In the first part,4% and 10%(mass fraction) Pt catalysts supported on MP-C-61 were prepared by an impregnation method using two different Pt precursors, ethanolic solution and aqueous solution of H2PtCl6.These Pt/MP-C-61 catalysts were characterized by XRD, N2-sorption, TEM and CO chemisorption. The Pt/MP-C-61 catalysts can be effectively applied in the asymmetric hydrogenation of ethyl pyruvate after chirally modified with cinchonidine. The Cat-4Pt-E catalyst derived from the ethanolic solution of H2PtCl6 afforded better conversions of ethyl pyruvate due to smaller Pt particle size with higher Pt dispersion. While the Cat-4Pt-W catalysts derived from the aqueous solution of H2PtCl6 showed higher chiral induction ability. The catalyst Cat-4Pt-W-150 that was calcined at 150℃under vacuum gave higher conversion and higher enantioselectivity than Cat-4Pt-W did, the highest TOF reaching 8820 h-1 in water. A 66% e.e. value was furnished by Cat-lOPt-E catalyst in acetic acid. In particular, the Cat-4Pt-W catalyst showed superior catalytic activity to the 5% mass fraction of commercial Pt/C catalyst, mainly due to the ordered mesoporous structure feature of MP-C-61 support. Moreover, Cat-4Pt-W can be recycled easily for more than 10 times without distinct loss activity or enantioselectivity in the water. The 4% Pt catalysts supported on MP-C-61 can also be effectively applied in the asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate, of which the hydrogenation product can be used to produce A.C.E inhibitors. Under the optimal conditions, the catalyst Cat-4Pt-W-150 gave a 61% e.e. value of (R)-(+)-ethyl 2-hydroxyl-4-phenylbutyrate in acetic acid.In recent years, Pt/Al2O3 has also been successfully applied to the heterogeneous enantioselective hydrogenation of a-functionalized ketones. It is a target to prepare ordered mesoporous alumina with high surface area, ordered pore channel and high thermal stability due toγ-Al2O3 has lower surface area and wide Pore-size distribution. Simple sol-gel route is a high-throughput method to synthesize MA as reported in the literature.In the second part, we prepared the highly ordered Pt-containing mesoporous alumina catalyst by one-pot synthesis and investigated the catalytic performance in the heterogeneous enantioselective hydrogenation of ethyl pyruvate after modifying the catalysts with cinchonidine. Among all the xPt/MA catalysts prepared by the one-pot method with different Pt loadings and ever calcined in different atomsphere, 3Pt/MA(E)-A, which possessed 3 wt.% Pt loading and was calcined in air before reduction, maintained the mesoporous structure well and had high dispersion of Pt particles, so it showed the best catalytic performance, as a result,83.5% conversion of ethyl pyruvate was obtained with 74.4% e.e. value of (R)-(+)-ethyl lactate, which is even better than 5Pt/MA prepared via an impregnation method.
Keywords/Search Tags:Mesoporous carbon materials, Supported Pt catalysts, Mesoporous alumina, One-pot method, Chiral modification, Enantioselective hydrogenation, Ethyl pyruvate, Ethyl 2-oxo-4-phenylbutyrate
PDF Full Text Request
Related items