RESUMO
To simplify separation procedures, improve the reusability and decrease the loss of Pt, two Pt catalysts anchored on superparamagnetic silica (Fe3O4@SiO2-EDTA@Pt and Fe3O4@SiO2-DTPA@Pt) were prepared for the first time. The stable magnetic properties made them easily recyclable using a magnet rather than filtration, decantation or centrifugation. After 12 catalytic runs for both 30-50 nm Pt catalysts, the yield of 1-heptylmethyldichlorosilane was still up to 90%. The average loss of Pt in each reaction was only 0.87% for Fe3O4@SiO2-EDTA@Pt and 0.66% for Fe3O4@SiO2-DTPA@Pt owing to the strong interaction between Pt and carboxyl. The unprecedented activity and selectivity of the two Pt nanoparticle catalysts were observed in the hydrosilylation of alkenes. The turnover number in the reaction between 1-hexene and methyldichlorosilane using 5 × 10-8 mol of the Pt approached 662 733 for Fe3O4@SiO2-EDTA@Pt and 579 947 for Fe3O4@SiO2-DTPA@Pt over 12 h. The corresponding hydrosilylation products in excellent yields were obtained when we employed a broad range of alkenes as substrates, including 5 isomerous hexenes and 14 important industry raw materials. Fe3O4@SiO2-DTPA@Pt showed a better activity. They have potential for catalyzing more reactions and replacing the current homogeneous Pt catalysts in industry.
RESUMO
A series of novel immobilized platinum catalysts was prepared by loading Pt onto silica particles modified with polycarboxylic acid groups such as diethylenetriaminepentaacetic acid (DTPA), nitrolotriacetic acid (NTA) and succinic acid (SA). The three modified heterogeneous Pt catalysts were characterized using infrared spectroscopy (IR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS) and atomic absorption spectroscopy (AAS). The residual H2PtCl6 solutions were characterized using ultraviolet spectroscopy (UV). The polycarboxylic acid-functionalized silica supported Pt catalysts were used to catalyze alkene hydrosilylation and 1-hexene was chosen as a model alkene. The data indicated that the catalytic performance was strongly dependent on the properties of the polycarboxylic acid group bonded to the silica particles. Among them, DTPA-functionalized silica supported Pt (SiO2-DTPA-Pt) showed the best catalytic activity and reusability. Furthermore, some hydrosilylation reactions between other linear alkenes (1-heptene, 1-octene, 1-decene, 1-do-decene, 1-tetra-decene, 1-hexa-decene, 1-octa-decene, styrene or cis-hex-2-ene), or ring type alkenes (norbornene) with methyldichlorosilane could be catalyzed in the presence of these three Pt catalysts. Their high activities were more than 90%, and their selectivities were more than 99%, which were apparently better than homogeneous Pt catalysts. In addition, reactions with cyclohexene were also successfully catalyzed by the Pt catalysts. These results indicate that the polycarboxylic acid-functionalized silica gel supported Pt catalysts have potential value in industrial hydrosilylation reactions.