Ciriminna Rosaria, Pagliaro Mario
Istituto per lo Studio dei Materiali Nanostrutturati, CNR, via Ugo La Malfa 153, 90146 Palermo, Italy, Fax: (+39) 091-680-93-99.
Chemistry. 2003 Oct 17;9(20):5067-73. doi: 10.1002/chem.200305146.
Sol-gel nanohybrid silica particles organically modified and doped with the ruthenium species tetra-n-propylammonium perruthenate (TPAP) are highly efficient catalysts for the selective oxidation of alcohols to carbonyl groups with O(2) at low pressure in toluene. The materials are easily prepared by a one-step sol-gel process, and their catalytic performance can be optimised by tailoring the conditions of their synthesis by hydrolytic co-polycondensation of tetramethoxysilane (TMOS) and alkyltrimethoxysilanes R-Si(OMe)(3) in the presence of TPAP. Eventually, heterogeneous catalysts considerably more active than the unsupported perruthenate were obtained, while also being leach-proof and recyclable. The correlation between the materials' activity, surface polarity and textural properties suggests valuable information on the chemical behaviour of sol-gel catalytic materials in oxidation catalysis; this is of interest in view of the importance of efficient solid catalysts for the selective oxidation of alcohols with O(2).
用钌物种四正丙基铵高钌酸盐(TPAP)进行有机改性和掺杂的溶胶-凝胶纳米杂化二氧化硅颗粒,是在甲苯中于低压下用O(2)将醇选择性氧化为羰基的高效催化剂。这些材料通过一步溶胶-凝胶法易于制备,并且通过在TPAP存在下由四甲氧基硅烷(TMOS)和烷基三甲氧基硅烷R-Si(OMe)3进行水解共缩聚来调整其合成条件,可以优化它们的催化性能。最终,获得了比无载体高钌酸盐活性高得多的多相催化剂,同时还具有抗浸出和可回收的特性。材料的活性、表面极性和织构性质之间的相关性为溶胶-凝胶催化材料在氧化催化中的化学行为提供了有价值的信息;鉴于高效固体催化剂对于用O(2)选择性氧化醇的重要性,这一点很有意义。