摘要
考察了几种硅胶负载贵金属催化剂和HRhCO(TPP) 3 催化剂的 1 己烯氢甲酰化反应 ,对Rh/SiO2 、HRhCO(TPPTS) 3 /SiO2 和TPPTS Rh/SiO2 上的 1 己烯氢甲酰化结果进行了比较 .结果表明 ,TPPTS Rh/SiO2 催化剂的醛的选择性和醛的正异比n/b接近HRhCO(TPPTS) 3 /SiO2 的相应的催化性能 ,而远高于Rh/SiO2 的相应的催化性能 ,7.0MPa高压下TPPTS Rh/SiO2 催化剂的活性大幅度增加 ,达到 0 .0 6 92S-1.实验排除了其他可能 ,认为是含有孤对电子的TPPTS和Rh/SiO2 中高度分散的Rh粒子产生了化学键的作用 ,形成了具有匀相性能的支撑水膜多相催化剂 :TPPTS Rh/SiO2 .
Hydroformylation of 1-hexene over a series of silica supported noble metal catalysts, HRhCO ( TPP)(3), HRhCO (TPPTS)(3)/SiO2 and TPPTS-Rh/SiO2 catalyst were investigated. The results show that the selectivity towards aldehydes and the ratio of liner to branched aldehyde (n/b) over Rh-TPPTS/SiO2 catalyst are near to those of HRhCO ( TPPTS)(3)/SiO2, but much higher than to those of Rh/SiO2. Under the higher pressure of 7.0 MPa, the TOF of aldehydes on Rh-TPPTS/SiO2 catalyst increase greatly up to 0. 0692 S-1. A possible of catalyst model of Ligands containing lone-pair electron tightly chemically connected to the highly dispersed Rh particles and formation of supported aqueous-film heterogeneous catalyst possessing of homogeneous catalytic performance has been tentatively proposed.
基金
国家自然科学基金资助项目 (2 0 0 730 4 6 )~~
