有机-无机杂化L-Rh/SiO_2氢甲酰化催化剂的研究 Ⅱ.L-Rh/SiO_2的催化性能及表征  

Study on Organic-Inorganic Hybrid L-Rh/SiO_2 Catalysts for Hydroformylation of Olefins Ⅱ. Catalytic Performance and Characterization of L-Rh/SiO_2 Catalysts

作　　者：朱何俊[1] 丁云杰[1,2] 严丽[1] 何代平[1] 王涛[1] 陈维苗[1] 吕元[1] 林励吾[1,2] 

机构地区：[1]中国科学院大连化学物理研究所天然气与应用催化实验室 [2]中国科学院大连化学物理研究所催化基础国家重点实验室,辽宁大连116023

出　　处：《催化学报》2004年第8期659-663,共5页

基　　金：国家自然科学基金资助项目 ( 2 0 0 73 0 46) ;国家重点基础研究规划项目 ( 2 0 0 3CB615 80 3 )

摘　　要：以具有不同电子结构的有机膦直接修饰Sh/SiO2 制备了有机 无机杂化L Rh/SiO2 催化剂 ,并考察了催化剂对 1 己烯氢甲酰化反应的催化性能 .结果表明 ,P(OPh) 3 Rh/SiO2 催化剂上 1 己烯氢甲酰化反应的TOF可高达 4 111h-1,而PCy3 Rh/SiO2 催化剂上生成醛的选择性为 10 0 % .不同催化剂活性的顺序为P(OPh) 3 Rh/SiO2 >PPh3 Rh/SiO2 >PCy3 Rh/SiO2 ,其选择性的顺序则与之相反 .TG表征结果表明 ,有机膦与Rh之间相互作用强度的顺序为PCy3 Rh/SiO2 >PPh3 Rh/SiO2 >P(OPh) 3 Rh/SiO2 .因此 ,有机膦给电子的能力越强 ,则与Rh之间相互作用的能力越强 ,催化剂体系越稳定 ,1 己烯氢甲酰化反应的活性越低 ,而庚醛的选择性越高 .The organic triphenyl-phosphine ligand was directly used to modify the Rh/SiO 2 catalyst to prepare PPh 3-Rh/SiO 2 catalyst for hydroformylation of olefins. The results showed that its catalytic activity for hydroformylation of 1-hexene under the mild conditions of 1.0 MPa and 373 K was higher than that of Rh/SiO 2 catalyst, and comparable to that of the corresponding homogeneous HRhCO(PPh 3) 3 catalyst. The PPh 3-Rh/SiO 2 catalyst possessed the advantages of both heterogeneous catalysis and homogeneous catalysis, such as high activity, high selectivity and easy separation. By means of 31 P MAS NMR and XPS techniques for characterization of PPh 3-Rh/SiO 2 catalyst, it was found that the coordination bond between Rh metal and PPh 3 with lone-pair electron was formed on the catalyst. The PPh 3-Rh/SiO 2 catalyst could be used in hydroformylation of olefins from C = 2 to C = 12 .

关 键 词：己烯 氢甲酰化 铑 负载型催化剂 有机膦 有机-无机杂化 

分 类 号：O643[理学—物理化学]