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负载型油溶性铑膦配合物的结构及其氢甲酰化催化性能; Structure and hydroformylation of supported rhodiumphosphinecomplexcatalyst
袁友珠 ; 张宇 ; 蔡阳 ; 杨意泉 ; 张鸿斌 ; 蔡启瑞
1999-06
关键词负载型催化剂 铑膦配合物 氢甲酰化 NMR IR supported catalyst phosphine-rhodium complex hydroformylation
英文摘要联系人:袁友珠; [中文摘要]用31P(1H)-NMR、IR表征了铑膦配合物HRh(CO)(PPh3)3负载SiO2前后及反应前后的结构变化,并用固定床加压连续流动微反-气相色谱联用装置评价了SiO2负载型铑膦配合物催化剂上丙烯氢甲酰化反应。结果表明,SiO2表面的膦物种与担载量有关。当担载量为00lmmolRh/gSiO2时,膦谱中化学位移在δ=45处具特征双峰的配合物HRh(CO)(PPh3)3负载于SiO2载体后,变成δ≈370的单峰,对应的IR谱显示,负载后配合物HRh(CO)(PPh3)3中Rh-H键基本消失,配位羰基C-O键的伸缩带从l928cm-1处代之在1980cm-1和l869cm-1处出现两个新吸收峰;推断在该担载量下,SiO2表面上主要的负载配合物物种是配位构型畸变的三膦单核配合物物种及少量双核配合物物种,反应后,可观察到游离的PPh3物种,氢甲酰化活性下降的催化剂中膦物种已经很少.[英文摘要]31P(1H)-NMR and IR were employed to characterize the structure of SiO2-supported HRh(CO)(PPh3)3.Propene hydroformy lation over HRh(CO)(PPh3)3/SiO2 was performed in a fixed- bed flow reactor-GC system.The results showed that phosphine species on SiO2 surface was related to the loading weight of the complex.The complex supported on the surface existed with a distored configuration of HRh(CO) (PPh3)3 as a main species( with δ=~37 peak of 31P(1H)-NMR spectra),corresponding to the IR observat ion of new bands at 1980cm-1 and 1869cm-1, with may be derived f rom the CO band at 1928cm-1 of the original complex.The experimental results suggested that being oxidized of the phophine ligands and lossing of the rhodium and/ or phosphine components during the reaction process were the main reasons leading to deact ivation of the catalyst.; 国家自然科学基金,教育部优秀年青教师基金
语种中文
出版者《天然气化工(C1化学与化工)》编辑部
内容类型期刊论文
源URL[http://dspace.xmu.edu.cn/handle/2288/10635]  
专题化学化工-已发表论文
推荐引用方式
GB/T 7714
袁友珠,张宇,蔡阳,等. 负载型油溶性铑膦配合物的结构及其氢甲酰化催化性能, Structure and hydroformylation of supported rhodiumphosphinecomplexcatalyst[J],1999.
APA 袁友珠,张宇,蔡阳,杨意泉,张鸿斌,&蔡启瑞.(1999).负载型油溶性铑膦配合物的结构及其氢甲酰化催化性能..
MLA 袁友珠,et al."负载型油溶性铑膦配合物的结构及其氢甲酰化催化性能".(1999).
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