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学科主题: 物理化学
题名: In Situ Formation of Homogeneuos Active Species for Hydroformylation Based on Heterogeneous Rh Catalyst
作者: Yan L(严丽) ;  Ding YJ(丁云杰) ;  Zhu HJ(朱何俊) ;  Wang T(王涛) ;  Lv Y(吕元) ;  Lin LW(林励吾)
会议名称: 13th International Symposium on Relation between Homogeneous and Heterogeneous Catalysis
会议日期: 2007-7-16
出版日期: 2007-07-16
会议地点: 美国
其他题名: 多相Rh基催化剂上匀相催化氢甲酰化反应活性位的原位形成
通讯作者: Yunjie Ding
部门归属: 八室
主办者: 美国加州大学
摘要: The CO insertion reaction such as hydroformylation is an excellent model for studying the relation between heterogeneous and homogeneous catalysis. So far, intensive work has been focused on developing efficient catalytic system for heterogenization of homogeneous catalysts [1], only minor attention has been given to heterogeneous catalysts, because they provide lower activity and selectivity when compared to homogeneous catalysts. In many cases, various metal promoters, such as Na, Zn, Ag, etc [2], are employed to improve the activity of heterogeneous catalysts Phosphine ligands are probably the most widely used ligands in homogeneous catalysis. Our previous study shows that PPh3 modified heterogeneous Rh/SiO2 is a new important class of catalyst (PPh3-Rh/SiO2), which combines the high activity and selectivity of homogeneous catalyst with the processing advantages of a heterogeneous catalyst [3, 4]. To further investigate how the Rh-phosphine carbonyl complexes form on the surface of heterogeneous Rh catalyst, we employed SBA-15 as a support in the PPh3-Rh/SBA-15 system. We have applied PPh3-Rh/SBA-15 catalysts to the hydroformylation of propylene to investigate its performance, and we also find that the pore size of support has a great influence on the catalytic performance of PPh3-Rh/SBA-15 catalysts. The activity of the PPh3-Rh/SBA-15 catalyst is far higher than that of the heterogeneous Rh/SBA-15 catalyst, but a little lower than HRh(CO)(PPh3)3/SBA-15 catalyst due to bareness of 80% of Rh particles, while the selectivity to aldehyde of PPh3-Rh/SBA-15 catalyst is comparable to that of HRh(CO)(PPh3)3/SBA-15 catalyst. And PPh3-Rh/SBA-15 catalyst even displays higher n/i ratio for butyraldehyde than HRh(CO)(PPh3)3/SBA-15 catalyst, that is because the active species for hydroformylation in situ form on the Rh nano-particles and lead to a larger steric hindrance on PPh3-Rh/SBA-15 than on heterogenizing homogeneous catalysts (HRh(CO)(PPh3)3/SBA-15). The catalysts and reaction were characterized by TG, solid-state 31P NMR, XPS, in situ FT-IR, ICP-AES, GC-MS to elucidate the structure, bonding, and interaction between Rh and triphenyl phosphine, and to verify the formation of homogeneous intermediates. Table 1 The reactivity of catalysts with different pore size Catalyst aTOF n/i ratio Selec. (%) Rh/SBA-15 2.74 2.6 19.2 PPh3-Rh/SBA-15 245 12.7 100 HRh(CO)(PPh3)3/SBA-15 301 10.7 100 Reference [1] Cole-Hamilton D.J.; Science 2003,299, 1702. [2] Naito S.; Tanimoto M.; J.Chem.Soc. Chem.Commun. 1989, 18, 1403. [3] Yan, L.; Ding, Y. J.; Zhu, H. J.; Xiong, J. M.; Wang, T.; Pan, Z. D.; Lin, L. W. J. Mol. Catal., A: Chem. 2005, 234, 1-7. [4]Zhu, H. J.; Ding, Y. J.; Yan, L.; Lu, Y.; Li, C.; Bao, X. H.; Lin, L. W. Chem. Lett. 2004, 33, 630-631. Reaction conditions: T=393 K; time on stream= 4 h; P=1.0 MPa; SV=2000 h-1. a TOF: mol butyraldehyde /mol Rh •hour.
语种: 中文
内容类型: 会议论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/112526
Appears in Collections:中国科学院大连化学物理研究所_会议论文

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Recommended Citation:
Yan L,Ding YJ,Zhu HJ,et al. In Situ Formation of Homogeneuos Active Species for Hydroformylation Based on Heterogeneous Rh Catalyst[C]. 见:13th International Symposium on Relation between Homogeneous and Heterogeneous Catalysis. 美国. 2007-7-16.
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