Chinese Journal of Catalysis ›› 2015, Vol. 36 ›› Issue (2): 168-174.DOI: 10.1016/S1872-2067(14)60228-X

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Rh-PPh3-polymer@mesosilica composite catalyst for the hydroformylation of 1-octene

Xiaoming Zhanga,b, Shengmei Lua, Mingmei Zhonga,b, Yaopeng Zhaoa, Qihua Yanga   

  1. a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
    b University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2014-07-25 Revised:2014-08-15 Online:2015-01-21 Published:2015-01-21
  • Supported by:

    This work was supported by the National Basic Research Program of China (973 Program, 2010CB833300) and the National Natural Science Foundation of China (21203184).

Abstract:

Rh-PPh3-polymer@mesosilica composites were prepared by the polymerization of mixtures of divinylbenzene (DVB) and 4-vinyl-triphenylphosphine monomer in the nanopores of mesoporous silicas followed by coordination with Rh(acac)(CO)2 (acac =acetylacetonate). These catalysts were characterized by XRD, N2 sorption, TEM, FT-IR, and TG, and could efficiently catalyze the hydroformylation of 1-octene with higher activity than a pure polymer catalyst because of their high surface area and large pore volume, which were beneficial for the exposure of active sites and mass transport. Through the control of pore size and pore connectivity by using different mesoporous silica (MCM-41, SBA-15, and FDU-12), the activity and selectivity can be controlled. Rh-PPh3-polymer@FDU-12 with a cage-like mesostrucuture showed lower activity but slightly higher selectivity than the catalyst with a 2-D hexagonal mesostructure (Rh-PPh3-polymer@SBA-15 or Rh-PPh3-polymer@MCM-41). By varying the polymer content in the nanopores of the mesosilica, the activity and selectivity (92%-96%) can also be tuned. The solid composite catalyst can be recycled without loss of activity, but a decrease in selectivity was observed.

Key words: Rh-PPh3-polymer@mesosilica composite, Heterogeneous catalysis, Hydroformylation reaction