Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (4): 738-742.doi: 10.3866/PKU.WHXB201502063

• CATALYSIS AND SURFACE SCIENCE • Previous Articles     Next Articles

Preparation of Silica-Bonded Phosphine and Its Influence on 1-Octene Hydroformylation Catalyzed by Rhodium Complex

ZHANG Xiao-Ya, ZHENG Cong-Ye, ZHENG Xue-Li, FU Hai-Yan, YUAN Mao-Lin, LI Rui-Xiang, CHEN Hua   

  1. Key Laboratory of Green Chemistry and Technology of the Ministry of Education, Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China
  • Received:2014-12-15 Revised:2015-02-05 Published:2015-04-03
  • Contact: YUAN Mao-Lin
  • Supported by:

    The project was supported by the Petrochemical Research Institute of China National Petroleum Corporation, China (2011B-2606) and Sichuan University Scientific Research Foundation for Young Teachers, China (2011SCU11084).


Using silica as a support, 2-(diphenylphosphino)ethyltriethoxysilane (DPPES) was anchored on silica surface by a grafting method to produce a bonded phosphine (denoted as SiO2(PPh2)), which displays excellent performance. The supported SiO2(PPh2)/Rh catalyst was formed in situ in 1-octene hydroformylation with SiO2(PPh2) as ligand and Rh(acac)(CO)2 as precursor (acac: acetylacetone). SiO2(PPh2) and SiO2(PPh2)/ Rh were characterized by Fourier transform infrared (FTIR) spectroscopy. The effects of the ratio of phosphine to rhodium ([P]/[Rh]) and reaction temperature on 1-octene hydroformylation were investigated. Results show that an increase of the ratio of phosphine to rhodium can greatly improve the selectivity for aldehydes and decrease the rhodium leaching in organic phase. Under the moderate conditions: [P]/[Rh]=12, 363 K, 2 MPa, and 1.5 h, the conversion of 1-octene and the selectivity for aldehydes were 98.4% and 95.3%, respectively. The catalytic activity could compare with homogeneous catalysis with DPPES or triphenylphosphine (TPP) as ligand. The reaction activity was clearly unchanged after the SiO2(PPh2)/Rh catalyst was reused four times, with the conversion of 1-octene remaining at 97.0%, the rhodium content leaching in organic phase detected by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) was less than 0.1%.

Key words: Silica, 2-(diphenylphosphino)ethyltriethoxysilane, 1-Octene, Hydroformylation, Selectivity for aldehyde, Rhodium complex, Catalyst recycle


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