Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (5): 932-942.doi: 10.3866/PKU.WHXB201403212

• CATALYSIS AND SURFACE SCIENCE • Previous Articles     Next Articles

Partial Hydrogenation of Benzene to Cyclohexene over Novel Ru-B/MOF Catalysts

TAN Xiao-He1, ZHOU Gong-Bing1, DOU Rong-Fei1, PEI Yan1, FAN Kang-Nian1, QIAO Ming-Hua1, SUN Bin2, ZONG Bao-Ning2   

  1. 1 Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, P. R. China;
    2 State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation, Beijing 100083, P. R. China
  • Received:2014-01-24 Revised:2014-03-21 Published:2014-04-25
  • Contact: QIAO Ming-Hua
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2012CB224804), National Natural Science Foundation of China (21373055), Science and Technology Commission of Shanghai Municipality, China (08DZ2270500), Beijing Synchrotron Radiation Facility, China and the China Petroleum & Chemical Corporation (S411063).


A series of metal-organic framework (MOF) materials were synthesized together with the corresponding amorphous Ru-B/MOF catalysts, which were prepared by the impregnation-chemical reduction method. These materials were subsequently evaluated for the first time as catalysts for the partial hydrogenation of benzene to cyclohexene. The results for the initial hydrogenation rate (r0) for the different catalysts followed the trend Ru-B/MIL-53(Al)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-53(Cr)> Ru-B/MIL-101(Cr)>>Ru-B/MIL-100(Fe), whereas the initial selectivity for cyclohexene (S0) was of the order of Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-101(Cr)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)≈Ru-B/MIL-100(Fe). The Ru-B/MIL-53(Al) catalyst exhibited the highest r0 and S0 values of 23 mmol·min-1·-1 and 72%, respectively. The characterization results demonstrated that the Ru-B amorphous alloy nanoparticles were highly dispersed on MIL-53(Al) with the average diameter of 3.2 nm. In contrast, the Ru-B nanoparticles on MIL-100(Fe) had an average diameter of 46.6 nm. The smaller Ru-B nanoparticles not only provided more active sites for the hydrogenation to occur, but could also be beneficial in the formation of cyclohexene. The reaction conditions were further optimized for the Ru-B/MIL-53(Al) catalyst. At 180 ℃ under a H2 pressure of 5 MPa, a cyclohexene yield of 24% was obtained, highlighting the potential of MOF materials as catalyst supports for the partial hydrogenation of benzene.

Key words: Metal-organic framework, Ruthenium, Benzene, Cyclohexene, Partial hydrogenation


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