化学学报 ›› 2006, Vol. 64 ›› Issue (9): 845-850. 上一篇    下一篇

研究论文

二氧化硅固载Ru基催化剂上二氧化碳加氢合成甲酸的研究(III): 配体对催化剂反应性能的影响

张一平1,2,费金华1,于英民1,郑小明*,1   

  1. (1浙江大学西溪校区催化研究所 杭州 310028)
    (2浙江教育学院化学系 杭州 310012)
  • 收稿日期:2005-10-25 修回日期:2006-01-16 出版日期:2006-05-15 发布日期:2006-05-15
  • 通讯作者: 郑小明

Silica Immobilized Ruthenium Catalyst for Formic Acid Synthesis from Carbon Dioxide Hydrogenation (III): Effect of Ligand on the Catalyst Performance

ZHANG Yi-Ping1,2, FEI Jin-Hua1, YU Ying-Min1, ZHENG Xiao-Ming*,1   

  1. (1 Institute of Catalysis, Xixi Campus, Zhejiang University, Hangzhou 310028)
    (2 Department of Chemistry, Zhejiang Education Institute, Hangzhou 310012)
  • Received:2005-10-25 Revised:2006-01-16 Online:2006-05-15 Published:2006-05-15
  • Contact: ZHENG Xiao-Ming*<

考察了不同配体对原位合成的固载Ru基催化剂上CO2加氢合成HCOOH反应活性的影响, 对于以单齿三苯基类ZPh3分子为配体的催化剂, 活性大小顺序为: PPh3>AsPh3>NPh3. 以PPh3为配体时, 其相应的原位合成催化剂上HCOOH的TOF值为656 h-1. 其次, 双齿膦配体的使用能带来比单齿膦配体更高的活性. 以dppe [1,2-双(二苯基膦基)乙烷]为配体时, 其相应的原位合成催化剂上HCOOH的TOF值为1190 h-1. 量子化学的理论计算结果表明, 具有适中的σ给予性和π接受性, 较小的空间位阻, 较好的电子离域作用的PPh3配体性能优于其它单齿三苯基类配体. 而具有较好的电子离域作用, 并且有螯合作用的双齿膦配体性能优于单齿膦配体.

关键词: 固载, 配体, 甲酸, Ru基催化剂

The effect of ligand on the activity of immobilized ruthenium complexes synthesized in situ was investigated. The activity of the catalyst containing ZPh3 ligand changed as follows: PPh3>AsPh3>NPh3. When PPh3 was used as ligand, the corresponding TOF of formic acid was 656 h-1 over the catalyst. In addition, using bidentate phenyl phosphine as ligand instead of PPh3 resulted in an even higher TOF, the value was 1190 h-1 when dppe was used as ligand. The results of quantum chemistry theoretic calculation indicated that the PPh3 ligand which had the moderate capability of σ-donor and π-acceptor, less steric hindrance and preferable electron delocalization, acted as a better ligand than the other ZPh3 ligand. The bidentate phenyl phosphine ligands which had good electron delocalization and chelation acted as a better ligand than monodentate phosphine ligand.

Key words: immobilized, ligand, formic acid, Ru-based catalyst