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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (4): 289-294. 上一篇    下一篇

研究论文

固载Ru基催化剂上二氧化碳加氢合成甲酸的研究(IV): 反应机理

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)
  • 投稿日期:2006-06-23 修回日期:2006-09-21 发布日期:2007-02-28
  • 通讯作者: 郑小明

Immobilized Ruthenium Catalyst for Formic Acid Synthesis from Carbon Dioxide Hydrogenation (IV): Reaction Mechanism

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:2006-06-23 Revised:2006-09-21 Published:2007-02-28
  • Contact: ZHENG Xiao-Ming

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被引次数

8 | 3

探讨了在CO2加H2合成HCOOH过程中原位合成的固载Ru基催化剂的可能结构、CO2的活化方式以及可能的反应机理. 在反应中, 固载Ru配合物中的一个P配体首先解离, 被质子型溶剂ROH取代而生成循环活性物质, 然后CO2正插入Ru—H键生成甲酸酯配合物, 之后甲酸酯配合物中的Ru—O2CH键被H2氢解生成HCOOH, 而本身重新转化为活性物质, 完成催化循环.

关键词: 固载, 甲酸, Ru基催化剂

The proposed structure of the immobilized ruthenium catalyst synthesized in situ during the carbon dioxide hydrogenation to formic acid, the activation of carbon dioxide and the possible reaction mechanism were discussed. In the reaction, a phosphine ligand in the Ru complexes was replaced by protonic solvent ROH to generate the chain carrier, subsequent normal insertion of carbon dioxide into the Ru—H bond occurred to give the formato complex. Then hydrogenolysis of the Ru-O2CH bond formed formic acid and regenerated the catalytic species to finish the catalytic cycle.

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