催化学报

催化学报 ›› 2017, Vol. 38 ›› Issue (3): 434-439.DOI: 10.1016/S1872-2067(17)62800-6

• 能源与环境新型催化剂专栏 • 上一篇    下一篇

氟催化废弃硅基还原剂与CO2还原转化反应

Ken Motokura, Masaki Naijo, Sho Yamaguchi, Akimitsu Miyaji, Toshihide Baba   

  1. 东京工业大学材料和化工技术学院化工科学与工程系, 横滨226-8502, 日本
  • 收稿日期:2016-09-27 修回日期:2016-10-20 出版日期:2017-03-18 发布日期:2017-03-22
  • 通讯作者: Toshihide Baba
  • 基金资助:

    This work was supported by JSPS KAKENHI (15H04182), JSPS Grant-in-Aid for Scientific Research on Innovative Areas “3D Active-Site Science (26105003)”, “Precisely Designed Catalysts with Customized Scaffolding (16H01010)”, and Grant for Challenging Research Award, Tokyo Institute of Technology.

Reductive transformation of CO2: Fluoride-catalyzed reactions with waste silicon-based reducing agents

Ken Motokura, Masaki Naijo, Sho Yamaguchi, Akimitsu Miyaji, Toshihide Baba   

  1. Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8502, Japan
  • Received:2016-09-27 Revised:2016-10-20 Online:2017-03-18 Published:2017-03-22
  • Supported by:

    This work was supported by JSPS KAKENHI (15H04182), JSPS Grant-in-Aid for Scientific Research on Innovative Areas “3D Active-Site Science (26105003)”, “Precisely Designed Catalysts with Customized Scaffolding (16H01010)”, and Grant for Challenging Research Award, Tokyo Institute of Technology.

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摘要：

CO2是最重要的可再生碳源之一.为了将CO2转化为有用的有机化合物，我们研究了二种模型硅基“废”材料—乙硅烷和硅粉的反应活性.在这些反应中，氟盐的催化活性最高，在常压、在质子源水和硅基还原剂的存在下，CO2可转化为甲酸.原位NMR和动力学分析表明，含氢硅烷和五配位的硅物种分别是反应中间物和活性物种.

关键词: 二氧化碳, 氟, 均相催化, 甲酸, 乙硅烷

Abstract:

CO2 is one of the most important “renewable” carbon sources. To transform CO2 to useful organic compounds, we examined the reactivity of two model silicon-based “waste” materials, disilanes and metallic Si powder, as reducing agents. In these reactions, fluoride salts were found to be active catalysts: CO2 was converted to formic acid at atmospheric pressure in the presence of H2O as a proton source and the silicon-based reducing reagents. Based on in-situ NMR and kinetics analyses, a hydrosilane and penta-coordinate Si species are proposed as the reaction intermediate and active species, respectively.

Key words: Carbon dioxide, Fluoride, Homogeneous catalysis, Formic acid, Disilane