催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (7): 641-645.

• 研究论文 • 上一篇    下一篇

CH4和CO2合成乙酸中CO2与•H及•CH3相互作用的理论计算

章日光,黄伟,王宝俊   

  1. 太原理工大学煤科学与技术教育部和山西省重点实验室, 山西太原 030024
  • 收稿日期:2007-07-25 出版日期:2007-07-25 发布日期:2011-07-25

Theoretical Calculation for Interaction of CO2 with •H and •CH3 in Synthesis of Acetic Acid from CH4 and CO2

ZHANG Riguang, HUANG Wei*, WANG Baojun   

  1. Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
  • Received:2007-07-25 Online:2007-07-25 Published:2011-07-25

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摘要： 采用量子化学密度泛函方法,对CO2与H及CH3自由基反应进行了理论计算,给出了CO2与H及CH3自由基相互作用的反应机理,提出了CO2与H及CH3自由基作用的4条反应路径. 其中以H和CH3自由基进攻CO2的C原子反应为优先路径,主要产物为乙酸,而甲酸甲酯为动力学禁阻产物. 计算结果与实验结果相当吻合. 为CH4和CO2两步反应合成含氧化合物提供了理论解释和指导.

关键词: 甲烷, 二氧化碳, 乙酸, 氢自由基, 甲基自由基, 量子化学计算

Abstract: The reactions of CO2 with H and CH3 radicals were systematically investigated using the quantum chemistry density functional theory. The reaction mechanism of CO2 with H and CH3 radicals was obtained. The pathway that H or CH3 radical attacked the C atom of CO2 was the preferential pathway in all the four designed reaction pathways. The main product was acetic acid, while methyl formate was inhibited by dynamics. The calculated result was in accordance with the experimental result, which provided a new illustration and guidance for the direct synthesis of oxygenated compounds from CH4 and CO2 by a two-step reaction method.

Key words: methane, carbon dioxide, acetic acid, hydrogen radical, methyl radical, quantum chemistry calculation