赵璞君,张旭斌.乙炔氢氯化反应铜系催化剂的反应机理[J].分子催化,2014,(3):259-267
乙炔氢氯化反应铜系催化剂的反应机理
Reaction mechanism of acetylene hydrochlorination in Cu-based catalyst
投稿时间:2014-01-24  修订日期:2014-03-28
DOI:
中文关键词:  乙炔氢氯化反应  Cu基催化剂  密度泛函理论  反应机理  N/P掺杂
英文关键词:acetylene hydrochlorination  Cu-based catalyst  DFT  Reaction mechanism  N/P doping
基金项目:
作者单位E-mail
赵璞君 天津大学化工学院 tjuzhao@sina.com 
张旭斌* 天津大学化工学院 tjuxb@tju.edu.cn 
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中文摘要:
      以电石乙炔法制备氯乙烯的非汞催化反应体系为研究对象, 用量子化学密度泛函理论(DFT)研究了以Cu基催化剂为代表的非汞催化剂的反应机理. 模拟了以石墨烯为载体的乙炔氢氯化反应在Cu基催化剂作用下的两条反应路径及其过渡态. 将该反应机理应用到不同金属氯化物催化剂中,通过计算相应的活化自由能和反应速率常数讨论了不同金属氯化物的活性顺序, 与实验结果相比较印证了反应机理的合理性. 讨论了Cu基催化剂的失活原因以及在载体中掺杂氮原子或磷原子对反应活性的影响. 为非贵金属无汞催化剂的研究提供了一定的理论指导.
英文摘要:
      The reaction mechanism of acetylene hydrochlorination in Cu-based catalyst was studied using the density function theory (DFT). Two possible paths for acetylene hydrochlorination reaction in Cu-based catalyst were illustrated with corresponding transition states. We applied the reaction mechanism to various metal chlorides and obtained an order of different catalyst by analyzing the activation free energies and reaction rate constants. The result was compared with experimental ones to verify the reaction mechanism. The deactivation reason of Cu-based catalyst and the reaction on the N/P-doped graphene were also discussed. The conclusion from this study will shed light on the experimental design of novel non-mercury catalysts with high performance.
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