文献类型：期刊文献

中文题名：银和铜催化草酸二甲酯加氢制乙醇酸甲酯反应机理的理论研究

英文题名：Insights into the reaction mechanism of dimethyl oxalate hydrogenation to methyl glycolate over Ag and Cu catalysts

作者：李祥祥[1];朱贻安[1];周静红[1];周兴贵[1];李伟[1]

机构：[1]华东理工大学化工学院,上海200237

年份：2018

卷号：43

期号：6

起止页码：17

中文期刊名：天然气化工—C1化学与化工

外文期刊名：Natural Gas Chemical Industry

收录：CSTPCD;;北大核心:【北大核心2017】；CSCD:【CSCD_E2017_2018】；

基金：国家自然科学基金项目(21473053;91645122)

语种：中文

中文关键词：草酸二甲酯;酰基物种;加氢;乙醇酸甲酯;反应机理

外文关键词：dimethyl oxalate;acyl species;hydrogenation;methyl glycolate;reaction mechanism

摘要：银基催化剂和铜基催化剂是常用的草酸二甲酯(DMO)部分加氢制乙醇酸甲酯(MG)催化剂。本文运用密度泛函理论(DFT)计算研究了Ag(111)和Cu(111)表面上该过程的反应机制。通过结构优化,得到了最稳定的吸附构型。计算并比较了可能基元反应的活化能和反应热,得到了最可能的反应中间物种和最合理的反应路径;分析了反应路径中各基元反应发生的难易程度,解释了实验中Ag基催化剂和Cu基催化剂的催化行为。
Density functional theory(DFT)was used to investigate the reaction mechanism of hydrogenation of dimethyl oxalate(DMO)to methyl glycolate(MG)on Ag-and Cu-based catalysts.The most stable adsorption configurations of all species were identified by optimizing initial configurations.By calculating and comparing the activation energies and reaction heats of possible elementary reactions,the most probable intermediates and dominant reaction pathways were determined.After analyzing the progress of every elementary reaction in this pathway,the catalytic behaviors of Ag-and Cu-based catalysts in previous literatures can be well elucidated.