高等学校化学学报Issue(9)：1926-1932,7.DOI:10.7503/cjcu20140426
甲醇氧化羰基化反应中CO和CH3 O在CuCl（111）表面上吸附作用的理论研究
Theoretical Studies on the Interaction of CO and CH3 O on CuCl(111) Surface for Methanol Oxidative Carbonylation
摘要
Abstract
Based on density functional theory method in the generalized gradient approximation, together with the periodic slab model, the single adsorption of CO and CH3 O, as well as the co-adsorption of CO and CH3 O on CuCl(111) surface involving in methanol oxidative carbonylation to dimethyl carbonate( DMC) were sys-tematically investigated. The reaction mechanisms of CO interaction with CH3 O leading to CH3 OCO and CH3OCO interaction with CH3O to DMC on CuCl(111) surface were discussed. The calculated results indi-cate that the interaction between CO and CH3 O in the co-adsorption system is stronger than that between free CO and CH3 O in gas phase, CO insertion into adsorbed CH3 O on CuCl(111) surface to CH3 OCO species are the rate-limiting step for the oxidative carbonylation of methanol to DMC, and the corresponding activation bar-rier is 113. 19 kJ/mol, the calculated results are in accordance with the reported experimental facts.关键词
氯化亚铜/一氧化碳(CO)/甲醇盐(CH3O)/共吸附/密度泛函理论/甲醇氧化羰基化反应Key words
CuCl(111)surface/Carbon monoxide/Methoxide/Coadsorption/Density functional theory/Methanol oxidative carbonylation分类
化学化工引用本文复制引用
郑华艳,章日光,李忠..甲醇氧化羰基化反应中CO和CH3 O在CuCl（111）表面上吸附作用的理论研究[J].高等学校化学学报,2014,(9):1926-1932,7.基金项目
国家自然科学基金(批准号:21276169,21276003和21106092)资助. Supported by the National Natural Science Foundation of China(Nos.21276169,21276003,21106092) （批准号:21276169,21276003和21106092）
