文献类型：期刊文献

英文题名：Identification of Synergistic Actions between Cu0 and Cu+ Sites in Hydrogenation of Dimethyl Oxalate from Microkinetic Analysis

作者：Yan, Wei-Qi[1];Zhang, Jun-Bo[1];Zhou, Rui-Jia[1];Cao, Yue-Qiang[1];Zhu, Yi-An[1];Zhou, Jing-Hong[1];Sui, Zhi-Jun[1];Li, Wei[1];Chen, De[2];Zhou, Xing-Gui[1]

机构：[1]East China Univ Sci & Technol, UNILAB, State Key Lab Chem Engn, Sch Chem Engn, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2020

卷号：59

期号：52

起止页码：22451

外文期刊名：INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH

收录：;EI(收录号：20210209734792);WOS:【SCI-EXPANDED(收录号:WOS:000605183600009)】；

基金：This work is supported by the National Key Research and Development Program of China (No. 2018YFB0604700), the Natural Science Foundation of China (Nos. 22073027, 91645122, and U1663221), the Natural Science Foundation of Shanghai (No. 20ZR1415800), and the Fundamental Research Funds for the Central Universities (No. 222201718003). The computational time provided by the Notur project is highly acknowledged.

语种：英文

外文关键词：Copper oxides - Hydrogenation - Molar ratio - Catalyst activity - Oxalic acid - Binding sites - Reaction intermediates

摘要：The kinetics of dimethyl oxalate (DMO) hydrogenation over Cu(111) and Cu2O(111) has been studied to understand the role of Cu-0 and Cu+ sites in ethyl glycol (EG) production over Cu-based catalysts by the combination of density functional theory calculations and microkinetic analysis. The calculated results suggest that the presence of the Cu+ sites would strengthen the binding of the reactants, products, and reaction intermediates to the substrate and thus promote the dissociation of DMO and H-2. The Cu-0 sites are found to be beneficial to the hydrogenation of the acyl species whereas the Cu+ sites are primarily responsible for the CH3OH formation. Microkinetic analysis indicates that the existence of the Cu+ sites would increase the turnover frequency for the EG formation on Cu(111) by a factor of 20, under typical operating conditions. Hence, the excellent catalytic performance of the Cu-based catalysts in the hydrogenation of DMO to EG is attributed to the synergistic effect between the Cu-0 and Cu+ sites, and a proper Cu-0/Cu+ molar ratio can dramatically improve the catalytic activity.