文献类型：期刊文献

英文题名：Understanding the Dual Active Sites of the FeO/Pt(111) Interface and Reaction Kinetics: Density Functional Theory Study on Methanol Oxidation to Formaldehyde

作者：Chen, Zongjia[1,2,3];Mao, Yu[3];Chen, Jianfu[1,2];Wang, Haifeng[1,2];Li, Yadong[4];Hu, P.[1,2,3]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[3]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland;[4]Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China

年份：2017

卷号：7

期号：7

起止页码：4281

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20172903956744);WOS:【SCI-EXPANDED(收录号:WOS:000405360800008)】；

基金：This project was supported by the National Natural Science Foundation of China (21333003, 21421004, 21303052, 21622305), the National Key Basic Research Program of China (2013CB933201), the Chen-Guang project (13CG24), and the Young Elite Scientist Sponsorship Program by CAST, Fundamental Research Funds for the Central Universities. Z.C. thanks the Chinese Scholarship Council for overseas living support.

语种：英文

外文关键词：density functional theory; FeO/Pt interface; methanol partial oxidation; multisite microkinetic model; turnover frequency

摘要：Identifying the active sites and reaction kinetics for a catalytic reaction can provide significant insight into the catalytic systems. By use of DFT calculations, the catalytic activity of FeO/Pt(111) interfacial sites, which is an important class of catalyst with excellent activity, for methanol partial oxidation is carefully examined and compared. The O-H cleavage barrier of methanol is significantly diminished to below 0.1 eV with the aid of interfacial oxygen, which is much lower than that on the Pt(111) surface (>0.8 eV). The CH3O* intermediate can further undergo a C-H bond breaking process to produce formaldehyde via a low barrier (similar to 0.2 eV) at the interfacial Pt sites. Assisted by an interfacial Pt-O ensemble, the O-H and C-H bond cleavages are greatly facilitated, suggesting that the FeO/Pt biphasic system could effectively combine the advantages of two individual phases. To investigate the rate-determining steps, a multisite microkinetic model is applied at the FeO/Pt interface. The results show that the overall rate can be significantly improved by lowering the activation energy of interfacial oxygen removal steps. Interestingly, the turnover frequency (TOF) can also be increased when the barriers of O-2 dissociative adsorption on the Pt flat surface are increased, which is a special feature in multiphasic systems in comparison with the monophasic system. The active site and microkinetic studies in our work can provide insights into the development of metal/oxide catalysts for the partial oxidation of methanol or other primary alcohols.