文献类型：期刊文献

英文题名：Solvent Water Controls Photocatalytic Methanol Reforming

作者：Xu, Bei-Bei[3,4];Zhou, Min[1,2];Zhang, Ran[3,4];Ye, Man[3,4];Yang, Ling-Yun[5];Huang, Rong[6];Wang, Hai Feng[1,2];Wang, Xue Lu[3,4];Yao, Ye-Feng[3,4]

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]East China Normal Univ, Sch Phys & Elect Sci, Phys Dept, Shanghai 200062, Peoples R China;[4]East China Normal Univ, Sch Phys & Elect Sci, Shanghai Key Lab Magnet Resonance, Shanghai 200062, Peoples R China;[5]ShanghaiTech Univ, iHuman Inst, Shanghai 201210, Peoples R China;[6]East China Normal Univ, Sch Phys & Elect Sci, Dept Elect Engn, Shanghai 200062, Peoples R China

年份：2020

卷号：11

期号：9

起止页码：3738

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY LETTERS

收录：;EI(收录号：20212410480413);WOS:【SCI-EXPANDED(收录号:WOS:000535177500082)】；

基金：This work was supported by National Natural Science Foundation of China (21603073, 21574043, and 21873028), Shanghai Shuguang Program (17SG30), and Microscale Magnetic Resonance Platform of ECNU.

语种：英文

外文关键词：Carbon dioxide - Activation analysis - Nuclear magnetic resonance - Reaction kinetics - Titanium dioxide - Molecular dynamics - Density functional theory - Platinum compounds - Calculations - Organic solvents

摘要：Understanding the role of different solvent molecules for practical solid-liquid heterogeneous photocatalytic reactions is critical for determining the pathway of the reaction. In this study, the operando nuclear magnetic resonance (NMR) method, combined with density functional theory (DFT) calculations, was employed to evaluate the control effect of solvent water in the photocatalytic reforming mechanism of methanol with a Pt-TiO2 catalyst. Results indicate that the presence of water effectively promotes the formation of the HCHO intermediate but inhibits the H-2 evolution originating from the switch of the hydrogen source of the H-2 formation from CH3OH to H2O. More interestingly, as detected directly in the ab initio molecular dynamics simulation, a small amount of H2O can dissociate, and the evolved -OH species at Ti-5c site can greatly reduce the C-H activation barrier of -CH3O, contributing to the formation of oxidation products (e.g., HOCH2OH and CH3OCH2OH) on the Pt-TiO2 surface.