文献类型：期刊文献

英文题名：Identifying the Role of Photogenerated Holes in Photocatalytic Methanol Dissociation on Rutile TiO2(110)

作者：Zhang, Jiawei[1,2];Peng, Chao[1,2];Wang, Haifeng[1,2];Hu, P.[1,2,3]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Res Inst Ind Catalysis, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Ctr Computat Chem, Shanghai 200237, Peoples R China;[3]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 54AG, Antrim, North Ireland

年份：2017

卷号：7

期号：4

起止页码：2374

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20172203710572);WOS:【SCI-EXPANDED(收录号:WOS:000398986700015)】；

基金：This project was supported by the National Key Basic Research Program of China (2013CB933201), National Natural Science Foundation of China (21303052, 21333003, 21622305), Chen-Guang project (13CG24), Young Elite Scientist Sponsorship Program by CAST, and Fundamental Research Funds for the Central Universities. We also gratefully thank Prof. Xueming Yang for the helpful discussions.

语种：英文

外文关键词：photocatalysis; methanol dissociation; density functional theory; role of photogenerated holes; TiO2

摘要：As an important model. reaction, photocatalytic methanol dissociation on rutile TiO2(110) has drawn much attention, but its reaction mechanism remains elusive. Using DFT+U calculations, we investigate the whole dissociation process of methanol into formaldehyde with and without photogenerated holes, aiming to illustrate how the hole is involved in the dissociation. We find that the O-H dissociation of methanol is a heterolytic cleavage process and is likely to be thermally driven; the presence of a hole has no promotion on the barrier and enthalpy change. In contrast, the subsequent C-H bond cleavage follows the homolytic cleavage mode and is likely to be photochemically driven; great enhancement can be made in both kinetics and thermodynamics when holes are introduced. The essential roles of holes in promoting C-H dissociation are identified, and what kinds of catalytic reactions can or cannot be facilitated by holes is discussed. Our findings may considerably broaden the understanding of photocatalytic chemistry.