文献类型：期刊文献

英文题名：Subtle Structure Matters: The Vicinity of Surface Ti5c Cations Alters the Photooxidation Behaviors of Anatase and Rutile TiO2 under Aqueous Environments

作者：Li, Fei[1,2];Chen, Jian-Fu[1,2];Gong, Xue-Qing[1,2];Hu, P.[1,2];Wang, Dong[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2022

卷号：12

期号：14

起止页码：8242

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20223312559777);WOS:【SCI-EXPANDED(收录号:WOS:000821851900001)】；

基金：The authors acknowledge the financial support from the National Key Research and Development Program of China (2018YFA0208602), the National Natural Science Foundation of China (21903025 and 21825301), and the Shanghai Science and Technology Development Funds (22QA1402900).

语种：英文

外文关键词：photocatalytic OER; water/TiO2 interface; ab initio molecular dynamics; microkinetic modeling; density functional theory

摘要：While the structure-function relationship is frequently referred in heterogeneous catalysis, the concept falls short of applications in photocatalysis owing to its complicated processes. Here, we take the photocatalytic oxygen evolution reaction (OER) as a case study and demonstrate the significance of subtle surface structures in altering the photooxidation functions of anatase and rutile TiO2 under aqueous environments. On the basis of our recent progresses in developing a solution simulation method and clarifying the photocatalytic OER process at rutile TiO2 (Nat. Catal. 2018, 1, 291-299), we successfully identified a complete OER mechanism at the water/anatase-TiO2(101) interface with an explicit involvement of photoholes/radicals and lattice oxygens. Kinetic analysis further revealed the leading reaction pathway varying with the concentration of surface-reaching photoholes (Ch+), as well as the most efficient way to boost the OER via enriching the Ch+ rather than lowering the reaction barriers (of water dissociation or O/O coupling). Anatase TiO2(101) generally shows poorer OER activity relative to the rutile TiO2(110) but much higher surface coverage of O-t(-) radicals under experimental conditions, rationalizing its good activity for photodegradation of organics. Such varied catalytic functions were found to be simply decided by the distance between two vicinal under-coordinated Ti cations on the surface that promotes or prohibits the key step of O/O coupling. These results not only provide essential understandings on the structure-function principles governing the photooxidation behaviors but also offer strategies to achieve efficient catalysis via matching proper surface structures with targeted reaction characteristics.