文献类型：期刊文献

英文题名：Subtle structure matters: boosting surface-directed photoelectron transfer via the introduction of specific monovalent oxygen vacancies in TiO2

作者：Li, Fei;Wang, Dong[1];Gong, Xue-Qing[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Ctr Computat Chem, Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China; East China Univ Sci & Technol, Sch Chem & Mol Engn, Res Inst Ind Catalysis, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2021

卷号：23

期号：35

起止页码：19854

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20213810924017);WOS:【SCI-EXPANDED(收录号:WOS:000691733400001)】；

基金：This work was supported by the National Natural Science Foundation of China (21903025, 21825301) and the National Key Research and Development Program of China (2018YFA0208602).

语种：英文

外文关键词：Density functional theory - Electron transitions - Photons - Photocatalysis - Oxide minerals - Titanium dioxide - Calculations - Photoelectrons

摘要：Oxygen vacancies (O-v) are widely considered to play crucial roles in photocatalysis, but how and why they contribute to improved performances remains controversial. In this work, we studied the promotional effect of O-v on photoelectron transfer in TiO2, using first-principles density functional theory calculations with correction for on-site Coulomb interactions. We explicitly identified three types of O-v with different charge states (i.e., charge-neutral , monovalent , divalent O-v(2+)) via electronic structure analysis. Electron transfer energy calculations revealed that the ionized O-v in anatase TiO2 are able to collect excess electrons whereas those in the rutile phase are not. The presence of ionized O-v further endows anatase TiO2 with directional electron transfer along the [100] orientation, in favor of anatase TiO2(101) for photocatalytic reduction surpassing the (001) termination. After examining various combination modes of ionized O-v involving different charge states and spatial distributions, we demonstrated that the vertical chain in anatase TiO2(101) is the most catalytically effective O-v pattern in TiO2. These results signify the importance of subtle defects in photocatalysis and may assist future photocatalyst design toward higher photocatalytic efficiency.