Traces of Potassium Induce Restructuring of the Anatase TiO2(001)-(1×4) Surface from a Reactive to an Inert Structure

Cong Fu; Fei Li; Zongfang Wu; Feng Xiong; Junfa Zhu; Xue-Qing Gong; Weixin Huang

doi:10.1021/acs.jpclett.3c02047

Traces of Potassium Induce Restructuring of the Anatase TiO₂(001)-(1×4) Surface from a Reactive to an Inert Structure

J Phys Chem Lett. 2023 Oct 12;14(40):8916-8921. doi: 10.1021/acs.jpclett.3c02047. Epub 2023 Sep 28.

Authors

Cong Fu¹, Fei Li², Zongfang Wu³, Feng Xiong¹, Junfa Zhu⁴, Xue-Qing Gong², Weixin Huang¹

Affiliations

¹ Key Laboratory of Precision and Intelligent Chemistry, iChEM, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China.
² Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
³ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, P. R. China.
⁴ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230026, P. R. China.

PMID: 37768115
DOI: 10.1021/acs.jpclett.3c02047

Abstract

Reconstruction of solid surfaces is generally accompanied by changes in surface activities. Here, via a combined experimental and theoretical study, we successfully identified that a trace amount of potassium dopant restructures the mineral anatase TiO₂(001) single-crystal surface from an added molecule (ADM) termination to an added oxygen (AOM) one without changing the (1×4) periodicity. The anatase TiO₂(001)-(1×4)-ADM surface terminated with 4-fold coordinated Ti_4c and 2-fold coordinated O_2c sites is (photo)catalytically active, whereas the anatase TiO₂(001)-(1×4)-AOM surface terminated with O_2c and inaccessible 5-fold coordinated Ti_5c sites is inert. These results unveiled a mechanism of dopant-induced transformation from a reactive to an inert TiO₂(001)-(1×4) surface, which unifies the existing arguments about the surface structures and (photo)catalytic activity of anatase TiO₂(001)-(1×4).