High Photoreactivity on a Reconstructed Anatase TiO2(001) Surface Predicted by Ab Initio Nonadiabatic Molecular Dynamics

Youyou Tu; Weibin Chu; Yongliang Shi; Wenguang Zhu; Qijing Zheng; Jin Zhao

doi:10.1021/acs.jpclett.2c01417

High Photoreactivity on a Reconstructed Anatase TiO₂(001) Surface Predicted by Ab Initio Nonadiabatic Molecular Dynamics

J Phys Chem Lett. 2022 Jun 30;13(25):5766-5775. doi: 10.1021/acs.jpclett.2c01417. Epub 2022 Jun 20.

Authors

Youyou Tu¹, Weibin Chu², Yongliang Shi³, Wenguang Zhu¹, Qijing Zheng¹, Jin Zhao^{1

1

4}

Affiliations

¹ Department of Physics and ICQD/Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.
² Key Laboratory of Computational Physical Sciences (Ministry of Education), Institute of Computational Physical Sciences, Fudan University, Shanghai 200433, People's Republic of China.
³ Center for Spintronics and Quantum Systems, State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi'an Jiaotong University, Xi'an, Shanxi 710049, China.
⁴ Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.

PMID: 35723976
DOI: 10.1021/acs.jpclett.2c01417

Abstract

Anatase TiO₂(001) surface with (4 × 1) reconstruction is proposed to be a highly active catalytic surface. In this work, using time-domain ab initio nonadiabatic molecular dynamics, we reveal that the ridge structure formed by anatase(001) surface reconstruction is the photoreactive site for hole migration and trapping. Moreover, the ridge structure is destroyed by low-coverage CH₃OH adsorption, leading to the suppression of its high photoreactivity. However, when the CH₃OH coverage is increased and intermolecular hydrogen bonds (H-bonds) form, the ridge structure and its high photoreactivity are restored. Furthermore, the hole trapping dynamics is strongly coherent with intermolecular proton transfer in structures with intermolecular H-bonds. Our study proves that anatase TiO₂(001)-(4 × 1) is a highly photoreactive surface where the ridge is the photoreactive site for hole trapping, which is coherent with the proton transfer process.