Manipulating the H2O2 Reactivity on Pristine Anatase TiO2 with Various Surface Features and Implications in Oxidation Reactions

Guohan Sun; Quan Wang; Yin-Song Liao; Yifan Cui; Linyuan Tian; Jyh-Pin Chou; Yufei Zhao; Yung-Kang Peng

doi:10.1021/acs.jpclett.4c02742

Manipulating the H₂O₂ Reactivity on Pristine Anatase TiO₂ with Various Surface Features and Implications in Oxidation Reactions

J Phys Chem Lett. 2024 Nov 12:11620-11628. doi: 10.1021/acs.jpclett.4c02742. Online ahead of print.

Authors

Guohan Sun¹, Quan Wang¹, Yin-Song Liao², Yifan Cui¹, Linyuan Tian¹, Jyh-Pin Chou³, Yufei Zhao⁴, Yung-Kang Peng¹

Affiliations

¹ Department of Chemistry, City University of Hong Kong, Hong Kong 999077, Hong Kong SAR, China.
² Tsing Hua Interdisciplinary Program, National Tsing Hua University, Hsinchu 300, Taiwan.
³ Graduate School of Advanced Technology, National Taiwan University, Taipei 106319, Taiwan.
⁴ State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China.

PMID: 39533860
DOI: 10.1021/acs.jpclett.4c02742

Abstract

Anatase TiO₂ is commonly used as a catalyst/support in reactions involving H₂O₂, yet the understanding of interactions between common TiO₂ surfaces and H₂O₂ remains limited. Herein, we synthesized well-defined TiO₂ crystallites with (101), (001), and fluorine-modified (001) [F-(001)] surfaces to examine how surface features, including the arrangement of five-coordinated Ti (Ti_5c) sites and the presence of fluorine, influence H₂O₂ activation. Our findings reveal that these surface features significantly affect the physiochemical properties of adsorbed H₂O₂. Specifically, fluorine on the F-(001) surface introduces an additional hydrogen bond to the Ti_5c-peroxo species, altering the electronic structure of H₂O₂ compared to those with the (101) and (001) surfaces. Using cyclohexene as a probe substrate, we successfully distinguished the reactivities of the Ti_5c-peroxo species. The activity of those on the F-(001) surface was significantly higher than the activity of those on the (001) surface, while the (101) surface showed negligible oxidation activity. These insights can guide the design of TiO₂-based catalysts for H₂O₂-related reactions.