{"title":"Manipulating the H2O2 Reactivity on Pristine Anatase TiO2 with Various Surface Features and Implications in Oxidation Reactions","authors":"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","DOIUrl":null,"url":null,"abstract":"Anatase TiO<sub>2</sub> is commonly used as a catalyst/support in reactions involving H<sub>2</sub>O<sub>2</sub>, yet the understanding of interactions between common TiO<sub>2</sub> surfaces and H<sub>2</sub>O<sub>2</sub> remains limited. Herein, we synthesized well-defined TiO<sub>2</sub> crystallites with (101), (001), and fluorine-modified (001) [F-(001)] surfaces to examine how surface features, including the arrangement of five-coordinated Ti (Ti<sub>5c</sub>) sites and the presence of fluorine, influence H<sub>2</sub>O<sub>2</sub> activation. Our findings reveal that these surface features significantly affect the physiochemical properties of adsorbed H<sub>2</sub>O<sub>2</sub>. Specifically, fluorine on the F-(001) surface introduces an additional hydrogen bond to the Ti<sub>5c</sub>-peroxo species, altering the electronic structure of H<sub>2</sub>O<sub>2</sub> compared to those with the (101) and (001) surfaces. Using cyclohexene as a probe substrate, we successfully distinguished the reactivities of the Ti<sub>5c</sub>-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 TiO<sub>2</sub>-based catalysts for H<sub>2</sub>O<sub>2</sub>-related reactions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpclett.4c02742","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
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 (Ti5c) 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 Ti5c-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 Ti5c-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.
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.