In-situ formation of carboxylate species on TiO2 nanosheets for enhanced visible-light photocatalytic performance

Jianing Li; Qiancheng Zhang; Juming Liu; Mengran Yu; Huiyan Ma; Jucai Yang; Sheng Ye; Tomas Ramirez Reina; Jian Liu

doi:10.1016/j.jcis.2020.05.054

In-situ formation of carboxylate species on TiO₂ nanosheets for enhanced visible-light photocatalytic performance

J Colloid Interface Sci. 2020 Oct 1:577:512-522. doi: 10.1016/j.jcis.2020.05.054. Epub 2020 May 19.

Authors

Jianing Li¹, Qiancheng Zhang¹, Juming Liu², Mengran Yu¹, Huiyan Ma¹, Jucai Yang³, Sheng Ye⁴, Tomas Ramirez Reina⁵, Jian Liu⁶

Affiliations

¹ Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China.
² Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China. Electronic address: liujuming@imut.edu.cn.
³ Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China; School of Energy and Power Engineering, Inner Mongolia University of Technology, Hohhot 010051, China.
⁴ State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 China.
⁵ DICP-Surrey Joint Centre for Future Materials, Department of Chemical and Process Engineering and Advanced Technology Institute, University of Surrey, Guildford, Surrey GU2 7XH, UK.
⁶ State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 China; DICP-Surrey Joint Centre for Future Materials, Department of Chemical and Process Engineering and Advanced Technology Institute, University of Surrey, Guildford, Surrey GU2 7XH, UK. Electronic address: jian.liu@surrey.ac.uk.

PMID: 32526540
DOI: 10.1016/j.jcis.2020.05.054

Abstract

It still remains challenge for expanding the photo-response range of TiO₂ with dominant {0 0 1} facets due to the hardly achieving modification of the electronic structure without destroying the formation of TiO₂ high energy facets. Herein, we report the construction of carboxylate species modified TiO₂ nanosheets with dominant {0 0 1} facets by employing ethanol as a carbon source through a low-temperature (300 °C) carbonization method. The as-obtained samples were investigated in detail by using various characterization techniques. The results indicate that the carboxylate species derived from the oxidation and carbonization of ethanol are coordinated to the {0 0 1} facets in a bidentate bridging mode. The electron-withdrawing carboxylate species induce TiO₂ to form a lower valence band edge and a narrower bandgap, which enhances the oxidation ability of photogenerated holes and expands the photo-response range. The partially carbonized carboxylate species can also act as a photosensitizer to induce visible-light photocatalytic activity of TiO₂ nanosheets. In addition, the carboxylate species can further promote the separation of photogenerated charge carriers. The findings of this work may provide a new perspective for tuning the band structure of TiO₂ with dominant {0 0 1} facets and improving its photocatalytic performance.

Keywords: Carboxylate; High energy facet; Low Valence band; Photocatalysis; TiO(2) nanosheets.