Ionothermal synthesis of black Ti3+-doped single-crystal TiO2 as an active photocatalyst for pollutant degradation and H2 generation

Guisheng Li; Zichao Lian; Xin Li; Yuanyuan Xu; Wenchao Wang; Dieqing Zhang; Fenghui Tian; Hexing Li

doi:10.1039/C4TA02873B

Ionothermal synthesis of black Ti³⁺-doped single-crystal TiO₂ as an active photocatalyst for pollutant degradation and H₂ generation†

Guisheng Li,*^a Zichao Lian,^a Xin Li,^a Yuanyuan Xu,^a Wenchao Wang,^a Dieqing Zhang,^a Fenghui Tian^b and Hexing Li*^c

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* Corresponding authors

^a Chinese Education Ministry Key Laboratory of Resource Chemistry, Shanghai Normal University, Shanghai 200234, China
E-mail: liguisheng@shnu.edu.cn

^b Institute of Computational Science and Engineering, Qingdao University, Qingdao, China

^c Shanghai University of Electric Power, Shanghai 200090, China
E-mail: Hexing-Li@shnu.edu.cn

Abstract

A black Ti³⁺-doped single-crystal TiO₂ (Ti³⁺/TiO₂) was one-pot synthesized by treating Ti metal in an ionic liquid containing LiAc and HAc under mild ionothermal conditions. The ionic liquid (1-methyl-imidazolium tetrafluoroborate) supplied an environment enriched with fluoride ions for dissolving titanium foil under ionothermal conditions, followed by reducing protons in acetic acid to form Ti³⁺ ions, leading to Ti³⁺-doped single-crystal TiO₂ as a black powder. EPR and XPS results indicated the high concentrations of both Ti³⁺-dopants and oxygen vacancies. The Ti³⁺ incorporated into the TiO₂ lattice could narrow the energy band gap of TiO₂via forming intermediate energy levels, leading to a visible photocatalyst. Meanwhile, the oxygen vacancies could inhibit the photoelectron–hole recombination. As expected, such a black Ti³⁺/TiO₂ exhibited high activity in the photocatalytic degradation of organic pollutants and water splitting for H₂ production under irradiation with visible light and/or simulated solar light.

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Article information

DOI: https://doi.org/10.1039/C4TA02873B
Article type: Paper
Submitted: 07 Jun 2014
Accepted: 24 Dec 2014
First published: 24 Dec 2014

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J. Mater. Chem. A, 2015,3, 3748-3756

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Ionothermal synthesis of black Ti³⁺-doped single-crystal TiO₂ as an active photocatalyst for pollutant degradation and H₂ generation

G. Li, Z. Lian, X. Li, Y. Xu, W. Wang, D. Zhang, F. Tian and H. Li, J. Mater. Chem. A, 2015, 3, 3748 DOI: 10.1039/C4TA02873B

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Journal of Materials Chemistry A