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Unraveling the evolution of oxygen vacancies in TiO2−x/Cu and its role in CO2 hydrogenation

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  • Special Issue: 2024 Emerging Investigator Issue
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Abstract

The remarkable contribution of oxygen vacancies has been revealed by the operando spectroscopies for methanol synthesis from CO2 hydrogeneration on the reducible metal oxide-supported copper catalysts. However, a challenge remains in the intrinsic understanding of the evolution and advantage of oxygen vacancies for methanol synthesis. Here we prepare the TiO2−x/Cu with different oxygen vacancy densities by adjusting the ball-milling frequency. At the optimal condition, a TiO2−x/Cu with more oxygen vacancies delivers an excellent methanol yield of 26.5 mmol g−1 h−1 at 300 °C with a selectivity of more than 70%. The combined analysis of experimental characterizations and theoretical calculations reveals that the mutual dispersions of TiO2−x and Cu driven by mechanical energy induce the electron rearrangement in the d orbital of the Ti atom and relax the Ti–O binding at the interface, which facilitates the formation of oxygen vacancies that further reduce the barrier of CO2 hydrogenation to *HCOO due to higher nucleophilicity of titanium ions.

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Acknowledgements

This work is supported by National Key Research and Development Program of China (2022YFE0128600, 2023YFA1508103), National Natural Science Foundation of China (22278365), Natural Science Foundation of Zhejiang Province (LR22B060002), the grant from Shanxi-Zheda Institue of Advanced Materials and Chemical Engineering (2021ST-AT-002).

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Authors and Affiliations

  1. College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310058, China

    Ke Wang, Fanxing Zhang, Ning Cao, Keping Yan & Pengfei Xie

  2. Institute of Zhejiang University-Quzhou, Quzhou, 324000, China

    Ke Wang & Pengfei Xie

  3. School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310058, China

    Mi Yan

  4. State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization, Baotou Research Institute of Rare Earths, Baotou, 014030, China

    Mi Yan & Pengfei Xie

  5. Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan, 030032, China

    Keping Yan

  6. Department of Chemistry, Western Washington University, Bellingham, WA, 98225, USA

    Ying Bao

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  1. Ke Wang
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Correspondence to Pengfei Xie.

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Supporting information The supporting information is available online at chem.scichina.com and link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Wang, K., Zhang, F., Cao, N. et al. Unraveling the evolution of oxygen vacancies in TiO2−x/Cu and its role in CO2 hydrogenation. Sci. China Chem. (2024). https://doi.org/10.1007/s11426-023-1995-6

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  • DOI: https://doi.org/10.1007/s11426-023-1995-6

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