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Bismuth clusters pinned on TiO2 porous nanowires boosting charge transfer for CO2 photoreduction to CH4

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Abstract

Artificial photosynthesis in carbon dioxide (CO2) conversion into value-added chemicals attracts considerable attention but suffers from the low activity induced by sluggish separation of photogenerated carriers and the kinetic bottleneck-induced unsatisfied selectivity. Herein, we prepare a new-style Bi/TiO2 catalyst formed by pinning bismuth clusters on TiO2 nanowires through being confined by pores, which exhibits high activity and selectivity towards photocatalytic production of CH4 from CO2. Boosted charge transfer from TiO2 through Bi to the reactants is revealed via in situ X-ray photon spectroscopy and time-resolved photoluminescence (PL). Further, in situ Fourier transform infrared results confirm that Bi/TiO2 not only overcomes the multi-electron kinetics challenge of CO2 to CH4 via boosting charge transfer, but also facilitates proton production and transfer as well as the intermediates ⋆CHO and ⋆CH3O generation, ultimately achieving the tandem catalysis towards methanation. Theoretical calculation also underlies that the more favorable reaction step from ⋆CO to ⋆CHO on Bi/TiO2 results in CH4 production with higher selectivity. Our work brings new insights into rational design of photocatalysts with high performance and the formation mechanism of CO2 to CH4 for solar energy storage in future.

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Acknowledgements

This work was financially supported in part by the National Natural Science Foundation of China (Nos. 52125103, 52071041 and 12074048), the Project for Fundamental and Frontier Research in Chongqing (Nos. cstc2020jcyj-msxmX0777 and cstc2020jcyj-msxmX0796). We would like to thank Ms. C. Y. Y. from the Analytical and Testing Center at Chongqing University for her helpful TRPL measurement and Ms. H. J. Z. for XRD characterization.

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Authors and Affiliations

  1. College of Physics and Institute of Advanced Interdisciplinary Studies, Chongqing University, Chongqing, 401331, China

    Jiazhi Meng, Yang Wang, Jiangping Ma, Chaogang Ban, Yajie Feng, Liyong Gan & Xiaoyuan Zhou

  2. School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 401331, China

    Danmei Yu

  3. College of Materials Science and Engineering, Chongqing University, Chongqing, 400044, China

    Guang Han

  4. Beijing Key Lab of Microstructure and Properties of Advanced Materials, Beijing University of Technology, Beijing, 100124, China

    Kaiwen Wang

  5. Analytical and Testing Center, Chongqing University, Chongqing, 401331, China

    Bin Zhang, Kai Zhou & Xiaoyuan Zhou

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  1. Jiazhi Meng
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  12. Xiaoyuan Zhou
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Correspondence to Guang Han, Danmei Yu or Xiaoyuan Zhou.

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Meng, J., Wang, K., Wang, Y. et al. Bismuth clusters pinned on TiO2 porous nanowires boosting charge transfer for CO2 photoreduction to CH4. Nano Res. 17, 1190–1198 (2024). https://doi.org/10.1007/s12274-023-5990-6

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