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Ag24Au cluster decorated mesoporous Co3O4 for highly selective and efficient photothermal CO2 hydrogenation

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Abstract

Photothermal carbon dioxide hydrogenation represents a promising route to reduce the emission of greenhouse gas CO2 and produce value-added chemicals, but the selectivity and stability of photothermal catalysts need to be improved. Herein, we report the rational fabrication of well-defined Ag24Au cluster decorated highly ordered nanorod-like mesoporous Co3O4 (Ag24Au/meso-Co3O4) for highly efficient and selective CO2 hydrogenation. The orderly assembled meso-Co3O4 nanorods were prepared via a nanocasting method, offering large surface area and abundant active sites for CO2 adsorption and conversion. Moreover, the catalytic activity and selectivity were further improved by molecule-like Ag24Au cluster decoration and reaction temperature optimization. The Ag24Au/meso-Co3O4 composite catalyst exhibited an ultrahigh CH4 yield rate of 204 mmol·g−1·h−1 and a greatly improved CH4 selectivity of 82% for CO2 hydrogenation, significantly higher than those of pristine meso-Co3O4 catalyst. The mechanism of the photothermal catalytic performance improvement was verified by CO2 temperature-programmed desorption and time-resolved transient photoluminescence, revealing that CO2 molecules underwent a vigorous adsorption and rapid activation process over Ag24Au/meso-Co3O4. The hot electrons created by the localized surface plasmon resonance effect of Ag24Au clusters facilitated the charge transfer for subsequent multi-electron CO2 hydrogeneration processes, resulting in a significant increase in the productivity and selectivity for CO2-to-CH4 conversion. This work suggests that the rational coupling of well-defined metal atom clusters and ordered transition metal compound nanostructures could open a new avenue towards photo-induced green chemistry processes for efficient CO2 recycling and reutilization.

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Acknowledgements

The authors thank the funding supports from the National Key Research & Development Program of China (No. 2017YFA0208200), the National Natural Science Foundation of China (Nos. 22022505 and 21872069), the Fundamental Research Funds for the Central Universities (No. 0205-14380266), and the 2021 Suzhou Gusu Leading Talents of Science and Technology Innovation and Entrepreneurship in Wujiang District.

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Authors and Affiliations

  1. MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China

    Yan Xiong, Xu Liu, Yi Hu, Minghang Jiang, Zuoxiu Tie & Zhong Jin

  2. Suzhou Tierui New Energy Technology Co. Ltd., Suzhou, 215228, China

    Yan Xiong, Yi Hu, Minghang Jiang, Zuoxiu Tie & Zhong Jin

  3. The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, China

    Dong Gu

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  1. Yan Xiong
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Correspondence to Zhong Jin.

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Xiong, Y., Liu, X., Hu, Y. et al. Ag24Au cluster decorated mesoporous Co3O4 for highly selective and efficient photothermal CO2 hydrogenation. Nano Res. 15, 4965–4972 (2022). https://doi.org/10.1007/s12274-022-4133-9

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  • DOI: https://doi.org/10.1007/s12274-022-4133-9

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