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Copper vacancy activated plasmonic Cu3−xSnS4 for highly efficient photocatalytic hydrogen generation: Broad solar absorption, efficient charge separation and decreased HER overpotential

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Abstract

Broad absorption spectra with efficient generation and separation of available charge carriers are indispensable requirements for promising semiconductor-based photocatalysts to achieve the ultimate goal of solar-to-fuel conversion. Here, Cu3−xSnS4 (x = 0−0.8) with copper vacancies have been prepared and fabricated via solvothermal process. The obtained copper vacancy materials have extended light absorption from ultraviolet to near-infrared-II region for its significant plasmonic effects. Time-resolved photoluminescence shows that the vacancies can simultaneously optimize charge carrier dynamics to boost the generation of long-lived active electrons for photocatalytic reduction. Density functional theory calculations and electrochemical characterizations further revealed that copper vacancies in Cu3−xSnS4 tend to enhance hydrogen’s adsorption energy with an obvious decrease in its H2 evolution reaction (HER) overpotential. Furthermore, without any loadings, the H2 production rate was measured to be 9.5 mmol·h−1·g−1. The apparent quantum yield was measured to be 27% for wavelength λ > 380 nm. The solar energy conversion efficiency was measured to be 6.5% under visible-near infrared (vis-NIR) (λ > 420 nm).

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Acknowledgements

The work is supported by the Science and Technology Commission of Shanghai Municipality (Nos. 19JC1412600, 20520741400, and 18230743400) and the National Natural Science Foundation of China (Nos. 21771124 and 21671134).

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Authors and Affiliations

  1. Shanghai Electrochemical Energy Devices Research Center, School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China

    Nazakat Ali, Tsegaye Tadesse Tsega, Saghir Abbas, Wenjing Li, Asma Iqbal, Hira Fazal, Jiantao Zai & Xuefeng Qian

  2. State Key Laboratory of Polyolefins and Catalysis, Shanghai Key Laboratory of Catalysis Technology for Polyolefins (Shanghai Research Institute of Chemical Industry Co., Ltd.), Shanghai, 200062, China

    Yucai Cao

  3. Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai University of Electric Power, 2103 Pingliang Road, Shanghai, 200090, China

    Zhiling Xin

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  1. Nazakat Ali
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Correspondence to Zhiling Xin, Jiantao Zai or Xuefeng Qian.

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Copper vacancy activated plasmonic Cu3−xSnS4 for highly efficient photocatalytic hydrogen generation: Broad solar absorption, efficient charge separation and decreased HER overpotential

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Ali, N., Tsega, T.T., Cao, Y. et al. Copper vacancy activated plasmonic Cu3−xSnS4 for highly efficient photocatalytic hydrogen generation: Broad solar absorption, efficient charge separation and decreased HER overpotential. Nano Res. 14, 3358–3364 (2021). https://doi.org/10.1007/s12274-021-3604-8

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