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Selective visible-light-driven photocatalytic CO2 reduction to CH4 mediated by atomically thin CuIn5S8 layers

Abstract

Due to the large number of possible products and their similar reduction potentials, a significant challenge in CO2 photoreduction is achieving selectivity to a single product while maintaining high conversion efficiency. Controlling the reaction intermediates that form on the catalyst surface through careful catalyst design is therefore crucial. Here, we prepare atomically thin layers of sulfur-deficient CuIn5S8 that contain charge-enriched Cu–In dual sites, which are highly selective towards photocatalytic production of CH4 from CO2. We propose that the formation of a highly stable Cu–C–O–In intermediate at the CuIn dual sites is the key feature determining selectivity. We suggest that this configuration not only lowers the overall activation energy barrier, but also converts the endoergic protonation step to an exoergic reaction process, thus changing the reaction pathway to form CH4 instead of CO. As a result, the CuIn5S8 single-unit-cell layers achieve near 100% selectivity for visible-light-driven CO2 reduction to CH4 over CO, with a rate of 8.7 μmol g−1 h−1.

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Fig. 1: Manipulating reactivity and selectivity by modulating the reaction pathways.
Fig. 2: Characterizations of the S deficient CuIn5S8 (VS-CuIn5S8) single-unit-cell layers.
Fig. 3: Electronic band structures and visible-light CO2 reduction properties of the VS-CuIn5S8 single-unit-cell layers and the pristine CuIn5S8 single-unit-cell layers.
Fig. 4: In situ FTIR spectroscopy characterization.
Fig. 5: Gibbs free energy calculations.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (2017YFA0207301 and 2017YFA0303500), the National Natural Science Foundation of China (U1632147, 21890754, U1532265 and 11621063), the Youth Innovation Promotion Association of CAS (CX2340000100), the Key Research Program of Frontier Sciences of CAS (QYZDY-SSW-SLH011), the Fundamental Research Funds for the Central Universities (WK2340000063 and WK2340000073), the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology (2017FXCX006) and the Fok Ying-Tong Education Foundation (161012). The Supercomputing USTC and National Supercomputing Center in Shenzhen are acknowledged for computational support.

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Y.X., Y.Sun and X.L. conceived the idea and co-wrote the paper. Y.Sun, X.L., Y.Shao, J.X., Y.P., H.J. and J.Z. carried out the sample synthesis, characterization and CO2 reduction measurement. Y.Sun, X.L., J.W. and X.X. discussed the catalytic process. All authors contributed to the overall scientific interpretation and edited the manuscript.

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Correspondence to Yongfu Sun or Yi Xie.

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Supplementary Figs. 1–24, Supplementary Tables 1–4, Supplementary refs.

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Li, X., Sun, Y., Xu, J. et al. Selective visible-light-driven photocatalytic CO2 reduction to CH4 mediated by atomically thin CuIn5S8 layers. Nat Energy 4, 690–699 (2019). https://doi.org/10.1038/s41560-019-0431-1

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