Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2

Abstract

The electrochemical reduction of CO2 could play an important role in addressing climate-change issues and global energy demands as part of a carbon-neutral energy cycle. Single-atom catalysts can display outstanding electrocatalytic performance; however, given their single-site nature they are usually only amenable to reactions that involve single molecules. For processes that involve multiple molecules, improved catalytic properties could be achieved through the development of atomically dispersed catalysts with higher complexities. Here we report a catalyst that features two adjacent copper atoms, which we call an ‘atom-pair catalyst’, that work together to carry out the critical bimolecular step in CO2 reduction. The atom-pair catalyst features stable Cu10–Cu1x+ pair structures, with Cu1x+ adsorbing H2O and the neighbouring Cu10 adsorbing CO2, which thereby promotes CO2 activation. This results in a Faradaic efficiency for CO generation above 92%, with the competing hydrogen evolution reaction almost completely suppressed. Experimental characterization and density functional theory revealed that the adsorption configuration reduces the activation energy, which generates high selectivity, activity and stability under relatively low potentials.

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Fig. 1: Structural characterizations of Cu(0.10%)-doped Pd10Te3 nanowires (Cu–APC).
Fig. 2: Catalytic performances of Cu–APC and other Pd10Te3 nanowire samples in CO2RR.
Fig. 3: Comparison between results of the XAFS spectroscopy and theoretical calculation with the depicted structures for Cu-doped Pd10Te3 nanowires.
Fig. 4: Free energy profiles for CO2 activation mode.

Data availability

Full data supporting the findings of this study are available within the article and its Supplementary Information, as well as from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2017YFA0700101 and 2016YFA0202801), and the National Natural Science Foundation of China (21872076, 21573119, 21590792, 21890383 and 51403114). We thank the 1W1B station in the BSRF and beamline 12B2 (SPring-8), BL01C1 (TLS) of the NSRRC for the X-ray absorption spectroscopy measurements. B.X. and X.Y. acknowledge the support of the US Department of Energy under grant no. DE-SC0016537.

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C.C. and J.J. conceived the project. J.J., W.-C.C. and Z.C. carried out the syntheses and structural characterizations. R.L. conducted the CO2 electrochemical reduction experiments. S.L., J.J., L.Z., S.-F.H. and H.M.C. provided the analyses of the XANES and EXAFS. B.X., Q.L. and X.Y. carried out the in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy experiment and provided the analyses. H.X. carried out computational investigation and provided theoretical analysis. C.Z. helped to write this manuscript. C.C. was responsible for the overall direction of the project. All the other authors participated in preparing the manuscript and contributed to the discussion.

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Correspondence to Hai Xiao or Chen Chen.

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Supplementary Information

Supplementary Methods, Supplementary Characterization, Supplementary Theory, Supplementary Figures 1–15, Supplementary Tables 1–8

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Jiao, J., Lin, R., Liu, S. et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2. Nature Chem 11, 222–228 (2019). https://doi.org/10.1038/s41557-018-0201-x

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