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Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction

Nature Catalysis volume 2, pages 86–93 (2019)Cite this article

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Abstract

Carbon dioxide electroreduction in aqueous media using Cu catalysts can generate many different C2 and C3 products, which leads to the question whether all products are generated from the same types of active sites or if product-specific active sites are responsible for certain products. Here, by reducing mixtures of 13CO and 12CO2, we show that oxide-derived Cu catalysts have three different types of active sites for C–C coupled products, one that produces ethanol and acetate, another that produces ethylene and yet another that produces 1-propanol. In contrast, we do not find evidence of product-specific sites on polycrystalline Cu and oriented (100) and (111) Cu surfaces. Analysis of the isotopic composition of the products leads to the prediction that the adsorption energy of *COOH (the product of the first step of CO2 reduction) may be a descriptor for the product selectivity of a given active site. These new insights should enable highly selective catalysts to be developed.

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Fig. 1: Hypothetical scenario in which the reduction of a mixture of 13CO and 12CO2 is carried out on a catalyst with two types of active sites, A and B.
Fig. 2: Isotopic compositions and 12C/13C distributions of products generated by oxide-derived Cu.
Fig. 3: Isotopic compositions and 12C/13C distributions of products generated by Cu(111)- and Cu(100)-oriented surfaces and polycrystalline Cu.
Fig. 4: Isotopic compositions of products generated in control experiments.

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The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This material is based on work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under award no. DE-SC0004993. Y.L. acknowledges the support of an A*STAR National Science Scholarship. We thank A. Buckley for assistance with the 13C NMR spectroscopy and W. R. Leow for assistance with the creation of the figures.

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Authors and Affiliations

  1. Joint Center for Artificial Photosynthesis and Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Yanwei Lum & Joel W. Ager

  2. Department of Materials Science and Engineering, University of California, Berkeley, CA, USA

    Yanwei Lum & Joel W. Ager

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Y.L. and J.W.A. conceived and designed the experiments. Y.L. conducted all the experimental work and analysed the data. Both authors discussed the results and wrote the manuscript.

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Correspondence to Joel W. Ager.

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Lum, Y., Ager, J.W. Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction. Nat Catal 2, 86–93 (2019). https://doi.org/10.1038/s41929-018-0201-7

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