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Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

Abstract

The reduction of carbon dioxide to renewable fuels and feedstocks offers opportunities for large-scale, long-term energy storage. The synthesis of efficient CO2 reduction electrocatalysts with high C2:C1 selectivity remains a field of intense interest. Here we present electro-redeposition, the dissolution and redeposition of copper from a sol–gel, to enhance copper catalysts in terms of their morphology, oxidation state and consequent performance. We utilized in situ soft X-ray absorption spectroscopy to track the oxidation state of copper under CO2 reduction conditions with time resolution. The sol–gel material slows the electrochemical reduction of copper, enabling control over nanoscale morphology and the stabilization of Cu+ at negative potentials. CO2 reduction experiments, in situ X-ray spectroscopy and density functional theory simulations revealed the beneficial interplay between sharp morphologies and Cu+ oxidation state. The catalyst exhibits a partial ethylene current density of 160 mA cm–2 (−1.0 V versus reversible hydrogen electrode) and an ethylene/methane ratio of 200.

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Fig. 1: Catalytic activity of ERD Cu catalysts.
Fig. 2: Growth of ERD Cu nanostructures.
Fig. 3: Surface characterization of ERD Cu.
Fig. 4: X-ray spectroscopy measurements.
Fig. 5: DFT studies of C1 and C2 electroproduction as a function of metal oxidation state.

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Acknowledgements

This work was supported by the Canadian Institute for Advanced Research (CIFAR) Bio-inspired Energy Program, the Ontario Research Fund (ORF-RE-08-034), and the Natural Sciences and Engineering Research Council (NSERC) of Canada. This work was also supported by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, of the US Department of Energy under contract no. DE-AC02-05CH11231 within the Catalysis Research Program (FWP No. CH030201). The authors thank the Canadian Light Source (CLS) for support in the form of a travel grant. The authors acknowledge Y. Li for valuable scientific discussion and assistance with TEM measurements, A. Kiani for assistance with SEM measurements, Y. Hu and M. Norouzi Banis for assistance with in situ XAS cell set-up, and P. Brodersen from the Ontario Centre for the Characterisation of Advanced Materials (OCCAM) Center for assistance with Auger microscopy measurements. P.D.L thanks the Research Council (NSERC) of Canada for the Canadian Graduate Scholarship — Doctoral award and the Michael Smith Foreign Supplement award. M.B.R. gratefully acknowledges support from the CIFAR Bio-Inspired Solar Energy Program. Computations were performed on the SOSCIP Consortium’s Blue Gene/Q computing platform. SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada Ltd., Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions.

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P.D.L. synthesized the catalyst, performed DFT calculations, SEM, TEM, XAS and electrochemical experiments, and data analysis, and wrote the manuscript. R.Q.-B. performed XAS, XPS and SAM experiments and data analysis, and edited the manuscript. C.-T.D. performed flow-cell experiments and edited the manuscript. M.B.R. edited the manuscript and guided the design of experiments. O.S.B. performed NMR experiments and analysis. P.T. performed XRD experiments. T.R. supervised and guided XAS experiments. P.Y. and S.O.K. supervised experiments. E.H.S designed the study, edited the manuscript and supervised experiments.

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Correspondence to Edward H. Sargent.

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Supplementary Methods, Supplementary Discussion, Supplementary Figures 1–16, Supplementary Tables 1–6, Supplementary References.

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De Luna, P., Quintero-Bermudez, R., Dinh, CT. et al. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat Catal 1, 103–110 (2018). https://doi.org/10.1038/s41929-017-0018-9

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