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Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide


The electrosynthesis of higher-order alcohols from carbon dioxide and carbon monoxide addresses the need for the long-term storage of renewable electricity; unfortunately, the present-day performance remains below what is needed for practical applications. Here we report a catalyst design strategy that promotes C3 formation via the nanoconfinement of C2 intermediates, and thereby promotes C2:C1 coupling inside a reactive nanocavity. We first employed finite-element method simulations to assess the potential for the retention and binding of C2 intermediates as a function of cavity structure. We then developed a method of synthesizing open Cu nanocavity structures with a tunable geometry via the electroreduction of Cu2O cavities formed through acidic etching. The nanocavities showed a morphology-driven shift in selectivity from C2 to C3 products during the carbon monoxide electroreduction, to reach a propanol Faradaic efficiency of 21 ± 1% at a conversion rate of 7.8 ± 0.5 mA cm−2 at −0.56 V versus a reversible hydrogen electrode.

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Fig. 1: Computed concentration and flux distribution of species.
Fig. 2: Structural characterization of the 3D cavity confinement in nanocatalysts.
Fig. 3: Characterization of the as-prepared Cu2O and post-CORR Cu nanocatalysts.
Fig. 4: CO electrochemical reduction performance in a flow cell system.

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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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This work was supported by the Ontario Research Fund Research-Excellence Program, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the CIFAR Bio-Inspired Solar Energy program and University of Toronto Connaught grant. The authors thank T. P. Wu, Z. Finfrock and L. Ma for technical support at the 9BM beam-line of the Advanced Photon Source (Lemont, IL). This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory and was supported by the US DOE under Contract no. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. S.H.Y. acknowledges funding from the National Natural Science Foundation of China (Grant 21431006) and the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (Grant 21521001). The authors thank X. Wang and A. Seifitokaldani from the University of Toronto for fruitful discussions.

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Authors and Affiliations



E.H.S. and D.S. supervised the project. T.-T.Z. designed the structures, carried out the experiments and wrote the paper. Y.P. carried out the FEM simulations. Z.Q.L. and Y.L. helped to synthesize the catalysts and collect the electroreduction performance data. Z.W. helped to do the DFT simulations. C.-S.T. and P.-L.H. helped to characterize the morphology of the catalyst. J.L. performed the X-ray spectroscopy measurements. M.L., A.P. and A.J. carried out the grazing incidence wide-angle X-ray scattering measurements. All the authors discussed the results and assisted during the manuscript preparation.

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Correspondence to David Sinton or Edward H. Sargent.

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Supplementary Methods, Supplementary Figures 1–18, Supplementary Tables 1–5 and Supplementary References

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Zhuang, TT., Pang, Y., Liang, ZQ. et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide. Nat Catal 1, 946–951 (2018).

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