Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis

Abstract

The electrosynthesis of C2+ hydrocarbons from CO2 has attracted recent attention in light of the relatively high market price per unit energy input. Today’s low selectivities and stabilities towards C2+ products at high current densities curtail system energy efficiency, which limits their prospects for economic competitiveness. Here we present a materials processing strategy based on in situ electrodeposition of copper under CO2 reduction conditions that preferentially expose and maintain Cu(100) facets, which favour the formation of C2+ products. We observe capping of facets during catalyst synthesis and achieve control over faceting to obtain a 70% increase in the ratio of Cu(100) facets to total facet area. We report a 90% Faradaic efficiency for C2+ products at a partial current density of 520 mA cm−2 and a full-cell C2+ power conversion efficiency of 37%. We achieve nearly constant C2H4 selectivity over 65 h operation at 350 mA cm−2 in a membrane electrode assembly electrolyser.

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Fig. 1: DFT calculations.
Fig. 2: The influence of intermediate adsorption on copper clustering.
Fig. 3: Analysis of the catalyst formation and the surface structures.
Fig. 4: CO2 electroreduction performance.

Data availability

The datasets generated and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

This work was supported financially by TOTAL American Services, the Connaught Fund, the Ontario Research Fund: Research Excellence Program, the Natural Sciences and Engineering Research Council of Canada and the CIFAR Bio-inspired Solar Energy programme. This research used synchrotron resources from the Advanced Photon Source (an Office of Science User Facility operated for the US Department of Energy) Office of Science by Argonne National Laboratory, supported by the US Department of Energy under contract no. DE-AC02-06CH11357) and the Canadian Light Source and its funding partners. All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform and Niagara supercomputer at the SciNet HPC Consortium. Southern Ontario Smart Computing Innovation Platform is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada, Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions. SciNet is funded by the Canada Foundation for Innovation; the Government of Ontario; Ontario Research Fund—Research Excellence; and the University of Toronto. We acknowledge the Toronto Nanofabrication Centre and the Ontario Centre for the Characterization of Advanced Materials for sample preparation and characterization facilities. The authors thank T. P. Wu, Z. Finfrock and L. Ma for technical support at 9BM beamline of the Advanced Photon Source. The authors also thank D. Jiang, N. Chen, C. Kim and W. Chen for their assistance at the HXMA beamline at the Canadian Light Source. D.S. acknowledges the Natural Sciences and Engineering Research Council of Canada—E.W.R Steacie Memorial Fellowship. A.S. acknowledges Fonds de Recherche du Quebec-Nature et Technologies for the postdoctoral fellowship award. J.L. and M.G.K. acknowledges the Banting postdoctoral fellowship from the Government of Canada. C.M.G. acknowledges Natural Sciences and Engineering Research Council of Canada for funding in the form of a postdoctoral fellowship. We acknowledge L. Huang and G. Zheng for the help in Brunauer–Emmett–Teller measurements and data analysis. We acknowledge D. Kopilovic for designing flow electrolysers. We thank M. Chekini and E. Kumachev for the help in dynamic light scattering measurements.

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Contributions

E.H.S. supervised the project. Y.W. and C.-T.D. designed the experiments. Y.W. carried out the catalyst synthesis, electrochemical tests, electrocatalysis tests and SEM measurements. Z.W. performed DFT calculations. J.L. performed all the XAS measurements and analysed the results. A.O. performed the tests in MEA electrolysers. M.G.K. prepared evaporated copper seeds. Y.L. and F.L. prepared sputtered copper seeds. C.-S.T. performed TEM measurements and data analysis. A.S. and C.M.G. carried out the operando Raman measurements. M. Luo synthesized copper nanocubes. C.M. performed the local pH simulations. Y.W., H.Z., M.Liu, A.P. and A.J. performed GIWAXS measurements and data analysis. Y.X. designed flow channels for electrolysers. A.P. and P.T. carried out the XPS measurements. T.-T.Z., S.O.K. and D.S. contributed to manuscript writing. All authors discussed, commented on and revised the manuscript.

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Correspondence to Edward H. Sargent.

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Competing interests

Y.W. and E.H.S. of the University of Toronto have filed provisional patent application no. 62/844,482 regarding the preparation of in-situ synthesized catalysts for CO2 reduction.

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Supplementary Information

Supplementary Figs. 1–44, Tables 1–19 and references.

Supplementary Data 1

Atomic coordinates of the optimized computational models.

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Wang, Y., Wang, Z., Dinh, C. et al. Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis. Nat Catal 3, 98–106 (2020). https://doi.org/10.1038/s41929-019-0397-1

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