Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons

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Abstract

The electrochemical reduction of CO2 to multi-carbon products has attracted much attention because it provides an avenue to the synthesis of value-added carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the efficiency of CO2 conversion to C2 products remains below that necessary for its implementation at scale. Modifying the local electronic structure of copper with positive valence sites has been predicted to boost conversion to C2 products. Here, we use boron to tune the ratio of Cuδ+ to Cu0 active sites and improve both stability and C2-product generation. Simulations show that the ability to tune the average oxidation state of copper enables control over CO adsorption and dimerization, and makes it possible to implement a preference for the electrosynthesis of C2 products. We report experimentally a C2 Faradaic efficiency of 79 ± 2% on boron-doped copper catalysts and further show that boron doping leads to catalysts that are stable for in excess of ~40 hours while electrochemically reducing CO2 to multi-carbon hydrocarbons.

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Fig. 1: DFT calculations on enhancing C2 electroproduction.
Fig. 2: Preparation and characterization of Cu(B).
Fig. 3: Oxidation state of copper in Cu(B) samples.
Fig. 4: CO2RR performance on Cu(B) and control samples.

Change history

  • 29 October 2019

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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Acknowledgements

This work was supported financially by funding from TOTAL S.A., the Ontario Research Fund: Research Excellence Program, the Natural Sciences and Engineering Research Council of Canada, the CIFAR Bio-Inspired Solar Energy programme, a University of Toronto Connaught grant, the Ministry of Science, Natural Science Foundation of China (21471040, 21271055 and 21501035), the Innovation-Driven Plan in Central South University project (2017CX003), a project from State Key Laboratory of Powder Metallurgy in Central South University, the Thousand Youth Talents Plan of China and Hundred Youth Talents Program of Hunan and the China Scholarship Council programme. This work benefited from the soft X-ray microcharacterization beamline at CLS, sector 20BM at the APS and the Ontario Centre for the Characterisation of Advanced Materials at the University of Toronto. H.Y. acknowledges financial support from the Research Foundation-Flanders (FWO postdoctoral fellowship). C.Z. acknowledges support from the International Academic Exchange Fund for Joint PhD Students from Tianjin University. P.D.L. acknowledges financial support from the Natural Sciences and Engineering Research Council in the form of the Canada Graduate Scholarship—Doctoral award. S.B. and E.B. acknowledge financial support from the European Research Council (ERC Starting Grant #335078-COLOURATOMS). The authors thank B. Zhang, N. Wang, C. T. Dinh, T. Zhuang, J. Li and Y. Zhao for fruitful discussions, as well as Y. Hu and Q. Xiao from CLS, and Z. Finfrock and M. Ward from APS for their help during the course of study. 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, Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions.

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Contributions

E.H.S. and G.C. supervised the project. Y.Z. and M.L. conceived the idea, designed the experiments and analysed the results. Y.Z. synthesized the samples, performed the electrochemical experiments and analysed the results. F.C. carried out the simulations and wrote the corresponding section. M.L., P.C. and P.D.L. conducted the XAS measurements. J.L., Z.W., T.-K.S. and D.S. assisted in analysing the XAS results. C.Z., Y.Z. and Z.L. ran the NMR tests. M.L. and C.Z. carried out the scanning electron microscope measurements. Y.Z. and H.Y. designed the ICP-OES experiments. C.Z. performed the ICP-OES tests. Z.L. ran the X-ray diffractometer tests. R.Q.-B., H.X. and H.L. performed the XPS measurements. E.B. conducted the TEM measurements. E.B., H.Y., S.B. and J.H. assisted in analysing the TEM results. All authors read and commented on the manuscript.

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Correspondence to Gang Chen or Edward H. Sargent.

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Supplementary information

Supplementary information

Supplementary computational simulation methods and data, Supplementary Figures 1–42, Supplementary Tables 1–14

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Zhou, Y., Che, F., Liu, M. et al. Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons. Nature Chem 10, 974–980 (2018). https://doi.org/10.1038/s41557-018-0092-x

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