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Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes

Abstract

Electrochemical conversion of CO2 into value-added chemicals holds promise to enable the transition to carbon neutrality. Enhancing selectivity for a specific hydrocarbon product is challenging, however, due to numerous possible reaction pathways of CO2 electroreduction. Here we present a Cu–polyamine hybrid catalyst, developed through co-electroplating, that significantly increases the selectivity for ethylene production. The Faradaic efficiency for ethylene production is 87% ± 3% at −0.47 V versus reversible hydrogen electrode, with full-cell energetic efficiency reaching 50% ± 2%. Raman measurements indicate that the polyamine entrained on the Cu electrode results in higher surface pH, higher CO content and higher stabilization of intermediates compared with entrainment of additives containing little or no amine functionality. More broadly, this work shows that polymer incorporation can alter surface reactivity and lead to enhanced product selectivity at high current densities.

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Fig. 1: Preparation of the Cu–polymer catalyst.
Fig. 2: Electrochemical CO2 conversion on the Cu–Pi electrodes.
Fig. 3: In situ electrochemical Raman spectroscopy measurements during the CO2RR.
Fig. 4: Calculated surface pH on different electrodes.
Fig. 5: Electrochemical characterization of the Cu–P1 catalyst in different concentrations of KOH electrolyte.

Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files.

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Acknowledgements

The authors gratefully acknowledge the support of the International Institute for Carbon Neutral Energy Research (WPI-I2CNER), sponsored by the Japanese Ministry of Education, Culture, Sports, Science and Technology. D.A.H., U.O.N. and P.J.A.K. gratefully acknowledge Shell’s New Energy Research and Technology (NERT) programme for providing funding. J.C. and S.C.Z. acknowledge support of the National Science Foundation (NSF CHE-1709718). We thank the School of Chemical Sciences, University of Illinois Mass Spectrometry Laboratory (especially F. Sun and X. Mao) for performing gas chromatography mass spectrometry measurements. We thank R.T. Haasch for performing XPS and the School of Chemical Sciences, University of Illinois Machine Shop for their help in designing the in situ flow cell for the Raman measurements. We also thank the School of Chemical Sciences, University of Illinois NMR Laboratory for their help with the NMR measurements.

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Contributions

X.C. and N.M.A. prepared the Cu–Pi electrodes and performed the electrochemistry experiments. J.C. synthesized the polymers and performed the NMR experiments. X.C. conducted the SEM and XRD experiments. X.C. and D.A.H. carried out the Raman measurements. R.Z. analysed the XPS data. U.O.N. prepared the anode electrodes. K.E.M. did the contact angle measurements. A.A.G., S.C.Z. and P.J.A.K. conceived the project and supervised the research work. X.C., J.C. and A.A.G. wrote the manuscript with input from the other authors.

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Correspondence to Andrew A. Gewirth.

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Supplementary Information

Supplementary Notes 1–4, Figs. 1–30 and Tables 1–5.

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Chen, X., Chen, J., Alghoraibi, N.M. et al. Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes. Nat Catal 4, 20–27 (2021). https://doi.org/10.1038/s41929-020-00547-0

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