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Energy- and carbon-efficient CO2/CO electrolysis to multicarbon products via asymmetric ion migration–adsorption

Abstract

Carbon dioxide/monoxide (CO2/CO) electrolysis provides a means to convert emissions into multicarbon products. However, impractical energy and carbon efficiencies limit current systems. Here we show that these inefficiencies originate from uncontrolled gas/ion distributions in the local reaction environment. Understanding of the flows of cations and anions motivated us to seek a route to block cation migration to the catalyst surface—a strategy we instantiate using a covalent organic framework (COF) in bulk heterojunction with a catalyst. The π-conjugated hydrophobic COFs constrain cation (potassium) diffusion via cation–π interactions, while promoting anion (hydroxide) and gaseous feedstock adsorption on the catalyst surface. As a result, a COF-mediated catalyst enables electrosynthesis of multicarbon products from CO for 200 h at a single-pass carbon efficiency of 95%, an energy efficiency of 40% and a current density of 240 mA cm−2.

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Fig. 1: Energy and carbon efficiency limitations in CO2/CO electrolysis.
Fig. 2: Local cation and anion transport in a zero-gap, catholyte-free MEA electrolyser.
Fig. 3: The CCBH catalyst.
Fig. 4: The CCBH catalyst for energy- and carbon-efficient CO2RR/CORR.

Data availability

All of the data supporting the findings of this study are available within the published article and its Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the Ontario Research Fund – Research Excellence programme, the Natural Sciences and Engineering Research Council (NSERC) of Canada and Natural Resources Canada’s Clean Growth Program. This research used synchrotron 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 number DE-AC02-06CH11357, as well as the Canadian Light Source and its funding partners. Support from the Canada Research Chairs Program is gratefully acknowledged, as is support from an NSERC E.W.R. Steacie Fellowship to D.S. J.L. thanks the National Natural Science Foundation of China (grant number BE3250011), the National Key Research and Development Program of China (grant number 2022YFA1505100), and Shanghai Jiao Tong University (grant number WH220432516) for support. F.P.G.d.A. acknowledges funding from CEX2019-000910-S (MCIN/AEI/10.13039/501100011033), Fundación Cellex, Fundació Mir-Puig, Generalitat de Catalunya through CERCA and the La Caixa Foundation (100010434; EU Horizon 2020 Marie Skłodowska-Curie grant agreement 847648).

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Authors and Affiliations

Authors

Contributions

D.S., E.H.S., M.E. and J.L. supervised the project. A.O., J.L. and S.K. conceived of the idea. A.O. and J.L. designed and carried out all of the electrochemical experiments. A.O. synthesized the catalysts and fabricated the electrodes and slim flow-cell electrolyser. A.O. performed the SEM, TEM and XPS measurements. S.L. performed the COMSOL simulations. S.K., V.S.K. and P.M.B. synthesized and characterized the Hex–Aza–COF nanosheets. Y.Z.F. performed the XAS measurements. Y.-K.W. performed the XRD measurements. X.-Y.L. performed the DFT calculations with the assistance of P.O. T.A., F.P.G.d.A. and A.H.I. contributed to data analysis. A.O. and J.L. cowrote the manuscript. D.S., E.H.S. and O.S. contributed to manuscript editing. All authors discussed the results and assisted during manuscript preparation.

Corresponding authors

Correspondence to Jun Li, Mohamed Eddaoudi, Edward H. Sargent or David Sinton.

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Nature Energy thanks Ezra Clark and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs., 1–57, notes 1–7, Tables 1–50 and references 1–15.

Supplementary Data

Source data for Supplementary Figs. 2a–f, 3a–f, 18a,b, 19a–f, 20, 24a–c, 26a,b, 27a,b, 29b,c, 32, 33, 35, 36a–f, 37, 38a–c, 39, 40a–c, 41, 42a–c, 43a–d, 51–54, 56 and 57.

Source data

Source Data Fig. 1

Source data for Fig. 1b.

Source Data Fig. 3

Source data for Fig. 3f–h.

Source Data Fig. 4

Source data for Fig. 4a.

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Ozden, A., Li, J., Kandambeth, S. et al. Energy- and carbon-efficient CO2/CO electrolysis to multicarbon products via asymmetric ion migration–adsorption. Nat Energy (2023). https://doi.org/10.1038/s41560-022-01188-2

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