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Improving the SO2 tolerance of CO2 reduction electrocatalysts using a polymer/catalyst/ionomer heterojunction design

Abstract

The high concentrations of CO2 in industrial flue gases make these point sources attractive candidates for renewably powered electrocatalytic conversion of CO2 to products. However, trace SO2 in common flue gases rapidly and irreversibly poisons catalysts. Here we report that limiting hydrogen adsorption in the vicinity of electrochemically active sites deactivates SO2 to enable efficient CO2 conversion. We realize this approach via a polymer/catalyst/ionomer heterojunction design with combined hydrophobic and highly charged hydrophilic domains that diminish hydrogen adsorption and promote CO2 over SO2 transport. We develop an SO2-tolerant system that maintains ~50% faradaic efficiency towards multi-carbon products for over 150 h (at 100 mA cm–2). Extending this strategy to a high-surface-area composite catalyst, we achieve faradaic efficiencies of 84%, partial current densities of up to 790 mA cm–2 and energy efficiencies of ~25% towards multi-carbon products with a CO2 stream containing 400 ppm SO2, a performance that is competitive with the best reports using pure CO2.

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Fig. 1: Processing of CO2 gas.
Fig. 2: Investigation of the SO2 poisoning mechanism.
Fig. 3: SO2-tolerant CO2 electrolysis at a modified planar Cu electrode.
Fig. 4: Structure and performance of a modified bulk Cu electrode for the co-electrolysis of CO2 and SO2.

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The datasets analysed and generated during the current study are included in the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (2022YFA1505100 and 2023YFA1507500 to J.L.), the National Natural Science Foundation of China (grant number BE3250011 to J.L.), the Fundamental Research Funds for the Central Universities (23×010301599 to J.L.), Shanghai Pilot Program for Basic Research, Shanghai Jiao Tong University (21TQ1400227 to J.L.), the Ontario Research Foundation: Research Excellence Program (to D.S.), the Natural Sciences and Engineering Research Council (NSERC) of Canada (to D.S and P.P.) and TOTAL SE (to D.S.). Part or all of the XAS measurements described in this paper were performed at the Soft X-ray Microcharacterization Beamline at the Canadian Light Source, a national research facility of the University of Saskatchewan, which is supported by NSERC, the Canada Foundation for Innovation (CFI), the National Research Council (NRC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan and the University of Saskatchewan. We gratefully acknowledge support from the Canada Research Chairs Program. The computational study is supported by the Marsden Fund Council from Government funding (21-UOA-237 to Z.W.) and Catalyst: Seeding General Grant (22-UOA-031-CGS to Z.W.), managed by Royal Society Te Apārangi. Z.W. and R.L. acknowledge the use of New Zealand eScience Infrastructure (NeSI) high-performance computing facilities, consulting support and/or training services as part of this research.

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Contributions

D.S. and J.L. supervised the project. J.L. and P.P. conceived the idea. J.L. and P.P designed and P.P. and R.K.M. carried out all the electrochemical experiments. H. Liu, X.W., A.O. and C.P.O. contributed to electrode fabrication and assisted with the electrochemical testing. R.L. performed DFT calculations with the supervision of Z.W.; S.L. performed COMSOL Multiphysics simulations and F.L. supported the related discussions. J.L. and P.P. performed XAS and Raman measurements, in which Y.H., M.S. and Q.X. assisted with the XAS testing and R.K.M. and J.E.H. assisted with the Raman testing. M.L. and J.Y.H. performed scanning electron microscopy, TEM and X-ray photoemission spectroscopy characterizations, with the contributions of Y.W., Q.Z. and P.L. for data analysis. A.S.Z., B.K. and K.G. assisted with the contact angle measurements. N.S. and Y.C.X. contributed to figure draughting. J.L. wrote the manuscript. D.S., E.H.S., H. Liang and P.P. contributed to manuscript editing. All authors discussed the results and assisted during the manuscript preparation.

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Correspondence to Ziyun Wang, Jun Li or David Sinton.

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Supplementary Notes 1–6, Figs. 1–49 and Tables 1–10.

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Statistical source data for Supplementary Fig. 34b.

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Papangelakis, P., Miao, R.K., Lu, R. et al. Improving the SO2 tolerance of CO2 reduction electrocatalysts using a polymer/catalyst/ionomer heterojunction design. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01577-9

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