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Conversion of CO2 to multicarbon products in strong acid by controlling the catalyst microenvironment

Nature Synthesis (2023)Cite this article

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Abstract

Electrosynthesis of multicarbon products from the reduction of CO2 in acidic electrolytes is a promising approach to overcoming CO2 reactant loss in alkaline and neutral electrolytes; however, the proton-rich environment near the catalyst surface favours the hydrogen evolution reaction, leading to low energy efficiency for multicarbon products. Here we report a heterogeneous catalyst adlayer—composed of covalent organic framework nanoparticles and cation-exchange ionomers—that suppresses hydrogen evolution and promotes CO2-to-multicarbon conversion in strong acid. The imine and carbonyl-functionalized covalent organic framework regulates the ionomer structure, creating evenly distributed cation-carrying and hydrophilic–hydrophobic nanochannels that control the catalyst microenvironment. The resulting high local alkalinity and cation-enriched environment enables C–C coupling between 100 and 400 mA cm−2. A multicarbon Faradaic efficiency of 75% is achieved at 200 mA cm−2. The system demonstrates a full-cell multicarbon energy efficiency of 25%, which is a twofold improvement over the literature benchmark acidic system for the reduction of CO2.

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Fig. 1: Catalyst microenvironment control in acidic media via proton-flux-constraining ionomer adlayer design.
Fig. 2: Structure and proton-flux-constraining property of COF:PFSA heterojunction.
Fig. 3: COF:PFSA adlayer enables efficient multicarbon electrosynthesis on copper in acidic electrolyte.
Fig. 4: Acidic CO2-to-multicarbon electrosynthesis in a slim flow-cell.

Data availability

All experimental data are available in the main text or the Supplementary Information. Source Data are provided with this paper.

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Acknowledgements

This work was financially supported by the Ontario Research Fund—Research Excellence Program (D.S.), the Natural Sciences and Engineering Research Council (NSERC) of Canada (D.S.), the Australian Research Council through a Discovery Early Career Researcher Award (grant no. DE200100477 to F.L.) and the National Natural Science Foundation of China (grant no. 51603114 to L.H.).

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  1. These authors contributed equally: Yong Zhao, Long Hao, Adnan Ozden, Shijie Liu.

Authors and Affiliations

  1. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    Yong Zhao, Adnan Ozden, Shijie Liu, Rui Kai Miao, Tartela Alkayyali, Yi Xu, Mengyang Fan, Jinqiang Zhang, Colin P. O’Brien & David Sinton

  2. School of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, University of Sydney, Sydney, New South Wales, Australia

    Yong Zhao, Shuzhen Zhang & Fengwang Li

  3. College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao, China

    Long Hao & Jing Ning

  4. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Pengfei Ou, Yongxiang Liang, Yuanjun Chen, Jianan Erick Huang, Ke Xie, Jinqiang Zhang & Edward H. Sargent

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Contributions

D.S. and F.L. supervised the project. Y.Z. designed and performed all of the electrochemical experiments. L.H. and J.N. synthesized and characterized the COF materials. A.O. prepared PTFE–Cu substrates and fabricated the slim flow-cell. R.K.M. and K.X. designed the permeation flow-cell. R.K.M. and S.Z. performed NMR and ICP analyses. Y.L. performed TEM, zeta potential and contact angle measurements. S.L. and T.A. performed COMSOL modelling. P.O. performed DFT calculations. Y.X., M.F., Y.C., J.E.H. and J.Z. assisted in electrochemical measurements and contributed to data analysis. Y.Z. wrote the manuscript. A.O., C.P.O'.B., F.L., E.H.S. and D.S. contributed to manuscript editing. All of the authors discussed the results and assisted during the manuscript preparation.

Corresponding authors

Correspondence to Fengwang Li or David Sinton.

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Nature Synthesis thanks Peng Kang, Anna Klinkova and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary Methods, Figs. 1–42 and Tables 1–6.

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Zhao, Y., Hao, L., Ozden, A. et al. Conversion of CO2 to multicarbon products in strong acid by controlling the catalyst microenvironment. Nat. Synth (2023). https://doi.org/10.1038/s44160-022-00234-x

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