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A covalent molecular design enabling efficient CO2 reduction in strong acids

Nature Synthesis (2024)Cite this article

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Abstract

Molecular complexes are an important class of catalysts for the electrochemical carbon dioxide reduction reaction (CO2RR). However, selective CO2RR in strong acids remains challenging due to competition with the hydrogen evolution reaction. Peripheral functionalization is effective for tailoring the intrinsic activity of molecular catalysts, mostly attributed to the inductive effect or to stabilization of reaction intermediates. Here we report that peripheral functionalization of immobilized molecular complexes with quaternary ammonium groups can regulate the catalytic activity by tuning the mass distribution surrounding the active sites, enabling high-performance CO2RR in strong acids. The positively charged and hydrophobic alkylammonium groups affect the migration of water and hydronium in the double layer, while their immobilized configuration enables a stable cationic layer, inhibiting the hydrogen evolution reaction over extended potential windows. Dodecyl ammonium-functionalized cobalt phthalocyanine and tin porphyrin suppress the hydrogen Faradaic efficiency to <10% in pH ~0.5 media, while providing a single-pass conversion efficiency up to ~85%. The selectivity can be maintained at 90% even in Li+ solutions, which often exhibit poor proton shielding. Our study underscores the role of second-sphere structure for selective molecular electrochemistry.

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Fig. 1: Schematic of electrochemical CO2RR in acidic electrolytes with various strategies.
Fig. 2: Synthesis and characterization of CoPc-derived electrocatalysts.
Fig. 3: Acidic electrochemical CO2RR performance of CoPc-derived electrocatalysts in flow cell.
Fig. 4: Mechanistic studies of interfaces by experiment and modelling.
Fig. 5: Performance of acidic CO2 reduction on extended electrocatalysts in a flow cell setup.

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

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Acknowledgements

This work was supported by the Guangdong Basic and Applied Basic Research Fund (2024A1515030164 and 2022A1515011333), the Hong Kong Research Grant Council (11309723), the State Key Laboratory of Marine Pollution (SKLMP/SCRF/0060) and the Shenzhen Science and Technology Program (JCYJ20220818101204009). B.Z.T. acknowledges support from Shenzhen Key Laboratory of Functional Aggregate Materials (ZDSYS20211021111400001), the Science Technology Innovation Commission of Shenzhen Municipality (KQTD20210811090142053 and JCYJ20220818103007014) and the Innovation and Technology Commission (ITC-CNERC14SC01). C.B.M. and W.A.G. acknowledge support from the Liquid Sunlight Alliance, which is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under award number DE-SC0021266.

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  1. These authors contributed equally: Qiang Zhang, Charles B. Musgrave III.

Authors and Affiliations

  1. Department of Chemistry, State Key Laboratory of Marine Pollution, City University of Hong Kong, Hong Kong, P. R. China

    Qiang Zhang, Yun Song, Jianjun Su, Libei Huang, Le Cheng, Geng Li, Yong Liu, Yinger Xin, Qiushi Hu, Ge Ye & Ruquan Ye

  2. City University of Hong Kong Shenzhen Research Institute, Shenzhen, P. R. China

    Qiang Zhang, Yun Song, Jianjun Su, Libei Huang, Le Cheng, Geng Li, Yong Liu, Yinger Xin, Qiushi Hu, Ge Ye & Ruquan Ye

  3. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA

    Charles B. Musgrave III & William A. Goddard III

  4. School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen, P. R. China

    Hanchen Shen & Ben Zhong Tang

  5. School of Energy and Environment, City University of Hong Kong, Hong Kong, P. R. China

    Xue Wang

  6. Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Hong Kong, P. R. China

    Ben Zhong Tang

  7. Hong Kong Institute for Clean Energy, City University of Hong Kong, Hong Kong, P. R. China

    Ruquan Ye

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Contributions

R.Y. conceptualized the project. R.Y., B.Z.T. and W.A.G. supervised the project. X.W. helped with experimental design. Q.Z. and J.S. developed and performed the catalyst synthesis. Q.Z. conducted most experiments and C.B.M. performed the calculations. Q.Z., J.S., Y.S., L.H., L.C., G.L., Y.L., Y.X., Q.H., G.Y. and H.S. carried out the materials characterization. R.Y., Q.Z., C.B.M. and W.A.G. analysed the data and wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Ben Zhong Tang, William A. Goddard III or Ruquan Ye.

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Nature Synthesis thanks Peng Kang, Shigeyuki Masaoka 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. 1–32, Tables 1–5 and References 1–35.

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Zhang, Q., Musgrave, C.B., Song, Y. et al. A covalent molecular design enabling efficient CO2 reduction in strong acids. Nat. Synth (2024). https://doi.org/10.1038/s44160-024-00588-4

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