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Revealing the impact of microenvironment on gold-catalysed CO2 electroreduction via Marcus–Hush–Chidsey kinetics

Nature Chemistry (2025)Cite this article

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Abstract

The microenvironment at electrochemical interfaces plays a crucial role in governing electrode-mediated electron transfer processes. However, elucidating the complex effects of the microenvironment remains challenging. The Butler–Volmer equation has been used in deducing reaction mechanisms and identifying rate-determining steps, but its empirical nature makes it challenging to deduce the molecular-level picture of interfacial electron transfer processes. By contrast, the application of the Marcus–Hush–Chidsey (MHC) electron transfer theory has been constrained by its tenuous connection to experimentally measurable parameters beyond reaction rates. Here we develop a mechanistic framework based on the MHC theory to systematically analyse the cation effect on the Au-catalysed CO2 reduction reaction using experimentally accessible variables. Our analysis reveals consistent trends for both inorganic and organic cations through thermodynamic and kinetic parameters derived from the MHC theory, with potential applications for probing ionomer–electrode interface microenvironments. This study establishes a universal strategy for investigating interfacial microenvironments in electron transfer processes by bridging theoretical parameters with experimental descriptors.

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Fig. 1: Cation dependence of CO2RR activities and fitting parameters from MHC theory.
Fig. 2: Cation dependence of reorganization energy and interfacial water structure with different cations.
Fig. 3: Cation effect on the pre-exponential factor in the rate expression of the CO2RR.
Fig. 4: Insights into the difference between alkali metal and organic cations.
Fig. 5: Fitted parameters in ionomer-modified systems.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work is supported by the Beijing Natural Science Foundation Key Research Program (grant no. Z240026) and the Beijing National Laboratory for Molecular Sciences. This work is also supported by the National Key R&D Program of China (grant no. 2023YFA1508001 to X.C.) and the National Natural Science Foundation of China (grant nos. 22278002 to X.C and 92261111 to H.X.).

Author information

Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Yifei Xu, Xiaoxia Chang & Bingjun Xu

  2. Beijing National Laboratory for Molecular Sciences, Beijing, China

    Yifei Xu, Xiaoxia Chang & Bingjun Xu

  3. Department of Chemistry, Tsinghua University, Beijing, China

    Yunze Qiu & Hai Xiao

  4. Ordos Laboratory, Inner Mongolia, China

    Bingjun Xu

Authors
  1. Yifei Xu
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  2. Yunze Qiu
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  3. Xiaoxia Chang
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  4. Hai Xiao
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Contributions

Y.X. and B.X. conceived of the idea and designed the experiments in this study. Y.X. conducted all the experiments and analyses. Y.Q. performed the density functional theory calculations. All authors analysed the data and co-wrote the paper.

Corresponding authors

Correspondence to Hai Xiao or Bingjun Xu.

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Nature Chemistry thanks Dong Young Chung, Anne Co 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. 1–21, Notes 1–7 and Table 1.

Source data

Source Data Fig. 1

Current–potential plots and fitting parameters.

Source Data Fig. 2

Reorganization energy and SEIRA spectra.

Source Data Fig. 3

Pre-exponential factors and fitted curve.

Source Data Fig. 4

Correlation among capacitance, hydration-free energy and pre-exponential factors.

Source Data Fig. 5

Reorganization and pre-exponential factors with ionomer modifications.

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Xu, Y., Qiu, Y., Chang, X. et al. Revealing the impact of microenvironment on gold-catalysed CO2 electroreduction via Marcus–Hush–Chidsey kinetics. Nat. Chem. (2025). https://doi.org/10.1038/s41557-025-02010-8

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