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Electrolyte effects in proton–electron transfer reactions and implications for renewable fuels and chemicals synthesis

Nature Catalysis volume 8, pages 986–999 (2025)Cite this article

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Abstract

Electrolyte effects play a fundamental role in electrocatalysis, influencing reaction kinetics, selectivity and catalyst stability by altering interfacial interactions and charge distribution. Here we report recent advances to rationalize non-covalent interactions between electrolyte and surface adsorbates in electrocatalysis. Three main schools of thought have rationalized the effect of electrolyte–adsorbates–surface interactions on the reaction kinetics, each based on different descriptors. The first suggests that non-covalent interactions with the electrolyte modify the binding energies of the adsorbed intermediates. The second highlights the role of charge and electric fields near the electric double layer, shaped by the potential of zero charge, in stabilizing the polar adsorbates and governing proton transfer. The third focuses on energy barriers arising from the restructuring of the water solvation spheres of both electrolyte and reactants. We critically examine the main arguments and limitations of each framework, with a focus on hydrogen evolution and carbon dioxide reduction, and outline experimental challenges and future directions for elucidating electrolyte effects in electrocatalysis.

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Fig. 1: Timeline of three schools of thought on electrolyte effects in the HER and CO2RR.
Fig. 2: School 1: Adsorbate binding energies govern reaction kinetics.
Fig. 3: School 2: Electrostatics stabilize polar adsorbates and control proton transfer.
Fig. 4: School 3: Water structure modulates the EDL and proton transfer.
Fig. 5: Characterization of the cation- and pH-dependent electrochemical double layer.

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Acknowledgements

We acknowledge support from the Bill & Melinda Gates Foundation through award INV-064006 (‘Developing efficient carbon and nitrogen feedstocks for GRAS microbes’). Research at MIT was supported by the US Department of Energy, Basic Energy Sciences (DOE-BES), through the Energy Frontier Research Center DE-SC0023415 (Center for Electrochemical Dynamics and Reactions on Surfaces). Additional support was provided by the MIT Climate Grand Challenge—Center for Electrification and Decarbonization of Industry (MIT-CEDI), Thrust 4—Ammonia. M.E.E. acknowledges the Pioneer Center for Accelerating P2X Materials Discovery (CAPeX), DNRF grant no. P3. ICN2 is supported by the Severo Ochoa Centres of Excellence Programme from the Spanish MCIN/AEI (grant no. CEX2021-001214-S) and funded by the CERCA Programme/Generalitat de Catalunya.

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Author notes

  1. These authors contributed equally: Paula Sebastián-Pascual, Antonia Herzog.

Authors and Affiliations

  1. Wallenberg Initiative Materials Science for Sustainability, Department of Chemistry, School of Engineering Science in Chemistry, Biochemistry and Health, KTH Royal Institute of Technology, Stockholm, Sweden

    Paula Sebastián-Pascual

  2. Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, MA, USA

    Antonia Herzog, Yirui Zhang & Yang Shao-Horn

  3. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Yirui Zhang & Yang Shao-Horn

  4. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Yang Shao-Horn

  5. Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and Barcelona Institute of Science and Technology, UAB Campus, Barcelona, Spain

    María Escudero-Escribano

  6. Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

    María Escudero-Escribano

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  1. Paula Sebastián-Pascual
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P.S.-P. and A.H. led the majority of this work. P.S.-P. was responsible for conceptualization, data curation, methodology, validation and drafting the initial manuscript. A.H. contributed to conceptualization, data curation, analysis, investigation, methodology, project administration, validation, visualization, supervision and writing. Y.Z. contributed to conceptualization and the initial draft. Y.S.-H. and M.E.-E. supervised conceptualization, funding acquisition, investigation, methodology, project administration, resources, supervision, validation and writing. All authors participated in proofreading the manuscript.

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Sebastián-Pascual, P., Herzog, A., Zhang, Y. et al. Electrolyte effects in proton–electron transfer reactions and implications for renewable fuels and chemicals synthesis. Nat Catal 8, 986–999 (2025). https://doi.org/10.1038/s41929-025-01421-7

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