Exploring dynamic solvation kinetics at electrocatalyst surfaces

The interface between electrocatalyst and electrolyte is highly dynamic. Even in absence of major structural changes, the intermediate coverage and interfacial solvent are bias and time dependent. This is not accounted for in current kinetic models. Here, we study the kinetics of the hydrogen evolut...

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Bibliographic Details
Published in:Nature communications 2024-09, Vol.15 (1), p.8204-11, Article 8204
Main Authors: Sarabia, Francisco, Gomez Rodellar, Carlos, Roldan Cuenya, Beatriz, Oener, Sebastian Z.
Format: Article
Language:English
Subjects:
639/638/161
639/638/440/951
639/638/77/886
Activation energy
Ammonia
Bias
Catalysts
Chemical reduction
Electrocatalysts
Electrochemistry
Energy charge
Entropy of activation
Humanities and Social Sciences
Hydrogen evolution
Intermediates
Kinetics
multidisciplinary
Oxidation
Oxygen reduction reactions
pH effects
Poisoning (reaction inhibition)
Reaction kinetics
Science
Science (multidisciplinary)
Solvation
Solvents
Time dependence
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Summary:The interface between electrocatalyst and electrolyte is highly dynamic. Even in absence of major structural changes, the intermediate coverage and interfacial solvent are bias and time dependent. This is not accounted for in current kinetic models. Here, we study the kinetics of the hydrogen evolution, ammonia oxidation and oxygen reduction reactions on polycrystalline Pt with distinct intrinsic rates and intermediates (e.g. *H, *OH, *NH 2 , *N). Despite these differences, we discover shared relationships between the pre-exponential factor and the activation energy that we link to solvation kinetics in the presence of electronic excess charge and charged intermediates. Further, we study dynamic changes of these kinetic parameters with a millisecond time resolution during electrosorption and double layer charging and dynamic *N and *NO poisoning. Finally, we discover a pH-dependent activation entropy that explains non-Nernstian overpotential shifts with pH. In sum, our results demonstrate the importance of accounting for a bias and time-dependent interfacial solvent and catalyst surface. Interfacial ion solvation is omnipresent in electrochemistry. Sarabia et al. now explore solvation kinetics with a millisecond time resolution and shine light on the critical role of the solvent during dynamic catalyst and electrosorption kinetics.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-024-52499-9