Exploring dynamic solvation kinetics at electrocatalyst surfaces.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39294140.
- Also identified by DOI 10.1038/s41467-024-52499-9 and PMC identifier 11411097.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
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<sub>2</sub>, *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.