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Revealing Distributed Kinetics in Electrochemical Nucleation and Growth through Local Electrochemistry

par Torres Morillo, Daniel ;Ustarroz Troyano, Jon
Référence European Conference on Applications of Surface and Interface Analysis(September, 2026: Brussels, Belgium), ECASIA 2026
Publication Publié, 2026-09

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Résumé :

Electrochemical nucleation and growth (EN&G) is a fundamental process governing the formation of metallic nanostructures on electrode surfaces. However, the earliest stages of nanostructure formation remain difficult to resolve experimentally because conventional electrochemical measurements average the response of a vast number of active sites, obscuring the true distribution of activity and nucleation behaviors across the surface. In our work, we combine Scanning Electrochemical Cell Microscopy (SECCM), co-located microscopy, and statistical analysis to probe electrochemical nucleation at the scale where these variations actually arise and to directly quantify spatial differences in activity across heterogeneous substrates. By performing hundreds of independent measurements on fresh regions of the same surface, this high-throughput approach captures the stochastic nature of nucleation events while preserving spatial resolution and enabling electrochemical and structural information to be compared at the samescale[1]. Our measurements reveal that both overpotential and surface state strongly influence the probability of nucleation, leading to a broad dispersion of nucleation kinetics between neighboring surface regions. These observations show that EN&G cannot be fully described by a single nucleation rate, but instead reflects a distribution of site-specific activation barriers associated with local surface features [2]. To rationalize this behavior, we introduce a distribution-based kinetic framework that accounts for the variability of nucleation rates across the surface. Within this approach, classical constant-rate descriptions emerge as a limiting case of a broader distributed rate law, in which the characteristic rate sets the overall time scale, and the local parameters provide a quantitative description of kinetic dispersion [3]. This framework links microscopic variability with macroscopic electrochemical observables, connecting local activity distributions to ensemble current transients and nanoparticle formation. More broadly, the results show how local electrochemistry combined with statistical and analytical modeling can uncover hidden distributions of activity at electrochemical interfaces. Ultimately, this approach provides new insight into interfacial phase formation and supports the rational design of tailored electrochemical interfaces and functional nanostructures. References: [1] [2] [3]. D. Torres et al., Journal of Solid State Electrochemistry 2024, 28, 1719. D. Torres et al., Small Methods 2025, 2401029, 1. D. Torres et al., To be submitted, 2026.