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This study investigates how cations in electrolyte solutions influence mass transport during the chlorine evolution reaction, a previously underexplored aspect compared to their well-documented effects on charge transfer. The researchers demonstrate that the structural entropy of cation hydration, which describes how cations organize surrounding water molecules, quantitatively governs the diffusion of chloride ions toward the electrode surface. This finding establishes a thermodynamic framework linking cation identity to reactant transport behavior in electrochemical systems.
Why it matters
Chlorine evolution is central to the chlor-alkali process, one of the largest industrial electrochemical processes globally, and understanding cation-controlled diffusion could inform the design of more efficient electrolytes and reduce energy consumption in industrial chlorine production.
Nature Chemistry, Published online: 08 December 2025; doi:10.1038/s41557-025-02014-4
Cation effects have been rigorously studied in electrochemical charge transfer, but their role in mass transport remains unexplored. Now, it has been shown that the structural entropy of cation hydration quantitatively explains how cations regulate reactant diffusion during the chlorine evolution reaction.