Electrons Meet Confined Electrolytes: Redefining the Electrochemical Interface

From the age of the mercury electrode to the era of sustainable development, the landscape of electrochemistry has transformed. Eighty years after David C. Grahame’s monumental review of the electrical double layer, electrochemical devices are no longer defined by simple planar interfaces, but by nanoporous electrodes and complex electrolytes. This feature article explores the frontier of this evolution, redefining our fundamental understanding of interfacial thermodynamics, reaction kinetics, and ion transport through experimental advances and multiscale modeling. As we look beyond Grahame’s idealized models, the synthesis of theory and experiment offers a new paradigm for engineering the next generation of electrochemical systems for energy storage and chemical transformation.