A crucial role of enhanced Volmer-Tafel mechanism in improving the electrocatalytic activity via synergetic optimization of host, interlayer, and surface features of 2D nanosheets

High-performance electrocatalysts have attracted growing interest because of their crucial roles in renewable energy technologies. In this study, the host, interlayer, and surface features of electrocatalytically-active 2D nanosheets (NSs) are systematically controlled with the synergetic combination of host−guest co-engineering and surface modification to develop a novel synthetic strategy for efficient electrocatalysts. Molecular-level control of interfacial electronic coupling and surface reactivity can be achieved by the self-assembly of MoS₂/RuO₂ NS mixtures with variable-sized tetraalkylammonium cations and subsequent thermal aging. The resulting optimization of the operation mechanisms of restacked MoS₂/RuO₂ NSs effectively improves the electrocatalyst functionality for hydrogen evolution reaction (HER). The extensive modifications of diverse structural and morphological parameters allow the elucidation of a linear correlation between electrochemical active surface area and HER overpotential. Systematic in-situ spectroscopic analyses clearly demonstrate the crucial role of enhanced Volmer−Tafel mechanism in improving the electrocatalytic activity via enhancement of proton adsorption and interfacial electron transfer.