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.

Automated summary

This study systematically controls the host, interlayer, and surface features of electrocatalytic nanosheets (NSs), and develops a novel synthetic strategy for efficient electrocatalysts. The molecular-level control of interfacial electronic coupling and surface reactivity improves the functionality of electrocatalytic NSs for the hydrogen evolution reaction (HER). The optimization of diverse structural and morphological parameters leads to a linear correlation between electrochemical active surface area and HER overpotential. In-situ spectroscopic analyses demonstrate the crucial role of enhanced Volmer-Tafel mechanism in improving the electrocatalytic activity.