Bio-inspired catalysts for enhanced N₂ electroreduction to NH3: Architecting molecular screening interfaces via active sites microenvironment engineering

The electrochemical nitrogen reduction reaction (ENRR) promises a sustainable route for ammonia (NH3) production but faces hurdles from competing hydrogen evolution reaction (HER) and insufficient N2 concentration. Drawing inspiration from Tropical Lizards' unique mechanism of creating a thin air layer on their hydrophobic skin, we modify the catalyst-water interface using alkyl thiols of different chain lengths on VS2 (Cx-VS2, x = 4,8,12). This novel approach suppresses HER and increases N2 availability. Among the tailored catalysts, C8-VS2 exhibits superior ENRR performance, with an ammonia yield of 58.43 μg h−1 mgcat−1 and a Faradaic efficiency of 34.69 % that surpasses unmodified VS2 (21.05 μg h−1 mgcat−1 and 8.87 %). Supporting measurements and density functional theory (DFT) calculations confirm the pivotal role of the modified interface in optimizing NH3 production. Our findings offer fresh perspectives for designing efficient electrocatalysts via tailoring interface microenvironments, with potential implications for various applications.