Engineering Catalytically Active Sites by Sculpting Artificial Edges on MoS2 Basal Plane for Dinitrogen Reduction at a Low Overpotential

Engineering catalytically active sites have been a challenge so far and often relies on optimization of synthesis routes, which can at most provide quantitative enhancement of active facets, however, cannot provide control over choosing orientation, geometry and spatial distribution of the active sites. Artificially sculpting catalytically active sites via laser-etching technique can provide a new prospect in this field and offer a new species of nanocatalyst for achieving superior selectivity and attaining maximum yield via absolute control over defining their location and geometry of every active site at a nanoscale precision. In this work, a controlled protocol of artificial surface engineering is shown by focused laser irradiation on pristine MoS2 flakes, which are confirmed as catalytic sites by electrodeposition of AuNPs. The preferential Au deposited catalytic sites are found to be electrochemically active for nitrogen adsorption and its subsequent reduction due to the S-vacancies rather than Mo-vacancy, as advocated by DFT analysis. The catalytic performance of Au-NR/MoS2 shows a high yield rate of ammonia (11.43 × 10-8 mol s-1 cm-2 ) at a potential as low as -0.1 V versus RHE and a notable Faradaic efficiency of 13.79% during the electrochemical nitrogen reduction in 0.1 m HCl.