Selective activation of MoS₂ grain boundaries for enhanced electrochemical activity

Molybdenum disulfide (MoS2) has emerged as a promising material for catalysis and sustainable energy conversion. However, the inertness of its basal plane to electrochemical reactions poses challenges to the utilization of wafer-scale MoS2 in electrocatalysis. To overcome this limitation, we present a technique that enhances the catalytic activity of continuous MoS2 by preferentially activating its buried grain boundaries (GBs). Through mild UV irradiation, a significant enhancement in GB activity was observed that approaches the values for MoS2 edges, as confirmed by a site-selective photo-deposition technique and micro-electrochemical hydrogen evolution reaction (HER) measurements. Combined spectroscopic characterization and ab-initio simulation demonstrates substitutional oxygen functionalization at the grain boundaries to be the origin of this selective catalytic enhancement by an order of magnitude. Our approach not only improves the density of active sites in MoS2 catalytic processes but yields a new photocatalytic conversion process. By exploiting the difference in electronic structure between activated GBs and the basal plane, homo-compositional junctions were realized that improve the photocatalytic synthesis of hydrogen by 47% and achieve performances beyond the capabilities of other catalytic sites.