Selective activation of MoS 2 grain boundaries for enhanced electrochemical activity.

Molybdenum disulfide (MoS 2 ) 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 MoS 2 in electrocatalysis. To overcome this limitation, we present a technique that enhances the catalytic activity of continuous MoS 2 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 MoS 2 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 MoS 2 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.