Catalytic Activity of Defect-Engineered Transition Metal Dichalcogenides Mapped with Atomic Scale Precision by Electrochemical Scanning Tunneling Microscopy

Unraveling structure–activity relationships is a key objective of catalysis. Unfortunately, the intrinsic complexity and structural heterogeneity of materials stand in the way of this goal, mainly because the activity measurements are area-averaged and therefore contain information coming from different surface sites. This limitation can be surpassed by the analysis of the noise in the current of electrochemical scanning tunneling microscopy (EC-STM). Herein, we apply this strategy to investigate the catalytic activity toward the hydrogen evolution reaction of monolayer films of MoSe₂. Thanks to atomically resolved potentiodynamic experiments, we can evaluate individually the catalytic activity of the MoSe₂ basal plane, selenium vacancies, and different point defects produced by the intersections of metallic twin boundaries. The activity trend deduced by EC-STM is independently confirmed by density functional theory calculations, which also indicate that, on the metallic twin boundary crossings, the hydrogen adsorption energy is almost thermoneutral. The micro- and macroscopic measurements are combined to extract the turnover frequency of different sites, obtaining for the most active ones a value of 30 s⁻¹ at −136 mV vs RHE.