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.