Directly Mapping Photoelectrochemical Behavior within Individual Transition Metal Dichalcogenide Nanosheets.

Spatial variations in photoelectrochemical reaction rates within individual p-type WSe2 nanosheets were mapped through the application of scanning electrochemical cell microscopy (SECCM). The simultaneous topographical and electrochemical information provided via SECCM directly revealed how both sheet thickness and the presence of defect structures affect the local rate of photoelectrochemical reactions for both outer sphere and inner sphere redox couples. Sheet thickness was found to play a dramatic role in reaction rates, with onset potentials shifting by as much as 0.5 V over thicknesses of 20-120 nm, attributable to the inability of thin sheets to support independent space charge layers. Step/edge features were found to play a detrimental role for the outer sphere redox couple investigated (Ru(NH3)63+ reduction), with taller steps having larger effects on performance. Shorter step features were found to be beneficial for hydrogen evolution, showing a controlled density of defect features is desirable for inner sphere processes. The studies presented here not only provide valuable, quantitative insights into the behavior of transitional metal dichalcogenide materials but also demonstrate the power of applying SECCM to the study of photoelectrochemical systems, particularly those involving two-dimensional (2D) materials.