Structural Features Dictate the Photoelectrochemical Activities of Two-Dimensional MoSe₂ and WSe₂ Nanostructures

The exfoliation of layered materials into two-dimensional (2D) semiconductors creates new structural domains, for example, basal planes, defect-rich in-planes, and edge sites. These surface species affect the photoelectrochemical (PEC) performance, which in turn determines their applicability in solar energy conversion technologies. In this study, a custom-designed microdroplet cell-based spatially resolved PEC approach was employed to identify the structural parts and to measure the PEC activity of the mechanically exfoliated MoSe₂ and WSe₂ nanosheets for bulk, few-layer, and monolayer specimens. The PEC performance decreased with the decreasing thickness of nanoflakes, and the relative PEC activity (photo/total current) reduced by introducing more defects to the 2D flakes: 1-3% loss was found for in-plane defects and 30-40% for edge defects. While edge sites act as charge carrier recombination centers, their electrocatalytic activity is higher than that of the basal planes. The comparison of PEC activity of micromechanically and liquid phase exfoliated bulk and few-layer MoSe₂ and WSe₂ flakes further confirmed that the PEC performance of 2D flakes decreases with an increasing number of edge sites.