Transition metal trichalcogenphosphites (MPX3), belonging to the class of 2D materials, are potentially viable electrocatalysts for the hydrogen evolution reaction (HER). Many 2D and layered materials exhibit different magnitudes of electrochemical and electrocatalytic activity at their edge and basal sites. To find out whether edges or basal planes are the primary sites for catalytic processes at these compounds, we studied the local electrochemical and electrocatalytic activity of FePSe3, an MPX3 representative that was previously found to be catalytically active. Using scanning electrochemical microscopy, we discovered that electrochemical processes and the HER are occurring at an increased rate at edge-like defects of FePSe3 crystals. We correlate our observations using optical microscopy, confocal laser scanning microscopy, scanning electron microscopy, and electron-dispersive X-ray spectroscopy. These findings have profound implications for the application of these materials for electrochemistry as well as for understanding general rules governing the electrochemical performance of layered compounds.

Department of Medical Research China Medical University Hospital China Medical University No 91 Hsueh Shih Road Taichung 40402 Taiwan

Energy Research Research Techno Plaza 10 Frontier Block Level 5 50 Nanyang Drive Singapore 637553 Singapore

Future Energy and Innovation Laboratory Central European Institute of Technology Brno University of Technology Purkyňova 123 Brno 61200 Czech Republic

New Technologies Research Centre University of West Bohemia Univerzitní 8 Plzeň 30100 Czech Republic

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