Unraveling and leveraging in situ surface amorphization for enhanced hydrogen evolution reaction in alkaline media

Surface amorphization provides electrocatalysts with more active sites and flexibility. However, there is still a lack of experimental observations and mechanistic explanations for the in situ amorphization process and its crucial role. Herein, we propose the concept that by in situ reconstructed amorphous surface, metal phosphorus trichalcogenides could intrinsically offer better catalytic performance for the alkaline hydrogen production. Trace Ru (0.81 wt.%) is doped into NiPS₃ nanosheets for alkaline hydrogen production. Using in situ electrochemical transmission electron microscopy technique, we confirmed the amorphization process occurred on the edges of NiPS₃ is critical for achieving superior activity. Comprehensive characterizations and theoretical calculations reveal Ru primarily stabilized at edges of NiPS₃ through in situ formed amorphous layer containing bridging S₂^2- species, which can effectively reduce the reaction energy barrier. This work emphasizes the critical role of in situ formed active layer and suggests its potential for optimizing catalytic activities of electrocatalysts.