Interfacial Microenvironment Modulation Boosts Efficient Hydrogen Evolution Reaction in Neutral and Alkaline

Abstract The design of highly efficient and stable electrocatalysts in hydrogen evolution reaction over a wide range of pH, especially in neutral or alkaline conditions, is of great significance but remains· challenging. Herein, a family of single‐atoms and clusters inside the N‐doped porous carbon matrix (NDPCM) are encapsulated. Specifically, the single‐atom platinum (Pt SA ) and cluster platinum (Pt C ) in NDPCM exhibited ultralow overpotentials of 20 and 14 mV at −10 mA cm −2 under neutral and alkaline conditions, respectively and superior long‐term durability. Theoretical calculations and operando Raman measurements revealed that the coexistence of Pt SA and Pt C can provide multiple H adsorption sites, contributing to the extremely low |Δ G H* | of H adsorption and constructing a local acidic microenvironment to trigger a unique H 3 O + ‐induced water reduction in neutral and alkaline conditions This unique configuration significantly promotes the catalytic activity and opens a new avenue for the crafted design of electrocatalysts.