Interfacial Electronic Structure Modulation and Surface Reconstruction in (Ni, Co)Se 2 /MoSe 2 Mott‐Schottky Heterojunction for pH‐Universal Hydrogen Evolution

ABSTRACT Achieving efficient hydrogen evolution across the entire pH range remains challenging because distinct reaction environments require fundamentally different interfacial catalytic properties. Herein, a (Ni, Co)Se 2 /MoSe 2 heterostructure was rationally constructed on carbon cloth through a hydrothermal‐selenization strategy to regulate the interfacial electronic structure and optimize hydrogen evolution reaction (HER) kinetics. Benefiting from the formation of a Mott‐Schottky heterointerface, pronounced charge redistribution and electronic coupling are achieved, leading to optimized hydrogen adsorption/desorption behavior and accelerated interfacial charge transfer. As a result, the optimized catalyst only requires overpotentials of 36, 83, and 67 mV to achieve 10 mA cm −2 in acidic, alkaline, and neutral electrolytes, respectively, together with enhanced long‐term stability over 100 h at 50 mA cm −2 under alkaline conditions. Density functional theory (DFT) calculations further reveal that the heterointerface induces d‐band‐center modulation and weakens the excessive interaction with hydrogen intermediates, thereby facilitating hydrogen desorption and reducing the HER energy barrier. In addition, in situ Raman and post‐catalytic characterizations demonstrate that surface reconstruction under alkaline conditions further contributes to the dynamic evolution of catalytically active sites. This study provides a general strategy for designing high‐performance electrocatalysts capable of adapting to diverse reaction environments.