MOF‐Based Materials for Alkaline Hydrogen Evolution Reaction: From Mechanism Foundation to Catalyst Design

ABSTRACT Currently, hydrogen energy, as a clean energy carrier, plays a crucial role in future energy development. Hydrogen evolution reaction (HER) is one of the essential half reactions in electrochemical water splitting for hydrogen production. However, HER under alkaline condition suffers from sluggish kinetics due to its complex reaction mechanism. Consequently, developing highly active, stable, and cost‐effective HER catalysts in alkaline media and understanding its underlying reaction mechanisms are indispensable for advancing the hydrogen energy economy. Metal‐organic framework (MOF) and their derivatives have emerged as a prominent class of alkaline HER catalysts, owing to their structural tunability, compositional diversity and coordination environment adjustability. Herein, we systematically review the recent research progress of MOF‐based materials for alkaline HER. First, the fundamental mechanisms of alkaline HER are summarized, including the classical hydrogen binding energy theory, bifunctional theory, and emerging insights related to the interfacial water structure and hydrogen‐bond networks at the catalyst‐electrolyte interface. Furthermore, the latest research on MOF‐based alkaline HER catalysts is categorized by heterostructure engineering, alloys, and doping strategies, with focus on illustrating the intrinsic relationship among the electrocatalytic performance, intermediate behaviors and interfacial microenvironment. Finally, current challenges and future perspectives, particularly, artificial intelligence‐assisted catalyst design are outlined.