Electrocatalysts Design Guided by Active Intermediates of Hydrogen Evolution Reaction

Abstract Hydrogen production from water electrolysis plays an important role for the development of hydrogen‐based energy sources. Developing efficient electrocatalysts is crucial for accelerating the reaction kinetics and achieving large‐scale water electrolysis. Despite the significant advancements in electrocatalysts for the hydrogen evolution reaction (HER) achieved over the past few decades, there remains a lack of comprehensive discussion on the in‐depth mechanism for the enhanced activity, particularly with regard to the active intermediates. Recently, with the development of state‐of‐the‐art characterization methods and theoretical computation, optimizing interaction between reaction intermediates and corresponding active sites has been demonstrated as an effective strategy to enhance the intrinsic catalytic activity. Herein, the recent advances in the electrocatalysts design guided by active intermediates of HER are presented. Emphasis is focused on the discussion of key intermediates that determine HER activity and the strategies to tune the interaction between active sites and reaction intermediates. Finally, an outlook on future challenges and perspectives on the development of electrocatalysts based on the active intermediates is given.