Heteroatom Doped Graphene Catalysts: Synthesis and Application in Electrochemical Hydrogen Evolution

This paper takes the structure-performance relationship and electronic tuning of graphene-based electrocatalysts as its core conceptual framework to systematically review research progress in the field of water electrolysis for hydrogen production. Water electrolysis is a key technology for green hydrogen production and achieving carbon neutrality; it currently faces four major scientific and technological challenges: slow kinetics of the hydrogen evolution and oxygen evolution reactions, reliance on precious metals, insufficient catalyst stability, and high costs associated with large-scale production. Given its high electrical conductivity, ultra-large specific surface area, and tunable electronic structure, graphene can serve both as a metal-free active substrate and as an efficient carrier. Through heteroatom doping, heterostructure construction, defect engineering, and interfacial electronic regulation, the electronic states of active sites and the adsorption energies of hydrogen and oxygen can be optimized, thereby significantly enhancing catalytic activity and stability. This paper reviews mainstream preparation techniques, including chemical vapor deposition, hydrothermal/solvothermal synthesis, and chemical reduction, and compares their performance in proton exchange membrane, alkaline, anion exchange membrane, and seawater electrolysis systems. It highlights that current key bottlenecks remain in controlling doping uniformity, ensuring long-term durability, achieving consistency in large-scale electrodes, and enabling low-cost, large-scale production. Finally, the paper looks ahead to the development of electrodes featuring precise electronic tuning, green large-scale production, and adaptability to multiple scenarios, providing theoretical references and technical insights to help graphene-based catalysts overcome barriers to industrial application.