Hydrogen is regarded as a key renewable energy source to meet future energy demands. Moreover, graphene and its derivatives have many advantages, including high electronic conductivity, controllable morphology, and eco-friendliness, etc., which show great promise for electrocatalytic splitting of water to produce hydrogen. This review article highlights recent advances in the synthesis and the applications of graphene-based supported electrocatalysts in hydrogen evolution reaction (HER). Herein, powder-based and self-supporting three-dimensional (3D) electrocatalysts with doped or undoped heteroatom graphene are highlighted. Quantum dot catalysts such as carbon quantum dots, graphene quantum dots, and fullerenes are also included. Different strategies to tune and improve the structural properties and performance of HER electrocatalysts by defect engineering through synthetic approaches are discussed. The relationship between each graphene-based HER electrocatalyst is highlighted. Apart from HER electrocatalysis, the latest advances in water electrolysis by bifunctional oxygen evolution reaction (OER) and HER performed by multi-doped graphene-based electrocatalysts are also considered. This comprehensive review identifies rational strategies to direct the design and synthesis of high-performance graphene-based electrocatalysts for green and sustainable applications.

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