| Summary: | The global climate crisis has cultivated the demand for sustainable energy resources as fossil derivative fuels are functional in catalyzing the rate of environmental breakdown. Sustainable energy solutions generate various renewable energy prospects capable of delivering efficient energy operations. Among these prospects, green H<sub>2</sub> energy generated via overall water splitting is an effective approach towards sustainability ascribed to the higher gravimetric density and efficiency of H<sub>2</sub> fuel. In this review, we sought to discuss the applicability and challenges of graphene-based derivatives in H<sub>2</sub> evolution operations through photochemical, electrochemical and photoelectrochemical water-splitting pathways. The unique layered structure of graphene-based derivatives alongside marvelous optoelectronic and physicochemical properties ease out the thermodynamic uphill of water splitting better than their non-layered counterparts. In addition, the heterojunction formation in the graphene derivatives with visible light catalysts propels the kinetics of HER. Functionalized GO and rGO derivatives of graphene are riveting catalysts that have received extensive interest from researchers attributed to their accelerated chemical and mechanical stability, tunable band structure and larger surface area, providing more exposed active sites for HER. The surface organic functional groups of GO/rGO assist in establishing synergetic interfacial contact with other catalysts. Thus, these groups provide structural and chemical versatility to GO/rGO-based heterostructured catalysts, which effectively improve their physicochemical parameters that drive their catalytic performance towards HER. In order to develop a cost-effective and highly efficient catalytic system, graphene-based derivatives are promising heterostructured catalysts that exhibit a good relationship between catalytic efficiency and robustness.
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