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The key challenge for scalable production of hydrogen from water lies in the rational design and preparation of high-performance and earth-abundant electrocatalysts to replace precious metal Pt and IrO2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Although atomic M-N-C materials have been extensively studied in heterogeneous catalysis field, the insufficient antioxidant capacity of carbonous substrates hinders their practical application in OER. Developing highly active and stable OER electrocatalysts is the key for electrochemical water splitting. This review presents feasible design strategies for fabricating carbon-free single-site catalysts and their applications in HER/OER and overall water splitting. The constitutive relationships between structure, composition, and catalytic performance for HER and OER are detailly discussed, providing ponderable insights into rationally constructing high-performance HER and OER electrocatalysts. The perspectives on the challenges and future research orientations in single-site catalysts for electrochemical water splitting are suggested.
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