Metal sulphides combined with graphene/reduced graphene oxide (rGO) represent a unique class of materials for hydrogen generation either through electrocatalytic or photo(electro) catalytic methods. Herein, we report a solvothermal synthesis of Cu3SnS4 decorated rGO resulting in a highly active electrocatalyst for hydrogen evolution reaction (HER) compared to its native Cu3SnS4. The Cu3SnS4‐rGO exhibited very low overpotential of 190 mV versus reversible hydrogen electrode (RHE), whereas Cu3SnS4 requires 250 mV versus RHE at a current density of 10 mA/cm2. Tafel slope of Cu3SnS4‐rGO and Cu3SnS4 is about 64 and 76 mV/dec, respectively. This suggests that Cu3SnS4‐rGO is a better electrocatalyst when compared to Cu3SnS4 and follows mixed Volmer and Heyrovsky mechanism for HER.
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