AbstractHydrogen generation from water using noble metal-free photocatalysts presents a promising platform for renewable and sustainable energy. Copper-based chalcogenides of earth-abundant elements, especially Cu₂ZnSnS₄ (CZTS), have recently arisen as a low-cost and environment-friendly material for photovoltaics and photocatalysis. Herein, we report a new heterostructure consisting of CZTS nanoparticles anchored onto a MoS₂-reduced graphene oxide (rGO) hybrid. Using a facile two-step method, CZTS nanoparticles were in situ grown on the surface of MoS₂-rGO hybrid, which generated high density of nanoscale interfacial contact between CZTS and MoS₂-rGO hybrid. The photoexcited electrons of CZTS can be readily transported to MoS₂ through rGO backbone, reducing the electron-hole pair recombination. In photocatalytic hydrogen generation under visible light irradiation, the presence of MoS₂-rGO hybrids enhanced the hydrogen production rate of CZTS by 320%, which can be attributed to the synergetic effect of increased charge separation by rGO and more catalytically active sites from MoS₂. Furthermore, this CZTS/MoS₂-rGO heterostructure showed much higher photocatalytic activity than both Au and Pt nanoparticle-decorated CZTS (Au/CZTS and Pt/CZTS) photocatalysts, indicating the MoS₂-rGO hybrid is a better co-catalyst for photocatalytic hydrogen generation than the precious metal. The CZTS/MoS₂-rGO system also demonstrated stable photocatalytic activity for a continuous 20 h reaction.