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Photoelectrochemical (PEC) water splitting for hydrogen generation has been considered as a promising route to convert and store solar energy into chemical fuels. In terms of its large-scale application, seeking semiconductor photoelectrodes with high efficiency and good stability should be essential. Although an enormous number of materials have been explored for solar water splitting in the last several decades, challenges still remain for the practical application. P-type copper-based chalcogenides, such as Cu(In, Ga)Se 2  and Cu 2 ZnSnS 4 , have shown impressive performance in photovoltaics due to narrow bandgaps, high absorption coefficients, and good carrier transport properties. The obtained high efficiencies in photovoltaics have promoted the utilization of these materials into the field of PEC water splitting. A comprehensive review on copper-based chalcogenides for solar-to-hydrogen conversion would help advance the research in this expanding area. This review will cover the physicochemical properties of copper-based chalco-genides, developments of various photocathodes, strategies to enhance the PEC activity and stability, introductions of tandem PEC cells, and finally, prospects on their potential for the practical solar-to-hydrogen conversion. We believe this review article can provide some insights of fundamentals and applications of copper-based chalco-genide thin films for PEC water splitting.

Towards efficient solar-to-hydrogen conversion: Fundamentals and recent progress in copper-based chalcogenide photocathodes