Controllable construction of direct Z-scheme Mo₂C-Cd_xZn_1-xIn₂S₄ heterojunction via defect-mediated modulation for enhanced visible-light photocatalysis

Direct Z-scheme semiconductor heterostructures possess fascinating merits for solar photocatalysis, including increased light harvesting, spatially isolated photogenerated charge carriers, and well-preserved strong redox capability. However, steering Z-scheme charge transfer of semiconductor heterojunction in a controllable manner is still a challenging task. In this work, unique direct Z-scheme Mo2C-CdxZn1-xIn2S4 heterojunction is constructed via a defect-mediated modulating strategy, where Cd-doping switches the charge transfer mode of Mo2C-CdxZn1-xIn2S4 heterojunction from type-I to Z-scheme through increasing S vacancies, up-shifting conduction band level, and narrowing bandgap of CdxZn1-xIn2S4 component. Moreover, the defect-induced Mo-S bond affords fast channels for built-in electric field-induced Z-scheme photo-electrons transporting from Mo2C conduction band to CdxZn1-xIn2S4 valence band, supporting by X-ray photoelectron spectroscopy, surface photovoltage spectroscopy, and radical testing results. Noticeably, under irradiation of visible light (lambda > 400 nm), Mo2C-CdxZn1-xIn2S4 Z-scheme heterojunction displays an excellent and stable photocatalytic H-2-evolving activity, reaching an outstanding H-2 generation rate of 28.12 mmolg(-1)h(-1) with the corresponding high apparent quantum efficiency of 21.1% at 400 nm, far surpassing that of Pt-loaded C(0.25)ZIS and most documented ZnIn2S4-containing photocatalysts. The present work could inspire the crafty design of efficient Z-scheme photocatalysts through defect-mediated heterostructure construction and energy band engineering.