Bare Cd_1–xZn_xS ZB/WZ Heterophase Nanojunctions for Visible Light Photocatalytic Hydrogen Production with High Efficiency

In this work, we report the synthesis of Cd1-xZnxS zinc blende/wurtzite (ZB/WZ) heterophase nanojunctions with highly efficient charge separation by a solvothermal method in a mixed solution of diethylenetriamine (DETA) and distilled water. l-Cysteine was selected as a sulfur source and a protecting ligand for stabilization of the ZB/WZ homojunction. The optimal ternary chalcogenide Cd0.7Zn0.3S elongated nanocrystals (NCs) without any cocatalyst loading show very high visible light photocatalytic activity with H2 production efficiency of 3.13 mmol h(-1) and an apparent quantum efficiency of 65.7% at 420 nm. This is one of the best visible light photocatalysts ever reported for photocatalytic hydrogen production without any cocatalysts. The charge separation efficiency, having a critical role in enhancing photocatalytic activity for hydrogen production, was significantly improved. Highly efficient charge separation with a prolonged carrier lifetime is driven by the internal electrostatic field originating from the type-II staggered band alignment at the ZB/WZ junctions, as confirmed by steady and time-resolved photoluminescence spectra. Further, the strong binding between the l-cysteine ligand and Cd1-xZnxS elongated nanocrystals protects and stabilizes NCs; the l-cysteine ligand at the interface could trap holes from Cd1-xZnxS NCs, while photogenerated electrons transfer to Cd1-xZnxS catalytic sites for proton reduction. Our results demonstrate that Cd1-xZnxS ZB/WZ heterophase junctions stabilized by l-cysteine molecules can effectively separate charge carriers and achieve highly visible light photocatalytic hydrogen production. The present study provides a new insight into the design and fabrication of advanced materials with homojunction structures for photocatalytic applications and optoelectronic devices.