Ligand-Assisted Coordinative Self-Assembly Method to Synthesize Mesoporous ZnxCd1-xS Nanospheres with Nano-Twin-Induced Phase Junction for Enhanced Photocatalytic H2 Evolution.

The designed synthesis of nanotwin architectures and thus-induced phase junctions expresses huge significance for semiconductor photocatalysts. However, current methods of producing nanotwins mainly involve high-temperature thermal treatment and tedious reaction steps, generally resulting in large bulk structure with ill-defined morphology and low specific surface area. Here, we propose a mild ligand-assisted coordinative self-assembly method to synthesize uniform mesoporous ZnxCd1-xS nanospheres with ultrahigh surface areas (148-312 m2 g-1) and controllable diameter (90-370 nm). Moreover, the sample possesses abundant phase junctions induced by nanotwins containing both hexagonal and cubic segments. With the synergy of the twin-induced phase junctions and high surface area, the as-prepared mesoporous Zn0.82Cd0.18S nanospheres exhibit a remarkable photocatalytic H2 evolution rate of 13.46 mmol h-1 g-1 with free noble metal. The mechanism of photocarrier dynamics was studied by transient photovoltage spectroscopy, manifesting that the photocarrier lifetime of Zn0.82Cd0.18S is largely prolonged and therefore improves the charge separation efficiency and photocatalytic activity.