A facile route to (ZnS)x(CuInS2)1−x hierarchical microspheres with excellent water-splitting abilityElectronic supplementary information (ESI) available: Detailed information on (ZnS)x(CuInS2)1−x samples; figure of TG profile, SEM images, and EDX spectra. See DOI: 10.1039/c2jm35166h

A series of (ZnS) x (CuInS 2 ) 1− x hierarchical micro/nano-structured solid solutions with precisely controlled chemical composition were synthesized via a facile one-pot solvothermal method. ZnO, Cu 2 O, and In(OH) 3 are used as the starting materials and dissolved in ethanol dithiocarbamic acid which is formed from CS 2 and ethanolamine in situ . The ethanol dithiocarbamic acid not only serves as a thermally-degradable ligand, but also acts as sulfur source during synthesis, and can be completely removed by a simple calcination process. As-prepared (ZnS) x (CuInS 2 ) 1− x microspheres have a hierarchical micro/nano structure composed of around 7 nm nanoparticles. These samples show excellent photocatalytic H 2 evolution activity under visible-light irradiation without any noble metal loading owing to their high surface area (as high as 101.6 m 2 g −1 ) and unique hierarchical structure. SEM images of as-prepared (ZnS) 8/9 (CuInS 2 ) 1/9 microspheres with a hierarchical micro/nano structure and the element mapping result.