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Independently controlling the shape anisotropy and chemical composition of multinary semiconductor particles is important for preparing highly efficient photocatalysts. In this study, we prepared ZnS–AgInS 2 solid solution ((AgIn) x Zn 2(1– x ) S 2, ZAIS) nanoparticles with well-controlled anisotropic shapes, rod and rice shapes, by reacting corresponding metal acetates with a mixture of sulfur compounds with different reactivities, elemental sulfur, and 1,3-dibutylthiourea, via a two-step heating-up process. The chemical composition predominantly determined the energy gap of ZAIS particles: the fraction of Zn 2+ in rod-shaped particles was tuned by the ratio of metal precursors used in the nanocrystal formation, while postpreparative Zn 2+ doping was necessary to increase the Zn 2+ fraction in the rice-shaped particles. The photocatalytic H 2 evolution rate with irradiation to ZAIS particles dispersed in an aqueous solution was significantly dependent on the chemical composition in the case of using photocatalyst particles with a constant morphology. In contrast, photocatalytic activity at the optimum ZAIS composition, x of 0.35–0.45, increased with particle morphology in the order of rice (size: ca. 9 × ca. 16 nm) < sphere (diameter: ca. 5.5 nm) < rod (size: 4.6 × 27 nm). The highest apparent quantum yield for photocatalytic H 2 evolution was 5.9% for rod-shaped ZAIS particles, being about two times larger than that obtained with spherical particles.
Torimoto et al. (Mon,) studied this question.