Controlling Shape Anisotropy of ZnS-AgInS₂ Solid Solution Nanoparticles for Improving Photocatalytic Activity

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-AgInS₂ solid solution ((AgIn)_xZn_2(1-x)S₂, 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 Zn²⁺ in rod-shaped particles was tuned by the ratio of metal precursors used in the nanocrystal formation, while postpreparative Zn²⁺ doping was necessary to increase the Zn²⁺ fraction in the rice-shaped particles. The photocatalytic H₂ 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 H₂ evolution was 5.9% for rod-shaped ZAIS particles, being about two times larger than that obtained with spherical particles.