Hydrothermal Cation Exchange Enabled Gradual Evolution of Au@ZnS–AgAuS Yolk–Shell Nanocrystals and Their Visible Light Photocatalytic Applications

Abstract

Yolk–shell hybrid nanoparticles with noble metal core and programmed semiconductor shell composition may exhibit synergistic effects and tunable catalytic properties. In this work, the hydrothermal cation exchange synthesis of Au@ZnS–AgAuS yolk–shell nanocrystals (Y–S NCs) with well-fabricated void size, grain-boundary-architectured ZnS–AgAuS shell and in situ generated Au cocatalyst are demonstrated. Starting from the novel cavity-free Au@AgAuS core-shell NCs, via aqueous cation exchange reaction with Zn2+, the gradual evolution with produced Au@ZnS–AgAuS Y–S NCs can be achieved successfully. This unprecedented evolution can be reasonably explained by cation exchange initialized chemical etching of Au core, followed by the diffusion through the shell to be AgAuS and then ZnS. By hydrothermal treatment provided optimal redox environment, Au ions in shell were partially reduced to be Au NCs on the surface. The UV–vis absorption spectra evolution and visible light photocatalytic performances, including improved photodegradation behavior and photocatalytic hydrogen evolution activity, have demonstrated their potential applications. This new one-pot way to get diverse heterointerfaces for better photoinduced electron/hole separation synergistically can be anticipated for more kinds of photocatalytic organic synthesis.