Au/BiOCl heterojunction within mesoporous silica shell as stable plasmonic photocatalyst for efficient organic...

A new mesoporous silica protected plasmonic photocatalyst, Au/BiOCl@mSiO2, was prepared by a modified AcHE method and a subsequent UV light induced photodeposition process. The surfactant-free heterojunction allows the electrons spontaneously flow from Au to nearby BiOCl surface, leading to the accumulation of positive charges on Au surface, and negative charges on Bi species under visible light. Au/BiOCl@mSiO2 exhibits high visible light photocatalytic efficiency in complete oxidation of aqueous formaldehyde and Rhodamin B. We showed that a positive relationship exists between the LSPR effect and rate enhancements, and leads to a hypothesis that the metallic Au LSPR enhances the photocatalytic rates on nearby semiconductors by transferring energetic electrons to BiOCl and increasing the steady-state concentration of active OH species by a multi-electron reduction of molecular oxygen. The OH species is the main oxidant in photocatalytic transformations, whose intensity is greatly enhanced in the dye-involving systems due to the synergetic effect between LSPR and dye sensitization processes. In addition, the mesoporous SiO2 shell not only inhibits the over growth of BiOCl nanocrystals within the silica frameworks, but also protects the dissolution of chloride or Au species into aqueous solution, which ultimately makes the Au/BiOCl@mSiO2 catalysts rather stable during photocatalysis.