Tailoring the catalytic sites by regulating photogenerated electron/hole pairs separation spatially for simultaneous selective oxidation of benzyl alcohol and hydrogen evolution.

ABSTRACT

Photocatalytic selective oxidation of alcohols into aldehydes and H2 is a green strategy for obtaining both value-added chemicals and clean energy. Herein, a dual-purpose ZnIn2S4@CdS photocatalyst was designed and constructed for efficient catalyzing benzyl alcohol (BA) into benzaldehyde (BAD) with coupled H2 evolution. To address the deep-rooted problems of pure CdS, such as high recombination of photogenerated carriers and severe photo-corrosion, while also preserving its superiority in H2 production, ZnIn2S4 with a suitable band structure and adequate oxidizing capability was chosen to match CdS by constructing a coupled reaction. As designed, the photoexcited holes (electrons) in the CdS (ZnIn2S4) were spatially separated and transferred to the ZnIn2S4 (CdS) by electrostatic pull from the built-in electric field, leading to expected BAD production (12.1 mmol g-1 h-1) at the ZnIn2S4 site and H2 generation (12.2 mmol g-1 h-1) at the CdS site. This composite photocatalyst also exhibited high photostability due to the reasonable hole transfer from CdS to ZnIn2S4. The experimental results suggest that the photocatalytic transform of BA into BAD on ZnIn2S4@CdS is via a carbon-centered radical mechanism. This work may extend the design of advanced photocatalysts for more chemicals by replacing H2 evolution with N2 fixation or CO2 reduction in the coupled reactions.