Photocatalytic hydrogen (H2) evolution coupled with
selective organic synthesis over semiconductor-based photocatalysts
is attractive because the clean H2 fuel and value-added
chemicals can be coproduced at ambient conditions using solar light
as the sole energy input. Here, we report the efficient merging catalysis
of photoredox-driven dehydrogenative C–C coupling of benzyl
alcohol (BA) into hydrobenzoin (HB) and H2 evolution over
the SiO2-supported semiconductor CdS quantum dots (QDs)
at ambient temperature and pressure. In this system, we utilize the
judicious interfacial engineering approach to rationally assemble
CdS QDs onto the spherical SiO2 support by which CdS QDs
can recycle the scattered light in the near field of SiO2 and achieve the significantly enhanced light-harvesting capability
and more efficient generation of charge carriers. Consequently, as
compared to bare CdS QDs and Pt/SiO2, the SiO2-supported CdS QDs (CdS/SiO2) exhibits distinctly boosted
photoredox-catalyzed activity and stability for C–C coupling
of BA into HB and H2 evolution. The underlying origin toward
an efficient C–C coupling reaction over CdS/SiO2 is analyzed accordingly. This work would open a conceptual vista
of utilizing a near-field scattering-promoted optical absorption model
and nanoscale interfacial assembly method to maneuver the light-capturing
property of semiconductor QDs without size alteration for solar fuel
production and organic synthesis of fine chemicals.