Nanostructuring Bridges Semiconductor-Cocatalyst Interfacial Electron Transfer: Realizing Light-Intensity-Independent Energy Utilization and Efficient Sunlight-Driven Photocatalysis.

ABSTRACT

Despite thermodynamic feasibility, the high activation energy originating from potential barriers and trap states kinetically prevents the interfacial transfer of electrons from semiconductor nanostructures to reduction cocatalysts, resulting in a lowered utilization of photogenerated charge carriers in photocatalysis. Nanostructuring-induced narrowing of potential barriers offers a rational solution to kinetically facilitate interfacial electron transfer by tunneling. Here, inspired by theoretical simulation, we manage to promote the separation of photogenerated charge carriers by coating the semiconductor nanostructures with a homogeneous interlayer. The low activation energy for interfacial electron transfer endows photocatalysis with nearly constant quantum yields and a quasi-first-order reaction to the incident photons and grants evident superiority over the photocatalyst without interlayers, especially under sunlight. In our demonstrated sunlight-driven hydrogen evolution integrated with benzylamine oxidation, the production rates for both reduction and oxidation half-reactions reach as high as ∼0.77 mmol dm-2 h-1, which are ∼10 times higher than that without an interlayer.