Engineering the Metal/Dielectric Interface to Unlock the Potential of Scattered Light for Boosted Photoredox Catalysis.

The recycling of scattered light by metals has been emerging as a promising light-manipulation-capture strategy, but how to bring its potential into better play remains to be explored. Herein, we present that constructing dual metal/high-refractive-index dielectric interfaces within the SiO2 core@TiO2 shell-Pd satellite@TiO2 shell effectively strengthens both the scattering efficiency of the dielectric SiO2 support and electric field confinement. Consequently, the absorption of Pd toward near-field scattered light and the interfacial charge carrier separation are both enhanced. The synergy of these effects leads to boosted photoactivity toward the aerobic oxidation of cyclohexanol to cyclohexanone and the anaerobic reduction of proton for hydrogen evolution under visible-light irradiation as compared to the counterparts with a single metal/dielectric interface and dual metal/dielectric interfaces consisting of low-refractive-index dielectric component. Notably, the similar enhancements in both optical absorption and photoactivity can be achieved through the present dual metal/high-refractive-index dielectric interfaces engineering strategy for other metals, such as Pt nanoparticles. This work presents an instructive avenue to upgrade the optical response of metals and thus the photocatalytic performance by engineering metal/dielectric interfaces.