Balancing Near-Field Enhancement and Hot Carrier Injection: Plasmonic Photocatalysis in Energy-Transfer Cascade Assemblies.

Photocatalysis stands as a very promising alternative to photovoltaics in exploiting solar energy and storing it in chemical products through a single-step process. A central obstacle to its broad implementation is its low conversion efficiency, motivating research in different fields to bring about a breakthrough in this technology. Using plasmonic materials to photosensitize traditional semiconductor photocatalysts is a popular strategy whose full potential is yet to be fully exploited. In this work, we use CdS quantum dots as a bridge system, reaping energy from Au nanostructures and delivering it to TiO nanoparticles serving as catalytic centers. The quantum dots can do this by becoming an intermediate step in a charge-transfer cascade initiated in the plasmonic system or by creating an electron-hole pair at an improved rate due to their interaction with the enhanced near-field created by the plasmonic nanoparticles. Our results show a significant acceleration in the reaction upon combining these elements in hybrid colloidal photocatalysts that promote the role of the near-field enhancement effect, and we show how to engineer complexes exploiting this approach. In doing so, we also explore the complex interplay between the different mechanisms involved in the photocatalytic process, highlighting the importance of the Au nanoparticles' morphology in their photosensitizing capabilities.