Multimodal Plasmonic Hybrids: Efficient and Selective Photocatalysts

Important efforts are currently under way in order to implement plasmonic phenomena in the growing field of photocatalysis, striving for improved efficiency and reaction selectivity. A significant fraction of such efforts has been focused on distinguishing, understanding and enhancing specific energy transfer mechanisms from plasmonic nanostructures to their environment. Herein we report a synthetic strategy that brings together two of the main physical mechanisms driving plasmonic photocatalysis into an engineered system by rationally combining the photochemical features of energetic charge carriers and the electromagnetic field enhancement inherent to the plasmonic excitation. We do so by creating hybrid photocatalysts that integrate multiple plasmonic resonators in a single entity, controlling their joint contribution through spectral separation and differential surface functionalization. This strategy allows us to study the combination of different photosensitization mechanisms when activated simultaneously. Our results show that hot electron injection can be combined with an energy transfer process mediated by near-field interaction, leading to a significant increase of the final photocatalytic response of the material. In this manner, we overcome the limitations that hinder photocatalysis driven only by a single energy transfer mechanism, and move the field of plasmonic photocatalysis closer to energy-efficient applications. Furthermore, our multimodal hybrids offer a test system to probe the properties of the two targeted mechanisms in energy-related applications such as the photocatalytic generation of hydrogen and open the door to wavelength-selective photocatalysis and novel tandem reactions.