Mastering the manipulation of chirality at the nanoscale has long been a priority for chemists, physicists, and materials scientists, given its importance in the biochemical processes of the natural world and in the development of novel technologies. In this vein, the formation of novel metamaterials and sensing platforms resulting from the synergic combination of chirality and plasmonics has opened new avenues in nano-optics. Recently, the implementation of chiral plasmonic nanostructures in photocatalysis has been proposed theoretically as a means to drive polarization-dependent photochemistry. In the present work, we demonstrate that the use of inorganic nanometric chiral templates for the controlled assembly of Au and TiO 2 nanoparticles leads to the formation of plasmon-based photocatalysts with polarization-dependent reactivity. The formation of plasmonic assemblies with chiroptical activities induces the asymmetric formation of hot electrons and holes generated via electromagnetic excitation, opening the door to novel photocatalytic and optoelectronic features. More precisely, we demonstrate that the reaction yield can be improved when the helicity of the circularly polarized light used to activate the plasmonic component matches the handedness of the chiral substrate. Our approach may enable new applications in the fields of chirality and photocatalysis, particularly toward plasmon-induced chiral photochemistry.

Plasmonic materials are intensively used in order to extend the photoactivity of large bandgap semiconductors into the visible light region. In this framework, the present study examines the joint role played by the morphology and composition of plasmonic nanoparticles in their photosensitizing capabilities. The critical influence of these parameters is evidenced by the effect of Au and core-shell Au@Ag nanorods on a TiO2-

Herein, we introduce a novel approach to achieve real‐time control over the hot‐electron injection process in metal–semiconductor photocatalysts. Such functionality is attained through the design of a hybrid nanocomposite in which plasmonic Au nanorods and TiO2 nanoparticles are synergistically integrated with a thermoresponsive polymer. In this manner, modifying the temperature of the system allows 1) precise regulation of the interparticle distance between the catalyst and the plasmonic component and 2) the reversible formation of plasmonic hot spots on the semiconductor. Both features can be simultaneously exploited to modulate the injection of hot electrons, thus boosting/inhibiting at will the photocatalytic activity of these heterostructures. This innovative conception enables dynamically adjustable performance of semiconductors, hence opening the door to the development of a new generation of plasmon‐operated photocatalytic devices.