Chiral Generation of Hot Carriers for Polarization-Sensitive Plasmonic Photocatalysis with Hybrid Nanostructures

Abstract

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. Nevertheless, the lack of synthetic procedures leading to the formation of robust plasmonic photocatalysts with chiroptical features has hindered the advancement of this field. In the present work, we demonstrate that the use of inorganic nanometric chiral templates for the controlled assembly of Au and TiO2 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.

Induced circular dichroism from helicoidal nano substrates to porphyrins: the role of chiral self-assembly

“…1A). 34,35 Using this system, we have reported ICD for various substances such as chromophores, 35 catalysts, 36,37 halide anions, 38 and nanoparticles 39,40 associated with the helices with different methods (Fig. 1B).…”