Ultrafast Surface‐Plasmon‐Induced Photodimerization of p‐Aminothiophenol on Ag/TiO₂ Nanoarrays

Abstract

Surface‐plasmon‐induced photocatalysis has been of increasing interest as a thriving new paradigm for catalytic reactions, while the efficiency of such kind of reactions remains very limited on metal nanostructures. Herein, an ultrafast photodimerization of p‐aminothiophenol (PATP) into p,p′‐dimercaptobenzene (DMAB) was witnessed on the hybrid system of Ag/TiO2 by visible‐light laser excitation, even under inert gas atmosphere. Hot electrons generated from plasmonic decay would transfer to the conduction band of TiO2, which enables the holes (generated in the metal nanoparticles) to trigger the immediate PATP–DMAB conversion. We believe such ultrafast reaction process, with highly enhanced efficiency, will greatly promote the research and applications of the surface‐plasmon‐induced or assisted catalytic reactions.

Photothermally Enhanced Plasmon‐Driven Catalysis on Fe5C2@Au Core–Shell Nanostructures

“…As previously discussed, plasmon‐driven conversion of 4‐ATP or 4‐NTP into DMAB based on Raman techniques has been widely studied in recent years, while the efficiency remains to be greatly improved . Here, the conversion of 4‐ATP or 4‐NTP into DMAB has been compared on the as‐prepared Fe 5 C 2 @Au and Au NPs.…”

“…This is another proof that the photothermal effect in the Fe 5 C 2 @Au core–shell nanostructures is beneficial to accelerate the reaction rate. Our previous work showed that the photogenerated hot holes in Ag from the Ag‐TiO 2 hybrid system led to ultrafast conversion of 4‐ATP into DMAB, which however does not occur in this case due to the absence of charge transfer from Au to Fe 5 C 2 .…”

On the Effect of Native SiO2 on Si over the SPR‐mediated Photocatalytic Activities of Au and Ag Nanoparticles

“…[41,42] Due to the SPR excitation, the accumulation of hot electrons that transiently occupy the highere mpty states above the Fermi level takes place. [43,44] This PATP oxidation pathway may also contribute to the DMAB formation. [20,21] In other words, the hot electrons can diffuse to the surfacea nd subsequently transfer to an unoccupied molecular state triggered by light irradiation.…”

SERS‐Based Plasmon‐Driven Reaction and Molecule Detection on a Single Ag@MoS2 Microsphere: Effect of Thickness and Crystallinity of MoS2

“…Some recent works show that semiconductors such as TiO 2 can be used for separating the hot electrons and accelerating the reaction process . The surface plasmon induced conversion of 4‐aminothiophenol (4‐ATP) or 4‐NTP have been demonstrated on Ag/TiO 2 substrate, where the holes generated in the metal nanoparticle can greatly improve the reaction efficiency . Two‐dimensional (2D) materials, like graphene, h‐BN and transition metal dichalcogenides (TMDs), due to the distinctive electronic and optical properties, have also been applied to couple with metal nanostructures for SERS‐related applications .…”