LAUSR

Plasmon‐driven catalysis has attracted great attention in recent years, but the reaction efficiency remains to be improved. Photothermal Fe5C2@Au core–shell nanostructures are fabricated through a self‐assembly process of Fe5C2 and Au nanoparticles (NPs) with the assistance of hexanethiol, which can be highly efficient surface enhanced Raman spectroscopy (SERS) platforms for the study of plasmon‐driven dimerization of 4‐aminothiophenol (4‐ATP) and 4‐nitrothiophenol (4‐NTP). As compared to bare Au NPs, much accelerated reaction kinetics can be achieved on the Fe5C2@Au core–shell nanostructures by quantitatively determining the Raman intensity of the ν(N=N) band in the generated 4,4′‐dimercaptobenzene (DMAB). The photothermal effect from the Fe5C2 NPs may lower the energy barrier and generate more hot electrons for the plasmon‐driven catalysis. This photothermal route may open up new avenues for enhancing the reaction rate and broadening the research area of the plasmon‐driven catalysis.