Controllable plasmon-induced catalytic reaction by surface-enhanced and tip-enhanced Raman spectroscopy

The controllable catalytic reaction plays a pivotal role in heterogeneous catalysis. Surface-enhanced Raman scattering (SERS) and tip enhanced Raman spectroscopy (TERS) are considered promising techniques for the study of catalytic reactions due to the highly localized sensitivity of SERS and the nanoscale spatial resolution of TERS. Herein, Ag/Au composite films were employed as catalyst for in situ monitoring of the catalytic reaction of 4‑nitrobenzenethiol (4NBT) to p, p'‑dimercaptoazobenzene (DMAB). The catalytic reaction of 4NBT adsorbed on Au film can be manipulated at the nanoscale using TERS by controlling the height between the tip-apex and the sample surface in Ag tip-Au substrate geometry. According to finite difference time domain (FDTD) simulations, the 'hot electron' induced by the localized surface plasmon is sufficient for promoting the catalytic reaction. These findings provide a novel way for controllable graph drawing of molecules at the nanoscale level.