Surface-Enhanced Raman Spectroscopy Assisted by Radical Capturer for Tracking of Plasmon-Driven Redox Reaction

The deep understanding about the photocatalytic reaction induced by the surface plasmon resonance (SPR) effect is desirable but remains a considerable challenge due to the ultrafast relaxation of hole-electron exciton from SPR process and a lack of an efficient monitoring system. Here, using the p-aminothiophenol (PATP) oxidation SPR-catalyzed by Ag nanoparticle as a model reaction, a radical-capturer-assisted surface-enhanced Raman spectroscopy (SERS) has been used as an in-situ tracking technique to explore the primary active species determining the reaction path. Hole is revealed to be directly responsible for the oxidation of PATP to p, p′-dimercaptoazobenzene (4, 4′-DMAB) and O(2) functions as an electron capturer to form isolated hole. The oxidation degree of PATP can be further enhanced through a joint utilization of electron capturers of AgNO(3) and atmospheric O(2), producing p-nitrothiophenol (PNTP) within 10 s due to the improved hole-electron separation efficiency.