Electrochemical And Plasmon Catalyzed Reaction At The Electrode/Solution Interfaces Probed By SERS

Surface plasmon(SP)-based surface-enhanced Raman spectroscopy(SERS)technique and plasmon-driven heterogeneous interface photo-catalyzed reactions have attracted considerable interests in recent years.Especially the combination of them realizes the control and monitoring of surface reactions simultaneously.The most part of surface plasmon resonance(SPR)catalyzed reactions mainly concentrate on a very small part of reactions and the relevant mechanisms have not been clarified at present.This thesis was based on broadening the type of SPR catalyzed reaction and combined with electrochemical adjustment,the Ag electrode with roughened surface was served as the substrate to research the behavior of electrochemical SPR catalyzed dehydroxylated reaction.The main results are listed as follows:1.The Ag electrode with roughened surface and the Au@Ag monolayer film(MLF)electrode,which were served as the substrates,and SERS technique were used to monitor the electrochemical behavior of para-hydroxythiophenol(PHTP)in situ.It was found that PHTP adsorbed on the electrodes in the region of applied potentials and underwent a dehydroxylated reaction to produce thiophenol(TP)under the synergistic effects of laser and potential in the region of more negative potentials.2.The influencing factors of electrochemical SPR catalyzed dehydroxylated reaction including laser(irradiation time,power,wavelength),media(pH values,the types of solvent and supporting electrolyte)and electrodes(materials,surface structure)and so on were explored systematically.It could be concluded that the catalyzed reactivity was highest in the system containing protonic solvent and highly active hot spots.3.The behaviors of catalyzed dehydroxylated reaction of isomerides of hydroxythiophenol were studied preliminarily and the electrochemical SPR catalyzed dehydroxylated reaction mechanism of such substances was proposed as follows:SPR dominated the reaction while potential adjustment took a synergistic effect.In addition,the supporting electrolyes like halogen were favorable for improving the SPR catalyzed dehydroxylated reactivity.