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Kinetic and Mechanistic Investigation of the Photocatalyzed Surface Reduction of 4-Nitrothiophenol Observed on a Silver Plasmonic Film via Surface-Enhanced Raman Scattering
摘要： Hot electrons generated by photo-induced plasmon decay from plasmonic metal surface can reduce 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP). Comparing to the reduction with a reducing agent such as sodium borohydride, Surface-Enhanced Raman scattering (SERS) measurements were performed here to elucidate the complex molecular mechanism of the reduction in presence of halide ions and hydrogen ions. The SERS measurements were performed using a simply prepared silver plasmonic film (AgPF), which enables monitoring of the reaction in different conditions at a solid-liquid surface, and eliminates the need for use of a reducing agent. As the concentration of H+ and Cl- could controlled, the observation of the reaction under a systematic set of condition was possible. Based on the kinetic traces of the intermediates, a reaction mechanism for the 4-NTP to 4-ATP reduction is suggested. Rate constants for the individual reactions are presented that fit the measured kinetic traces, and the role of hydrogen in each reaction step is characterized. This work provides clarification on the molecular transformation directly using protons as hydrogen source and demonstrates an effective method of applying a simple and low-cost silver surface catalyst for SERS studies. Moreover, the monitoring of Cl--concentration-dependent spectra gained insight into the hot-electron conversion process during the photoreduction and strongly support the formation of AgCl for activation of H+.
关键词： in-situ SERS spectra,kinetic rate constants,reaction mechanism,time-resolved measurements,selective surface photocatalytic reaction
更新于2025-09-23 15:19:57
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Atomic Force Microscope Guided SERS Spectra Observation for Au@Ag-4MBA@PVP Plasmonic Nanoparticles
摘要： Recently polymer encapsulated surface-enhanced-Raman-scattering (SERS) probes with internal noble metal core–shell structure has found growing applications in biomedical applications. Here we studied the SERS spectra of Au@Ag–4MBA@PVP (4MBA: 4-mercaptobenzoic acid; PVP: polyvinylpyrrolidone) plasmonic nanoparticles produced from a chemical reduction method. By linking the atomic force microscope (AFM) with the homebuilt confocal Raman spectrometer thus to use AFM images as guidance, we realized the measurement of the SERS spectra from separated nanoparticles. We investigated the cases for single nanoparticles and for dimer structures and report several observed results including SERS spectra linearly scaled with laser power, abrupt boosting and abnormal shape changing of SERS spectra for dimer structures. Based on the finite element method simulation, we explained the observed ratio of SERS signals between the dimer structure and the single nanoparticle, and attributed the observed abnormal spectra to the photothermal effect of these plasmonic nanoparticles. Our study provides valuable guidance for choosing appropriate laser power when applying similar SERS probes to image biological cells.
关键词： SERS probes,AFM imaging,confocal Raman spectrometer,SERS spectra,photothermal effect,plasmonic nanoparticles
更新于2025-09-11 14:15:04