SERS Studies on the Electrochemical and SPR Synergistic Catalytic Interfacial Reaction of 4-Chlorothiophenol

doi:10.6023/A21080405

Abstract

Surface-enhanced Raman spectroscopy (SERS) has become a promising technique widely utilized in the field of interface science due to its extremely high sensitivity and selectivity. Among this, surface plasmon resonance (SPR)-driven interfacial reactions have been attracted considerable attention because of their potential practical applications in the field of photocatalysis and photoelectrocatalysis. However, the relevant investigation was mainly focused on the single interfacial reaction for producing new compounds catalyzed by SPR or other external fields and it still remains significant challenge in designing of surface reaction and achieving the interfacial organic reaction with multi-steps. In this paper, 4-chlorothiophenol (4-CBT) was served as the probe molecule and glassy carbon electrode attached with gold nanoparticle monolayer film (Au MLF@GC electrode) was used as substrate due to its excellent uniformity. The extremely high surface sensitivity of SERS was utilized to realize the precise in situ monitoring of the interface catalytic reaction and its process with the synergistic effect of electrochemistry and SPR. In addition, several effects, involving potential, laser power, the pH value of solution and substituents, were systematically investigated. The results reveal that the surface catalysis reaction was absent by the control of single external field, such as potential or laser irradiation. In the relatively negative potential region, 4-CBT underwent a dechlorination reaction to produce thiophenol (TP) under the photoelectric synergistic catalysis, then dechlorination of 4-CBT was followed with a coupling reaction to generate biphenyl-4,4'-dithiol (4,4'-BPDT) as the potential further negatively shifts. The increase of laser power allows to significantly accelerate the reaction rate. The reaction rate is fastest in the neutral solution. Both 4-bromothiophenol (4-BTP) and ortho- or meta-dichloro-substituted thiophenol undergo similar dehalogenation substituents and surface coupling reactions. For ortho-dichloro-substituted thiophenol, the coupling efficiency is reduced due to steric hindrance. It provides a novel approach for surface multi-step organic synthesis reactions.

Key words: surface plasmon resonance, surface enhanced Raman spectroscopy, electrochemistry, 4-chlorothiophenol, coupling reaction

Cite this article

Hongyu Yuan, Minmin Xu, Jianlin Yao. SERS Studies on the Electrochemical and SPR Synergistic Catalytic Interfacial Reaction of 4-Chlorothiophenol[J]. Acta Chimica Sinica, 2021, 79(12): 1481-1485.

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Fig. & Tab. 6

Figure 1. Potential-dependent SERS of 4-CBT adsorbed on Au MLF@GC electrode

Figure 2. (a) SERS of 4-CBT from the same spot at –0.8 V and OCP with the laser power of 6 mW (upper column), and potential-dependent SERS of 4-CBT with the laser power of 0.12 mW (lower column); (b) SERS of TP, 4-CBT and reactant with the laser power of 6 mW

Figure 3. (a) SERS of 4,4'-BPDT (upper column) and time-dependent SERS of 4-CBT at –0.8 V (lower column), the laser power is 6 mW; (b) time-dependent absolute intensities of 996, 1280 and 1584 cm-1 (upper column) and their relative intensities (lower column)

Figure 4. (a) SERS of 4-CBT from different spots at OCP after kept 8 h at –0.8 V (upper column) and time-dependent SERS of 4-CBT at OCP (lower column), the laser power is 6 mW; (b) SERS of 4-CBT at –0.9 V under different laser power; (c) pH dependent SERS of 4-CBT with the laser power of 6 mW

Figure 5. Potential-dependent SERS of 4-BTP adsorbed on Au MLF@GC electrode with the laser power of 6 mW

Figure 6. Potential-dependent SERS of 3,5-dichlorophenol (upper column) and 2,6-dichlorophenol (lower column), the laser power is 6 mW

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