电化学SPR协同催化对氯苯硫酚界面反应的SERS研究

doi:10.6023/A21080405

摘要/Abstract

表面等离激元共振(SPR)驱动的催化反应近年来广受关注, 研究集中在SPR等外场作用下发生单一的界面催化反应生成新的物质, 这对于表面反应设计和实现多步骤界面有机合成反应仍存在一定困难. 本工作以对氯苯硫酚(4-CBT)为探针, 利用表面增强拉曼光谱(SERS)的极高表面灵敏度并结合金粒子单层膜(Au MLF)的玻碳电极(Au MLF@GC电极)作为基底在均匀性方面的优势, 实现了电化学和SPR协同作用下界面催化反应及其过程的精准监测. 结果表明, 较负电位区间内, 在光电协同催化作用下, 4-CBT先发生脱氯反应生成苯硫酚(TP), 然后4-CBT脱氯与偶联同时发生生成联苯-4,4'-二硫醇(4,4'-BPDT). 提高激光功率可显著加快反应速率, 且在中性溶液中反应速率最快. 溴代苯硫酚以及邻位或间位二氯取代苯硫酚均可发生类似的脱卤素取代基和偶联反应, 但邻位二氯取代物因空间位阻而导致偶联效率降低.

关键词: 表面等离激元共振, 表面增强拉曼光谱, 电化学, 对氯苯硫酚, 偶联反应

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

引用此文

袁宏宇, 徐敏敏, 姚建林. 电化学SPR协同催化对氯苯硫酚界面反应的SERS研究[J]. 化学学报, 2021, 79(12): 1481-1485.

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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图/表 6

图1. Au MLF@GC电极表面4-CBT随电位变化的SERS谱图

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

图2. (a) –0.8 V和开路电位下同一位置4-CBT的SERS谱图(上部, Plaser=6 mW)以及0.12 mW激光功率下不同电位的4-CBT的SERS谱图(下部); (b) TP、4-CBT和反应物的SERS谱图(Plaser=6 mW)

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

图3. (a) 4,4'-BPDT的SERS谱图(上部)和–0.8 V时随时间变化的4-CBT的SERS谱图(下部)(Plaser=6 mW); (b) 996、1280和1584 cm-1处谱峰随时间变化的绝对强度(上部)及相对比值(下部)

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)

图4. (a) –0.8 V下保持8 h后, 在开路下不同位置上4-CBT的SERS谱图(上部)和无电位控制下4-CBT随时间变化的SERS谱图(下部)(Plaser=6 mW); (b) –0.9 V时, 不同激光功率下4-CBT的SERS谱图; (c) 不同pH条件下4-CBT的SERS谱图(Plaser=6 mW)

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

图5. Au纳米粒子单层膜电极表面4-BTP随电位变化的SERS谱图(Plaser=6 mW)

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

图6. 随电位变化的3,5-二氯苯硫酚(上部)和2,6-二氯苯硫酚(下部)的SERS谱图(Plaser=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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