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应用电化学现场表面增强拉曼光谱(SERS)以及直接电化学合成技术分别研究了非水体系中苯并咪唑及2-巯基苯并咪唑在铜电极表面的吸附行为及其与三苯基膦(pph3)共存的表面过程.在较负电位区间苯并咪唑主要以分子形式吸附在电极表面.在较正电位区间,电极表面生成类高分子(CuBIM)n膜,具有缓蚀作用,对含有pph3的该体系,Cu+首先与pph3配位形成稳定的阳离子,进入溶液之后与BIM配位生成稳定的配合物,导致不能在表面有效地成膜而破坏了苯并咪唑的缓蚀作用.2-巯基苯并咪唑在Cu表面主要通过自组装单层方式在电极表面吸附,且在实验测试的电位区间内,MBI均是以S端与金属表面作用,其吸附取向随电位正移由倾斜逐渐向接近垂直过渡,并在金属表面形成MBI单分子层膜.pph3的加入不影响MBI在Cu电极表面的成膜行为.电化学现场模拟合成及产物结构组成解析为推断表面反应过程提供了直接证据.
The adsorption behavior of benzimidazole and 2-mercaptobenzimidazole on copper electrode surface in non-aqueous system was investigated by electrochemical surface-enhanced Raman spectroscopy (SERS) and direct electrochemical synthesis, respectively. The adsorption behavior of benzimidazole and 2- pph3) coexisted surface process. In the more negative potential range, benzimidazole mainly adsorbed on the surface of the electrode in molecular form.In the positive potential range, the electrode surface produced a type of polymer (CuBIM) n membrane, with inhibition, containing pph3 Of the system, Cu + first and pph3 coordination to form a stable cation, into the solution and BIM coordination to form a stable complex, resulting in the film can not be effectively formed on the surface and destroy the inhibition of benzimidazole .2-mercapto Benzimidazole adsorbed on the Cu surface mainly through the self-assembled monolayer, and in the experimental potential range, the MBI were all interacting with the metal surface by the S-terminal. The adsorption orientation of the benzimidazole gradually shifted from tilted to approaching Vertical transition, and the formation of MBI monolayer on the metal surface film .pph3 addition does not affect the MBI film formation behavior of the Cu electrode surface. Electrochemical field simulation synthesis and product structure analysis to infer the surface reaction Cheng provides direct evidence.