Preparation, characterization and application of protective phosphonic acid monolayers formed by 1-Aminohexyl phosphonic acid (AHP), 1,4-butanediphosphonic acid (BDPA), 1-amino-1,3-dimethylbutyl phosphonic acid (ADBP) on copper surface as anticorrosive self-assembled molecular monolayers (SAMs) have been investigated by atomic force microscopy (AFM) analysis, electrochemical impedance spectroscopy (EIS) and in situ electrochemical quartz crystal microbalance (EQCM) techniques. Film formation and growth were monitored by EQCM and the step-by-step construction of monolayer was investigated through measurement of the frequency change, which corresponds to mass change due to the adsorption of molecules. Observed increase in electrode mass suggests that SAMs formed on copper surface by the adsorption of phosphonic acids. Results clearly demonstrate that adsorbed amounts of phosphonic acids were strongly influenced by immersion time and molecular structure. Quantum chemical calculations were performed by semi-empirical PM6 method, in order to explain the relationship between molecular structure and adsorption mechanism. Quantum chemical parameters of phosphonic acids propound that adsorption of molecules on copper surface has a chemical mechanism. Corrosion protection ability of SAMs against the acidic corrosion of copper has been evaluated in 0.1[Formula: see text]M H2SO4 solution. It was found that phosphonic acid SAMs act as protective barrier and the protection efficiencies increased in the following order: [Formula: see text].

中文翻译：

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用于铜腐蚀保护的膦酸单层：EQCM 和 EIS 研究

1-氨基己基膦酸(AHP)、1,4-丁二膦酸(BDPA)、1-氨基-1,3-二甲基丁基膦酸(ADBP)形成的保护性膦酸单分子层在铜表面防腐的制备、表征及应用自组装分子单分子层 (SAM) 已通过原子力显微镜 (AFM) 分析、电化学阻抗谱 (EIS) 和原位电化学石英晶体微天平 (EQCM) 技术进行了研究。通过 EQCM 监测膜的形成和生长，并通过测量频率变化来研究单层的逐步构建，频率变化对应于分子吸附引起的质量变化。观察到的电极质量增加表明 SAM 通过吸附膦酸在铜表面形成。结果清楚地表明，膦酸的吸附量受浸泡时间和分子结构的强烈影响。通过半经验PM6方法进行量子化学计算，以解释分子结构与吸附机理之间的关系。膦酸的量子化学参数表明分子在铜表面的吸附具有化学机理。SAMs对铜的酸性腐蚀的腐蚀防护能力在0.1[公式：见正文]MH 膦酸的量子化学参数表明分子在铜表面的吸附具有化学机理。SAMs对铜的酸性腐蚀的腐蚀防护能力在0.1[公式：见正文]MH 膦酸的量子化学参数表明分子在铜表面的吸附具有化学机理。SAMs对铜的酸性腐蚀的腐蚀防护能力在0.1[公式：见正文]MH2所以4解决方案。发现膦酸SAMs起到保护屏障的作用，保护效率按以下顺序增加：[公式：见正文]。