Abstract A tert-butyl protected phenol is covalently link to a mixed self-assembled monolayer on a gold or platinum electrode. The phenol reduction potential shows the expected pH-dependence of a one-electron, one-proton couple with a decrease in formal reduction potential of 59 ± 5 mV per pH. A titration of the phenol is observed with a pKa of 13.2 and the reduction potential for the phenolate is 0.11 V . NHE. The kinetic behavior of the proton-coupled oxidation deviates substantially from the commonly used models for a step-wise reaction that assume the proton transfer reactions are in equilibrium throughout the reaction. A novel model for step-wise proton-coupled reactions is presented that fully accounts for the pH dependent kinetics and allows the formal rate constants and the transfer coefficients to be determined.

中文翻译：

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来自界面苯酚单层的质子耦合电子转移

摘要 叔丁基保护的苯酚与金或铂电极上的混合自组装单层共价连接。苯酚还原电位显示了单电子、单质子对的预期 pH 依赖性，每个 pH 值的形式还原电位降低 59 ± 5 mV。观察到苯酚滴定，pKa 为 13.2，苯酚盐的还原电位为 0.11 V。NHE。质子耦合氧化的动力学行为与假设质子转移反应在整个反应过程中处于平衡状态的逐步反应的常用模型有很大不同。提出了一种用于逐步质子耦合反应的新模型，该模型充分考虑了 pH 依赖性动力学，并允许确定正式的速率常数和转移系数。