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该模型认为溶液中部分过剩离子因静电吸引和范德华吸引的双重作用紧靠电极表面形成"紧密层"(Stern层),另一部分离子因热运动和同号电荷排斥作用形成"分散层",二者共同构成双电层结构。 基于上述推断,Helmholtz提出了双电层的平板模型,即认为金属-溶液界面上有电性相反的,间隔分子量级的电荷层,相当于平板电容器。 科学是一个无限趋近于真理的渐进过程,其核心是模型的构建。 这篇文章想介绍电化学中一个很优雅的概念,并阐释这个概念如何通过建立模型而不断完善。
文章探讨了自发形成和人为控制的双电层结构,包括过剩离子、离子特性吸附、偶极分子定向排列以及通过外加电源调控。 介绍了紧密层、分散层和Stern理论对双电层模型的描述,强调双电层在电化学反应中的关键作用。 当一种物体(如固体、液滴、气泡等)浸入到液体中时,物体的表面电荷与带相反电荷的离子(反离子)构成平行的两层电荷结构。 亥姆霍兹姆最先提出带电电极浸入电解液中将排斥同种电荷并将吸引异种电荷到电极表面, 两层具有相反极性的电荷组成了电极与电解液界面间的双电层,并且两层之间间隔为分子距离级别,如图 (a)。
斯特恩模型是斯特恩于1924年提出的双电层静电模型,通过整合亥姆霍兹紧密双电层模型与古依-恰帕曼分散层模型的合理部分,形成古依-恰帕曼-斯特恩(GCS)理论框架。
亥姆霍兹-佩林模型 (Stern Model)结合了亥姆霍兹模型和古依-查普曼模型的特点,提出双电层由内层的紧密层(Helmholtz Layer)和外层的分散层(Diffuse Layer)组成。 1924年,斯特恩(Stern)提出了一种改进后的zeta电位双层模型。 他是在古依(Gouty)—查普曼(Chapman)分散双层模型基础上发展起来的,同时又吸取了亥姆霍茨紧密双层模型的合理部分。 根据O.斯特恩的观点,一部分反离子由于电性吸引或非电性的特性吸引作用(例如范德瓦耳斯力)而和表面紧密结合,构成 吸附层 (或称斯特恩层)。
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