Solution Structure Effects on the Properties of Electric Double Layers with Surface Charge Regulation Assessed by Density Functional Theory.
Solution Structure Effects on the Properties of Electric Double Layers with Surface Charge Regulation Assessed by Density Functional Theory.
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DOI：
10.1021/acs.langmuir.8b02453
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发表时间：
2018-10
期刊：
影响因子：
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通讯作者：
F. van Swol;D. Petsev
中科院分区：
文献类型：
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作者：
F. van Swol;D. Petsev
双电层中电解质溶液的结构主要由溶剂决定，尽管溶剂通常是中性的并且不受库仑相互作用的影响。典型电解质溶液中溶剂分子的数量可能明显大于离子的数量。因此，带电物质与大量中性分子竞争空间，这对带电表面附近的密度分布有很大影响。即使对于非常稀的电解质溶液，密度分布也类似于液体结构，这完全是由于稠密溶剂的存在。我们的工作表明，溶剂结构效应与控制电荷和电势的表面化学密切相关。我们认为，综合的统计力学方法，例如明确包含所有溶液种类的经典密度泛函理论，与界面处的表面电荷调节条件相结合，为描述带电界面提供了一种极好的方法。它可以揭示重要的物理特征，并包括非库仑贡献，例如离子和表面溶剂化。
The structure of electrolyte solutions in electric double layers is primarily determined by the solvent, despite the fact that it is usually neutral and not subject to Coulombic interactions. The number of solvent molecules in a typical electrolyte solution may be significantly greater that the number of ions. Hence, the charged species compete for space with a much larger number of neutral molecules, which has a strong effect on the density distributions near charged surfaces. Even for very dilute electrolyte solutions, the density profiles resemble liquidlike structure, which is entirely due to the presence of the dense solvent. Our work demonstrates that the solvent structural effect strongly couples to the surface chemistry, which governs the charge and potential. We argue that a comprehensive statistical-mechanical approach, such as classical density functional theory that explicitly includes all solution species, in combination with a surface charge regulation condition at the interface, provides an excellent approach for describing charged interfaces. It allows for revealing important physical features and includes non-Coulombic contributions such as ionic and surface solvation.