Capacitance of electrical double layer formed inside a single infinitely long cylindrical pore
Capacitance of electrical double layer formed inside a single infinitely long cylindrical pore
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单个无限长圆柱形孔内形成的双电层电容
DOI：
10.1088/1742-5468/aaddb1
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发表时间：
2018-10
期刊：
影响因子：
--
通讯作者：
S. Zhou
中科院分区：
文献类型：
--
作者：
S. Zhou
利用经典密度泛函理论，研究了在单一无限长圆柱孔中形成的原始模型和扩展原始模型电双层（EDL）的电容。我们得到了EDL差分电容与表征电解质-电极系统的参数之间的关系。结果表明：(1)反离子的高价电子和小尺寸有助于提高其电导率，两者具有协同效应；在高体积浓度下，随着co-ion尺寸的增大而增大，而在低体积浓度下，对co-ion尺寸不敏感。（ii）无论电解质类型和体积浓度如何，表面电荷密度曲线完全随圆柱孔半径向上移动，曲线是骆驼形曲线还是钟形曲线。（iii）在低浓度下，无论电解质类型和孔径大小，曲线都呈驼峰形，当体积浓度上升到适当值时，曲线最终由驼峰形向钟形过渡。此外，高价电子倾向于延迟跃迁和提高跃迁浓度。（iv）对于骆驼形曲线，在曲线超过其最大值后，随曲线的增大而减小；表面电荷强度（对应最大值）随反离子价和孔径的增大而增大，随体积浓度的增大而减小。然而，仅存在一个价反离子时，浓度效应很小，而存在两个价反离子时，浓度效应会变得明显。(v)在确定曲线形状时，增加离子间中性和非hs相互作用的吸引强度与降低体积浓度具有相同的效果，即使骆驼形曲线的特征更加明显。相反，离子间中性和非hs相互作用的排斥性将原本不明显的骆驼形曲线转变为钟形曲线。通过分析盐离子的吸附和由此产生的筛选效果及其影响因素，可以自洽地解释上述观察结果。
By using classical density functional theory, we investigate the capacitance of a primitive model and an extended primitive model electrical double layer (EDL) formed in a single infinitely long cylindrical pore. We obtain dependencies of the EDL differential capacitance on the parameters characterizing the electrolyte-electrode system. It is shown that (i) high electrical valence and small size of counter-ions help to raise the and the two factors have a synergistic effect; the increases with the co-ion size at high bulk concentrations, but is not sensitive to the co-ion size at lower concentrations. (ii) The curve of the versus (surface charge density) moves upwards completely with the cylindrical pore radius regardless of the electrolyte types and bulk concentrations and whether the curve is a camel-shaped or bell-shaped curve. (iii) At low concentrations, the curve is camel shaped regardless of the electrolyte types and pore sizes, and a transition from a camel-shaped to bell-shaped curve will eventually occur when the bulk concentration rises to an appropriate value. Moreover, the high electrical valence tends to delay the transition and raise the transition concentration. (iv) In the case of the camel-shaped curve, the tends to decrease with the after the curve goes beyond its maximal value; the surface charge strength (corresponding to the maxima) increases with the counter-ion valence and pore size, but decreases with the bulk concentration. However, the concentration effect is very small in the presence of only one valence counter-ion, whereas it will become obvious with the presence of two valence counter-ions. (v) In determining the shape of the curve, increasing the strength of an attractive interionic neutral and non-HS interaction has the same effect as decreasing the bulk concentration, i.e. it makes the characteristics of the camel-shaped curve more obvious. Conversely, the incorporation of a repulsive interionic neutral and non-HS interaction transforms an originally not obvious camel-shaped curve into a bell-shaped curve. The above observations can be explained self-consistently by analyzing the adsorption of salt ions and the resulting screening effect and their influencing factors.
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DOI：
10.1063/1.4997420
发表时间：
2017-11
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Alexandre P Dos Santos;M. Girotto;Y. Levin
通讯作者：
Alexandre P Dos Santos;M. Girotto;Y. Levin
影响因子：
3.7
作者：
J. Kłos;S. Lamperski
通讯作者：
J. Kłos;S. Lamperski
影响因子：
3.2
作者：
H. Jones;F. Zerilli
通讯作者：
H. Jones;F. Zerilli
影响因子：
5
作者：
Michel L. Trudeau
通讯作者：
Michel L. Trudeau
DOI：
--
发表时间：
1998-08
期刊：
--
影响因子：
--
作者：
F. Ree;M. Thiel;J. Viecelli
通讯作者：
F. Ree;M. Thiel;J. Viecelli