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On the physics of both surface overcharging and charge reversal at heterophase interfaces

Abstract

The conventional paradigm for characterizing surface overcharging and charge reversal is based on the so-called Stern layer, in which surface dissociation reaction and specific chemical adsorption are assumed to take place. In this Article, a series of Monte Carlo simulations have been applied to obtain useful insights into the underlying physics responsible for these two kinds of anomalous phenomena at the interface of two dielectrics, with a special emphasis on the case of divalent counterions that is more relevant in natural and biological environments. At a weakly charged surface, it is found that independent of the type of surface charge distribution and the dielectric response of the solution, the overcharging event is universally driven by the ion size-asymmetric effect. Exceptionally, the overcharging still persists when the surface is highly charged but only restricted to the case of discrete surface charge in a relatively low dielectric medium. As compared to the adsorption onto the homogeneously smeared charge surface that has the same average affinity for counterions, on the other hand, charge reversal under the action of dielectric response can be substantially enhanced in the discrete surface charge representation due to strong association of counterions with interfacial groups, and the degree of enhancement depends in a nontrivial way on the reduction of the medium dielectric constant and the steric effects of finite ion size. Rather interestingly, the charge reversal is of high relevance to the overcharging of interfaces because the overwhelming interfacial association forces the coions closer to the surface due to their smaller size than the counterions. Upon addition of monovalent salt into the solution, the interfacial association with divalent counterions makes surface overcharging and charge reversal widely unaffected, in contrast to the prevailing notion that screening of surface charge of a homogeneous nature is determined by the competitive effects between size-exclusion effects and energetic contributions. Overall, the present work highlights that the complex interplay between the electrostatic and steric interactions coupled to the realistic character of surface charge must be satisfied to establish a faithful description of the overcharging and charge reversal at heterophase interfaces.

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Publication details

The article was received on 04 Dec 2017, accepted on 03 Jan 2018 and first published on 04 Jan 2018


Article type: Paper
DOI: 10.1039/C7CP08117K
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    On the physics of both surface overcharging and charge reversal at heterophase interfaces

    Z. Wang, P. Zhang and Z. Ma, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C7CP08117K

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