期刊
JOURNAL OF COLLOID AND INTERFACE SCIENCE
卷 488, 期 -, 页码 180-189出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcis.2016.10.084
关键词
Electric double layer; Charged interfaces; Electrolyte solutions
资金
- Air Force Academy from Corrosion Policy and Oversight office [FA7000-14-2-0017]
- United States Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering
- UNM Center for Advanced Research Computing
The physical origin of charged interfaces involving electrolyte solutions is in the thermodynamic equilibrium between the surface reactive groups and certain dissolved ionic species in the bulk. This equilibrium is very strongly dependent on the precise local density of these species, also known as potential determining ions in the solution. The latter, however, is determined by the overall solution structure, which is dominated by the large number of solvent molecules relative to all solutes. Hence, the solvent contribution to the molecular structure is a crucial factor that determines the properties of electric double layers. Models that explicitly account for the solvent structure are often referred to as civilized as opposed to the primitive ones that consider the solvent as a structureless continuum. In the present paper, we demonstrate that for a physically correct description of charged interfaces that involve electrolyte solutions (electric double layers), the full solution structure needs to be taken into account in conjunction with the precise surface chemistry governed by the thermodynamic equilibrium. The analysis shows how the surface charge depends on various experimentally relevant parameters, many of which are outside the realm of simple electrostatics. We present results on the effects of solvent molecular dimensions, ionic solvation, surface chemistry, solvophilicity and solvophobicity. (C) 2016 Elsevier Inc. All rights reserved.
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