Molecular Theory of Solvation and Electrical Double Layer in Nanoporous Carbon Electrodes

Abstract

Electrical double layer (EDL) in a nanoporous electrode is very different from a planar electrochemical capacitor. The statistical-mechanical, Replica RISM-KH-VM molecular theory for electrolyte solution sorbed in disordered nanoporous materials provides full microscopic details of the solvation structure and thermodynamics and electrochemical properties averaged over the thermal motion of sorbed solution and over quenched morphology of host nanoporous material. The method reveals the molecular mechanisms and driving forces of sorption of electrolyte solution in a nanoporous carbon electrode which are drastically different from the electrical double layer in electrolyte solution at a planar electrode. These include nanoporous confinement morphology and external charge, size and chemical specificities of solvent and electrolyte, osmotic forces, the internal EDL at the surface of nanopores and the external EDL at the contact with bulk solution. The interplay of these factors determines the efficiency of an electrosorption cell and the specific capacitance of the electrochemical supercapacitor.

Solvation Thermodynamics of Organic Molecules by the Molecular Integral Equation Theory: Approaching Chemical Accuracy

“…In this section we provide several examples of successful RISM applications in different areas of life sciences, chemical engineering, and biotechnology. More examples can be found in recent topical reviews and future articles. ,,,, …”

“…More examples can be found in recent topical reviews and future articles. 3,6,7,15,138 6.1. Solvation Phenomena at Complex Molecular Interfaces 6.1.1.…”

“…The situation has changed during the past decade. Recent developments in theoretical and computational aspects of IET have made it possible to make accurate calculations of thermodynamic and structural properties of solvation across multiple classes of molecular systems at relatively low computational expense. − IET methods have been implemented in several open-source and proprietary pieces of computational chemistry software including Amber, ADF, and MOE . Furthermore, IET has found an ever-increasing number of successful applications, including computing solubility of druglike molecules, fragment-based drug design, , molecular recognition, modeling the binding of water and ions by proteins and DNA, − predicting tautomer ratios, interpreting solvent densities around biomacromolecules, and sampling molecular conformations. ,,− As a result, more and more groups around the world have become involved in either using the existing IET methods or developing new ones, and it is anticipated that the popularity of IET methods will rapidly increase in the near future.…”