We develop a replica generalization of the reference interaction site model (replica RISM) integral equation theory to describe the structure and thermodynamics of a polar molecular liquid sorbed in a quenched disordered porous matrix including polar chemical groups. It provides a successful approach to realistic models of molecular liquids, and properly allows for the effect of a quenched disordered medium on the sorbed liquid. The description can be readily extended to a mobile liquid comprising a mixture of ionic and polar molecular species. The replica RISM integral equations are complemented by the HNC closure and its partial linearization (PLHNC), adequate to ionic and polar molecular liquids. In these approximations, closed expressions for the excess chemical potentials of the quenched-annealed system are derived. We extend the description to the case of soft core interaction potentials between all species of the quenched-annealed system, in which the liquid and matrix equilibrium distributions are characterized in general by two different temperatures. The replica RISM/PLHNC-HNC theory is applied to water sorbed in a quenched matrix roughly modelling porous carboneous material activated with carboxylic (-COOH) groups. The results are in qualitative agreement with experiment for water confined in disordered materials.

No abstract

No abstract

We develop a molecular theory of aqueous electrolyte solution sorbed in a nanoporous carbon aerogel electrode, based on the replica reference interaction site model (replica RISM) for realistic molecular quenched-annealed systems. We also briefly review applications of carbon aerogels for supercapacitor and electrochemical separation devices, as well as theoretical and computer modelling of disordered porous materials. The replica RISM integral equation theory yields the microscopic properties of the electrochemical double layer formed at the surface of carbon aerogel nanopores, with due account of chemical specificities of both sorbed electrolyte and carbon aerogel material. The theory allows for spatial disorder of aerogel pores in the range from micro-to macroscopic size scale. We considered ambient aqueous solution of 1 M sodium chloride sorbed in two model nanoporous carbon aerogels with carbon nanoparticles either arranged into branched chains or randomly distributed. The long-range correlations of the carbon aerogel nanostructure substantially affect the properties of the electrochemical double layer formed by the solution sorbed in nanopores.

No abstract