Selective adsorption of divalent and trivalent cations in porous electrodes

The capacitive deionization technology uses the electrochemical adsorption of ions in porous electrodes to desalinate seawater or brackish water. Recently, capacitive deionization has gained significant attention as a technology for selective adsorption of ionic species from multicomponent aqueous electrolytes. To investigate the mechanism of selective adsorption at the molecular level, we performed molecular dynamics simulations of aqueous electrolytes and porous electrodes with different divalent or trivalent ions, electrode pore sizes, and applied voltages. We calculated the free energy barriers preventing ions from entering the pores of the electrode and the structure of the water molecules near the ions and the electrode surface under various conditions. Our results suggest that, when the pore and ion sizes are comparable, the steric and electrostatic interactions between the hydrated ions and electrode pores are comparable in magnitude. Moreover, the relative importance of the two interactions can be reversed by slight changes in the external conditions, such as the ion size, valence of the ions, electrode pore size, and applied voltage. Thus, by finely tuning the electrode pore size and the applied voltage, it may be possible to selectively adsorb a particular ionic species from a multicomponent electrolyte through capacitive deionization using a porous electrode.