title: Selective Molecularly Mediated Pseudocapacitive Separation of Ionic Species in Solution.
abstract: We report the development of a dual-electrode pseudocapacitive separation technology (PSST) to capture quantitatively, remotely, and in a reversible manner value-added carboxylate salts of environmental and industrial significance. The nanostructured pseudocapacitive cell exhibits elegant molecular selectivity toward ionic species: upon electrochemical oxidation, a poly(vinylferrocene) (PVF)-based anodic electrode shows high selectivity toward carboxylates based on their basicity and hydrophobicity. Simultaneously, on the other side of the electrochemical cell, a poly(anthraquinone) (PAQ)-based cathodic electrode undergoes electrochemical reduction and captures the counterions of these carboxylates. The separation and regeneration capability of the electrochemical cell was evaluated through the variations in concentration of the carboxylates in polar organic solvents (often used in electrocatalytic processes) upon electrochemical charging and neutralization of the polymeric cargo of the electrodes, respectively. The strong separation efficiency of the system was indicated by its ability to capture an individual carboxylate (acetate, formate, or benzoate) selectively over other competing ions present in solution in significant excess, with an electrosorption capacity in the range of 122-157 mg anions/gcell(polymer and CNT components on the anodic and cathodic side of the cell). The ion sorption capacity of the cell was high even after five adsorption/desorption cycles (18 000 s of continuous operation). In addition, the cell exhibited molecular selectivity even between two carboxylates (e.g., between benzoate and acetate or formate) which differ only in terms of basicity and hydrophobicity. We anticipate that this strategy can be employed as a versatile platform for selective ion separations. In particular, the functionalization of electrochemical cells with the proper polymers would enable the remote and economically viable electro-mediated separation of the desired ionic species in a quantitative and reversible manner.
authors.affiliation: Department of Chemical Engineering, Massachusetts Institute of Technology , 77 Massachusetts Ave., Cambridge, Massachusetts 02139, United States.
authors.forename: Demetra S
authors.initials: DS
authors.lastname: Achilleos
authors.affiliation: Department of Chemical Engineering, Massachusetts Institute of Technology , 77 Massachusetts Ave., Cambridge, Massachusetts 02139, United States.
authors.forename: T Alan
authors.initials: TA
authors.lastname: Hatton
keywords: carboxylate salts; high electrosorption capacity; molecular selectivity; poly(anthraquinone); poly(vinylferrocene); pseudocapacitors