Elucidating the Mechanism of Electro-Adsorption on Electrically Conductive Ultrafiltration Membranes via Modified Poisson-Boltzmann Equation.

Electrically conductive membranes (ECMs) were prepared by coating porous ethylenediamine-modified polyacrylonitrile (PAN-EDA) UF membranes with an ultrathin layer of platinum (Pt) nanoparticles through magnetron sputtering. These ECMs were used in electrofiltration to study the removal of brilliant blue dye from an aqueous solution under positive electrical potentials (0-2.5 V). Negative electrical potentials (-1.0--2.5 V) were also investigated to regenerate the membrane by desorbing the dye from the ECM surface. At +0 V, the EC PAN-EDA membrane adsorbed the dye due to its intrinsic positive charge. Application of -2.0 V resulted in a maximum of 39% desorption of the dye. A modified Poisson-Boltzmann (MPB) model showed that -2.0 V created a repulsive force within the first 24 nm of the membrane matrix, which had a minimal effect on dye ions adsorbed deeper within the membrane, thus limiting the electro-desorption efficiency to 39%. Moreover, increasing positive potentials from +0.5 V to +2.5 V led to increased dye electro-adsorption by 9.5 times, from 132 mg/m² to 1112 mg/m² at pH 8 (equivalent to the membrane's isoelectric point). The MBP simulations demonstrated that increasing electro-adsorption loadings are related to increasing attractive force, indicating electro-adsorption induced by attractive force is the dominant mechanism and the role of other mechanisms (e.g., electrochemical oxidation) is excluded. At pH 5, electro-adsorption further increased to 1390 mg/m², likely due to the additional positive charge of the membrane (zeta potential = 9.2 mV) compared to pH 8. At pH 8, complete desorption of the dye from the ECM surface was achieved with a significant repulsive force at -2.0 V. However, as pH decreased from 8 to 5, the desorption efficiency decreased by 3.9% due to the membrane's positive charge. These findings help elucidate the mechanisms of electro-adsorption and desorption on ECMs using dye as a model for organic compounds like humic acids.