6533b831fe1ef96bd1298767

RESEARCH PRODUCT

Nanopore charge inversion and current-voltage curves in mixtures of asymmetric electrolytes

Isabelle PauseMubarak AliVicente GomezJosé A. ManzanaresSalvador MafePatricio RamirezJavier CerveraWolfgang Ensinger

subject

inorganic chemicalsCharged nanoporeMaterials scienceKineticschemistry.chemical_elementFiltration and Separation02 engineering and technologyElectrolyte010402 general chemistry01 natural sciencesBiochemistryDivalentIonLanthanumGeneral Materials SciencePhysical and Theoretical ChemistryMaterialsAsymmetric electrolyteschemistry.chemical_classificationCharge inversionNanotecnologiaCurrent rectification021001 nanoscience & nanotechnology0104 chemical sciencesNanoporeHysteresisMembranechemistryChemical physicsCurrent-voltage curveFISICA APLICADA0210 nano-technology

description

[EN] We consider the screening of the negative charges (carboxylic acid groups) fixed on the surface of a conical-shaped track-etched nanopore by divalent magnesium (Mg2+) and trivalent lanthanum (La3+). The experimental current (I)-voltage (V) curves and current rectification ratios allow discussing fundamental questions about the overcompensation of spatially-fixed charges by multivalent ions over nanoscale volumes. The effects of charge inversion or reversal on nanopore transport are discussed in mixtures of asymmetric electrolytes (LaCl3 and MgCl2 with KCl). In particular, pore charge inversion is demonstrated for La3+ as well as for mixtures of this trivalent ion at low concentrations with monovalent potassium (K+) and divalent Mg2+ ions at biologically relevant concentrations. It is found that small concentrations of multivalent ions can modulate the nanopore rectification and the transport of other majority ions in the solution. We study also the kinetics of the nanopore electrical recovery when the electrolyte solutions bathing the single-pore membrane are changed and show the hysteretic effects observed in the I-V curves. Finally, we describe the hysteresis observed in the I-V curves of CaCl2, MgCl2, and BaCl2 and mixtures. We also give a qualitative description of the effects of charge reversal on the pore rectification using the Nernst-Planck flux equations for multivalent ion mixtures.

10.1016/j.memsci.2018.06.032https://dx.doi.org/10.1016/j.memsci.2018.06.032