Bilayer

Catalysis

Adsorption

Polyelectrolyte adsorption

Engineering

Polymer chemistry

Nafion

Electrochemistry

Materials science

Ion-exchange membranes

Chromatography

Ion exchange

Biochemistry

Inorganic chemistry

Chemical engineering

Hydroxide

Physical chemistry

Electrodialysis

Polymer

Organic chemistry

Membrane

Layered double hydroxides

Limiting current

Chemistry

Selectivity

Polyelectrolyte

Electrode

Nafion membranes coated with 5.5-bilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films show Li+/Co2+ and K+/La3+ selectivities >1000 in electrodialysis (ED). The corresponding selectivities of bare Nafion are <2. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, water splitting near the polyelectrolyte/Nafion interface reduces current efficiency because protons and hydroxide ions carry current in the membrane. Moreover, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000 because the diffusion-limited K+ or Li+ currents exceed the applied current. However, ED selectivities gradually decline with time. Thus, future research should aim to increase membrane stability and limiting currents to fully exploit the remarkable selectivity of these membranes.

Highly selective separations of multivalent and monovalent cations in electrodialysis through Nafion membranes coated with polyelectrolyte multilayers