Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers
Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+/Mg2+ selectivity of bare Nafion 115 is <2. However, water-splitting at strongly overlimiting current densities may lead to a local pH increase close to the membrane surface and alter film permeability or allow passage of Mg(OH)x species to decrease selectivity. When the source phase contains high salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions.The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K+/La3+. 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, 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.PEMs deposited on commercial ultrafiltration (UF) membranes also show high rejections of organic dyes. Coating the surface of polyethersulfone (PES) membranes imparts a selective barrier to dye molecules used in textile production. These films achieve dye rejections >98% and may be useful for wastewater treatment and dye recovery. Other studies in microfluidic channels exploit ion transport phenomena in the vicinity of ion-selective junctions, such as cation-exchange membranes. These studies suggest that ion concentration polarization (ICP) could remove charged species from feed streams.
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- In Collections
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Electronic Theses & Dissertations
- Copyright Status
- In Copyright
- Material Type
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Theses
- Authors
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White, Nicholas
- Thesis Advisors
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Bruening, Merlin L.
- Committee Members
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Spence, Dana M.
Tarabara, Volodymyr V.
Blanchard, Gary J.
- Date Published
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2015
- Subjects
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Ion exchange
Ion-permeable membranes
Nanofiltration
Polyelectrolytes
Thin films, Multilayered
Ions
- Program of Study
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Chemistry - Doctor of Philosophy
- Degree Level
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Doctoral
- Language
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English
- Pages
- xix, 177 pages
- ISBN
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9781339323695
1339323699
- Permalink
- https://doi.org/doi:10.25335/cnmd-z640