Engineering Li/Na selectivity in 12-Crown-4-functionalized polymer membranes.

Lithium is widely used in contemporary energy applications, but its isolation from natural reserves is plagued by time-consuming and costly processes. While polymer membranes could, in principle, circumvent these challenges by efficiently extracting lithium from aqueous solutions, they usually exhibit poor ion-specific selectivity. Toward this end, we have incorporated host-guest interactions into a tunable polynorbornene network by copolymerizing 1) 12-crown-4 ligands to impart ion selectivity, 2) poly(ethylene oxide) side chains to control water content, and 3) a crosslinker to form robust solids at room temperature. Single salt transport measurements indicate these materials exhibit unprecedented reverse permeability selectivity (∼2.3) for LiCl over NaCl-the highest documented to date for a dense, water-swollen polymer. As demonstrated by molecular dynamics simulations, this behavior originates from the ability of 12-crown-4 to bind Na+ ions more strongly than Li+ in an aqueous environment, which reduces Na+ mobility (relative to Li+) and offsets the increase in Na+ solubility due to binding with crown ethers. Under mixed salt conditions, 12-crown-4 functionalized membranes showed identical solubility selectivity relative to single salt conditions; however, the permeability and diffusivity selectivity of LiCl over NaCl decreased, presumably due to flux coupling. These results reveal insights for designing advanced membranes with solute-specific selectivity by utilizing host-guest interactions.

Origins of Lithium/Sodium Reverse Permeability Selectivity in 12-Crown-4-Functionalized Polymer Membranes.

Direct lithium extraction via membrane separations has been fundamentally limited by lack of monovalent ion selectivity exhibited by conventional polymeric membranes, particularly between sodium and lithium ions. Recently, a 12-Crown-4-functionalized polynorbornene membrane was shown to have the largest lithium/sodium permeability selectivity observed in a fully aqueous system to date. Using atomistic molecular dynamics simulations, we reveal that this selectivity is due to strong interactions between sodium ions and 12-Crown-4 moieties, which reduce sodium ion diffusivity while leaving lithium ion mobility relatively unaffected. Moreover, the ion diffusivities in the membrane, when scaled by their respective solution diffusivities and free ion fractions, can be collapsed to an almost universal relationship depending on solvent volume fraction.

Preparation of Chemically-Tailored Copolymer Membranes with Tunable Ion Transport Properties.

Membranes derived from copolymer materials are a promising platform due to their straightforward fabrication and small yet tunable pore structures. However, most current applications of these membranes are limited to the size-selective filtration of solutes. In this study, to advance the utility of copolymer membranes beyond size-selective filtrations, a poly(acrylonitrile-r-oligo(ethylene glycol) methyl ether methacrylate-r-glycidyl methacrylate) (P(AN-r-OEGMA-r-GMA)) copolymer is used to fabricate membranes that can be chemically modified via straightforward schemes. The P(AN-r-OEGMA-r-GMA) copolymer is cast into asymmetric membranes using a nonsolvent induced phase separation technique. Then, the surface charge of the membrane is modified to tailor its performance for nanofiltration applications. The oxirane groups of the glycidyl methacrylate (GMA) moiety that line the pore walls of the membrane allows for both positively charged and negatively charged moieties to be introduced directly without any prior activation. Notably, the highly size-selective nanostructure of the copolymer materials is retained throughout the functionalization processes. Specifically, amine moieties are attached to the pore walls using the aminolysis of the oxirane groups. The resulting amine-functionalized membrane is positively charged and rejects up to 87% of the salt dissolved in a 10 mM magnesium chloride feed solution. Further modification of the amine-functionalized membrane with 4-sulfophenyl isothiocyanate results in pore walls lined by sulfonic acid moieties. These negatively charged membranes reject up to 90% of a 10 mM sodium sulfate feed solution. Throughout the modification scheme, the membrane permeability remains equal to 1.5 L m(-2) h(-1) bar(-1) and the rejection of neutral solutes (i.e., sucrose and poly(ethylene oxide)) is consistent with the membrane having a single well-defined pore diameter of ∼5 nm. The performance of the membrane as a function of ion valence number, solution pH, and ionic strength is investigated.