Nanoporous lyotropic liquid crystal polymer membranes with reversibly tuned pore size and selectivity, and methods using same
The invention includes methods of reversibly tuning the effective pore size and/or solute rejection selectivity of a nanoporous lyotropic liquid crystal (LLC) polymer membrane. The membranes of the invention have high levels of pore size uniformity, allowing for size discrimination separation, and may be used for separation processes such as liquid-phase separations.
1. A method of modifying the effective pore size or a solute transport of a nanoporous lyotropic liquid crystal (LLC) polymer membrane, the method comprising:
providing a membrane comprising a cationic LLC polymer and at least one first anionic counterion,
wherein the LLC polymer-comprising membrane comprises at least one pore in which the at least one first anionic counterion is located, and
wherein the effective size of the at least one pore is less than about 2 nm, and
reversibly replacing the at least one first anionic counterion by contacting the at least one first anionic counterion with an aqueous solution of at least one second anionic counterion at room temperature,
wherein the effective pore size or solute rejection of the membrane comprising the at least one first anionic counterion is distinct from that comprising the at least one second anionic counterion.
2. The method of claim 1 , wherein the at least one first anionic counterion has a distinct molecular volume (V mol ) from the at least one second anionic counterion.
3. The method of claim 1 , wherein the membrane comprising the at least one second anionic counterion has distinct % rejection for an uncharged solute than the membrane comprising the at least one first anionic counterion.
4. The method of claim 3 , wherein the Stokes diameter of the uncharged solute is approximately equal to the effective pore radius for the membrane comprising the at least one second anionic counterion.
5. The method of claim 1 , wherein the at least one anionic counterion is selected from the group consisting of linear, cyclic, or branched C 1 -C 6 alkanesulfonate, benzenesulfonate, naphthalenesulfonate, trifluoromethanesulfonate, camphorsulfonate, alkyl- or aromatic carboxylates, alkyl phosphonates, and aromatic phosphonates, each of which is optionally independently substituted with at least one substituent selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, fluoro, chloro, bromo, iodo, cyano, nitro, —SR′, —C(═O)R′, —N(R′)(R′), —OR′, —C(═O)OR′, and C(═O)NR′R′, wherein each occurrence of R′ is independently H or C 1 -C 6 alkyl.
6. The method of claim 1 , wherein the at least one pore has a structure selected from the group consisting of type I bicontinuous cubic (Q I ) LLC phase structure, and inverted hexagonal (H II ) LLC phase structure.