Nanoscale membrane for removing trace organic contaminants in a fluid and methods of making and using the same
A membrane for filtering one or more hydrophobic organic contaminants can include a porous nanostructure that includes one or more of a metal, a metal oxide, and a metal alloy nanostructure component functionalized with one or more amphiphilic ligands.
1. A membrane for filtering one or more hydrophobic organic contaminants from an aqueous fluid as the aqueous fluid is flowed through the membrane comprising:
a porous nanostructure formed of metal-containing nanowires; and
one or more thiol modified cyclodextrins attached to or assembled on the porous nanostructure thereby functionalizing the porous nanostructure, wherein the one or more thiol modified cyclodextrins have an inner hydrophobic region and an outer hydrophilic region, the one or more thiol modified cyclodextrins are arranged on the porous nanostructure such that aqueous fluid can flow through the membrane and the one or more hydrophobic organic contaminants are attracted to the inner hydrophobic region of the one or more thiol modified cyclodextrins, and the membrane is configured to absorb one or more hydrophobic contaminants from an aqueous flow through attraction of the one or more hydrophobic contaminants to the inner hydrophobic region while the aqueous fluid flows through the membrane.
2. The membrane of claim 1 , wherein the one or more thiol modified cyclodextrins is per-6-thiol-ß-cyclodextrin.
3. The membrane of claim 2 , wherein the metal-containing nanowires comprise gold nanowires.
4. The membrane of claim 1 , wherein the one or more thiol modified cyclodextrins comprises thiol modified α-cyclodextrin, thiol modified ß-cyclodextrin, and/or thiol modified γ-cyclodextrin.
5. The membrane of claim 1 , wherein the metal-containing nanowires comprises a gold alloy selected from the group consisting of gold-copper alloys, gold-silver alloys, gold-iron alloys, and oxides and combinations thereof.
6. The membrane of claim 1 , wherein the metal-containing nanowires comprise one or more of gold, copper, silver, iron, nickel, alloys thereof, and oxides thereof.
7. A method of making the membrane claim 1 for filtering one or more organic contaminants from a fluid comprising:
contacting a solution comprising metal-containing nanowires with a porous substrate under conditions sufficient to dispose the nanowires on top of the porous substrate;
drying the nanowires on the porous substrate by applying a vacuum or pressurized air, wherein upon drying the nanowires entangle to form a porous nanostructure disposed on the porous support; and
functionalizing the nanowires by contacting the nanowires with a solution comprising one or more thiol modified cyclodextrins, wherein the one or more thiol modified cyclodextrins self-assemble onto the nanowires in solution to form functionalized nanowires.
8. The method of claim 7 , wherein functionalizing the nanowires comprises flowing the solution comprising the one or more thiol modified cyclodextrins through the porous nanostructure under conditions sufficient to allow the one or more thiol modified cyclodextrins to self-assemble on the nanowires of the nanostructure.
9. The method of claim 7 , wherein functionalizing the nanowires comprises admixing the solution of nanowires with the solution comprising the one or more thiol modified cyclodextrins under conditions sufficient to allow the one or more thiol modified cyclodextrins to self-assemble on the nanowires, wherein the nanowires are functionalized prior to forming the porous nanostructure.
10. The method of claim 7 , wherein the one or more thiol modified cyclodextrins is per-6-thiol-ß-cyclodextrin.
11. The method of claim 7 further comprising contacting the porous substrate with a solvent after the porous substrate is contacted with the solution comprising the nanowires to thereby precipitate the nanowires from the solution onto the porous substrate.
12. The method claim 7 , wherein the metal-containing nanowires comprise a transition metal, a transition metal alloy, a transition metal oxides, and combinations thereof.
13. The method of claim 7 , wherein the metal-containing nanowires comprise one or more of gold, copper, silver, iron, nickel, alloys thereof, and oxides thereof.
14. A method of making the membrane of claim 1 for filtering one or more organic contaminants from a fluid comprising:
depositing a solution of metal-containing nanowires onto an immiscible liquid, under conditions sufficient to allow the nanowires to self-assemble into a sheet-like porous nanostructure at a liquid-liquid interface or upon solvent evaporation at a liquid-air interface;
transferring the sheet-like nanostructure to a porous support; and
functionalizing the nanowires by contacting the nanowires with a solution comprising the one or more amphiphilic ligands, wherein the one or more amphiphilic ligands self-assemble onto the nanowires in solution to form functionalized nanowires.
15. A method of filtering a fluid using the membrane of claim 1 , comprising flowing water containing or suspected of containing one or more hydrophobic organic contaminants through the membrane, wherein as the water flows through the nanostructure, hydrophobic organic contaminants are trapped by a hydrophobic region of the one or more thiol modified cyclodextrins.
16. The method of claim 15 , wherein the hydrophobic organic contaminant is an estradiol.
17. The method of claim 15 , further comprising cleaning the membrane by flowing through a cleaning solution that removes hydrophobic contaminants trapped in the hydrophobic region of the one or more thiol modified cyclodextrins.
18. A membrane for filtering one or more hydrophobic organic contaminants from an aqueous fluid flowing through the membrane, comprising:
a porous nanostructure formed of metal-containing nanowires, wherein the metal-containing nanowires are noble metal nanowires and/or transition metal nanowires; and
amphiphilic ligands attached to or assembled on the porous nanostructure, wherein the amphiphilic ligands have a hydrophobic portion and a hydrophilic portion and are attached to or assembled on the porous nanostructure such that the hydrophobic portion is an inner region of the amphiphilic ligand and the hydrophilic portion is an outer region of the amphiphilic ligand, thereby functionalizing the porous nanostructure to be adapted for flow-through of the aqueous fluid and attraction of the one or more hydrophobic contaminants to the inner hydrophobic portion from the aqueous fluid, such that the membrane is configured to absorb the one or more hydrophobic contaminants from the aqueous fluid during the flow through of the aqueous fluid through the membrane.
19. The membrane of claim 18 , wherein the amphiphilic ligands are dendrimers that have an inner hydrophobic region and an outer hydrophilic polyethylene glycol region, or
the amphiphilic ligands have a hydrophobic alkane segment connected with a hydrophilic polyethylene glycol segment.
20. The membrane of claim 18 , wherein the membrane is adapted to allow flow of an aqueous fluid through the membrane without externally applied pressure.
21. The membrane of claim 18 , wherein the hydrophilic portion is polyethylene glycol.