Functionalized porous polymer networks for per- and / or poly-fluoroalkyl binding

Abstract

The disclosure provides for functionalized porous adsorbents and networks and uses thereof, including for use in selectively capturing and / or separating per- and poly-fluoroalkyl substances.

Description

FUNCTIONALIZED POROUS POLYMER NETWORKS FOR PER- AND / OR POLY -FLUOROALKYL BINDINGCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 U.S.C. §119 from U.S. Provisional Application Serial No. 63 / 643,334, filed May 6, 2024, the disclosures of which are incorporated herein by reference in its entirety.STATEMENT REGARDING FEDERALLY SPONOSORED RESEARCH

[0002] This invention was made with government support under Grant Numbers DE-AC02-05CH11231 and DE-SC0019992 awarded by the Department of Energy The government has certain rights in the invention.TECHNICAL FIELD

[0003] The disclosure provides for functionalized porous adsorbents and networks and uses thereof, including for use in selectively capturing and / or separating per- and poly-f luoroalkyl substances .BACKGROUND

[0004] Per- and polyfluoroalkyl substances (PEAS) are a class of synthetic organof luorine molecules that typically have a hydrophobic fluorinated alkyl "tail" and a hydrophilic "head". This amphipathic nature makes PEAS excellent surfactants and has led to their widespread implementation in consumer and commercial products. However, PEAS leached from manufactured products can remain in the environment almost indefinitely due to their strong C-F bonds. As a result, PEAS are now detected in almost all components of the water cycle at concentrations as high as in the mg / L regime. Furthermore, PEAS bioaccumulate in the human body, and repeated exposure to even trace amounts can have consequences such as endocrine disruption, developmental toxicity, kidney and testicular cancer, immunotoxicity, and genotoxicity.

[0005] The scope and severity of PEAS contamination in water, combined with the associated health risks, has led to significant regulatory action. In April 2024, the United States EnvironmentalProtection Agency announced the final National Primary Drinking Water Regulation for six different PFAS. While these regulations are an important step forward, they are likely only the first of many to come. There are hundreds of PFAS of environmental concern, but the occurrence and toxicity of most are severely under studied. It is therefore imperative that water treatment technologies target the removal of all PFAS, including those that are not yet regulated.SUMMARY

[0006] The increasingly stringent regulations on per and polyfluoroalkyl substances (PFAS) has highlighted the need to develop adsorbents with higher capacity and selectivity towards PFAS in the presence of interfering adsorbates . A comprehensive understanding of the molecular-level interactions governing the removal of PFAS by sorption-based processes is useful for the development of adsorbents with enhanced PFAS removal performance. By appending different functional groups onto a representative porous polymer network (PPN) , the disclosure elucidated the relative significance of different PFAS binding interactions. The importance of hydrophobic, electrostatic, f luorophilic , and hydrogen-bonding interactions were systematically investigated for the removal of a wide range of PFAS from complex water matrices . While electrostatic and hydrophobic interactions served as the dominant mechanisms for PFAS binding, fluorophilic and hydrogen-bonding interactions were found to further enhance the selectivity of these adsorbents towards PFAS. Furthermore, the functionalized PPNs described herein exhibited superior PFAS adsorption capacities, selectivities , and kinetics compared to commercial adsorbents including granular activated carbon (GAC) , surface-modified clay (SMC) , and anion exchange resin (AER) during the treatment of deionized (DI) water, groundwater (GW) , and wastewater (WW) .

[0007] The disclosure provide a functionalized porous-aromatic framework (PAF) , -organic polymer (POP) , -organic framework (POF) , conjugated microporous polymer (CMP) , covalent organic framework (COF) , polymer of intrinsic microporosity (PIM) , or porous-polymernetwork (PPN) having nodes (e. g. , tetrahedral nodes) connected by linkers having the general structure of Formula A, Al, B or Bl:Formula Al wherein, m is 0, 1, 2, 3, 4, or 5, wherein R1-R6are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR11R12)y- (CR13R14)z- (CR1DR1SR17) , or wherein R1-R6can be bound to a node of formula I-VI; wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR1SR19, 0, SO2, NR18, and N+R1SR19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted ( C1-C89 ) alkyl , an optionally substituted (C1-C8 ) alkenyl , an optionally substit(uCt1e-dC9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R3-R5is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group havingthe general formula - (CR9R10)X-Z- (CRX1R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CRX8R19, O, SO2, NR18, and N+RX8R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C8 ) alkyl , an optionally substituted (C1-C8 ) alkenyl , an optionally substituted (C1-C8 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl, an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of Rx-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:Formula Bl wherein, n is 0, 1, 2, 3, 4, or 5, wherein R1-R8are each independently selected from H, D, an optionally substituted alkoxy andoptionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R1O)X-Z- (CRUR12)y- (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substitu (Ct1e-dC8 ) alkenyl , an optionally substitu (Ct1e-dC9) alkynyl , an optionally substitu (Ct1e-dC8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substitu (Cte1-dC8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR21R12)y- (CR13R14)z- (CR15R18R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR13, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substitu (Ct1e-dC8 ) alkyl , an optionally substitu (tCe1-dC8 ) alkenyl , an optionally substitu (Ct1e-dC9) alkynyl , an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substitu (Ct1e-dC8 ) heteroalkenyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R1-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:fluorinated . In another embodiment , the linkers have the structure of :wherein, R is selected from

[0008] The disclosure also provides a device comprising a functionalized porous-aromatic framework (PAF) , -organic polymer(POP) , -organic framework (POP) or -polymer network (PPN) having nodes connected by linkers having the general structure of Formula A, Al, B or Bl:Formula Al wherein, m is 0, 1, 2, 3, 4, or 5, wherein R1-R6are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR21R12)y- (CR13R14)z- (CR13R18R17) , or wherein R2-R6can be bound to a node of formula I-VII; wherein x, y and z are independently selected from 0, 1, 2, 3, 4,5, or 6; and Z is selected from CR13R19, O, SOg, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally (C1-C9 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R4-R5is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - ( CR9R10)X-Z- ( CR14R12)y- (CR13R14)z- (CR15R16R17) , where x,y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substitu (Ct1e-dC8 ) alkyl , an optionally substitu (tCe1-dC8 ) alkenyl , an optionally substituted (C1-C8) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R9-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:Formula Bl wherein, n is 0, 1, 2, 3, 4, or 5, wherein R2-R8are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR21R12)y- (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, 0, SOg, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted ( C1-C89 ) alkyl , an optionallysubstituted (C1-C8 ) alkenyl , an optionally substituted(C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR11R12)v- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C8 ) alkenyl , an optionally substituted (C1-C8 ) alkynyl, an optionally substituted (Cg- Cg ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R2-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:6. In another embodiment, the linkers have the structure of:wherein, R is selected fromn=0, 1, 2, 3, 4, 5, or 6. In one embodiment, the functionalized PAF, POP, POF or PPN is configured to selectively capture or separate per- and / or poly-f luoroalkyl substances (PFAS) . It should be noted that the PFAS can be linear, cyclic, branched, long-chain or short-chain, fluorinated to different degrees, be neutral, cationic, anionic, or zwitterionic, contain N, 0, S, or P heteroatoms at various positions in the molecule. In a further embodiment, the PFAS are long-chain, short-chain, carboxylated, or sulfonated. In still another or further embodiment, the functionalized PAF is configured to selectively capture or separate PFAS in a fluid. In a further embodiment, the fluid is selected from groundwater, surface water, freshwater, seawater, wastewater, well water, mining water, or brackish water. In another or further embodiment, the device is a separation or a sensor device that selectively separates, or indicates the capture, of PFAS. In yet another or further embodiment, the functionalized PAF, POP, POF or PPN is integrated into membranes, films, resins, electrodes, coatings, pellets, co-polymers, porous substrates, or indicators. In a further embodiment, the device comprises an adsorption column and the adsorption column comprises the functionalized PAF, POP, POF or PPN that has been pelletized. In another embodiment, the device is a water treatment device wherein the functionalized PAF has been incorporated into a treatment membrane or resin.

[0009] In other embodiments, any number of existing PAFs, PPNs and the like can be functionalized. Examples of such functionalizedvariants include, but are not limited to: PAF-1, 2, 3, 4, 4F, 5, 6, 7, 8, 8F 11, 12, 16, 16-2, 18, 19, 20, 23, 24, 25, 26, 30, 31, 32, 33, 34, 35, 40, 40-Fe, 40-Mn, 41, 42, 43, 44, 45, 46, 47, 48, 49, 52, 56, 70, 76, 76-Fe, 76-Mn, 76-Zn, 79, 80, 93, 94, 100, 101, 110, 111, 112A, 112B, 113, 131, 132, 133, 144, 150, 151, 152, 153, 154, 155, 165, 166, 182, 183, 202, 203, 220, 303, 361, 362, 363; PPN-1, 2, 3, 4, 5, 6, 10, 12, 13, 101; JUC-Z2, Z4, Z5, Z7, Z8, Z9, Z10, Z15, Z17, Z18, Z19; PSN- 1, 2, 3; Li@PAF-l; PAF-1-350, 380, 400, 450; K-PAF-1-500, 600, 750; NPAF-1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12; PAF-5-PEI; F-PAF-1, NO2- PAF-1 (or just nitro groups) ; NPG-1, NPG-2; MIPAF-lOa, b, c, d, e; MIPAF-lla, b, c, d; ANP-5; iPAF-1, 5, 7, 167, 168; Salen-PAF, Zn / Salen-PAF; AlPor-iPAF-1 , 2, 3; AlPor-PAF; PAF-T; TZ-PAF; THPS; STP- 1, 2; SMP-1; COP-3, 148, 150; YSN-1; HP; SMP-4; Ir-PAF; SPF-TB-PAF; TEPE-TB-PAF; TEPM-TB-PAF; CQDs / PAF-45; PAF-P5; PPI, PP2, 3 to 15; HUST-1, wherein the functionalized variants comprise an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SOg , NR13, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C9 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of is appended to the PAF, PPN or other derivatives thereof:

[0010] In yet another embodiment, the disclosure provides for a composite membrane comprising a polymer / membrane matrix that contains or is embedded with one or more metal organic frameworks (MOFs) , covalent organic frameworks (COFs) , zeolitic imidazolate frameworks (ZIFs) , porous polymer networks (PPNs) , porous aromatic frameworks(PAFs) and / or the like that are functionalized to comprise an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula -(CR9R10)x-Z- (CR11R12) y— (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2 , NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl an optionally substituted (C1-C9 ) alkenyl, an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl, an optionally substituted (C1-C88 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the following structure is appended to the MOF, COF, ZIF, PPN or PAF:wherein, X- is a suitable counter ion and n=0, 1, 2, 3, 4 , 5, or 6.

[0011] The disclosure also provides a method for the selective capture or separation of per- and / or polyfluoroalkyl substances (PFAS) comprising: contacting the per- and / or polyfluoroalkyl substances (PFAS) with a porous adsorbent that has been functionalized to comprise one or more nodes connected by linkers having the general structure of Formula A, Al, B or Bl:Formula Al wherein, m is 0, 1, 2, 3, 4, or 5, wherein R1-R6are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR41R13)y- (CR13R14)z- (CRloR16R17) , or wherein R4-R6can be bound to a node of formula I-VII; wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, 0, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted ( C1-C89 ) alkyl , an optionally substit(uCt1e-Cd9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C83) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R4-R5is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - ( CR9R10)X-Z- ( CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR1SR19, O, SO2, NR13, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substit(uCt1e-Cd9 ) alkyl , an optionally substit(uCt1e-dC9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (Ci- Ce) heteroalkyl, an optionally substituted (Ci-Ct ) heteroalkenyl , an optionally substituted (C1-C8) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R4-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:wherein, n is 0, 1, 2, 3, 4, or 5, wherein R1-R3are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R1O)X-Z- (CRUR12) - (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SOg, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substit(uCt1e-Cd9 ) alkenyl , an optionally substit(uCt1e-Cd9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted(C1-C9 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle;wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - ( CR9R10)X-Z- ( CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SO2, NR13, and N+R13R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substitu (tCe1-dC8 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substitu (Ct1e-dC8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R4-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:, wherein, X' is a suitable counter ion and n=0, 1, 2, 3, 4, 5, or 6. In one embodiment, the porous adsorbent is a porous polymer network. In another or further embodiment, the porous adsorbent is selected from porous organic polymers, porous metal particles, porous metal oxide particles, metal organic frameworks (MOF), a zeolitic organic frameworks (ZIFs), covalent organic frameworks (COFs), and porous aromatic frameworks (PAFs). In still a further embodiment, the porous adsorbent is a PAF. In yet another or further embodiment, the porous adsorbent is configured to selectively capture or separate PFAS in a fluid. In a further embodiment, the fluid is groundwater, surface water, freshwater, seawater, wastewater, well water, mining water, or brackish water.

[0012] The disclosure also provides a composite membrane comprising a polymer / membrane matrix that contains or is embedded with a functionalized porous organic framework ( PAF ) to form pores , wherein the PAF has nodes connected by linkers having the general structure of Formula A, Al , B or Bl :Formula AFormula Al wherein, m is 0, 1, 2, 3, 4, or 5, wherein R1-R6are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR11R12)y_(CR13R14)z- (CR1DR16R17) , or wherein R1-R6can be bound to a node of formula I-VII; wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted ( C1-C89 ) alkyl , an optionally substi (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C83) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R1-R5is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO?, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substit(uCt1e-Cd9 ) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (Ci- Cg ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substitutedheterocycle. In one embodiment, at least one of R1-R1:is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:n=0, 1, 2, 3, 4, 5, or 6.wherein, n is 0, 1, 2, 3, 4, or 5, wherein R1-R3are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R1O)X-Z- (CRUR12) - (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SOg, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted(C1-C9 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle;wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - ( CR9R10)X-Z- ( CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SO2, NR13, and N+R13R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substit(uCt1e-dC9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substitu (Ct1e-dC8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R4-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:, wherein, X' is a suitable counter ion and n=0, 1, 2, 3, 4, 5, or6. In another embodiment, the linkers have the structure of:wherein, R is selected from, wherein, X' is a suitable counter ion and n=0, 1, 2, 3, 4, 5, or 6. In a further embodiment of any of the foregoing, the polymer / membrane matrix is selected from the group consisting of polyolefins; polystyrene; silicones; polyacetylenes; polysulfones; polysulfonamides; polyacetals; polyethers; polyethylenimines; polycarbonates; cellulosic polymers; polyamides; polyimides; polyetherimides; polyamide imides; polyketones; polyether ketones; polyarylene oxides; polyurethanes; polyureas; polyazomethines; polyesters; polysulfides; heterocyclic thermoplastics; polycarbodiimides; polyphosphazines; polyhydrazides; and copolymers thereof, including block copolymers, grafts, and blends thereof. In sill a further embodiment, the polymer / membrane matrix is selected from the group consisting of cellulose acetate, polysulfones, perfluoropolymers, polyphenylene oxide, polyamides, polyimides, aryl poly etherimides, polyetherimides, Ultem 1000, (4,4’-hexafluoroisopropylidene) diphthalic anhydride (6FDA)-based polyimides, 6FDA-DAM, 6FDA-DAT, 6FDA-Durene, 6FDA- DAT:DAT, and Matrimid 5218.DESCRIPTION OF DRAWINGS

[0013] Figure 1 shows ( Top ) Schematic of functionalized PPN-6 pores used in this work, where R indicates an appended functional group . ( Bottom) Functional groups appended onto PPN- 6 , along with the corresponding names of the resulting materials . QA : quaternary ammonium, BE : butyl ether , FBE : 3 , 3 , 4 , 4 , 4 -pentaf luorobutyl ether , NDMB : N, N-dimethyl -butylamine , FNDMB : N, A7-dimethyl-3 , 3 , 4 , 4 , 4 - pentaf luorobutylamine , NB : butylamine , FNB : 3 , 3 , 4 , 4 , 4 - pentaf lurobutylamine . SABET : Brunauer-Emmett-Teller specific surface area . FG : functional group loading per gram of functionali zed PPN material . % : the percentage of biphenyl linkers that are appended with one of the respective functional groups ( e . g. , 100 % signifies one functional group per biphenyl ) . Gray-s cale indicate the expected PFAS binding interactions present in each adsorbent .

[0014] Figure 2A-B shows single-solute PFAS equilibrium adsorption data presented as (A) gravimetric PFAS capacity (mmol / g ) , and ( B)normalized PFAS adsorption efficiency (mmol PFAS / mmol functional group) . "LC" (long-chain) and "SC" (short-chain) represent the average adsorption efficiency for PFOA and PFOS, and PFPeA and PFBS, respectively. Dashed lines are present as a visual aid. Error bars represent the standard deviation of triplicate experiments . Arrows indicate overlapping data points. Tabulated data shown in Table 9.

[0015] Figure 3 shows simulated PFPeA interactions with molecular analogs of functionalized PPNs, along with their associated adsorption energies .

[0016] Figure 4 shows measured PFAS adsorption capacities in deionized water (DI, left bars) and wastewater (WW, right bars) for PPN and commercial adsorbents. Data indicated by an asterisk (*) was collected in WW adjusted to pH 4. Each adsorbent was dispersed into a solution containing 250 nmol / L each of PFOA, PFOS, PFPeA, and PFBS for 8 h. In all cases, there remained detectable concentrations of PFAS in solution after adsorption. Error bars represent the standard deviation of triplicate experiments. Numerical values are listed in Table 10.

[0017] Figure 5 shows removal of PFAS from an AFFF-impacted groundwater sample by PPN and commercial adsorbents. A volume to adsorbent mass ratio of 50 L / g was used, with an 8 h equilibration time. The groundwater sample contained a mixture of perfluorosulfonic acids, perfluorocarboxylic acids, f luorotelomers , perfluorosulfonamides, and a branched, cyclic PFAS. Bars from left to right are: QA, NB, NDMB, FNDMB, SMC, GAC, AER.

[0018] Figure 6A-B shows adsorption kinetics for the removal of 250 nmol / L each of PFOA, PFOS, PFPeA, and PFBS in deionized water and wastewater (WW) . Full experiment length (A) , and the first 3 min (B) are shown.

[0019] Figure 7 shows adsorption cycling performance for PPN-6- FNDMB in AFFF-impacted groundwater. Long-chain PFAS represents: PFHxS, PFHpS, PFOS, PFNS, PFHpA, PFOA, PFNA, 6:2 FTS, 8:2 FTS, FHxSA, FOSA, and PFEtCHxS. Short-chain PFAS represents: PFBS, PFPeS, PFBA, PFPeA, PFHxA, 4:2 FTS, FBSA, and FPeSA.

[0020] Figure 8A-B shows (A) Full FTIR spectra of synthesized PPN materials, along with (B) a zoom-in of the spectra for clarity. The spectra of PPN-6-QA, PPN-6-NDMB, PPN-6-NB, PPN-6-FNB and PPN-6-FNDMB showed new adsorption bands in the region of 1580-1700 cm , corresponding to the C-N vibration, while PPN-6-BE and PPN-6-FBE gained signals associated with C-0 stretching at approximately 1100 cm4. Meanwhile, the prominent signal at 1200 cm4observed for PPN-6- FNB, PPN-6-FNDMB and PPN-6-FBE is indicative of the similar C-F stretches found in each of these fluorinated adsorbents.

[0021] Figure 9 shows nitrogen adsorption isotherms collected at 77 K for the synthesized PPN materials used to calculate BET surface areas. Desorption profiles are omitted for clarity. The variability in surface area between adsorbents could potentially be due to various interactions between multiple functional groups, or interactions between functional groups and the polymer backbone, changing the accessible surface area.

[0022] Figure 10A-B shows performance of PPN (A) and commercial adsorbents (B) for the removal of PFAS from AFFF-impacted groundwater at a volume to mass ratio of 15 L / g.

[0023] Figure 11 shows individual PFAS adsorption kinetics data for PPN-6-FNDMB in deionized water (left) and wastewater (right) spiked with 250 nmol / L each of PFOS, PFOA, PFBS, and PFPeA. In the left figure, all data points are overlapping. In the right figure, the PFOA and PFOS data are overlapping.

[0024] Figure 12 shows adsorption kinetics of PPN-6-FNDMB for PFAS for PPN-6-FNDMB in deionized water containing 0.8 mmol / L of either PFOS or PFPeA.DETAILED DESCRIPTION

[0025] As used herein and in the appended claims, the singular forms "a, " "an, " and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a functional group" includes a plurality of such functional groups and reference to "the pore" includes reference to one or more pores and equivalents thereof known to those skilled in the art, and so forth.

[0026] Also, the use of "or" means "and / or" unless stated otherwise. Similarly, "comprise," "comprises," "comprising" "include," "includes," and "including" are interchangeable and not intended to be limiting.

[0027] It is to be further understood that where descriptions of various embodiments use the term "comprising," those skilled in the art would understand that in some specific instances, an embodiment can be alternatively described using language "consisting essentially of" or "consisting of."

[0028] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although many methods and reagents are similar or equivalent to those described herein, the exemplary methods and materials are disclosed herein .

[0029] All publications mentioned herein are incorporated herein by reference in full for the purpose of describing and disclosing the methodologies, which might be used in connection with the description herein. Moreover, with respect to any term that is presented in one or more publications that is similar to, or identical with, a term that has been expressly defined in this disclosure, the definition of the term as expressly provided in this disclosure will control in all respects .

[0030] It should be understood that this disclosure is not limited to the particular methodology, protocols, and reagents, etc. , described herein and as such may vary. The terminology used herein is for the purpose of describing particular embodiments or aspects only and is not intended to limit the scope of the present disclosure.

[0031] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein should be understood as modified in all instances by the term "about." The term "about" when used to described the present disclosure, in connection with percentages means ±1%. The term "about," as used herein can mean within an acceptableerror range for the particular value as determined by one of ordinary skill in the art, which can depend in part on how the value is measured or determined, e. g. , the limitations of the measurement system. Alternatively, "about" can mean a range of plus or minus 20%, plus or minus 10%, plus or minus 5%, or plus or minus 1% of a given value. Alternatively, particularly with respect to biological systems or processes, the term can mean within an order of magnitude, within 5-fold, or within 2-fold, of a value. Where particular values are described in the application and claims, unless otherwise stated the term "about" meaning within an acceptable error range for the particular value can be assumed. Also, where ranges and / or subranges of values are provided, the ranges and / or subranges can include the endpoints of the ranges and / or subranges. In some cases, variations can include an amount or concentration of 20%, 10%, 5%, 1 %, 0.5%, or even 0.1 % of the specified amount.

[0032] For the recitation of numeric ranges herein, each intervening number there between with the same degree of precision is explicitly contemplated. For example, for the range of 6-9, the numbers 7 and 8 are contemplated in addition to 6 and 9, and for the range 6.0-7.0, the number 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are explicitly contemplated.

[0033] Treatment technologies for the removal of PFAS from water include adsorption, membrane separation, electrochemical degradation, and foam fractionation. Of these, adsorption-based processes are often considered among the best available technologies due to their low cost, high uptake capacity, and ease of implementation. Common commercial PFAS adsorbents include granular activated carbons (GACs) , anion exchange resins (AERs) , and surface-modified clays (SMCs) . These materials leverage non-covalent interactions with PFAS molecules to drive their uptake. While GACs rely predominantly on hydrophobic interactions for PFAS adsorption, AERs and SMCs employ a combination of both electrostatic and hydrophobic interactions. However, these commercial adsorbents can suffer from low selectivities over competing solutes (especially for short-chain PFAS) , long equilibration times,and are typically marketed as single-use. These drawbacks highlight the significant need to develop reuseable adsorbents that provide high-performance removal of a broad variety of PFAS.

[0034] Porous polymer networks (PPNs) , also known as porous aromatic frameworks (PAFs) , are a class of exceptionally porous and tunable polymers that have been developed and studied for the removal of a wide range of contaminants from water. Functionalized porous polymer networks (PPNs) , comprise covalently linked organic monomers, are an emerging class of material that have been used in the high- performance removal of various organic and inorganic contaminants from water. The high porosity, tunability, and structural robustness of PPNs also make them ideal candidates for the removal of PFAS from water .

[0035] The high surface area (>5600 m2 / g) , tunable pore size and functionality, as well as chemical stability of PPNs has made them ideal adsorbents for the removal of contaminants such as Cu2+, Fe3+, Hg+, Au3+, B(OH)3, U0;2+, and Nd3+from water, achieving among the highest reported capacities, fastest kinetics, and unprecedented selectivity for these species. In a recent study, PPNs were employed for the removal of PFOA from deionized (DI) water, exhibiting 32.0 and 24.1 times higher adsorption capacities than DFB-CDP ( [3-cyclodextrin ([3- CD) -based polymer network) and activated carbon, respectively, under similar operating conditions.

[0036] One of the major distinctions between PPNs and commercial adsorbents is the capacity of PPNs to be appended with various functional groups. The ability to modify both the pore structure and functionality of PPNs with excellent chemical precision can be leveraged to optimize the desired interactions between PPNs and PFAS, enabling more effective removal performance. For example, the fluorination of adsorbents is of recent interest due to fluorophilic interactions. The combination of steric and electronic effects between fluorinated alkyl chains has been shown to be more energetically favorable than traditional hydrophobic interactions between nonfluorinated alkyl chains, leading to more selective PFAS adsorption.Systematic chemical modification of PPNs provides a useful method for discerning the contribution of governing interactions (i.e. , electrostatic, hydrophobic, hydrogen bonding, and f luorophilic ) in the long- and short-chain PFAS sorption process during the treatment of complex water matrices .

[0037] To date, the majority of studies evaluating the PFAS removal performance of novel adsorbents (i.e. , metal organic frameworks (MOF) , carbon nanotubes (CNTs) , functionalized organic polymers, etc. ) have focused on the determination of adsorption capacities of long-chain PFAS (i.e. , PFOA and PFOS) in simple water matrices. However, due to the challenges associated with the removal of short-chain PFCAs from real water matrices such as groundwater (GW) and wastewater (WW) , a comprehensive characterization of a novel adsorbent's performance necessitates a rigorous evaluation of its capability to remove both short- and long-chain perfluorosuf onic acids (PFSA) and PFCAs in the presence of interfering DOC.

[0038] Although PPNs can provide a robust, highly-porous adsorbent scaffold, it is the covalently appended functional groups that are responsible for PFAS binding. Understanding PFAS binding mechanisms is thus a prerequisite for the development of improved PFAS adsorption sites in not only PPNs but any adsorbent material. When targeting PFAS uptake, favorable interactions with both the polar head and non-polar tail of the molecule can be leveraged. While the PFAS head can engage in hydrogen-bonding and electrostatic interactions, the tail can participate in hydrophobic and f luorophilic interactions. To enable the design of next-generation PFAS adsorbents, the relative importance of these interactions must be elucidated.

[0039] The efficacy of PFAS removal by sorption-based processes is complex and depends on the physicochemical properties of both the targeted PFAS (i.e. , chain length / linearity, degree of fluorination, and polarity of headgroup) and adsorbent media (e.g. , available adsorbent surface area, porosity, surface functionalization, and polarity) , as well as the presence and identity of competitive adsorbates in the impacted water. Electrostatic and hydrophobicinteractions are considered the dominant mechanisms responsible for the adsorption of PFAS onto commercial adsorbents. However, hydrogenbonding, van der Waals interactions, and fluorophilic interactions can also lead to improved PFAS removal. Depending on the adsorbent, however, not all binding mechanisms may be leveraged simultaneously. For example, GAC relies predominantly on hydrophobic interactions for PFAS adsorption, leading to poor capacities and selectivities . Meanwhile, the relatively high observed perfluoroalkyl acid (PFAA) capacity of AER and AER-like adsorbents (e.g. , SMC) is believed to be due to the combination of both electrostatic and hydrophobic interactions. To date, the assessment of the removal mechanisms of PFAS by adsorbents has been predominantly conducted qualitatively. Thus, a systematic evaluation of the contribution of different PFAS binding interactions would provide insights into the development of next generation adsorbents, ultimately leading to improved PFAS removal by sorption-based processes. Through the installation of distinct functional groups onto a representative polymer backbone, factors critical to the optimization of PFAS binding can be probed experimentally .

[0040] The disclosure provides porous polymers functionalized with an absorbent having PFAS-selective binding groups. The adsorbent is synthesized by the post-synthetic modification of porous polymer network 6 (PPN-6, aka PAF-1) , or a similar porous polymer backbone (please note that node or linker chemical structure can be modified as elucidated herein) . The material features PFAS-selective binding groups, which are in the form of, for example, fluorinated alkylamines or ammoniums, non-f luorinated alkylamines or ammoniums, fluorinated ethers, non-f luorinated ethers, or fluorinated thioethers. The materials also feature high surface areas and exceptional stability in harsh conditions. Because of the appended functional groups, the PPN is an excellent adsorbent for PFAS. The data provided herein show that these adsorbents remove a multitude of different PFAS (long-chain, short-chain, carboxylate, and sulfonate) from water with very high capacities, fast kinetics, high selectivity, and good recyclability.Furthermore , the data demonstrates that these adsorbents work well to remove PFAS from real contaminated water samples , with little consequence of the chemical complexity of the water matrix . The material exhibits excellent performance because it leverages electrostatic , hydrogen-bonding , hydrophobic , and fluorophilic interactions with the target PFAS molecules , strongly binding them within the pores of the polymer . Furthermore , these adsorbents can be incorporated into mixed-matrix membranes and pellets , allowing for their application in electrodialys is cells , diffus ion dialysis cells , and adsorption columns . These materials are unique because most of these functional groups have never been appended onto a porous polymer in the past . Similar porous polymer networks are rare in the literature , and rarer still is their application towards the removal of PFAS from solution . The materials and their applications described in this disclosure are unique compared to all other materials reported in the literature .

[0041] To this end, a representative porous polymer network ( PPN- 6 ) was post-synthetically appended with the functional groups illustrated in Figure 1 . These functional groups were selected because they are expected to engage in unique combinations of electrostatic , hydrogen-bonding , hydrophobic , and fluorophilic interactions with various PFAS molecules . For instance , functional groups containing cationic ammonium moieties can engage in electrostatic interactions with anionic PFAS , but the neutral ether derivatives cannot . Meanwhile , the quaternary ammonium cations rely on electrostatic interactions , but the secondary ammonium cations can also engage in hydrogen-bonding . Hydrophobic and fluorophilic interactions are generated by including alkyl or fluoroalkyl moieties within the functional group . The investigation of these functionalized PPNs not only revealed the relative importance of PFAS binding interactions but also yielded some of the most effective PFAS adsorbents reported to date .

[0042] The library of functionali zed porous polymer networks ( PPNs ) presented in the disclosure allow for the direct comparison ofelectrostatic , hydrophobic , hydrogen-bonding , and fluorophilic interactions with respect to their impact on PFAS adsorption . Batch adsorption experiments , along with computational analysis revealed that electrostatic interactions originating from positively charged adsorbents play a role in PFAS binding and uptake of short-chain PFAS . In water matrices , adsorbents featuring a combination of electrostatic and hydrophobic or fluorophilic interactions exhibit stronger PFAS binding and greater selectivity compared to those capable exclusively of electrostatic , hydrophobic , or fluorophilic interactions . With regard to the latter two interactions , fluorinated adsorbents bind PFAS with greater selectivity than their non-f luorinated counterparts . In the binding of short-chain PFAS , hydrogen-bonding proved to be a significant driving interaction . In one embodiment , a pH-independent positive charge is used when treating complex water matrices . PPN- 6- FNDMB , functionali zed with N, N-dimethyl-3 , 3 , 4 , 4 , 4 - pentaf luorobutylamine ( as described more fully elsewhere herein ) , exhibited strong PFAS adsorption performance compared to the other PPNs and commercial adsorbents .

[0043] As des cribed , the disclosure provides a high-performing adsorbent for PFAS . This adsorbent could be implemented at multiple levels and has use in a wide-range of systems . The most obvious and poss ibly best use of the compositions of the disclosure is to remove PFAS from various water sources in remediation and treatment efforts . The compos ition can be implemented in column or pellet form for use in water treatment cells ( electrodialysis or diffusion dialys is ) or columns . Some other potential applications are :• Large- or small-scale municipal wastewater treatment to remove PFAS by public or private companies ;• Drinking water treatment by government , companies , or individual consumers to remove PFAS ;• Integration of the adsorbent into home water treatment systems at any scale ;• Landfill leachate treatment by government or companies to remove PFAS ;• Groundwater , brine , saltwater , or other water treatment to remove PFAS ;• Integration of the adsorbent into membranes for use in electrodialysis cells , diffusion dialysis cells , or other treatment systems to remove PFAS ;• Integration of the adsorbent into pellets for use in columns or resin beds for the treatment of water to remove PFAS ;• Incorporation of the adsorbent into a coating to be used for water treatment applications ;• The separation of different PFAS from one another;• The pre-concentration of PFAS for destruction purposes ;• Use of the PPN in battery or fuel cells , where having a highly porous fluorinated material may be beneficial ;• The treatment of water to remove other organic contaminants not clas sified as PFAS . These do not neces sarily have to be fluorinated;• Treatment of volatized PFAS . By passing the vapor or aerosol through the adsorbent , the PFAS could be selectively removed ;• Use of the adsorbents during the manufacturing of fluorinated polymers or other industries where PFAS are used as surfactants ( such as the electroplating industry) ; and• Use of the adsorbents for treating fire-fighting foam- impacted water or ground sources .

[0044] The compos itions of the disclosure can be used over similar / competing technologies ( or in combination with similar / competing technologies ) because the compos itions of the disclosure provide a s ignificantly better PFAS adsorbent than what is already described in the literature and is being used commercially . The compos ition / material dis closed herein has excellent performance for PFAS removal in the form of high capacities , fast kinetics , good selectivity, high stability, and good recyclability . The material can also be integrated into a variety of form-factors ( such as pellets and membranes ) that expand the range of potential applications and lowersthe barriers to implementation at the commercial scale. The high degree of tunability of the PPN also presents a significant advantage over competing technologies. Modifications can be made with relative synthetic ease to adapt the material to specific applications.

[0045] The compositions of the disclosure were evaluate to determine their: 1) role of different functional groups within PPNs and the importance of their associated binding mechanisms (i.e. , electrostatic, hydrophobic, f luorophilic, and hydrogen bonding) on PFAS removal performance; 2) adsorption capacities and kinetics for individual PFAS, as well as the extent of competitive adsorption between long- and short-chain PFSAs and PFCAs; 3) adsorption selectivity for PFAS in the presence of interfering DOC in ground water (GW) and waste water (WW) ; and 4) regeneration and cyclability potential of the adsorbent, concurrent with PFAS recovery and concentration for disposal or destruction. To meet these objectives, a representative PPN-6 was appended with various PFAS-selective functional groups to experimentally probe the significance of individual binding interactions. The adsorption performance of the PPNs in GW and WW samples was compared directly with commercially available adsorbents including GAC, SMC, and AER.

[0046] As used herein a "porous absorbent" refers to a molecular entity that is porous and which can effectively bind and separate from a mixture of components fluorinated contaminant. In another embodiment a porous absorbent is a porous polymer network. In a further embodiment, a porous absorbent comprises porous organic polymers, porous metal particles, porous metal oxide particles, metal organic frameworks (MOF) , a zeolitic organic frameworks (ZIFs) , covalent organic frameworks (COFs) , or porous aromatic frameworks ( PAFs ) . In certain embodiments, an absorbent is functionalized to be selective for a particular molecular entity. For example, a useful functionalization can be an optionally substituted alkoxy and optionally substituted quaternary ammonium ions. In certain embodiments, the pore of a MOF, ZIF, COF, PAF is functionalized tocontain one or more optionally substituted alkoxy and / or optionally substituted quaternary ammonium ions.

[0047] The term "functional group" or "FG" refers to specific groups of atoms within molecules that are responsible for the characteristic chemical reactions of those molecules. While the same functional group will undergo the same or similar chemical reaction (s) regardless of the size of the molecule it is a part of, its relative reactivity can be modified by nearby functional groups . The atoms of functional groups are linked to each other and to the rest of the molecule by covalent bonds . Examples of FG that can be used in this disclosure, include, but are not limited to, fluorinated alkylamines or ammoniums, non-f luorinated alkylamines or ammoniums, fluorinated ethers, non-f luorinated ethers, or fluorinated thioethers. In a particular embodiment, the functional group or "FG" may be optionally substituted with additional functional groups. For example, an "FG" that is an amine may be optionally substituted with one or more hydroxyls. In a certain embodiment, the "FG" comprises one or more optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion groups.

[0048] As used herein a "fluid" refers to a liquid or gas. The fluid can be a multicomponent fluid containing a plurality of molecular entities. In a particular embodiment, the fluid is groundwater, surface water, freshwater, seawater, wastewater, well water, mining water, or brackish water. In a further embodiment, the fluid comprises PFAS contaminants.

[0049] As used herein a "membrane" refers to a permeable, selectively permeable or non-permeable film that can be used to divide or separate a first fluid from a second fluid.

[0050] The term "porous aromatic framework" or "PAF", refers to a framework characterized by a rigid aromatic open-framework structure constructed by covalent bonds (Ben et al. , 2009, Angew. Chem. , Inti Ed. 48 :9457; Ren et al. , 2010, Chem. Commun. 46:291; Peng et al. , 2011, Dalton Trans. 40:2720; Ben et al. , 2011, Energy Environ. Sci . 4:3991; Ben et al. , J. Mater. Chem. 21:18208; Ren et al. , J. Mater.Chem. 21:10348; Yuan et al. , 2011, J. Mater. Chem. 21: 13498; Zhao et al. , 2011, Chem. Commun. 47: 6389; Ben & Qiu, 2012, Cryst Eng Comm, DOI : 10.1039 / c2ce25409c) . PAFs show high surface areas and excellent physicochemical stability, generally with long range orders and, to a certain extent, an amorphous nature. Porous aromatic frameworks lack the extended conjugation found in conjugated microporous polymers. A porous aromatic framework can have a surface area from about 50 m2 / g to about 7, 000 m2 / g, about 80 m2 / g to about 1, 000 m2 / g, 1, 000 m2 / g to about 6, 000 m2 / g, or about 1,500 m2 / g to about 5, 000 m2 / g. A PAF can have a pore width of about 7 angstroms to about 30 angstroms (e.g. , 10, 15, 20, 25 angstroms of any value between any of the foregoing) . PAFs can have a differential pore volume of 0.02 to 0.30 cm3g-1A_1(e.g. , 0.02, 0.05, 0.10, 0.15, 0.20, 0.25 cm3g-1A-1of any value between any of the foregoing values) . The rigid, phenyl-rich structures of PAFs result in ultra-high Brunauer-Emmett-Teller surface areas (SABET) of up to 6000 m2 / g, while imparting chemical resistance to harshly acidic, alkaline, and humid environments . The resonance-stabilized aromatic building units also allow the facile incorporation of functional groups . Appropriately functionalized PAFs have yielded among the highest selectivities , capacities, and uptake kinetics for the adsorption of species like Cu2+, Fe3+, B (OH)3, Nd3+, and Hg2+from complex water samples .

[0051] The disclosure provides a system featuring an optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion functionalized porous adsorbent to overcome the shortcomings of existing Se treatment technologies. In a particular embodiment, the porous adsorbent is a porous aromatic framework (PAF) . The disclosure provides optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion-functionalized porous adsorbents (e.g. , PPN-6- QA, -BE, -OB, -OC4, -NDMB, -DMC4, -NB, -FBE, -FNDMB, -FNB and -C4) . The porous adsorbents functionalized with an optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion groups bound to PFAS. The optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion-functionalized porous adsorbents of thedisclosure (e.g. , PPN-6-QA, -BE, -OB, -OC4, -NDMB, -DMC4, -NB, -EBE, - FNDMB, -FNB and -C4) exhibited useful binding to PFAS entities.

[0052] In a particular embodiment, the disclosure provides for a functionalized porous organic framework (PAF) having nodes connected by linkers having the general structure of Formula A, Al, B or Bl:Formula Al wherein, m is 0, 1, 2, 3, 4, or 5, wherein R1-R6are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CRnR12)y- (CR13R14)z- (CR15R16R17) , or wherein R4-R6can be bound to a node of formula I-VII; wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substitu (Ct1e-dC9) alkyl an optionally substit(uCt1e-Cd9 ) alkenyl , an optionally substituted (C1-C8) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8) heteroalkynyl ,an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R1-R5is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - ( CR9R10)X-Z- ( CR11R12)Y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR1GR19, O, SO2, NR10, and N+R1GR19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C8 ) alkynyl, an optionally substituted (Cg- (C1-C8 ) heteroa ,lk aenny olptionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R4-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:Formula Bl wherein, n is 0, 1, 2, 3, 4, or 5, wherein R1-R8are each independently selected from H, D, an optionally substituted alkoxy andoptionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R1O)X-Z- (CRUR12)y- (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substitu (C1-C8 ) alkenyl , an optionally substituted (C1-C8 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR21R12)y- (CR13R14)z- (CR15R18R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR13, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substitu (C1-C8 ) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C8 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R1-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:6.

[0053] In another embodiment , the dis closure provides for a functionalized PAF having tetrahedral carbon nodes connected by linkers having the structure of :wherein, R1-R8are each independently selected from H, D, an optionally substituted functional group (FG) , an optionally substituted (C1-C8 ) alkyl , an optionally substituted (C1-C8 ) alkenyl , an optionally substituted (C1-C8 ) alkynyl, an optionally substituted (Cg- Cg) heteroalkyl, an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle, wherein at least one of R1-R8is an optionally substituted FG having the structure of

[0054] In one embodiment , the one or more types of PAFs comprise a series of nodes linked together by linkers of the disclosure , wherein the series of nodes have a formula selected from Formula I or FormulaFormula V Formula VI Formula VI andL - X - LFormul a VI I . wherein, X is selected from C, N, Ge, Al, Si, B” and P+; and L is a linker and wherein X in formula VII can further be (CH2)nor (CH)n, wherein n is 0, 1, 2, 3, 4, or 5. In some embodiments, Formula A can also serve as a node, wherein R1-R6can comprise "L" (linker) . In still further embodiments, a material can comprise any combination of nodes and / or linkers [e. g. , multiple node formulas coupled to each other, or only multiple linker formulas coupled together, or different variations of Formula A coupled to each other within one given synthesized material) .

[0055] The disclosure further provides for a device that comprises a porous adsorbent or a PAF that has been functionalized with one or more optionally substituted alkoxy and optionally substituted quaternary ammonium ions groups. Examples of devices include, but are not limited to, water treatment devices, water purification devices, fuel cells, sensors, scrubbers, and the like. In a further embodiment, the device comprises an optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion-functionalized porous adsorbent or PAF that is configured to selectively capture or separate PFAS contaminants. In a yet a further embodiment, the device comprises an optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion-functionalized porous adsorbent or PAF that is configured to selectively capture or separate PFAS molecules in a fluid, such as a liquid or gas. Examples of a fluid include, but are not limited to, groundwater, surface water, freshwater, seawater, wastewater, well water, mining water, or brackish water. The device can be used in water purification and treatment, and can comprise one or more adsorption columns. In such a case, the adsorption columns can comprise an optionally substituted alkoxy and / or optionally substituted quaternary ammonium ion-functionalized porous adsorbent or PAF of the disclosure that have been pelleted. Alternatively, or in addition, the device can comprise membranes or resins that comprise anoptionally substituted alkoxy and / or optionally substituted quaternary ammonium ion-functionalized porous adsorbent or PAF of the disclosure.

[0056] The disclosure additionally provides methods for the selective capture or separation of PFAS molecules. For example, the disclosure provides a method for the selective capture or separation of PFAS molecules comprising: contacting a fluid comprising a PFAS molecule with a porous adsorbent that has been functionalized to comprise one or more optionally substituted alkoxy and / or optionally substituted quaternary ammonium ions. In a further embodiment, the porous adsorbent is a porous polymer network. In other embodiments, the porous adsorbent is selected from porous organic polymers, porous metal particles, porous metal oxide particles, metal organic frameworks (MOF) , a zeolitic organic frameworks (ZIFs) , covalent organic frameworks (COFs) , and porous aromatic frameworks (PAFs) . In a particular embodiment, the porous adsorbent is a PAF that has been functionalized as shown in Figure 1 (e.g. , PPN-6-QA, -BE, -OB, -0C4, - NDMB, -DMC4, -NB, -FBE, -FNDMB, -FNB and -C4) .

[0057] The disclosure provides a composite comprising a polymer / membrane matrix that contains or is embedded with, e.g. , a functionalized porous aromatic framework (PAF) having nodes (e.g. , tetrahedral carbon nodes) connected by linkers having the general structure of Formula A, Al, B or Bl:Formula AFormula Al wherein, m is 0, 1, 2, 3, 4, or 5, wherein R1-R6are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R1U)X-Z- (CR12R12)y_(CR18R14)z- (CR1DR16R17) , or wherein R2-R6can be bound to a node of formula I-VI; wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted ( C1-C89 ) alkyl , an optionally substituted (C1-C89 ) alkenyl , an optionally substituted (C1-C89) alkynyl, an optionally substituted (C1-C88 ) heteroalkyl , an optionally substituted (C1-C88 ) heteroalkenyl , an optionally substituted (C1-C83) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R1-R5is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR21R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO?, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C89 ) alkyl , an optionally substituted (C1-C89 ) alkenyl , an optionally substituted (C1-C89) alkynyl, an optionally substituted (Ci- C8 ) heteroalkyl , an optionally substituted (C1-C88 ) heteroalkenyl , an optionally substituted (C1-C88) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substitutedheterocycle. In one embodiment, at least one of R1-R1:is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:n=0, 1, 2, 3, 4, 5, or 6.wherein, n is 0, 1, 2, 3, 4, or 5, wherein R1-R3are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R1O)X-Z- (CRUR12) - (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SOg, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted(C1-C9 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle;wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - ( CR9R10)X-Z- ( CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SO2, NR13, and N+R13R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substitu (Ct1e-dC8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R4-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:

[0058] The disclosure provides a composite comprising a polymer / membrane matrix that contains or is embedded with, e.g. , a functionalized porous aromatic framework (PAF)nodes connected by linkers having the general structure ofA, Al, B or Bl:Formula Al wherein, m is 0, 1, 2, 3, 4, or 5, wherein R1-R6are each independently selectei from H, D, an optionally substituted alkoxy and optionally substitute< quaternary ammonium ions or a group having thegeneral formula: - (CR9R10)X-Z- (CR12R12)y- (CR13R14)z- (CR13R16R17) , or wherein R3-R6can be bound to a node of formula I-VI; wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R3-R5is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR11R12)y- (CR13R14)z- (CR15R13R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR13, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substitu (Ct1e-dC8 ) alkyl , an optionally substitu (tCe1-dC8 ) alkenyl , an optionally substituted (C1-C9) alkynyl , an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R3-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:wherein, n is 0, 1, 2, 3, 4, or 5, wherein R1-R3are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R1O)X-Z- (CRUR12) - (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SOg, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkyl , an optionally substituted(C1-C9 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle;wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - ( CR9R10)X-Z- ( CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, O, SO2, NR13, and N+R13R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C9 ) alkenyl , an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted (C1-C8 ) heteroalkenyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle. In one embodiment, at least one of R4-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:

[0059] Exemplary polymers that may be used to construct the composite membranes include, but are not limited to: polyolefins such as polyethylene, polypropylene, polybutene-1 , and poly ( 4-methyl pentene-1) , including polyvinyls and fluoropolymer variants thereof, for example polyvinylidene fluoride (PVDF) , polytetrafluoroethylene (PTFE) , polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl ester (e.g. , polyvinyl acetate and polyvinyl propionate) , polyvinyl pyridine, polyvinyl pyrrolidone, polyvinyl ether, polyvinyl ketone, polyvinyl aldehyde (e. g. , polyvinyl formal and polyvinyl butyral) , polyvinyl amide, polyvinyl amine, polyvinyl urethane, polyvinyl urea, polyvinyl phosphate, and polyvinyl sulfate; polystyrene (e.g. , isotactic polystyrene and syndiotactic polystyrene) , including styrene-containing copolymers such as acrylonitrilestyrene copolymers, styrene-butadiene copolymers and styrene-vinylbenzylhalide copolymers; thermoplastic elastomers (TPE) ; silicones such as polydimethylsiloxane (EDMS) and polymethylphenylsilicone (PMPS) ; polyacetylenes such as polytrimethylsilylpropyne; polysulfones including polyethersulfones (PESs) as well as sulfonated PESs, with specific mention being made to poly ( 1 , 4 -phenylene ether -ether -sulf one ) , poly ( 1 -he adecene -sulf one ) , poly ( 1 -tetrade cene -sulf one ) , poly ( oxy-1 , 4phenylenesulf onyl-1 , 4- phenylene ) , poly ( oxy-1 , 4 -phenylenesulf onyl-1 , 4 -phenylene ) , poly ( oxy- 1, 4-phenylenesulfonyl-l, 4-phenylene) , poly (oxy-1, 4 -phenylenesulf onyl-1 , 4-phenylene ) , polyphenylsulfone, and ULTRASON S 6010 from BASF; polysulfonamides such as poly [ 1- [ 4- ( 3-carboxy- hydr oxyphenylazo ) benzenesulf onamido ] -1 , 2 -ethanediyl ] - ) ; poly cetals ; polyethers; polyethylenimines ; polycarbonates; cellulosic polymers such as cellulose acetate, cellulose triacetate, cellulose acetatebutyrate, cellulose propionate, ethyl cellulose, methyl cellulose, and nitrocellulose; polyamides including aromatic polyamides and aliphatic polyamides, such as Nylon 6 and polyphthalamide; polyimides with specific mention being made to KAPTON (poly ( 4 , 4 ' -oxydiphenylene- pyromellitimide ) by DuPont, MATRIMID® by Huntsman Advanced Materials, P84 by HP Polymers GmbH, poly ( 3 , 3 ' , 4 , 4 ' -benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride-3 , 3 ' , 5 , 5 ' -tetramethyl-4 , 4 ' - methylene dianiline) (or poly ( BTDA-PMDA-TMMDA) ) , poly ( 3 , 3 ' , 4 , 4 ' - benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride- 4, 4' -oxydiphthalic anhydride-3 , 3 ' , 5 , 5 ' -tetramethyl-4 , 4 ' -methylene dianiline) ( or poly ( BTDA-PMDA-ODPA-TMMDA) ) , poly ( 3 , 3 ' , 4 , 4 ' - diphenylsulfone tetracarboxylic dianhydride-3 , 3 ' , 5 , 5 ' -tetramethyl- 4 , 4 ' -methylene dianiline) (or poly (DSDA-TMMDA) ) , poly ( 3 , 3 ' , 4 , 4 ' - benzophenone tetracarboxylic dianhydride-3 , 3 ' , 5 , 5 ' -tetramethyl-4 , 4 ' - methylene dianiline) (or poly ( BTDA-TMMDA) ) , poly ( 3 , 3 ' , 4 , 4 ' - diphenylsulfone tetracarboxylic dianhydride-pyromellitic dianhydride- 3 , 3 ' , 5 , 5 ' -tetramethyl-4 , 4 ' -methylene dianiline) (or poly (DSDA-PMDA- TMMDA) ) , and poly [ 2 , 2 ' -bis- ( 3 , 4-dicarboxyphenyl ) hexafluoropropane dianhydride-2 , 2-bis ( 3-amino-4-hydroxyphenyl ) -hexafluoropropane] (or poly ( 6FDA-APAF ) ) , poly [2,2 ' -bis- ( 3 , 4-dicarboxyphenyl ) hexafluoropropane dianhydride-2, 4, -trimethyl-l , 3-phenylenediamine ] (or poly ( 6 FDA- DAM) , poly [ 3 , 3 ' , 4 , 4 ' -benzophenonetetracarboxylic dianhydride-2, 2-bis ( 3-amino-4-hydroxyphenyl ) -hexafluoropropane] (or poly (BTDA-APAF) ) , poly(3,3' , 4, 4' -benzophenonetetracarboxylic dianhydride-3 , 3 ' -dihydroxy- 4 , 4 ' -di amino -biphenyl ) (or poly (BTDA-HAB ) ) , poly [4,4' -oxydiphthalic anhydride-2 , 2-bis ( 3-amino-4-hydroxyphenyl ) - hexafluoropropane] (or poly (ODPA-APAF) ) , poly [ 3 , 3 ' , 4 , 4 ' - diphenylsulfone tetracarboxylic dianhydride-2 , 2-bis ( 3-amino-4- hydroxyphenyl) -hexafluoropropane] (or poly (DSDA-APAF) ) ,poly ( 3 , 3 ' , 4 , 4 ' -diphenylsulf one tetracarboxylic dianhydride -3 , 3 ' - dihydroxy-4 , 4 ' -diamino-biphenyl ) (or poly ( DSDA-HAB ) ) , poly [2 , 2 ' -bis- ( 3 , 4 -dicarboxyphenyl ) hexafluoropropane dianhydride-3 , 3 ' , 4 , 4 ' - benzophenonetetracarboxylic dianhydride-2 , 2-bis (3-amino-4- hydroxyphenyl) -hexafluoropropane] (or poly ( 6FDA-BTDA-APAF) ) , poly [4,4' -oxydiphthalic anhydride-2 , 2-bis ( 3-amino-4-hydroxyphenyl ) - hexaf luoropropane-3, 3 ' -dihydro- xy-4 , 4 ' -diamino-biphenyl] (or poly (ODPA-APAF-HAB ) ) , poly [3 , 3 ' , 4 , 4 ' -benzophenonetetracarboxylic dianhydride-2 , 2-bis ( 3-amino-4-hydroxyphenyl ) -hexaf luoropropane-3 , 3 ' - dihyd- roxy-4 , 4 ' -diamino-biphenyl] (or poly ( BTDA-APAF-HAB ) ) , poly [2,2' -bis- (3, 4 -di carboxyphenyl ) hexaf luor opr opane dianhydride- 3 , 3 ' -dihydroxy-4 , 4 ' -diamino-biphenyl ] (or poly ( 6FDA-HAB ) ) , and poly ( 4 , 4 ' -bisphenol A dianhydride-3 , 3 ' , 4 , 4 ' - benzophenonetetracarboxylic dianhydride-2, 2-bis (3-amino-4- hydroxyphenyl ) -hexaf luoropropane ) (or poly (BPADA-BTDA-APAF) ) ; polyetherimides such as ULTEM products manufactured by Sabie Innovative Plastics; polyamide imides; polyketones; polyether ketones such as polyether ether ketone, sulfonated polyether ether ketone and the like; polyarylene oxides such as polyphenylene oxide, polyxylene oxide, sulfonated polyxylene oxide and brominated polyxylene oxide; polyurethanes; polyureas; polyazomethines ; polyesters including polyarylates such as polyethylene terephthalate and polyphenylene terephthalate; acrylates such as polyalkyl (meth) acrylate, polyacrylate, polyacrylate-polyacrylamide copolymers; polysulfides; heterocyclic thermoplastics such as polybenzimidazoles, polyoxadiazoles, polytriazoles, polybenzoxazole , and polybenzimidazole; polycarbodiimides; polyphosphazines; polyhydrazides; and copolymers thereof, including block copolymers, grafts, and blends thereof .

[0060] In one embodiment, the disclosure provides a composite membrane comprising a functionalized porous adsorbent or PAF that can separate or selectively capture PFAS in a fluid stream. The functionalized PAF may be uniformly distributed in the membrane or may be non-unif ormly distributed. The plurality of functionalized PAF mayhave a uniform pore size or a non-uniform pore size. By "uniform pore size" is meant that the pore size between two absorbents does not differ by more than 0.1%, 0.5% or 1%. In one embodiment, composite membrane can contain from 5 wt% to 40 wt% of the one or more functionalized PAFs of the disclosure.

[0061] The following examples are meant to further illustrate, but not limit the described invention.EXAMPLES

[0062] Chemicals and Standards. All reagents and starting materials were purchased from Sigma-Aldrich, Alfa Aesar, or Acros Organics and used as received unless stated otherwise. Four per- and polyfluoroalkyl substances (PFAS) including the representative perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs) with different chain lengths were chosen to be tested for their removal performance by porous polymer networks (PPNs) against commercial adsorbents. The selected PFAS included PFOS (sulfonic acid, 8 carbon atoms) , PFOA (carboxylic acid, 8 carbon atoms) , PFBS (sulfonic acid, 4 carbon atoms) , and PFPeA (carboxylic acid, 5 carbon atoms) . Description of chemicals and standards used are provided in Table 1. A Millipore RiOs system was used to source the ultrapure deionized (DI) water (18.2 MO cm electrical resistivity and < 5.4 ppb total organic carbon) used in all experiments. Schlenk line techniques under an argon atmosphere were performed to complete all porous aromatic framework syntheses. A PerkinElmer 2400 Series II combustion analyzer at the Microanalytical Facility at the University of California, Berkeley was used to measure carbon, hydrogen, and nitrogen elemental analyses.

[0063] Table 1. CAS numbers and purities of the tested PFAS, all of which were purchased from Sigma Aldrich and used as-received.Abbreviation, number ofCompound CAS No. Purity carbonsPerfluoropentanoic acid 2706-90-3 PFPeA, C5 97%Perfluorohexanoic acid 307-24-4 PFHxA, C6 >97%Perfluorooctanoic acid 335-67-1 PFOA, C8 95%Perfluorobutanesulfonic acid 375-73-5 PFBS, C4 97%Perfluorooctanesulfonic acid 1763-23-1 PFOS, C8 >98%Perfluorononanoic acid 375-95-1 PFNA, C9 97%

[0064] Table 2 provides physical characteristics of the studied PFAS .

[0065] Table 2. Physical characteristics of six studied PFAS including names, abbreviations, number of carbon atoms, bulk diffusivity (£>) ," octanol-water partition coefficient (log K:iw) ,pmolecular weight, acid dissociation constant (pPQ) .13a Estimated values using SPARC (ARChem, [http: / / wlww.archemcalc.com / ).0 Estimated data adapted from Marvin Sketch 22.2 (ChemAxon Ltd., [http: / / wlww.chemaxon.com / ).

[0066] Commercial Adsorbents. Filtrasorb 400 (F400) , a bituminous coal-based granular activated carbon (GAC) product (Calgon Carbon Corp. , Pittsburg, PA) , was selected to be tested against PPNs as currently GAC is one of the most widely implemented adsorbents for PFAS removal. Surface-modified clay (SMC) , obtained under the product name Fluoro-Sorb200 (FS200) from Colloid Environmental Technologies Company (CETCO, Hoffman Estates, IL) , is an emerging surface-modified clay adsorbent in which the exchangeable sodium cations are replaced by quaternary ammonium functional groups. SMC was chosen to be tested against GAC and PPNs as it previously reported high PFAS removalperformances compared to GAC. Further details on the adsorbents' specifications supplied by manufacturers are provided in Tables 3-5.

[0067] Table 3. GAC (F400) physical properties.

[0068] Table 4. SMC (FS200) properties.

[0069] Table 5. AER (CalRes2301) properties.

[0070] Groundwater and Wastewater Samples. The performance of the investigated adsorbents for the removal of a wide range of PFAS from real water samples was tested using both an aqueous film forming foam (AFFF) -impacted groundwater and a treated wastewater effluent. Tables6 and 7 provide summaries of PFAS concentrations and other water quality parameters for the tested water samples . The investigated AFFF-impacted groundwater was collected from an Air Force Base in the United States in a 275 -gallon tote . The treated wastewater effluent used for different batch isotherm experiments was obtained from a 30 m3 / d pilot-s cale sequencing batch membrane bioreactor ( SBMBR ) . Raw wastewater from a student complex was discharged to the SBMBR with a total solid concentration of ~5 . 1 g / L and a solid retention time of 25 days . The PFAS concentrations in the parent wastewater effluent were below 5 ng / L for all target compounds .

[0071] Table 6 . Water quality parameters of the investigated wastewater ( WW ) , synthetic wastewater ( SWW ) , and groundwater ( GW ) . The SWW was made by dissolving appropriate amounts of salts in deionized water .Table 7. Detected PFAS concentrations in AFFF-impacted groundwater.

[0072] Synthesis of PPNs

[0073] Synthesis of 3, 3, 4, 4, 4-pentafluorobutyl azidequaReflux, 16 h

[0074] The synthesis of 3, 3, 4, 4, 4-pentaf luorobutyl azide was carried out following a modified procedure. Briefly, a 25 mL pear- shaped flask equipped with a reflux condenser was charged with 3, 3, 4, 4, 4-pentaf luorobutyl iodide (10.0 g, 5.20 mL, 36.5 mmol) , a 30% aqueous solution of sodium azide (4.75 g, 73.0 mmol, in 11.0 mL of water) , and methyltridecylammonium chloride (Aliquat 336, 73.0 mg, 1.81 mmol) . The mixture was heated to reflux and stirred for 16 h. The mixture was then cooled to room temperature and allowed to separate into two layers. The top organic layer was extracted and dried over sodium sulfate to yield a clear yellow liquid. Placing the liquid in a freezer overnight led to its separation into a clear and colorless bottom layer containing the azide and a dark yellow top layer containing methyltridecylammonium chloride. The dark yellow layer was removed and discarded, leaving the 3, 3, 4, 4, 4- pentaf luorobutyl azide (4.61 g, 23.0 mmol, 63% yield) , which was used without further purification.NMR (CDCI3, 25 °C, 500 MHz) : 5 = 3.59 (t, JHH= 7.2 Hz, 2H) , 2.34 (tt, JHH= 7.2 Hz,17.7 Hz, 2H) .19F NMR (CDCI3, 25 °C, 500 MHz) : <5 = -85.67 (s, 3F) , -117.93 (t, 17.7 Hz, 2F) .

[0075] Synthesis of 3 , 3 , 4 , , 4-pentaf luorobutyl amineH2, 300 psi 25 °C, 16 h

[0076] 3, 3, 4, 4, 4 -Pentafluorobutyl azide (3.54 g, 18.7 mmol) was placed in a 150 mL Pyrex jar along with palladium on carbon (0.35 g, 10 wt%) , and 40.0 mL of EtOH. The uncapped jar was then placed in a 500 mL Parr bomb and pressurized to 300 psi of hydrogen. The mixture was stirred overnight at 25 °C. The reaction jar was recovered, and the solution was filtered through Celite to obtain a clear solution which was directly used in the synthesis of PPN-6-FNB. Aliquots of the reaction solution were prepared for NMR by carefully concentrating the ethanolic solution by blowing nitrogen gas onto the solution. Owing to the volatility of the product, an isolated yield was not obtained.1H NMR (CD3OD, 25 °C, 500 MHz) : 5 = 2.94 (t,18.8 Hz, 2H) .19F NMR(CD3OD, 25 °C, 500 MHz) : 5 = -87.33 (s, 3F) , -119.02 (t, JFH= 18.8 Hz, 2F) .

[0077] Synthesis of 3 , 3 , 4 , 4 , 4 -pentafluorobutyl ammonium chloride

[0078] 3, 3, 4, 4, 4-Pentaf luorobutyl ammonium chloride was prepared following the synthesis of 3, 3, 4, 4, 4-pentaf luorobutyl amine from the synthetic procedure outlined above. To the solution of 3, 3, 4, 4,4- pentaf luorobutyl amine in EtOH was added aqueous HCI (12 M (M = mol / L) , 5 mL) and the mixture was stirred for 15 min to precipitate a white powder. Solvent was removed by vacuum filtration and the powder was washed with chloroform (50 mL) and dried on the filter to yield 3, 3, 4, 4, 4-pentaf luorobutyl ammonium chloride (4.17 g, 20.8 mmol, 90% yield from azide) . ^H NMR (CD3OD, 25 °C, 500 MHz) : 5 = 3.29 (t, JHH= 7.5 Hz, 2H) , 2.61 (tt, JHH= 7.5 Hz, JHF = 18.1 Hz, 2H) .19F NMR{1H} (CDjOD, 25 °C, 500 MHz) : 5 = -87.28 (s, 3F) , -119.31 (s, 2F) .

[0079] Synthesis of N, N-dimethyl-3 , 3 , 4 , 4 , 4-pentaf luorobutyl amineReflux, 16 h

[0080] 3, 3, 4, 4, 4-Pentaf luorobutyl ammonium chloride (4.17 g,20.8 mmol) was added to a 100 mL round bottom flask containing formic acid (15.0 mL) . Formaldehyde (33%, 20.0 mL) was added dropwise, and the mixture was refluxed for 16 h. Concentrated aqueous NaOH was then added dropwise to the mixture until a pH of 14 was reached. The mixture was extracted with Et3O (4 x 100 mL) , and the organic phase was dried over sodium sulfate. Aqueous HCI (12 M, 5 mL) was added to this solution, and solvent was removed in vacuo. The white precipitate was redissolved in H3O (5 mL) , and concentrated NaOH was added (5 mL) . The bottom layer was isolated and dried over sodium sulfate to yield N, N-dimethyl-3 , 3, 4, 4, 4- pentaf luorobutyl amine as a colorless oil (1.50 g, 7.85 mmol, 38%yield from ammonium chloride) . NMR (CD3OD, 25 °C, 500 MHz) : 5 =2.63 (m, 2H) , 2.34 (tt, JHH= 8.4 Hz, JHF= 18.4 Hz, 2H) , 2.29 (s, 6H) .19F NMR (CD3OD, 25 °C, 500 MHz) : 5 = -87.20 (s, 3F) , -119.14 (t,JFH= 18.4 Hz, 2F) .

[0081] Synthesis of PPN-6

[0082] PPN-6 was synthesized according to a previously procedure. NiBr? (1.25 g, 5.72 mmol) and 2 , 2 ' -bipyridine (1.78 g, 11.4 mmol) were added to an oven-dried 250 ml 3-neck round bottom flask equipped with a Claisen adapter. The flask was equipped with a solid addition funnel loaded with tetrakis ( 4-bromophenyl) methane (0.750 g, 1.18 mmol) , and another solid addition funnel loaded with freshly activated zinc dust (0.466 g, 7.14 mmol) . The flask was evacuated, and subsequently filled with Ar. Anhydrous DMF (60 mL) was then added by syringe, followed by 1 , 5-cyclooctadiene (2.13 mL,17.4 mmol) . The mixture was then heated to 80 °C and stirred for 1 h under Ar, yielding a green solution. The zinc dust was then added to the mixture with stirring. After 5 min, the solution had changed color from green to purple, and the tetrakis (4-bromophenyl) methane was added slowly to the reaction. The mixture was stirred for 16 h at 80 °C under flowing Ar. The mixture was then cooled to room temperature and exposed to air. In air, aqueous HC1 (6 M, 70 mL) was added slowly to the reaction. The mixture was stirred open to air at room temperature for 16 h, and was then filtered and washed with DMF, methanol, chloroform, dichloromethane and THF (150 mL each, in sequence) . Drying the residue at 180 °C under vacuum gave PPN-6 as a white solid (0.369 g, 99% yield based on theoretical structure) . Elemental analysis: % calc. C 94.9, H 5.1; % found C 94.3, H 5.6.

[0083] Synthesis of PPN-6-CH2Cl

[0084] PPN-6-CH2CI was synthesized according to a previous procedure with slight modifications. PPN-6 (0.300 g) , paraformaldehyde (1.50 g) , glacial acetic acid (9.0 mL) , phosphoric acid (4.5 mL) , and hydrochloric acid (30 mL, 12 M) were added to a 150 mL pressure vessel and stirred for 3 d at 90 °C. The mixture was filtered, and the collected solid was washed with methanol (1 L) before being dried under vacuum at 110 °C to yield PPN-6-CH2CI as a tan powder (0.360 g) . Elemental analysis: % calc. C 78.1, H 4.8, Cl 17.1; % found C 75.0, H 4.7, Cl unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation.

[0085] Synthesis of PPN-6-QA

[0086] PPN-6-QA was synthesized according to a previous procedure with slight modifications. PPN-6-CH2CI (0.500 g) and trimethylamine (33% in ethanol, 8.6 mL, 36 mmol) were added to a 350 mL pressure vessel along with absolute ethanol (100 mL) . The mixture was stirred for 3 d at 72 °C before filtering and washing with first water (500 mL) and then methanol (500 mL) . The solid was then dried at 110 °C under vacuum to yield PPN-6-QA as a tan powder (0.588 g) .Elemental analysis: % calc. C 74.6, H 6.8, N 5.3, Cl 13.3; % found C69.2, H 7.4, N 4.4, Cl unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation .

[0087] Synthesis of PPN-6-NDMB

[0088] PPN-6-NDMB was synthesized according to a previously reported procedure. PPN-6-CH2Cl (0.327 g) , N, N-dimethylbutylamine (6.20 g, 8.60 mL, 61.3 mmol) , and EtOH (70 ml) were combined in a 150 mL pressure vessel. The mixture was stirred at 90 °C for 3 d before being filtered and washed with MeOH (1 L) . The solid was dried at 110 °C under vacuum to give PPN-6-NDMB as a tan powder (0.380 g) . Elemental analysis: % calc. C 76.1, H 7.9, N 4.5, Cl 11.5; % found C 70.5, H 8.7, N 3.8, Cl unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation.

[0089] Synthesis of PPN-6-NB

[0090] PPN-6-CH2Cl (0.150 g) and n-butylamine (30 mL, 304 mmol) were combined in a 75 mL pressure vessel and stirred for 3 d at 70 °C. The mixture was then filtered and washed with MeOH (750 mL) . The solid was dried at 110 °C under vacuum to give PPN-6-NB as a tan powder (0.167 g) . Elemental analysis: % calc. C 75.7, H 6.5, N 5.0Cl 12.8; % found C 82.2, H 7.8, N 5.1, Cl unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation.

[0091] Synthesis of PPN-6-FNB

[0092] 3, 3, 4, 4, 4-Pentaf luorobutyl azide (3.54 g, 18.7 mmol) was converted into a solution of 3, 3, 4, 4, 4-pentaf luorobutyl amine in EtOH as described above. This solution was placed in a 75 mL pressure vessel along with PPN-6-CH2Cl (0.100 g) , and the mixture was stirred for 3 d at 45 °C before being filtered and washed with MeOH (500 mL) . Drying the residue at 110 °C under vacuum gave PPN-6- FNB as a tan powder (0.143 g) . Elemental analysis: % calc. C 56.8, H 4.1, N 3.8, Cl 9.6, F 25.7; % found C 65.1, H 4.4, N 3.5, Cl unmeasured, F unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation .

[0093] Synthesis of PPN-6-FNDMB

[0094] N, N-dimethyl-3, 3, 4, 4, 4-pentafluorobutyl amine (1.27 g,6.60 mmol) was combined in a 75 mL pressure vessel along with PPN-6-CH2C1 (0.150 g) , and MeOH (20 mL) . The mixture was stirred at 60 °C for 3 days before being filtered and washed with MeOH (750 mL) . The solid was dried at 95 °C under vacuum to give PPN-6-FNDMB as a tan powder (0.163 g) . Elemental analysis: % calc. C 58.9, H 4.8, N 3.5, Cl 8.9, F 23.9; % found C 72.0, H 5.8, N 2.7, Cl unmeasured, F unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation.

[0095] Synthesis of PPN-6-BE

[0096] An oven-dried 25 mL Schlenk flask was loaded with NaH(60% in mineral oil, 1.5 g total, 37.0 mmol) , and the flask was evacuated and subsequently filled with Ar. Anhydrous, degassed n- butanol (15 mL, 162 mmol) was added by syringe dropwise over 5 min, and the mixture was stirred at room temperature for an additional 5 min. PPN-6-CH2CI (0.100 g) was then added, and the mixture was stirred at 90 °C under dynamic Ar for 3 d. The mixture was filtered and the isolated solid was washed with EtOH, H2O, MeOH, and CHCl? (150 L each) . The solid was dried at 110 °C under vacuum to give PPN-6-BE as a tan powder (0.112 g) . Elemental analysis: % calc. C 86.0, H 7.4, 0 6.5; % found C 83.1, H 7.7, 0 unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation.

[0097] Synthesis of PPN-6-FBE

[0098] An oven-dried 25 mL Schlenk flask was loaded with NaH (60% in mineral oil, 1.5 g total, 37.0 mmol) , and the flask was evacuated and subsequently filled with Ar. Anhydrous, degassed n- 3, 3, 4, 4, 4-pentaf luorobutanol (20 mL, 89 mmol) was added dropwise by syringe over 5 min, and the mixture was stirred at room temperature for an additional 5 min. PPN-6-CH2CI (0.100 g) was then added under positive Ar, and the mixture was stirred at 90 °C under dynamic Ar for 3 d. The mixture was filtered and the isolated solid was washed with EtOH, H2O, MeOH, and CHCI3 (150 mL each) . The solid was dried at 110 °C under vacuum to give PPN-6-FBE as a tan powder (0.121 g) . Elemental analysis: % calc. C 62.9, H 3.9, 0 4.8, F 28.4; % found C 65.4, H 4.2, 0 unmeasured, F unmeasured. Note that the expected elemental analysis results are for the case of having one functionality per biphenyl linker. The discrepancy between the expected and measured elemental analysis results can be attributed to the amorphous nature of the PPN and the variability in the extent of functional group incorporation.

[0099] Elemental Analysis. Elemental analysis data (C, H, and N) were obtained from the Microanalytical Facility at the University of California, Berkeley using a Perkin Elmer 2400 Series II CHNS elemental analyzer.

[0100] Table 8. Binding group loadings on the functionalized PPNs calculated from elemental analysis or quantitative solid-state NMR.a Functional group loading calculated using carbon elemental analysis. b Functional group loading calculated using nitrogen elemental analysis. c Functional group loading calculated using quantitative 'll solid-state NMR. d Functional group loading calculated using quantitative19F solid-state NMR.

[0101] Fourier-Transform Infrared (FTIR) Spectroscopy. Infrared spectra were collected at ambient conditions on a PerkinElmer Spectrum 100 Optica FTIR spectrometer equipped with an attenuated total reflectance accessory.

[0102] Nuclear Magnetic Resonance (NMR) Spectroscopy.

[0103] Solution-state: Proton and19F NMR spectra were collected at Bo = 11.75 T (500 MHz for1H) in the NMR Core facility of the Pines Magnetic Resonance Center at UC Berkeley using a Bruker BioSpin spectrometer equipped with an Avance IV NEO console. Samples temperature was regulated at 298 K unless otherwise noted. Proton NMR chemical shift was referenced to residual solvent peaks for deuterated solvents: CDCI3 (7.26 ppm,XH) and CD3OD (3.31 ppm,1H) , while19F NMR chemical shifts were automatically referenced based on theXH shift of the deuterated solvents used and scaled by the difference of the gyromagnetic ratio ofXH and19F.

[0104] Solid-state: Proton and19F NMR spectra were collected atBo = 9.4 T (400 MHz forXH) in the NMR Core facility of the Pines Magnetic Resonance Center at UC Berkeley using a Bruker BioSpin spectrometer, equipped with an Avance IV NEO console and a 1.3 mm double resonance HX magic angle spinning (MAS) probes tuned toXH (400.1 MHz) or19F (376.5 MHz) . Samples were loaded in 1.3 mm zirconia rotors, closed using Vespel® caps, and spun at the magic angle at vR= 50, 55, or 60 kHz using dry nitrogen. Solid-state NMR (ssNMR)XH and19F chemical shift were externally referenced using adamantane 5iSO(1H) = 1.85 ppm and LiF 5iSO(X9F) = -204 ppm.

[0105] QuantitativeXH or19F spin-echo spectra were obtained using a rotor synchronized spin-echo sequence(90° - T?- 180° - TR- AQ, with iR= 1 rotor period) using 90° radiofrequency (RF) pulse of 1.4 or 1.35 s . A total of 16 or 64 transients were average using a repetition time of 5 s which was long enough to reach full relaxation of allor19F signals in all samples, respectively.

[0106] Functional group loading of fluorinated PPNs was determined and using an external reference of CaF2by integrating the relevant13F signals, scaled by the compounds molecular weight. Functional group loading of PPN-6-BE was determined by comparing the integrated intensity of the functional group protons to the one obtained for the benzylic protons.

[0107] All solid-state NMR spectra were processed using Topspin 4.3 while fitting and analysis was performed using the DMfit software .

[0108] Scanning Electron Microscopy (SEM) . Particles of PPN samples were imaged via field emission scanning electron microscopy (FESEM) . A Hitachi S-5000 SEM was used in the Electron Microscope Laboratory at the University of California, Berkeley. Samples were prepared by first dispersing the PPNs in methanol by stirring sonicating for ~30 min. The dispersed PPN solutions were then drop casted onto silicon chips. The samples were sputter-coated with gold via a Tousimis sputter coater before imaging to dissipate charge.

[0109] Water Quality Analysis. Dissolved organic carbon (DOC) concentration of the groundwater and wastewater effluent samples were analyzed using a carbon analyzer (Shimazu ion TOC-L, Columbia, MD) . Anions were analyzed using ion chromatography (IC; ICS-900, Dionex, Sunnyvale, CA) and cations / metals were measured with inductively coupled plasma optical emission spectroscopy (ICPOES; optima 5300 DV, PerkinElmer, Fremont, CA) .

[0110] PFAS Analysis. Samples for PFAS analysis were collected in 15- and 50-mL polypropylene Falcon™ tubes during the experiment. Prior to PFAS analysis, optima® LCMS-grade methanol, ammonium hydroxide, optima® LCMS-grade isopropanol, extra pure 2,2,2- trifluoroethanol (TFE) , and mass labeled internal standards were added to the raw sample. All PFAS analytical standards were obtained from Wellington Laboratories (Guelph, ON, Canada) . PFAS concentrations were quantified using a liquid chromatography quadrupole time-of-f light mass spectrometry SCIEX X500R (LC-QTOF-MS)system (Framingham, MA) employing modified USEPA 537.1 method encompassing all the 1633 method compounds. The QTOF-MS was operated using electrospray ionization (ESI-) in negative mode with SWATH® Data-independent Acquisition for both TOF-MS and MS / MS mode. The target PFAS compounds of EPA 1633 method were quantified using at least 10 data points for each analyte's calibration curve with concentrations ranging from 0.5 ng / L to 10, 000 ng / L and a correlation coefficient (A)2value of > 0.98. After every 10 samples, a laboratory blank as well as a quality control sample (concentration 300 ng / L) were analyzed to ensure the instrument sensitivity.

[0111] Chromatography: Samples were injected onto a SCIEX ExionLC™ high-pressure liquid chromatograph (HPLC) connected to a Gemini C18 analytical column (3 mm * 100 mm x 5 pm; Phenomenex, Torrance, CA) , a SecurityGuard™ C18 guard cartridge (4 mm * 2 mm I.D. ; Phenomenex, Torrance, CA) , and two Zorbax DIOL guard columns (4.6 mm * 12.5 mm * 6 pm; Agilent, Santa Clara, CA) . The temperature in column oven was set to 40 °C. 20 mM ammonium acetate (Fischer Scientific, Waltham, MA) in Optima® LCMS-grade water was employed as the mobile phase (A) while 100% Optima® LCMS-grade methanol was the organic mobile phase (B) . Total eluent flow rate was set to 0.60 mL / min, which was ramped from 90% A to 50% A within the first 0.5 minutes, then reduced to 10% A at 8 minutes and remain steady until 13 minutes, then ramped to 90% A again at 13.5 minutes and remain constant till the end of sample acquisition time (20 minutes) .

[0112] Ma ss Spectrometry: PFAS were analyzed employing a SCIEXX500R Quadrupole Time-of-Flight Mass Spectrometer (QTOF-MS) system (Framingham, MA) using electrospray ionization in negative mode (ESI-) with SWATH® Data-independent Acquisition for both TOF-MS and MS / MS mode. Precursor ion data was collected for m / z 100-1200 for 1283 cycles with a total scan time of 842 ms and accumulation time of 20 ms. Ion spray voltage and temperature were set at - 4500 V and 550 °C, respectively. The ion source, curtain, and collision (CAD) gas were set to 60 psi, 35 psi, and 10 psi, respectively. The collision energy was set to -5 V with spread of 0 V and the declustering potential to -20 V with spread of 0 V. Product ion (MS / MS) scanning was conducted for m / z 50-1200 Da. The accumulationtime for each SWATH window was 50 ms and collision energy was -35 V with 30 V spread. The instrument performed autocalibration with every 5 injections using SCIEX ESI Negative calibrant solution.

[0113] PFAS Batch Adsorption Experiments. In PFAS batch equilibrium adsorption experiments, a known mass of either PPN or commercial adsorbent was added to a known volume of PFAS-containing water. Adsorbents were suspended in solution via sonication to create a homogeneous suspension. The mixtures were then shaken at room temperature for 8 h at 150 rpm, and then centrifuged. The supernatant was analyzed for PFAS removal by these adsorbents. All the batch and control experiments were conducted in duplicates. Solute adsorption capacities (Qe, mg / g or mmol / g) were calculated using the equation:where Co and Ceare the initial and equilibrium solute concentrations (mg / L) , respectively, V is the solution volume (L) , and m is the dry adsorbent mass (g) . Control experiments were also conducted to measure any potential solute concentration changes in solution arising from the solutes sticking to plastic throughout the experiment or during the analyses. The solution used for determining C) in each adsorption experiment was prepared in the same way as the test samples, except that no adsorbent was added to the solution. The concentrations measured in these control experiments were taken as the Co values.

[0114] Single-solute PFAS adsorption experiments were conducted by adding a fixed mass of the investigated PPN or commercial adsorbent (5 ± 0.2 mg) to a known volume (30 mL) of a solution containing a single PFAS (PFOA, PFOS, PFPeA, or PFBS) in deionized water at a concentration of approximately 1 mmol / L.

[0115] Multi-solute PFAS adsorption experiments were conducted in a similar manner by adding a fixed mass of the investigated PPN or commercial adsorbent (2.5 ± 0.2 mg) to 50 mL of PFAS-spiked deionized water or wastewater at a concentration of 250 nmol / L of each individual PFAS (PFOA, PFPeA, PFOS, and PFBS) .

[0116] For comparing the performance of the investigated adsorbents for the removal of a wide range of PFAS from an AFFF-impacted groundwater, (PFAS concentrations and other water qualities summarized in Tables 6 and 7) , 3.0 ± 0.2 mg of each adsorbent was added to 150 mL of the AFFF-impacted groundwater.

[0117] Table 9. Single-solute PFAS adsorption capacities and efficiencies in deionized water.

[0118] Table 10. Multi-solute PFAS adsorption in deionized water (top) , wastewater (middle) , and simulated wastewater (bottom) for each adsorbent.

[0119] PFAS Adsorption Kinetics. The PFAS adsorption kinetics were evaluated for both deionized and wastewater spiked with a mixture of PFAS (PFOA, PFOS, PFPeA, and PFBS) at an initial individual PFAS concentration of 250 nmol / L. In these experiments, 5.0 ± 0.2 mg of each adsorbent was first dispersed in either deionized water or wastewater by sonication until a homogeneous suspension was achieved. While stirring at -1, 000 rpm under ambient conditions, PFAS-containing stock solution in deionized water or wastewater was added quickly such that the total volume was 50 ml, and the individual PFAS concentrations were 250 nmol / L each. While stirring at -1, 000 rpm under ambient conditions, 1.0 mL aliquots of the solution were collected at fixed time intervals and immediately filtered through a 0.45-]jm polyethersulf one syringe filter before analysis .

[0120] When investigating the effect of particle size on adsorption kinetics, commercial adsorbents were ball-milled in 25 mL steel jars with three 12 mm steel balls for 30 min at 30 Hz. The above adsorption kinetics experimental procedure was then followed with these materials.

[0121] Adsorbent Cycling Experiments. Adsorbent cycling experiments were conducted for PPN-6-FNDMB over three or four adsorption-desorption cycles. Cycling experiments were conducted in either PFOA-spiked deionized water or AFFF-impacted groundwater. For the deionized water experiments, PPN-6-FNDMB was added to the PFOA- spiked deionized water at an adsorbent mass to volume ratio of 0.25 g / L and an initial PFOA concentration of 1.0 mN. The samples were shaken at room temperature at 150 rpm for 8 h. The samples were then centrifuged, and the supernatant was analyzed by LCMS-MS for quantification of the residual PFAS. For the groundwater experiments, PPN-6-FNDMB was added to groundwater samples at an adsorbent mass to volume ratio of 0.08 g / L. The samples were then shaken and filtered similarly to in the deionized water experiments. The lower adsorbent mass to volume ratio used for the groundwater experiments was to ensure that residual PFAS would be detectable in the centrifuged supernatant for analysis. The adsorbed PFAS was then desorbed from PPN-6-FNDMB using a 1: 1 mixture of methanol and 1.0 M aqueous sodium hydroxide at an adsorbent mass to regeneration solution volume ratio of 3:1 or 1:5 g / L. The mixture was shaken at 150 rpm for 8 h and the PPN-6-FNDMB was recovered by centrifugation. The PFAS concentration in the supernatant from the deionized water experiment was measured to quantify the extent of PFOA desorption from PPN-6-FNDMB. However, due to the limited volume and high salinity of the desorption supernatant, combined with low PFAS levels limiting the ability to dilute the samples, the desorbed PFAS concentrations from the groundwater experiments were not measured. The recovered PPN-6-FNDMB was then resuspended in 1 mN aqueous HC1 before being filtered and washed with H2O and MeOH (300 mL each) . The PPN-6-FNDMB was then dried at 110 °C overnight before being reweighed and used in the next adsorption cycle.

[0122] DFT Calculations. First-principles DFT calculations were performed using Gaussian 16 package. All structures were fully optimized at the B3LYP level of theory, utilizing the 6-311+G(d,p) basis set, and the polarized continuum model (PCM) was applied to simulate the water-solvated state. The DFT-calculated adsorption energy Eads) of PFPeA on a PPN-6 derivative, namely PPN-6-FBE, -QA, -NDMB, -FNDMB, or -FNB, was obtained by the following definition:Eads Ecompiex(EpPN-6 derivative+ EPFPeA) (2)Here, Ecompiexdepicts the DFT-calculated energy of PFPeA adsorbed on the geometrically optimized PPN-6 derivative, while EPPN-6derivative and EpppeA represent the DFT-calculated energies of the PPN-6 derivative and PFPeA, respectively. Notably, PFPeA was modeled in a deprotonated state to reflect experimental environments. The deprotonation of PFPeA in aqueous solution phase was confirmed by calculating acid dissociation constant pKaby following equation.Here, AGsoinrepresents the change in the Gibbs free energy associated with the deprotonation of PFPeA in the solution phase. The hydrogen bonding strengths of two pairs, namely C-H (PPN-6- FNDMB) • • ■ 0 (PFPeA) and N-H (PPN-6-FNB) ■ • • 0 (PFPeA) , were further examined through the natural bond orbital (NBO) analysis with the aim of understanding the second-order perturbation energy(stabilization energy Ek ) related to i-to-j delocalization described in the following equation:Here, q, represents the donor orbital occupancy, Fjj is the off- diagonal element of the NBO Fock matrix, and £j(L) and SjQNE) are the energies of the Lewis and non-Lewis orbitals, respectively. The electrostatic potential (ESP) surfaces of computational models were visualized to understand the electronic distributions.

[0123] Molecular Dynamics Simulations. Simulation models ofPPN-6 and its derivative, PPN-6-FNDMB, were constructed to explore the permeation behaviors of PFAS molecules through the frameworks. A diamond-like bulk model was introduced to design the PPN-6 framework through the insertion of biphenyl unit between every C-C bond. Subsequently, the PPN-6-FNDMB framework was designed through the additional modification of PPN-6 via the integration of a FNDMB moiety onto each biphenyl unit, replacing a hydrogen atom on the ortho position of each biphenyl group with FNDMB functional group. The designed models were geometrically optimized using Materials Studio. The physical properties of the constructed PPN-6 model wereconfirmed by assessing its surface area and pore volume against their reference values, exhibiting the reliable representation of the simulation model with a close correspondence with errors of only 4% and 6%, respectively. For the constructed models, classical molecular dynamics (MD) simulations were conducted using the large- scale atomic / molecular massively parallel simulator in conjunction with the DREIDING force field. The total potential energy (Etotai') of each model was determined using the following equation:Etotai Evdw + EQ + Ebond+ Eangie+ Etorsion(5)In the equation, fij^j^and EQ represent the non-bonded van der Waals and electrostatic interaction energies, respectively. Bonded interaction energies, such as bond stretching (Eboncl') , angle bending Wangle} , and torsional (Etorsion) energies, were also included in the equation to update the time-evolved molecular behaviors . The electrostatic component within the simulation domain was handled using the particle-particle particle-mesh solver. Notably, charges of all the atoms in the simulation models were refined via density functional theory calculations, implemented in the Gaussian 16 package with the B3LYP functional and 6-311+G(d,p) basis set, to mirror the molecular electrostatic potentials. These models were first equilibrated through a sequential introduction of NVT (298 K) and NPT (298 K and 1 atm) ensembles, each for a duration of 2 ns, utilizing Nose-Hoover thermostat and barostat to calibrate temperature and pressure, respectively. The steered MD simulations were further employed to predict the changes in the free energy (i.e. , potential of mean force) for PFAS molecules, namely PFOS, PFBS, PFOA, and PFPeA, passing through the designed frameworks of PPN-6 and PPN-6-FNDMB, with the aim of elucidating the energetic preferences for molecular pathways. These simulations were conducted through applying an additional force to PFAS molecules in a positive x direction under the conditions of a spring constant of 1000 kcal / mol / A2and a pulling speed of 2xl0~5A / fs for a period of 2 ns.

[0124] Synthesis and Structural Characterization of Functionalized PPN-6. The parent PPN-6 framework, having tetrahedral carbon nodes bridged by biphenyl linkers, was synthesized via the Yamamoto coupling of a tetrakis (4-bromophenyl) methane monomer. Afteraromatic chloromethylation of the biphenyl units, PPN-6-QA, -NDMB, - NB, -FNB, and -FNDMB were isolated via nucleophilic substitution with the corresponding amine (Figure 1) . Two other materials, PPN-6- BE and -FBE were prepared through a Williamson ether synthesis between the chloromethylated PPN-6 and the corresponding alcohol.

[0125] The successful incorporation of these functional groups was confirmed qualitatively by Fourier-trans f orm infrared (FTIR) spectroscopy. The spectra of PPN-6-QA, -NDMB, -NB, -FNB, and -FNDMB showed new absorption bands in the region of 1580-1700 cnr1, corresponding to the C-N stretches, while the spectra of PPN-6-BE and -FBE gained signals associated with C-0 stretching at approximately 1100 cm-1(Figure 8A-B) . Meanwhile, the prominent signal at 1200 cm-1observed for PPN-6-FNB, -FNDMB, and -FBE is characteristic of the similar C-F stretches found in each of these fluorinated adsorbents.

[0126] The extent of functional group incorporation into the PPN was determined to be 3.1, 3.6, 2.7, 2.5, and 1.9 mmol / g for PPN-6- QA, -NB, -NDMB, -FNB, and -FNDMB, respectively, based on nitrogen content from CHN elemental analysis (Figure 1 and Table S8) . The functional group loadings in PPN-6-BE and -FBE were approximately 4.1 and 0.6 mmol / g, respectively, as determined by quantitative2H and19F solid-state NMR spectroscopy. The NMR spectra of PPN-6-FBE also revealed that during the Williamson ether synthesis, one methylene fluorine atom was partially exchanged for a hydrogen atom(Figure 1) .

[0127] The permanent microporosity of the PPNs was confirmed by N2adsorption isotherms collected at 77 K. The Brunauer-Emmett- Teller (BET) surface area of PPN-6 was 4780 m2 / g, and that of the functionalized PPNs ranged from 2110-690 m2 / g, depending on functional group identity and extent of incorporation (Figures 1 and 9) . The decrease in surface area upon functionalization of the PPN is similarly described in previous reports and is due to the partial occupation of the pores by the functional groups and their additional mass. The low surface areas of PPN-6-BE and -FBE compared to the other PPNs could potentially be due to residual synthesis byproducts not being removed during adsorbent washing and activation. Nonetheless, the relatively high surface area of the functionalizedPPNs suggests the high accessibility of the functional groups within the materials.

[0128] Gravimetric PFAS Adsorption Capacities. Adsorption capacities of the synthesized materials were evaluated using singlesolute adsorption experiments conducted in deionized water with high initial PFAS concentrations (~1 mmol / L) and long equilibration times (8 h) to ensure adsorbent saturation. Specifically, per f luorooctanoic acid (PFOA) , perfluoropentanoic acid (PFPeA) , perfluorooctane sulfonic acid (PFOS) , and perfluorobutane sulfonic acid (PFBS) were chosen as representative long- and short-chain perfluorinated carboxylic and sulfonic acids, respectively. The concentration of the PFAS were measured by liquid chromatography quadrupole time-of-f light mass spectrometry. Figure 2A and Table 9 provide the gravimetric equilibrium PFAS adsorption capacities of the adsorbents in terms of mmol PFAS / g adsorbent. Commercially available samples of F400 granular activated carbon (GAC) , FS200 surface-modified clay (SMC) , and CalRes2301 anion exchange resin (AER) were also tested for comparison (see Tables 3-5 for commercial adsorbent properties) .

[0129] Unfunctionalized PPN-6 displayed low adsorption capacities (<1.0 mmol / g) for all tested PFAS, suggesting only weak interactions between PFAS and the PPN backbone. The PPNs possessing positively charged functional groups (e.gr., PPN-6-QA, -NB, -NDMB, - FNB, and -FNDMB) exhibited high adsorption capacities for both long- chain (up to 4.0 mmol / g for PFOA and PFOS) and short-chain PFAS (up to 2.3 mmol / g for PFPeA and 3.5 mmol / g for PFBS) . Meanwhile, the PPNs employing only hydrophobic or fluorophilic interactions (PPN-6- BE and -FBE) exhibited low adsorption capacities for both shortchain (<0.25 mmol / g for PFPeA and PFBS) and long-chain PFAS (~1.0 mmol / g for PFOA, and up to 2.5 mmol / g for PFOS) . Compared to commercial adsorbents, the positively charged PPNs exhibited an order of magnitude higher capacity than GAC and SMC for all tested PFAS, and up to 3.5 times the capacity of AER (Figure 2A) .

[0130] PFAS Binding Efficiency. The adsorption efficiency (i.e., the adsorption capacity normalized by functional group loading) can be used to evaluate the performance of different functional groups within the PPNs more accurately. The adsorption efficiency of thePPNs for long-chain (average of PFOA and PFOS capacities) and shortchain (average of PFPeA and PFBS capacities) PFAS is shown in Figure 2B, with individual PFAS data in Table 9. From these data, several preliminary assessments on PFAS binding interactions can be made:(1) Electrostatic interactions - Although the neutral PPN-6-BE and -FBE do bind long-chain PFAS, their short-chain PFAS adsorption efficiency is significantly lower than that of the cationic PPNs (PPN-6-QA, -NB, -FNB, -NDMB, and -FNDMB) . Unlike long-chain PFAS, short-chain PFAS lack large non-polar regions that can participate in van der Waals interactions with adsorbents. Electrostatic interactions are thus vital for the adsorption of short-chain PFAS.(2) Hydrophobic interactions - The adsorption efficiency of PPN-6- BE suggests that hydrophobic interactions alone are not sufficient for the adsorption of short-chain PFAS, but do enable the uptake of long-chain PFAS. However, the effect of complimentary hydrophobic interactions on the long-chain PFAS adsorption efficiencies of the cationic PPNs is ambiguous, with PPN-6-QA having a higher efficiency than PPN-6-NB and -FNB but a lower efficiency than PPN-6-NDMB and - FNDMB. Given that this experiment is conducted in deionized water and that the PFAS do not have to compete with other non-target solutes for adsorbent binding sites, the advantages of combined electrostatic and hydrophobic interactions are likely suppressed.(3) Hydrogen-bonding interactions - While PPN-6-QA, -BE, -FBE, - NDMB, and -FNDMB display much greater binding efficiencies for long- chain PFAS compared to short-chain PFAS, PPN-6-NB and -FNB adsorb almost equivalent amounts of each. This suggests that hydrogenbonding interactions play a more important role in the uptake of short-chain PFAS than for long-chain PFAS. Unlike long-chain PFAS that can engage in significant van der Waals interactions with binding groups via their tail, short-chain PFAS adsorption is more reliant on binding interactions with their polar head group.(4) Fluorophilic interactions - Fluorinating the PPNs generally leads to increased PFAS adsorption efficiency. Compared to their non-f luorinated counterparts, PPN-6-FBE and -FNDMB adsorb significantly more long- and short-chain PFAS per functional group. While the difference in binding efficiency between PPN-6-NB and -FNBis les s clear , the overall results suggest that fluorophilic interactions are more favorable than hydrophobic interactions alone .

[0131] Besides the abovementioned binding interactions , another pos sible factor driving PFAS uptake is the aggregation of PFAS within the pores of the PPNs . Indeed, PPN- 6-QA, -FBE , -NDMB, and - FNDMB have long-chain PFAS adsorption efficiencies >1 . This aggregation is expected to be more prominent for long-chain PFAS due to their low critical micelle concentrations . Lower functional group loadings could also allow for increased PFAS aggregation due to reduced steric constraints . This could potentially explain the exceptionally high long-chain adsorption efficiency of PPN- 6-FBE .

[0132] Calculated PFPeA Adsorption Energies . To more quantitatively elucidate the relative importance of di fferent binding interactions on PFAS adsorption, dens ity functional theory calculations were performed . Select PPNs were represented as a single functionalized biphenyl unit, and a molecule of PFPeA was used in these calculations because it had proven the most di fficult to adsorb in the single-solute experiments .

[0133] The calculated adsorption energies support the experimentally determined importance of electrostatic interactions in short-chain PFAS binding (Figure 3 ) . The presence of a cationic ammonium moiety causes the binding energy to at least quadruple in magnitude compared to that of the neutral PPN- 6-FBE model . Further supporting the results of the previous section, hydrophobic interactions lead to minimal increases in PFAS binding in this ideali zed scenario . Compared to the PPN- 6-QA model , the PPN- 6-NDMB model has j ust a ~1 kJ / mol greater in magnitude PFPeA binding energy . Meanwhile , the introduction of fluorophilic interactions leads to a ~4 kJ / mol more energetically favorable binding of PFPeA, when comparing the PPN- 6-FNDM and -NDMB models .

[0134] The computational data also corroborates the importance of hydrogen-bonding interactions on short-chain PFAS binding . Compared to the PPN- 6-FNDMB model , the PPN- 6-FNB model has an adsorption energy ~23 kJ / mol greater in magnitude . The secondary ammonium of the FNB binding group is not only capable of engaging in stabili zing hydrogen-bonding interactions , but the smaller stericprofile also allows the PFPeA carboxylate to get approximately 0.6 A closer to the nitrogen atom of the ammonium cation.

[0135] PFAS Binding Selectivity Over Competing Solutes. Often, PFAS-impacted waters contain complex mixtures of long- and shortchain PFAS at concentrations that are orders of magnitude lower than the 1 mmol / L used for the determination of maximum adsorption capacities and efficiencies. Moreover, it is well reported that long- and short-chain PFAS often compete for adsorbent binding sites, with the long-chain molecules being adsorbed. Typical water samples also contain other inorganic and organic solutes at concentrations much higher than that of the targeted PFAS. By testing the adsorbents in deionized water and wastewater (water composition shown in Table 6) spiked with 250 nmol / L each of PFOA, PFOS, PFPeA, and PFBS, the binding selectivity between different PFAS and for PFAS over competing solutes was evaluated (Figure 4) .

[0136] In deionized water (Figure 4) , the PPNs containing cationic ammonium moieties (PPN-6-QA, -NB, -FNB, -NDMB, and -FNDMB) exhibited excellent removal of both the long- and short-chain PFAS (<10% less short-chain PFAS removed than long-chain PFAS) .Meanwhile, the uncharged PPN-6-BE and -FBE removed 74% and 65% less short-chain PFAS than long-chain, respectively. Under these dilute conditions in the absence of competing ions, the commercial SMC, GAC, and AER removed 27%, 44%, and 17% less short-chain PFAS than long-chain, respectively. With respect to total PFAS removal from deionized water, PPN-6-QA, -NB, -FNB, -NDMB, and -FNDMB outperformed both the neutral PPN-6-BE and -FBE, as well as the tested commercial adsorbents .

[0137] All of the adsorbents tested exhibited a decrease in total gravimetric PFAS adsorption capacity in wastewater (Figure 4) compared to deionized water. In addition to the spiked ~1 pmol / L of PFAS, the wastewater contains over 300 mg / L of inorganic solutes and 4.5 mg / L of dissolved organic matter. The decrease in PFAS adsorption capacity can be attributed to interference from a combination of these inorganic and organic solutes, as determined from experiments conducted in synthetic wastewater containing similar concentrations of inorganic ions, but no dissolved organic carbon. Notably, the majority of this decrease originated from lessuptake of short-chain PFAS, particularly PFPeA. Considering that short-chain PFAS engage in weaker van der Waals interactions than their long-chain analogs, non-target solutes can more readily compete with short-chain PFAS for adsorbent binding sites. Consequently, the relative importance of different PFAS binding interactions in wastewater differs slightly compared to those established in deionized water.

[0138] Limited in deionized water, the short-chain PFAS adsorption capacity of the neutral PPN-6-BE becomes negligible in wastewater. Meanwhile, PPN-6-QA, engaging primarily in electrostatic interactions, retained the ability to bind short-chain PFAS despite exhibiting a 24% decrease in total PFAS adsorption capacity in wastewater compared to deionized water. As for the single-solute experiments in deionized water, electrostatic interactions remain vital to the adsorption of short-chain PFAS in wastewater.

[0139] Unlike PPN-6-QA, PPN-6-NDMB can engage in both electrostatic (with the PFAS head) and hydrophobic (with the PFAS tail) interactions, limiting the capacity drop to only 14% in wastewater. Ambiguous in the single-solute experiments, the benefits of complementary hydrophobic interactions in the cationic PPNs become apparent in these wastewater results. In wastewater, nontarget solutes compete for adsorbent binding sites and leveraging both electrostatic and hydrophobic interactions helps retain PFAS at adsorption sites within the PPN.

[0140] While the total capacity of PPN-6-FNDMB and -FBE decreased by 9% and 21%, respectively, that of their non-f luorinated analogs, PPN-6-NDMB and -BE, decreased by 14% and 32% in wastewater. Like the single-solute experiments in deionized water, the results of the multi-solute wastewater experiments indicate that in both neutral and cationic PPNs, fluorophilic interactions lead to stronger PFAS binding compared to hydrophobic interactions.

[0141] The positive effect of hydrogen-bonding on PFAS binding selectivity is realized by comparing PPN-6-NB, which contains a secondary ammonium, and PPN-6-NDMB, which contains a quaternary ammonium. Relative to in deionized water, the capacities of PPN-6-NB and -NDMB decrease by 10% and 14%, respectively, in wastewater. As noted in the single-solute deionized water experiments, hydrogen-bonding interactions can play a role in short-chain PFAS adsorption due to their limited ability to participate in binding interactions via their tail.

[0142] Given these established trends in binding interactions, it was hypothesized that PPN-6-FNB, which can engage in electrostatic, hydrophobic, hydrogen-bonding, and fluorophilic interactions, would have the highest retained PFAS capacity in wastewater. In reality, the adsorption capacity of PPN-6-FNB decreased by 33% — the largest decrease of all the PPNs. While the secondary ammoniums in PPN-6-NB and -FNB allow them to engage in hydrogen-bonding, it also makes them susceptible to deprotonation and loss of electrostatic interactions. The simulated pA% of a molecular analog of PPN-6-NB is 9.85, but the same molecular analog of PPN-6-FNB has a p i of only 8.16 due to the electron withdrawing nature of the fluoroalkyl chain. The low short-chain PFAS adsorption capacity of PPN-6-FNB in wastewater is thus likely due to the partial deprotonation of the adsorbent. Further evidence supporting this is that the adsorption capacity of PPN-6-FNB increases in wastewater adjusted to pH 4 (Figure 4) .

[0143] When changing from deionized water to wastewater, PPN-6- NB, -NDMB, and -FNDMB significantly outperformed commercial GAC, SMC, and AER, which exhibited decreases in total PFAS adsorption capacity of 55%, 37%, and 24%, respectively (Figure 4) . The combination of binding interactions present in the PPNs, along with their high density of functional groups, are likely responsible for their improved performance over commercial adsorbents.

[0144] PFAS Removal from AFFF- Impacted Groundwater. Aqueous film-forming foam (AFFF) is a proprietary mixture of PFAS and hydrocarbon surfactants used as fire extinguishers at airports, fire stations, refineries, military sites, and other facilities across the globe. The widespread use of AFFF during emergencies and firefighting training activities has led to significant PFAS contamination of groundwater and surface water near these sites. As a more practically relevant test of adsorbent performance, the PPN and commercial adsorbents were dispersed into an unmodified sample of AFFF-impacted groundwater collected from a US Air Force base.

[0145] The detected PFAS and their concentrations in the AFFF- impacted groundwater are summarized in Table 7. In this sample, 21 anionic PFAS were identified with a total PFAS concentration of over 78, 000 ppt. These PFAS can be categorized as perfluorosulfonic acids, perfluorocarboxylic acids, perfluorosulfonamides, f luorotelomers , and cyclic PFAS (Figure 5) . Although many of these PFAS are currently unregulated by environmental protection agencies, they are contaminants of emerging concern that demonstrate high bioaccumulation potentials .

[0146] A high water volume to adsorbent mass ratio (50 L / g) was used in these experiments to afford quantifiable PFAS concentrations in the water samples post-adsorption. As such, insight into the adsorbent selectivity towards different PFAS molecules could be elucidated. When a ratio of 15 L / g was used, almost complete removal of all PFAS was observed, highlighting the excellent performance of the PPN adsorbents, but leaving little room for comparison between adsorbents (Figure 10A-B) .

[0147] The re are several PFAS adsorption trends consistent across all the tested adsorbents (Figure 5) :(1) Long-chain PFAS were more effectively removed than their short-chain analogs with the same head group (e.g. , removal of PFOS > PFBS) . When compared to shorter PFAS, longer fluoroalkyl chains are expected to engage in stronger and more numerous van der Waals interactions with adsorbents.(2) Sulfonic acids are removed more effectively than carboxylic acids of equal tail length, with the removal of sulfonamides falling between them (e.g., removal of PFPeS > FPeSA > PFHxA) . Calculated electrostatic potential maps suggest that sulfonic acid head groups are softer and more polarizable than carboxylic acids, meaning they engage more readily in electrostatic interactions with adsorbents.(3) The removal of f luorotelomers , in which two of the tail carbons are not fluorinated, is significantly lower than that of their fully fluorinated analogs (e.g. , removal of 4:2 FTS < PFHxS) . Thus, modulating the polarity of the tail has implications on adsorbability .(4) According to the performance of SMC and GAC, the cyclic PFAS is removed to a slightly lesser degree than its linear counterpart with the same number of carbons (e.g., removal of PFEtCHxS < PFOS) . The larger steric profile and decreased flexibility of the cyclic PFAS likely lead to weaker interactions with adsorbents.

[0148] Together, these trends illustrate some of the nuances of PFAS adsorption and the importance of developing adsorbents capable of removing a broad range of PFAS.

[0149] Although the adsorbents all followed the above-mentioned trends, individual adsorbent performance varied significantly. As expected from the selectivity experiments, PPN-6-FNDMB outperforms PPN-6-NDMB, which outperforms PPN-6-QA in the removal of short-chain PFAS (e.g. , PFBA, PFPeA, FBSA, and 4:2 FTS) . This again demonstrates the importance of combining electrostatic and hydrophobic or fluorophilic interactions and reaffirms that fluorophilic interactions are more advantageous than hydrophobic interactions.

[0150] Notably, while PPN-6-NB outperformed PPN-6-QA in wastewater (Figure 4) , the opposite was true in the AFFF-impacted groundwater. As with PPN-6-FNB in wastewater, the slightly basic nature of the groundwater (pH ~ 8.9) likely led to the partial deprotonation of PPN-6-NB and loss of electrostatic interactions with PFAS molecules. Hydrogen-bonding via the secondary ammonium group in PPN-6-NB and -FNB may lend additional selectivity in neutral or acidic water matrices, but anion exchange interactions via a quaternary ammonium are more reliable when it comes to treating a broader range of PFAS-impacted water samples.

[0151] The PFAS removal from the AFFF-impacted groundwater by commercial adsorbents increased from GAC < SMC < AER, consistent with reported trends suggesting that the AER (CalRes2301) is one of the best commercially available PFAS adsorbents. Remarkably, both PPN-6-NDMB and -FNDMB achieved more complete PFAS removal than AER, especially with respect to short-chain PFAS. The exceptional performance of PPN-6-NDMB and -FNDMB places them among the most effective PFAS adsorbents reported to date.

[0152] Other promising PFAS adsorbents are reported in the literature, but adsorption experiments are often limited to long-chain legacy PFAS (e.g. , PFOA and / or PFOS) removal from simple water matrices (e.g., deionized water) . Future research towards novel adsorbents should emphasize the treatment of real contaminated waters, allowing for more meaningful and relevant conclusions and comparisons to be drawn.

[0153] PFAS Adsorption Kinetics. As the best-performing adsorbent, PPN-6-FNDMB warranted further investigation into its PFAS removal metrics. Adsorption kinetics are among the most important adsorbent properties due to their direct implications on the determination of industrially relevant parameters such as empty bed contact time and adsorbent bed size. Experiments were conducted in deionized water and wastewater spiked with PFOA, PFOS, PFPeA, and PFBS at individual concentrations of 250 nmol / L (Figure 6) .

[0154] Near-complete PFAS removal from deionized water was achieved in under 30 s by PPN-6-FNDMB (Figure 6) . The exceptionally fast adsorption kinetics of PPN-6-FNDMB can be attributed to its high surface area and porosity, and small particle size, facilitating PFAS access to binding sites. Individual PFAS adsorption data (Figure 11) reveals that PPN-6-FNDMB removed each PFAS at the same rapid rate.

[0155] Commercial GAC and SMC did not reach adsorption equilibrium during the 3h testing period (Figure 6A) but displayed an initial rapid uptake of PFAS within the first 3 min of the experiment (Figure 6B) . Similarly, AER removed approximately 60% of PFAS within the first 3 min, but adsorption of the remaining 40% required the full 3h. Unlike for PPN-6-FNDMB, the rate of PFAS adsorption in the commercial adsorbents was dependent on PFAS identity. Adsorption rates followed similar trends as adsorption capacity, with PFOS being removed the quickest, and PFPeA the slowest. Thus, adsorption kinetics are not only dictated by intraparticle diffusion but also binding affinity. The equally rapid adsorption of each PFAS by PPN-6-FNDMB attests to the high binding affinity of the FNDMB functional group for both long- and shortchain PFAS.

[0156] When these kinetics experiments were repeated in wastewater, PPN-6-FNDMB exhibited the expected decrease in PFAS adsorption capacity but still reached equilibrium within 30 s(Figure 6, hollow circles) . Similarly rapid equilibration times (<30 s) were recorded for PPN-6-FNDMB in the presence of 0.8 mN PFOS or PFPeA, confirming that adsorption occurs within the pores of the PPN and not solely on the particle surface (Figure 12) . Rapid kinetics are likewise reported in the literature for PPNs towards their respective target solutes, further highlighting the advantages of this class of material for water purification.

[0157] Adsorbent Recyclability. The regeneration potential of an adsorbent holds significant importance for practical applications, decreasing spent media waste and providing a recyclability advantage over their single-use counterparts. A combination of brine (or caustic brine) and organic cosolvent has been shown to successfully desorb PFAS from adsorbents through disruption of non-covalent interactions. In this work, PFAS were desorbed from PPN-6-FNDMB using a 50 / 50 mixture of methanol and 1 M aqueous NaOH solution. The PPN-6-FNDMB was then reused in additional adsorption experiments.

[0158] To validate the effectiveness of the desorption conditions before more rigorous testing, recycling experiments were first conducted in deionized water spiked with PFOA. After three consecutive adsorption / desorption cycles, the adsorption capacity of PPN-6-FNDMB for PFOA in deionized water decreased by less than 5%. The desorbed PFOA was also quantified, confirming the successful leaching and regeneration of PPN-6-FNDMB.

[0159] Adsorbent cycling experiments were then repeated in AFFF- impacted groundwater to explore the effect of interfering solutes on the PFAS removal performance of recycled PPN-6-FNDMB (Figure 7) . While the removal of long-chain PFAS from the groundwater samples remained relatively constant, the degree of short-chain PFAS removal by PPN-6-FNDMB decreased with each cycle, reaching 45% after 4 cycles. This decline in performance could be attributed to the fouling of PPN-6-FNDMB through either binding site occupation or pore blocking by competing organic or inorganic solutes.

[0160] Decreasing the volume of desorption solution used per gram of PFAS-loaded PPN-6-FNDMB from 5.0 L to 0.3 L led to only ~7% less PFAS being removed from the AFFF-impacted groundwater during the third adsorption cycle. However, by using a minimal amount of desorption solution, the PFAS is isolated in a stream that issigni ficantly more concentrated than the original contaminated source . This PFAS concentration factor is upwards of 50 times for the AFFF-impacted groundwater , based on initial concentrations and as suming complete desorption .

[0161] It will be understood that various modi fications may be made without departing from the spirit and scope of this disclosure . Accordingly, other embodiments are within the scope of the following claims .

Claims

WHAT IS CLAIMED IS:

1. A functionalized porous-aromatic framework (PAF) , -organic polymer (POP) , -organic framework (POF) or -polymer network (PPN) having nodes connected by linkers, wherein the linkers having the general structure of:wherein, R1-R6r1-R3are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR11R12)y— (CR13R14)z- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, 0, SO2, NR1S, and N+R1SR19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substit (uCt1e-dC9) alkyl , an optionally substituted (C1-C8) alkenyl, an optionally substituted (C1-C8) alkynyl, an optionally substituted (C1-C8) heteroalkyl, an optionally substituted (C1-C8) heteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R2-Rsis an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR12R12)y- (CR19R14)z-(CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, 0, S02, NR13, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C88) alkyl, an optionally substituted (C1-C88) alkenyl, an optionally substituted (C1-C88) alkynyl, an optionally substituted (C1-C88) heteroalkyl, an optionally substituted (C1-C8) heteroalkenyl, an optionally substituted (C1-C88) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle.

2. The functionalized RAF, POP, POF or PPN of claim 1, wherein at least one of R1-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:

3. The functionalized RAF, POP, POF, CMP or PPN of claim 1, wherein the linkers have the structure of:wherein, R is selected fromwherein, X is a suitable counter ion and n=0, 1, 2, 3, 4, 5, or 6.A device comprising the functionalized PAF, POP, POF, CMP orPPN of any one of the preceding claims.

5. The device of claim 4, wherein the functionalized PAF, POP, POF, CMP or PPN is configured to selectively capture or separate per- and / or polyfluoroalkyl substances (PFAS) .

6. The device of claim 5, wherein the PFAS are long-chain, shortchain, carboxylated, or sulfonated.

7. The device of any one of claims 4 to 6, wherein the functionalized PAF is configured to selectively capture or separate PFAS in a fluid.

8. The device of claim 7, wherein the fluid is selected from groundwater, surface water, freshwater, seawater, wastewater, well water, mining water, or brackish water.

9. The device of any one of claims 4 to 8, wherein the device is a separation or a sensor device that selectively separates, or indicates the capture, of PFAS .

10. The device of any one of claims 4 to 9, wherein the functionalized PAF, POP, POF, CMP or PPN is integrated into membranes, films, resins, electrodes, coatings, pellets, copolymers, porous substrates, or indicators.

11. The device of claim 10, wherein the device comprises an adsorption column and the adsorption column comprises the functionalized PAF, POP, POF, CMP or PPN that has been pelletized.

12. The device of claim 10, wherein the device is a water treatment device wherein the functionalized PAF, POP, POF, CMP or PPN has been incorporated into a treatment membrane or resin.

13. A method for the selective capture or separation of per- and / or polyfluoroalkyl substances (PFAS) comprising: contacting the per- and / or polyfluoroalkyl substances (PFAS) with a porous adsorbent that has been functionalized to comprise one or more nodes connected by linkers having the general structure of:wherein, Rx-R8are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)z-Z- (CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C88) alkyl, an optionally substituted (C1-C88) alkenyl, an optionally substituted (Ci- Ccj) alkynyl, an optionally substituted (C1-C8) heteroalkyl, an optionally substituted (C1-C88) heteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle, wherein at least one of R1-R8is anoptionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)z-Z- (CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9 ) alkyl, an optionally substituted(C1-C9 ) alkenyl an optionally substituted (C2- C9) alkynyl, an optionally substituted (C1-C8) heteroalkyl, an optionally substit (C1-C8 ) heteroalkenyl, an optionally substituted (C1-C8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle.

14. The method of claim 13, wherein the porous adsorbent is a porous polymer network.

15. The method of claim 13 or claim 14, wherein the porous adsorbent is selected from porous organic polymers, porous metal particles, porous metal oxide particles, metal organic frameworks (MOF) , a zeolitic organic frameworks (ZIFs) , covalent organic frameworks (COFs) , and porous aromatic frameworks (PAFs) .

16. The method of claim 15, wherein the porous adsorbent is a RAF.

17. The method of any one of claims 15 to 20, wherein the porous adsorbent is configured to selectively capture or separate PFAS in a fluid .

18. The method of claim 17, wherein the fluid is groundwater, surface water, freshwater, seawater, wastewater, well water, mining water, or brackish water.

19. A composite membrane comprising a polymer / membrane matrix that contains or is embedded with a functionalized porous organic framework (PAF) to form pores, wherein the PAF has nodes connected by linkers having the general structure of:wherein, R1-R8are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR11R12)y- (CR13R14) (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl, an optionally substituted (C1-C8) alkenyl, an optionally substituted (C2- Cg) alkynyl, an optionally substituted (C1-C8) heteroalkyl, an optionally substituted (C1-C8) heteroalkenyl, an optionally substit (uCt1e-dC8 ) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle, wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)x-Z- (CR11R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, O, SO2, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9) alkyl , an optionally substituted (C1-C8) alkenyl, an optionally substituted (C2- Cg) alkynyl, an optionally substituted (C1-C8) heteroalkyl, an optionally substituted (C1-C88) heteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl, an optionally substitutedcycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle.

20. The composite membrane of claim 19, wherein at least one of R1-R3is an FG comprising the structure of:

21. The composite membrane of claim 19, wherein the linkers have the structure of:wherein, R is selected from22. The composite membrane of claim 21, wherein the polymer / membrane matrix is selected from the group consisting of polyolefins; polystyrene; silicones; polyacetylenes; polysulfones;polysulfonamides; polyacetals; polyethers; polyethylenimines ; polycarbonates; cellulosic polymers; polyamides; polyimides; polyetherimides ; polyamide imides; polyketones; polyether ketones; polyarylene oxides; polyurethanes; polyureas; polyazomethines ; polyesters; polysulfides; heterocyclic thermoplastics; polycarbodiimides; polyphosphazines; polyhydrazides; and copolymers thereof, including block copolymers, grafts, and blends thereof.

23. The composite membrane of claim 22, wherein the polymer / membrane matrix is selected from the group consisting of cellulose acetate, polysulfones, perfluoropolymers, polyphenylene oxide, polyamides, polyimides, aryl polyetherimides , polyetherimides , Ultem 1000, ( 4 , 4 ' -hexaf luoroisopropylidene) diphthalic anhydride (6FDA) -based polyimides, 6FDA-DAM, 6FDA-DAT, 6FDA-Durene, 6FDA-DAT : DAT, and Matrimid 5218.

24. A covalent organic framework (COF) functionalized to comprise an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula -( CR9R10)X-Z- ( CR11R12)y- ( CR13R14)z- ( CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, 0, SO2, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substit(Cu1t-eCd9 ) alkyl, an optionally substituted (C1-C9 ) alkenyl, an optionally substit(Cu1t-eCd9 ) alkynyl, an optionally substituted (C1-C8) heteroalkyl, an optionally substituted (C1-C9 ) heteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle.

25. The COF of claim 24, functionalized with:wherein, R1-R8are each independently selected from H, D, an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula: - (CR9R10)X-Z- (CR11R12)y- (CR13R14)2- (CR15R16R17) , wherein x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, 0, SO2, NR18, and N+R18R19; and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C8) alkyl, an optionally substit(Cu1t-eCd9 ) alkenyl an optionally substituted (C1-C8) alkynyl, an optionally substituted (C2-C8) heteroalkyl, an optionally substituted (C1-C8) heteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle; wherein at least one of R1-R8is an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR12R12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR18R19, 0, S02, NR18, and N+R18R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9 ) alkyl, an optionally substit(Cu1t-eCd9 ) alkenyl an optionally substituted (C2-C9) alkynyl, an optionally substituted (C2-C8) heteroalkyl, an optionallysubstituted (C1-C8) heteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle.

26. The functionalized COF or claim 25, wherein at least one of R1-R12is an FG comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the structure of:

27. A composite membrane comprising a polymer / membrane matrix that contains or is embedded with one or more metal organic frameworks(MOFs) , covalent organic frameworks (COFs) , zeolitic imidazolate frameworks (ZIFs) , porous polymer networks (PPNs) , porous aromatic frameworks (PAFs) and / or the like that are functionalized to comprise an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CRnR12)y- (CR13R14)z- (CR15R16R17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, 0, SO2, NR1S, and N+R13R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substituted (C1-C9 ) alkyl, an optionally substituted (C1-C9 ) alkenyl an optionally substituted (C1-C88) alkynyl, an optionally substituted (C1-C8 h ) eteroalkyl, an optionally substituted (C1-C8 h ) eteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl, an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle.

28. The composite membrane of claim 27, comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the following structure is appended to the MOF, COF, ZIF, PPN, or PAF :

29. A porous composite material comprising an optionally substituted alkoxy and optionally substituted quaternary ammonium ions or a group having the general formula - (CR9R10)X-Z- (CR11R12)y- (CR13R14)z- (CR15R1GR17) , where x, y and z are independently selected from 0, 1, 2, 3, 4, 5, or 6; and Z is selected from CR13R19, 0, SO2, NR13, and N+R13R19and wherein R9-R19are independently selected from H, halogen, hydroxyl, optionally substitu(Ct1e-dC9 ) alkyl, an optionally substitu(Ct1e-dC9 ) alkenyl, an optionally substituted (C1-C9 ) alkynyl, an optionally substituted (C1-C8) heteroalkyl, an optionally substituted (C1-C8) heteroalkenyl, an optionally substituted (C1-C8) heteroalkynyl , an optionally substituted cycloalkyl, an optionally substituted aryl, an optionally substituted heterocycle.

30. The porous composite material of claim 29, comprising an ammonium, amine, alkylamine, alkylammonium, ether, or the fluorinated analogs of these groups having the following structure:The porous composite material of claim 29 having a pore diameter of about 0.5-3 nanometers.

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