US 2017.0007871A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2017/0007871 A1 Landers et al. (43) Pub. Date: Jan. 12, 2017

(54) MULTICATALYST POLYELECTROLYTE C08.5/22 (2006.01) MEMBRANES AND MATERALS AND C08, 7/04 (2006.01) METHODS UTILIZING THE SAME A62D 3/38 (2006.01) BOI 3L/06 (2006.01) (71) Applicant: Rutgers, The State University of New BOI 3/10 (2006.01) Jersey, New Brunswick, NJ (US) BOI 3L/38 (2006.01) BOI 3/34 (2006.01) (72) Inventors: John Landers, Riverton, NJ (US); BOI 3L/28 (2006.01) Alexander V. Neimark, Princeton, NJ C08, 7/06 (2006.01) (US); Tewodros Asefa, Princeton, NJ BOI 35/06 (2006.01) (US); Aleksey Vishnyakov, North (52) U.S. Cl. Brunswick, NJ (US), Anandarup CPC. A62D 5/00 (2013.01); C08J 7/06 (2013.01); Goswami Riverton, NJ (US), Jonathan C09D 153/025 (2013.01); C08J 5/2275 Colon Ortiz, Highland Park, NJ (US) (2013.01); C08J 5/2281 (2013.01); C08J 7/045 (2013.01); B01J 35/06 (2013.01); B01.J (21) Appl. No.: 15/154,219 3L/06 38. BOI 3/10 33. BOI. 3 1/38 (2013.01); B01J 3 1/34 (2013.01); B01.J (22) Filed: May 13, 2016 3 I/28 (2013.01); A62D 3/38 (2013.01); C08.J Related U.S. Application Data 2327/18 (2013.01); C08.J. 2353/02 (2013.01); C08J 2400/12 (2013.01); A62D 2101/02 (60) Provisional application No. 62/162,402, filed on May (2013.01) 15, 2015. Publication Classification (57) ABSTRACT (51) Int. Cl. A multi-catalytic material that includes a polyelectrolyte A62D 5/00 (2006.01) membrane and methods of preparing the same are provided C09D 53/02 (2006.01) herein. US 2017/0007871 A1 Jan. 12, 2017

MULTICATALYST POLYELECTROLYTE CWAS therethroughby degrading or otherwise decomposing MEMBRANES AND MATERALS AND such CWAs. These materials or membranes provide high METHODS UTILIZING THE SAME water vapor permeability and are impermeable to CWAs. 0001. This application claims priority under 35 U.S.C. Such multi-catalytic materials of the invention may have S119(e) to U.S. Provisional Patent Application No. 62/162, multiple layers with metal catalysts (e.g., POMs and/or 402, filed May 15, 2015. The foregoing application is MOs) disposed at those layers, interior to the PEM of the incorporated by reference herein. material. 0002 This invention was made with government support 0011. In addition, the multi-catalytic materials of the under HDTRA 1-11-16-BRCWMD-BAA awarded by the invention may have an outer Surface (e.g., configured to face Defense Threat Reduction Agency. The government has and interact with CWAS) and an inner Surface (e.g., config certain rights in the invention. ured to face a wearer of such material and receive water vapor for transmission). The outer surfaces of the multi FIELD OF THE INVENTION catalytic materials may have metal catalysts (e.g., POMs and/or MOs) disposed thereon. For example, the multi 0003. The present invention relates generally to catalyst catalytic materials of the invention may have certain metal bearing polymeric materials and more particularly, but not catalysts disposed at an outer Surface while having metal exclusively, to multicatalytic materials that contain poly catalysts (the same or different) disposed interior to or electrolyte membranes. otherwise placed within the material (e.g., interior to the PEM of the materials of the invention). In certain embodi BACKGROUND OF THE INVENTION ments, an outer Surface or portion of the materials of the 0004. The development and use of novel polymeric mem invention may oxidize a molecule, which may be an oxida branes as suitable permselective diffusion barriers has been tive substrate, for example. In addition, or alternatively an engineering challenge in the area of new protective thereto, the materials of the invention may have an interior materials. These membranes must provide high water vapor portion that may hydrolyze a molecule, which may be a permeability and be impermeable to chemical warfare hydrolytic substrate, for example. Moreover, the materials of agents (CWA). the invention may transmit water vapor through the material 0005. The present invention provides solutions to the while inhibiting the transmission of CWAs. challenges in the field by providing multicatalyst polyelec 0012 Regarding the PEM of the invention, such mem trolyte membrane (MC-PEM) containing materials that may brane may represent the bulk of the material of the inven transmit water vapor therethrough. These materials may tion. The PEM may be composed of a polymer. As used further prevent the transmission of chemical warfare agents herein, the term “polymer refers to the product of a (CWAS) through such materials by decomposing and/or polymerization reaction, and is inclusive of homopolymers, degrading the CWAs. copolymers, terpolymers, etc. As used herein, the term “homopolymer refers to a polymer resulting from the SUMMARY OF THE INVENTION polymerization of a single monomer, i.e., a polymer con sisting essentially of a single type of repeating unit. Fur 0006. The present invention includes a multi-catalytic thermore, as used herein, the term “copolymer refers to material that may degrade, decompose, and otherwise render polymers formed by the polymerization reaction of at least inert CWAs. The material of the invention may include a two different monomers and, moreover, the term copolymer polyelectrolyte membrane (PEM). Moreover, the material of is inclusive of random copolymers, block copolymers, graft the invention may include a polyoxometalate (POM). The copolymers, etc. As used herein, the term “terpolymer.” material of the invention may also include a metal oxide refers to a polymer that includes at least three monomers. (MO). 0013. In certain instances, the PEM may include a block 0007. In certain embodiments, the multi-catalytic mate copolymer having hydrophobic units or blocks and hydro rials of the invention may include PEM, having a POM philic units or blocks of hydrophobic polymers and hydro disposed or applied to an outer surface of the PEM. The philic polymers, respectively. In other words, the PEM may PEM may also include an MO disposed interior to the PEM. be amphiphilic. Indeed, the PEM of the invention may 0008. In another aspect, the present invention may include a diblock copolymer or a triblock copolymer, for include a self-decontaminating cloth that includes the multi example. The blocks of certain embodiments of the inven catalytic material of the invention, which may, for example, tion may have a molecular weight, for example of between decompose a CWA while transmitting water vapor there about 1 kD to about 500 kD. In other embodiments, the through. blocks of certain embodiments of the invention may have a 0009. The materials of the invention may be useful in molecular weight of about 10 kD to about 100 kD. In degrading, decomposing, or otherwise rendering inert a specific examples, different blocks of the material make up variety of CWAS, including, but not limited to, G-agents, the block copolymers of the invention may have varying H-agents, and V-agents, as set forth herein. molecular weights. For example, certain copolymers of the invention may have a first block having a molecular weight DETAILED DESCRIPTION OF THE of about 10-20 kD with a second block having a molecular INVENTION weight of about 50-100 kD. 0010. The present invention encompasses multi-catalytic 0014. The hydrophobic and hydrophilic units may have materials that may include a polyelectrolyte membrane varying morphologies, as needed to adjust the properties of (PEM), a polyoxometalate (POM); and/or a metal oxide the resulting polymers, and may include linear morpholo (MO). The materials of the invention provide solutions in gies, branched morphologies, or combinations thereof. the field as materials for preventing the transmission of Moreover, such hydrophobic and hydrophilic units may US 2017/0007871 A1 Jan. 12, 2017

have a length that may be adjusted, as understood by a and a central block of person having ordinary skill in the art, to tune the desired properties of the resulting polymeric materials. The PEM may be ionic. The PEM may include portions in which an ion exchange may occur. Therefore, the PEM may include --cis-cis-cis ion exchanging functional groups, such as, for example, CHCH3 Sulfite, Sulfate, and the like. For example, the ion exchanging In a particular embodiment, each end block is independently functional group may be SO, but the ion exchanging about 10 to about 20 kD and the middle block is about 50 to functional group may be any Suitable anionic functional about 100 kD. group, as would be understood by a person having ordinary 0018. The PEM may also include a counterion (e.g., a skill in the art. cationic counterion) that may associate with the ion 0015. In particular aspects, the PEM may include a exchanging functional group. For example, the cation may include one or more monovalent cations, bivalent cations, sulfonated tetrafluoroethylene based fluoropolymer-copoly trivalent cations, tetravalent cations, pentavalent cations, mer (e.g., a polymer having a polytetrafluoroethylene back hexavalent cations, or a combination thereof. Indeed, the bone (hydrophobic) with side chains comprising a Sulfonic cation may be one or more of K", Na", Mg, Ca", Zn, acid group (such as the side chain depicted below); e.g., Ni2+, Co?", Co.", Fe2", Fe", A12", A1*, Mn2", W2+, Cr2", Nafion(R) (e.g., Nafion(R) 112, Nafion(R) 117, etc.)), sulfonated Cr", Zr2", Y3+, Nb?", Mo'", Mo?", Mo", Mo", Mo", styrene-ethane/butadiene-styrene (sSEBS), or a combination Mo'", or a combination thereof. In a particular embodiment, thereof. In a particular embodiment, the PEM may include the counterion is Fe" or Ca". a sulfonated tetrafluoroethylene based fluoropolymer-copo (0019 Regarding the POMs of the invention, such POMs lymer (e.g., Nafion(R). may be on the exterior and/or in the interior of the multi catalytic material. In a particular embodiment, the POMs 0016. An example of a sulfonated tetrafluoroethylene may be disposed at a surface of the PEM. In certain aspects based fluoropolymer-copolymer (e.g., Nafion(R) is a com of the invention, the POMs are disposed at a surface of the pound of the formula: PEM in order to preferentially interact with specific CWAS that may be decomposed or degraded by the POMs. In a particular embodiment, a solution of POM with a polymer is dropcast and then dried. -et-crite-cis-- (0020. The POMs of the invention may include the build O ing blocks of MO MOs, or MO, where M may be a metal from the periodic table (e.g., the d-block metals). Such --o), critiso POMs may include POM nanoparticles and/or nanoclusters CF that may be disposed at a surface of the PEM. In a particular embodiment, the diameter or longest dimension of the POM nanoparticle or nanocluster is about 0.1 to about 250 nm, wherein each of n, n, n, and n is independently selected about 0.1 nm to about 200 nm, about 0.5 nm to about 150 from 1 to about 20. In a particular embodiment, each of n, nm, about 0.5 nm to about 100 nm, or about 0.5 nm to about n, n, and n is independently selected from 1 to about 15 10 nm. In a particular embodiment, the average size is less or from 1 to about 10. In a particular embodiment, n is from than 10 nm. In certain embodiments of the invention, the 1 to about 15, from 1 to about 10, from about 5 to about 10, POMs may be Keggin polyoxometalates. 0021. In certain embodiments, the POMs of the invention or from 6 to 10. In a particular embodiment, n is from 1 to may have the structure of YXMO", where X is a about 15 or from 1 to about 10, from 1 to about 5, from 1 heteroatom that may be, for example, V. Mo, W. Nb, Ta, P. to about 3, or is 1. In a particular embodiment, n is from and/or K: M may be a d-block metal; n is an integer from about 1 to about 3 or is 1. In a particular embodiment, n is about 1 to 10; and Y may be one or more positively charged from 1 to about 5, from 1 to about 3, or is 2. The compound counterions, including, but not limited to, Na', K", NH.", of the above group may be altered such that the n group may and the like. In certain embodiments, M may be Co or W. In be substituted with the depicted in group, so long as the certain other embodiments, the POM may be resultant polymer has at least one side chain (the n group as KsCo'WOao, Ko (Fe(H2O)2),(PWoO)), V.MooOo. depicted). and/or (NH)PWO. In a particular embodiment, the 0017. An example of a sulfonated styrene-ethane/butadi POM is KCo'WO. ene-styrene (sSEBS) is a triblock copolymer comprising 0022 Referring to the POMs more generally, the coun terminal blocks of terions (Y) used in the above-referenced formula may serve as the counterions with any atom, as would be understood by a person having ordinary skill in the art, or combination -(-CH-CH-)- thereof from the periodic table that may be capable of balancing the charge of associated anion. Moreover, the size of the POM may range from a single building block on the Angstrom Scale (e.g., MO), up to, or exceeding, nanometer r sized POM (e.g., H. MoscoOo(H2O). (SO)s", N-X {Moses) or greater. SO 0023 The present materials of the invention may include MOs that may be disposed within the material and/or interior to the PEM. The MOs of the invention may further US 2017/0007871 A1 Jan. 12, 2017

include MO nanoparticles, such as, for example, clusters, components also allows the material to act as a sensor for alloys, core-shell particles, or a combination thereof. An MO CWAS (e.g., by measuring the change in resistance in the nanoparticle will generally be up to about 1 um in diameter material). (e.g., Z-average diameter). In a particular embodiment, the 0029. The materials of the instant invention may also diameter or longest dimension of the nanoparticle is about 1 comprise a plasticizer (e.g., a phthalate) in order to be made to about 500 nm, about 5 nm to about 250 nm, about 5 nm. elastic and/or flexible. to about 200 nm, about 5 nm to about 150 nm, or about 10 0030 The materials of the invention may degrade and/or nm to about 100 nm. decompose, or otherwise render harmless to a human 0024 MOs may be introduced into the materials of the wearer, a variety of CWAs. The materials of the invention invention (e.g., introduced into or at the PEM used in the may also be used as a chemical sensor, particularly for invention) as MOs or as MO precursors during the prepa CWAS. In a particular embodiment, a CWA may be an agent ration of the materials of the invention. As used herein, the classified as a schedule 1, 2, or 3 agent under the Chemical term “metal oxide precursor or “MO precursor may Weapons Convention of 1993. The CWA may be in liquid include any metal and oxygen containing salts or complexes form, gas form, Solid form, or combinations thereof. The that allow for the introduction of an MO and may encompass CWA may be a nerve agent, blood agent, blister agent, metal carbonates, metal halides, metal nitrates, metal Sul pulmonary agent, incapacitating agent, and/or toxin. In a fates, metal nitrites, metal Sulfites, metal phosphites, metal particular embodiment, the CWA is a nerve agent. The phosphates, metal acetates, metal hydroxides, metal CWAS that may be degraded or decomposed by the inven hydrated oxides, metal oxohydroxides, metal oXoperoxohy tion may include, for example, G-agents, H-agents, and/or droxides, and the like. The MOs of the invention may V-agents. CWAS that are G-agents include, but are not include, for example, Al-O, ZnO, MgO, CaO, TiO, CoO, limited to, tabun, Sarin, Soman, cycloSarin, ethyl sarin, Fe2O, NiO, Ni2O. AgO, AgO, AgO, CoO, CoO, O-isopentyl sarin, 2-(dimethylamino)ethyl N,N-dimethyl CoO or a combination thereof. The MO precursors of the phosphoramidofluoridate, or a combination thereof. invention that may result in the introduction of an MO may H-agents include, but are not limited to, Sulfur mustard, include, for example, AgNO, Ni(NO), Fe(NO), 2-chloroethyl ethylsulfide (CEES: half mustard), or a com Co(NO), Zn(NO), or the like (e.g., nitrates of the MO). bination thereof. V-agents include, but are not limited to, In a particular embodiment, the MO is selected from the S-2-(diethylamino)ethyl O-ethyl ethylphosphonothioate, group consisting of ZnO, MgO, Al2O, CaO, TiO, and S-2-(diethylamino)ethyl O-ethyl methylphosphonothioate, FeO. In a particular embodiment, the MO is selected from 3-pyridyl 3,3,5-trimethylcyclohexyl methylphosphonate, the group consisting of ZnO, MgO, and FeO. In a par O-isobutyl S-(2-diethaminoethyl) methylphosphothioate, ticular embodiment, the MO is ZnO. ethyl ({2-bis(propan-2-yl)aminoethylsulfanyl)(methyl) 0025. The materials of the invention may further include phosphinate (VX), O.O-diethyl-S-2-(diethylamino)ethyl a polyelectrolyte coating disposed on a Surface (e.g., the phosphorothioate, or a combination thereof. Other CWAS outer surface) of the material. Indeed, the polyelectrolyte that may be degraded or decomposed by the materials of the coating may be disposed on the outer surface of the PEM invention may include, but are not limited to, diisopropyl and may be configured to overlay the material. The poly fluorophosphonate, dimethyl-methylphosphonate, mala electrolyte coating may include any positively charged poly thion, or a combination thereof. electrolyte known by a person having ordinary skill in the art 0031 Regarding the materials of the invention more (e.g., chitosan of PDDA). The polyelectrolyte coating may broadly, research has been concentrated on segregated further include an additional polymer component that may hydrated PEMs, whose selective transport properties are enhance a particular property of the polyelectrolyte coating. related to their inhomogenous microstructure caused by the For example, the polyelectrolyte coating may include poly contrast between hydrophilic and hydrophobic fragments of vinyl alcohol (PVA) by crosslinking to increase the strength the polymer. Upon hydration, PEM may segregate into of the polyelectrolyte coating. hydrophilic and hydrophobic subphases (Eisenberg and Yea 0026. In specific aspects of the invention, the multi ger, eds. (1982) Perfluorinated Ionomer Membranes, Ameri catalyst material may include a Nafion(R) PEM, a can Chemical Society; Pineri and Eisenberg, eds. (1987) KCo'WO POM, and a ZnO or NiO MO. Structure and properties of Ionomers, Dordrecht, Holland: 0027. The materials of the present invention may be D. Reidel Publishing Co., 1987; Mauritz, K. A. (1988) J. useful in preparing self-decontaminating protective clothing Macromol. Sci., Rev. Macromol. Chem. Phys., C28:65). In and cooperative catalysts, for example. Regarding self certain circumstances, water may diffuse through the hydro decontaminating protective clothing, the multi-catalyst philic Subphase, which may be composed of water and ionic materials may be prepared as or with protective cloths. groups. On the other hand, toxins, which may contain a good Indeed, the multi-catalyst materials may be applied to the share of hydrophobic groups, may be trapped in the hydro Surface of a cloth to be used in the preparation of garments phobic subphase formed by the polymer backbone. that may protect a wearer from CWAS. For example, the 0032. One of the biggest challenges in the development multi-catalyst materials may be coated on fabrics (e.g., of PEM-based protective materials comes from phosphoo cotton) and the coating thickness may be varied as desired. rganic nerve agents and originates from their molecular 0028. The materials of the instant invention may also interactions with hydrated PEM. Phosphororganic CWA comprise a conductive component in order to be made molecules may interact favorably with both water and the conductive. For example, the materials of the instant inven hydrophobic backbone of PEM (Rivinet al. (2004) J. Phys. tion may further comprise nanotubes (e.g., carbon nano Chem. B 108:8900-09; Lee et al. (2011) J. Phys. Chem. B tubes), nanowries (e.g., silver nanowires), carbon fibers, or 115:13617-23; Lee et al. (2013) J. Phys. Chem. B 1 17:365 graphene. The inclusion of the conductive components 72; Vishnyakov et al. (2008) J. Phys. Chem. B 112:14905 results in flexible electrodes. The inclusion of conductive 10). US 2017/0007871 A1 Jan. 12, 2017

0033. In solving the problems in the field, the invention B, 115:13617-23; Alametal. (2015) J. Mol. Model., 21:182: includes materials having self-detoxifying perm-selective Balboa et al. (2007) “Vapor Pressure of GD,” U.S. Army multi-catalyst polyelectrolyte membranes (MC-PEM) that Edgewood Biological Center: Aberdeen Proving Ground, may include (i) nanosegregated PEMs that trap/absorb toxic MD; Tevault et al. (2006) Intl. J. Thermophys., 27:486-93; agents and allow water permeability, and (ii) multicompo Ault et al. (2004) J. Phys. Chem. A, 108:10094-98: Bizzig nent catalysts (MC) that facilitate decomposition of toxic otti et al. (2010) Chem. Rev., 110:3850-50; Bartelt-Hunt et agents by hydrolysis and/or oxidation. The MC-PEMs of the al. (2008) Crit. Rev. Environ. Sci. Tech., 38:112-36). invention may provide a barrier that may employ at least two 0036 Vapor interaction energies and aqueous solutions different catalytic agents: metal oxide (MO) catalytic nano of DMMP, DIFP, sarin, and soman have been studied with clusters that may be created by Sol-gel technique, and classical molecular dynamics simulations and thermody polyoxometalate (POM) catalysts deposited at the outer namic experiments (Lee et al. (2011) J. Phys. Chem. B. surface via layer-by-layer deposition. Such hierarchical 115:13617-23; Lee et al. (2013) J. Phys. Chem. B., 117:365 architecture may resemble the complex structure of 72; Vishnyakov et al. (2011).J. Phys. Chem. A, 115:5201-09: biomembranes and may provide a versatile platform for Vishnyakov et al. (2004) J. Phys. Chem. A, 108:1435–39). It computationally aided design of optimized Substrate-medi has been concluded that common simulants mimic the ated multicatalyst systems. interactions of G-agents with water reasonably well and 0034. The present invention deploys PEM not only as a semi-quantitatively represents a number of important prop Suitable catalyst Support that may provide extended reactive erties of G-agents, such as strongly negative excess mixing Surface and efficient transport of the reaction components, Volume and enthalpy. Alkylphosphonates of the same but also as a 'second skin' protective medium that may molecular size turned out generally more hydrophilic, and block toxins and transport water from the human body. PEM fluorophosphates more hydrophobic than G-agents. The is compliant and may self-assemble while absorbing water, aqueous solutions of the organophosphorous compounds which may serve as one of the components of the hydrolysis displayed distinct non-trivial dynamic properties explained catalytic reactions of agent decontamination. Furthermore, by competition of the interactions between strongly hydro the idea of heterogeneously distributing different catalytic phobic and hydrophilic groups. species within the membrane's interior and outer Surface, 0037 Nafion(R) and sPS-based block copolymers were which would communicate through the nanoscale network explored in this invention as protective PEMs. The concept of water channels created within the membrane upon hydra ofusing PEM for breathable protective films originated from tion stems from the hierarchical architecture of physiologi their nanostructure. When perfluorinated ionomers like cal membranes. As such, the materials of the present inven Nafion(R) are exposed to water, water first forms clusters tion may be advantageous in a broad class of chemical around the hydrophilic sidechains. As the water content engineering and biomedical applications including, but not increases, the clusters coalesce into hydrophilic aggregates, limited to, materials for CWA protective clothing, fuel cell forming a hydrophilic Subphase. The regions around the technologies, and the creation of multifunctional membranes perfluorinated backbone form a hydrophobic subphase. The for artificial organs, vessels, skin, and patches for topical segregation morphology is generally thought to be irregular, delivery. with the segregation scale up to several nm as determined by 0035. The present invention includes materials that may extensive experimental studies with SAXS, SANS, NMR, decompose and/or degrade CWAS, including the most com DSC, ESR conductance, and IR techniques (Eisenberg and mon CWAS, which include, but are not limited to, phospho Yeager, eds. (1982) Perfluorinated Ionomer Membranes, roroganic G-type and V-type nerve agents and vesicant American Chemical Society; Pineri and Eisenberg, eds. H-agents, of which large Stockpiles still exist in many (1987) Structure and Properties of Ionomers, Dordrecht, countries. Because of their extreme toxicity, CWAS are often Holland: D. Reidel Publishing Co.: Capek, I. (2005) Adv. mimicked in experiments by simulants, that is, similar Colloid Interface Sci., 118:73-112: Giotto et al. (2003) compounds of low toxicity whose chemistry and transport Macromolecules 36:4397-403; Meresi et al. (2001) Polymer properties are close to those of CWAs. G-agents may be 42:6153-60; Paddison, S.J. (2003) Ann. Rev. Mater. Res., mimicked by alkylphosphonates and fluorophosphates 33:289-319). Transport in the hydrophilic subphase may be (Frishman et al. (2000) Field Anal. Chem. Tech., 4:170-94: determined by solvent motion between the aggregates (Vish Suzin et al. (2000) Carbon 38:1129-33; Vo-Dinh et al. (1999) nyakov et al. (2001) J. Phys. Chem. B., 105:7830-34). Field Anal. Chem. Tech., 3:346-56). Such compounds are 0038. By means of sorption and permeation experiment strongly polar, Such as, for example, malathion, a simulant in conjunction with molecular dynamics simulations, it has for V-agents (Kosolapoff et al. (1954) J. Chem. Soc., 3222 been demonstrated that a Nafion(R) membrane is permeable 25). Agents and simulant conformations and single-mol to water and hydrophilic solvents, such as 1-propanol and ecule properties are well-explored by ab initio modeling and dimethyl methylphosphonate (Rivin et al. (2004) J. Phys. spectroscopy, and forcefields of standard form having been Chem. B., 108:8900-09). Sorption of DMMP and water is developed for classical simulations (Suenram et al. (2004) J. much less competitive than Sorption of water and propanol. Mol. Spectr., 224:176-84; Suenram et al. (2002) J. Mol. Cation-substituted dry Nafion(R) samples showed near zero Spectr., 211:110-18: Walker et al. (2001) J. Mol. Spectr., DMMP permeation, but hydrated samples showed high 207: 77-82; Kaczmarek et al. (2004) Struct. Chem., 15:517 permeability. This effect is related to a complex microphase 25: Sokkalingam et al. (2009).J. Phys. Chem. B., 113:10292 segregation in the membranes Swollen in aqueous solutions 97: Vishnyakov et al. (2011) J. Phys. Chem. A, 115:5201 of polar solvents. 09). Thermodynamic properties of phosphororganic 0039. Unlike Nafion(R), block ionomers such as SSEBS chemicals with water have been measured, while molecular tend to segregate into a variety of regular (e.g., cubic, interactions in vapor phase where characterized by interac hexagonal, lamellae, etc.) and irregular morphologies deter tion energies and IR spectra (Lee et al. (2011) J. Phys. Chem. mined by the block length and solvent composition (Lu et al. US 2017/0007871 A1 Jan. 12, 2017

(1993) Macromolecules 26:3615). It is generally believed activity is not hindered by polymer and the NP surface that the segregation structure of ionomers is less regular remains accessible, toxic agents will be gradually decom compared to that in parental non-sulfonated diblocks and posed to form non-toxic compounds that will compete triblocks (Lu et al. (1993) Macromolecules 26:3615; Kim et against external outside CWA for preferential sorption sites. al. (2001) Korea Polymer J., 9:185-96; Won et al. (2003) J. Composites with just 5% of MgO NP may be more reactive Membr. Sci., 214:245-57). Nevertheless, a strong segrega than the currently used charcoal (Sundarrajan et al. (2007) J. tion between sulfonated polystyrene and olefin blocks may Materials Sci., 42:8400-07). Feasibility of modification of be observed in numerous studies devoted to block ionomer PEM surfaces and interior with catalyst NP is confirmed by structure (Kim et al. (2001) Korea Polymer J., 9:185-96: availability of such membranes for fuel cells applications Schneider et al. (2006) Polymer 47:3119-31; Mauritz et al. (Zhang, J. (2008) PEM Fuel Cell Electrocatalysts and Cata (2002) Polymer 43:4315-23; Xu et al. (2007) Chem. Mate lyst Layers: Fundamentals and Applications; Springer). rials, 19:5937–45). Water sorption and diffusion in sPS of 0042. For example, nanocrystalline ZnO materials have different sulfonation levels, mostly in acid form, have also been prepared via Sol-gel method and characterized by been studied (Xu et al. (2007) Chem. Materials 19:5937-45: X-ray diffraction, SEM, thermogravimetry (TGA), nitrogen Brandao et al. (2005) Polymer Bull., 55:269-75; Manojet al. adsorption and infrared spectroscopy (FTIR) (Mahato et al. (2004) Macromolecular Res., 12:26-31; Baradie et al. (2009) J. Hazardous Mater, 165:928-32). The average crys (1999) Macromolecular Symposia, 138:85-91. Hietala et al. tallite size was 55 nm. Obtained material has been tested as (1999) J. Polymer Sci. Part B-Polymer Phys. 37:2893-900; destructive absorbent for the decontamination of sarin and Smitha et al. (2003) J. Membrane Sci., 225:63-76). the reaction may be followed by GC-NPD and GC-MS 0040 Regarding the protective properties of SSEBS films techniques. In Such experiments, Sarin was hydrolyzed to and composites, DMMP was found to sorb mostly inside the form surface bound non-toxic phosphonate on the Surface of hydrophilic (hydrated sPS) subphase, which sorbed consid nano-zinc oxide. Indeed, MONPs may hydrolyze phospho erable (about 54% of the total polymer weight) amounts of rorganic compounds. the simulant at the saturation pressure (Jung et al. (2010) J. 0043 Hydrolysis of phosphoroorganic compounds on Membrane Sci., 361:63-70; Jung et al. (2010) J. Membrane MONP has been documented at the interface between Sci., 362:137-42). Moreover, in the presence of substantial MONP and vapour or a homogenous aqueous solution. The amounts of DMMP or sarin, the structure of hydrated sPS rates of decomposition of sarin and DMMP were similar in becomes strongly inhomogeneous: SPS-based block iono homogenously catalyzed hydrolysis, but this may be more mers are segregated on at least two scales: hydrophilic spS complex at the surfaces of MONP (Falco et al. (2008) is separated from hydrophobic polyolefin (the scale is deter “Development of agent-simulant correlations for catalytic mined by block length and water content), and inside the air purification”. In CBDP (New Orleans: DoD), tO007). hydrophilic subphase, with cluster size of about 1-1.5 nm. 0044) Certain membranes block H-agents in the field, DMMP and sarin diffusion accelerated fast with phosphor including those having Zeolite particles that provide satis organic content. Accordingly, heterogeneous structure factory low permeability to mustard gas simulant (CEES) caused by contrast between hydrophilic and hydrophobic (Hudiono et al. (2012) Ind. Engr. Chem. Res., 51:7453-56). groups of phosphororganic agents is their typical behavior. However, the same technology may demonstrate varying In segregated PEM, their ability to interact favorably with efficiency against G-agents. Because H-agents such as Sulfur both water and hydrophobic backbone is the main obstacle mustard are more hydrophobic compounds, they may be for the development of protective membranes. Their behav oxidized at surface of the membrane, and use different ior is similar to Small Surfactant molecules, leading to high catalysts and decomposition mechanisms. Sorption and facilitated transport. General Method for Preparing a Multicatalyst of the 0041 Turning to the catalytic elements of the invention, Invention. certain catalytic nanoparticles are known to cause decom position of CWA and simulants via hydrolysis and/or oxi 0045. The polyelectrolyte membrane (e.g., Nafion(R) (e.g., dation. In some examples, metal-oxide nanoparticles Nafion(R) 112)) may be placed in a metal salt solution (e.g., (MONP), such as Al-O, ZnO, MgO, CaO, TiO, and others, a metal nitrate) at a concentration, for example, of about were shown to catalyze the hydrolysis of phosphororganic 0.05 M for a period of about 24 hours. Afterwards, the film agents and mustards, as well as some Toxic Industrial may be removed and placed in a basic solution (0.5 M Chemicals (TICs) (Sundarrajan et al. (2007) J. Materials NaOH) to form a metal hydroxide at 60° C. for about 6 Sci., 42:8400-07: Wagner et al. (2000) J. Phys. Chem. B. hours. Other concentrations, different temperatures, and/or 104:5118-23; Wagner et al. (2001) J. Amer. Chem. Soc., other durations of times may be used. Finally, the film may 123:1636–44). Catalytically active polyoxometalates (POM) be removed from the basic solutions and converted to the can be obtained as a layer on metal or metal-oxide NP and metal oxide by heating to 100° C., for example, for a stabilize particle small size (Wang et al. (2012) Chem. Soc. duration of about 24 hours. Rev., 41:7479-96). Keggin-type POM such as 0046. The polyelectrolyte coating responsible for adher KCo'WOo were proven efficient in detection (which is ing the POM nanoparticles may be applied to the surface of based on significant color change of the POM upon reduc the Nafion R membrane by a dropcasting procedure, layer tion by the CWA) and oxidation of H-agents with air by-layer technique, spincoating, sprayed on, or any other oxygen, but can also facilitate hydrolysis of V-agents (John feasible technique known in the art. Specifically, the poly son et al. (1999) J. Appl. Tox., 19:S71-S75; Mizrahi et al. mer may be dropcasted onto the Nafion(R). (2010) J. Hazard. Mater, 179:495-99). The detection and 0047. The POM may be first dispersed in a solvent, not catalytic oxidation mechanisms suggest that POM-decorated limited to water, methanol, ethanol, propanol (e.g., 1-pro NP should be located at the PEM surface, while MONP panol. 2-propanol), or others commonly known in the art, or should be located deep inside the PEM. Provided that NP a combination thereof, and then applied to the polyelectro US 2017/0007871 A1 Jan. 12, 2017 lyte coating. The application of the POM may be performed Prevention of MONP Aggregation. by spraying (i.e., atomizing) onto the polyelectrolyte, but any other conceivable method such as dropcasting, doctor 0.052 To prevent MONP aggregation, which will cause blade method, or layer-by-layer technique can be performed. loss of catalytic activity of PEM, hydrophilic polymer The POM can be applied using these methods with the chains may be chemically attached to pre-synthesized application or absence of heat, they may or may not assist in MONP. Entropic repulsion between the polymer chains will dispersing the particles. The concentration of metal and/or reduce nanoparticle aggregation. solvent ratio may be varied to effect the particle size and shape. The POM can also be applied directly to the Nafion(R). Introducing POM to the PEM Surface. 0053. After synthesis of the MONP-immobilized poly Alternative Synthetic Strategy for Preparing Multicatalyst mer films, the outer surfaces of the material may be coated Films with a positively charged polymer by layer-by-layer self assembly. This can be achieved by dip-coating the polymer 0048 MC-PEM films may be fabricated to introduce the film in a solution containing poly(diallyldimethylammo morphology and particle distributions to effect the desired nium chloride) (PDDACl). Alternatively, the POMs may be protective properties. mixed in instead of using dip coating. PDDA is expected to adhere strongly on the surfaces of the Nafion(R) or sulpho PEM Preparation. nated block copolymer films through electrostatic interac tion. The positively charged polymer will then allow for the 0049 PEM films (e.g., Nafion(R) and sSEBS films) may deposition of the polymers in a solution of POM. The POMs be obtained from a variety of sources including, for of the invention will stick to the surfaces of the positively example, Natick RDEC, DuPont, Ion Power (New Castle, charged polymer Surfaces. The polymeric materials may Del.), and Kraton (Houston, Tex.), or prepared following then be removed and washed and kept in desiccators until well-established protocols (e.g., thin films may be generated characterization and further use. The amount of Keggin-type by spin-coating an acetonitrile solution of block-copolymer POMs can be quantified by measuring the amount of the on glass slides). POMs in the supernatant by UV-vis spectrometry. (NH) In-Situ Impregnation of PEM with MO Nanoparticles (NP) PWO POM or an A-type sandwich POM KI(Fe(OH) Via Sol-Gel Process. 2) (PWO), which is reported to be among the best 0050. After this, polymers may be impregnate by MONP catalysts for the selective air-based oxidation of CEES under precursors (e.g., by soaking in aqueous/ethanoloic solutions ambient conditions, may be used (Zhang et al. (1997) such as Zn(NO), .6H2O, ZnO may be an MO catalyst) that Inorganic Chem. 36:4381-86). can Subsequently undergo the sol-gel reaction in situ within the pores of the polymers. Sol-gel process has been applied Experimental Characterization of MC-PEM Structure, and to the preparation of polyelectrolytes-nanoparticle compos CWA Simulant Sorption, Permeation Through a ited (Li et al. (2010) J. Membrane Sci., 347:26-31; Shao et Degradation in PEM-NP Composite Membranes al. (1995) Chem. Materials, 7:192-200). Then, the PEM may be taken out of the precursor Solution and kept in air at about 0054 The structure, sorption behavior, and reactivity of 75-80° C. This will then produce ZnO nanoclusters within fabricated MC-PEM samples may be determined by a vari the pores of polymer films. By changing the concentration of ety of different analytical methods. the Zn(NO), .6HO solution, different size ZnO NPs within 0055. The materials and their NPs may be characterized Nafion(R) or sPS may be formed. The size and amount of by transmission electron microscopy (TEM), powder X-ray MONP can be controlled by varying the precursor chemis diffraction (XRD), extended X-ray absorption fine structure try, Solvent composition, as well as polymer equivalent (EXAFS) analysis, energy dispersive X-ray spectroscopy weight, which affects water sorption and the segregation (EDX), and field-emission scanning electron microscopy scale. MONP will start forming in the hydrophilic subphase, (FE-SEM). EXAFS, in conjunction with high-angle annular but will be larger than segregation scale in Nafion(R). The dark-field SEM, may be performed. in-situ formation of nanoparticles may be controlled by 0056 CWA simulants sorption may be determined gra changing the solvent composition and conditions of synthe vimetrically through immersion experiments such as where sis that allows one to tailor not only the size, but also the a sample film is periodically blotted out and weighed as a nanoparticle shape, giving a preference to growth of a function of time (Rivin et al. (2004) J. Phys. Chem. B. particular crystal facet. The high-resolution TEM, SEM/ 108:8900-09). Gravimetric techniques may also be utilized EDX, UV-vis and XRD studies can confirm the homoge where a sample is exposed to simulant (DMMP, CEES) neous distribution of crystalline nanoparticles on the nano vapor and the uptake may be measured through an auto meter scale. mated microbalance (Cahn and/or Hiden) as a function of time for each partial pressure of a simulant. Alternative Route of Synthesis of MONP-PEM Composites. 0057 Permeation experiments may be carried out on thin films using the various cells and detectors. The film may be 0051. As an alternative synthetic route, especially if fine held in a rigid cell where one side can be challenged with a controlled size and shapes of the MONPs are desired, the vapor, droplets, or liquid and the other side Swept with a MONPs may be synthesized separately and the resulting Sweep stream of nitrogen to a detector for analysis. Vapor pre-made MONPs may then be immobilized within the permeation experiments may be performed using a standard inside (e.g., within the hydrophilic domains) of the polymer aerosol-vapor-liquid-assessment-group (AVLAG) cell. films by using an appropriate solvent. This technique may be Experiments are typically carried out in the 32 to 35° C. more appropriate to polymers with large segregation scale, range, mimicking the conditions near skin temperature. such as, for example, sSEBS. When the sample has no reactivity to the simulant, the US 2017/0007871 A1 Jan. 12, 2017 detector is typically selected for optimum sensitivity to the exact, but may be approximate and/or larger or Smaller, as simulant. The permeant traces only represent the concentra desired, reflecting tolerances, conversion factors, rounding tion of simulant in when no reaction occurs inside the PEM off measurement error and the like, and other factors known (that is, controlled samples and permeation through PEM to those of skill in the art. In general, a dimension, size, with POM attached to the surface). The permeation curve formulation, parameter, shape or other quantity or charac can be used to develop diffusion constants for the simulant/ teristic is “about' or “approximate' whether or not expressly sample combination. stated to be such. It is noted that embodiments of very 0058 Permeation through MONP-PEM catalytic protec different sizes, shapes and dimensions may employ the tive films may be characterized in a similar fashion, but with described arrangements. a different detector, which can distinguish both the simulant 0064. Furthermore, the transitional terms “comprising, and multiple reaction products that are formed. A GC/MS “consisting essentially of and "consisting of, when used in may be utilized to separate the permeation Sweep stream the appended claims, in original and amended form, define with the GC and analyze the individual peaks with the MS. the claim scope with respect to what unrecited additional This allows for the determination of reaction rates. claim elements or steps, if any, are excluded from the scope 0059. The catalytic hydrolysis of simulant may be studied of the claim(s). The term “comprising is intended to be by NMR experiments. The films may be introduced to the inclusive or open-ended and does not exclude any addi NMR sample tubes and an amount of appropriate CWA tional, unrecited element, method, step or material. The term simulant is added to the tube. The disappearance of the key “consisting of excludes any element, step or material other simulant chemical bonds indicating reactivity and the for than those specified in the claim and, in the latter instance, mation of new chemical bonds may be followed as a impurities ordinary associated with the specified material(s). function of time to determine the rate and extent of detoxi The term “consisting essentially of limits the scope of a fication. For example, the DMMP and decomposition prod claim to the specified elements, steps or material(s) and ucts could easily be identified by NMR (Lee et al. (2011) J. those that do not materially affect the basic and novel Phys. Chem. B 115:13617-23). The final products and/or characteristic(s) of the claimed invention. All materials, intermediates may be identified. manufactures, and methods described herein that embody 0060. The structure and composition of the nanocatalysts the present invention can, in alternate embodiments, be more after catalytic reaction or in-situ may also be characterized. specifically defined by any of the transitional terms “com After a catalytic reaction, the materials may be separated prising.” “consisting essentially of” and "consisting of.” from the reaction mixture by centrifugation and analyzed by What is claimed is: various methods. Possible aggregation or changes in the shapes and sizes of the nanoparticles may be determined by 1. A multi-catalytic material, comprising: high resolution TEM and FE-SEM. The changes in the pore a. a polyelectrolyte membrane (PEM); structure of the polymer may be analyzed by Nagas adsorp b. a polyoxometalate (POM); and tion. The compositions and any changes in composition of c. a metal oxide (MO). the materials may be characterized by TGA, XRD, FTIR, 2. The material of claim 1, comprising a polyelectrolyte XPS, EA, and/or FT-IR. Any possible changes in the oxi coating. dation states of the MONP and POMs within the samples may be characterized by X-ray absorption (XAS) and 3. The material of claim 2, wherein the polyelectrolyte extended X-ray absorption for fine structure (EXAFS). The coating comprises a positively charged polyelectrolyte. distribution of the NPs may be analyzed by using EDX 4. The material of claim 1, wherein the polyelectrolyte based elemental mapping, electron energy loss spectroscopy membrane comprises a block co-polymer comprising cova (EELS), and/or micro-Raman spectroscopy. The permeation lently bonded hydrophobic and hydrophilic units. experiments serve as a test of the MC-PEM membranes, but 5. The material of claim 4, wherein at least one of the Sorption and permeation results interpreted in the frame of hydrophobic and hydrophilic units comprises a linear mor theoretical models also provide valuable information of phology, a branched morphology, or a combination thereof. reaction diffusion mechanisms, reaction rate, and the effi 6. The material of claim 1, wherein the polyelectrolyte ciency of catalytic MONP imbedded in the polyelectrolyte membrane comprises an ion exchanging functional group. matrix. 7. The material of claim 6, wherein the ion exchanging 0061. A number of patent and non-patent publications functional group comprises a sulfite, a Sulfate, or a combi may be cited herein in order to describe the state of the art nation thereof. to which this invention pertains. The entire disclosure of each of these publications is incorporated by reference 8. The material of claim 1, wherein the polyelectrolyte herein. membrane comprises sulfonated tetrafluoroethylene based 0062. While certain embodiments of the present inven fluoropolymer-copolymer, Sulfonated styrene-ethane/buta tion have been described and/or exemplified above, various diene-styrene (sSEBS), or a combination thereof. other embodiments will be apparent to those skilled in the art 9. The material of claim 1, wherein the polyelectrolyte from the foregoing disclosure. The present invention is, membrane comprises a cation selected from the group therefore, not limited to the particular embodiments consisting of a monovalent cation, a bivalent cation, a described and/or exemplified, but is capable of considerable trivalent cation, a tetravalent cation, a pentavalent cation, a variation and modification without departure from the scope hexavalent cation, and combinations thereof. and spirit of the appended claims. 10. The material of claim 9, wherein the cation comprises 0063 Moreover, as used herein, the term “about” means Na", Mg", Ca?", Zn?", Ni2+, Co?", Co", Fe?", Fe", Al?", that dimensions, sizes, formulations, parameters, shapes and A13+. Mn2+, W2+. Cr2+. Cr3+, Zr2+. Y3+. Nb2+, Molt. Mo?+ other quantities and characteristics are not and need not be Mo", Mo'", Mo'", Mo'", or a combination thereof. US 2017/0007871 A1 Jan. 12, 2017

11. The material of claim 1, wherein the polyelectrolyte 31. The material of claim 29, wherein the V-agent com membrane comprises a copolymer selected from the group prises S-2-(diethylamino)ethyl O-ethyl ethylphosphonoth consisting of a diblock copolymer, a triblock copolymer, and ioate, S-2-(diethylamino)ethyl O-ethyl methylphosphono combinations thereof. thioate, 3-pyridyl 3,3,5-trimethylcyclohexyl 12. The material of claim 1, wherein the polyoxometalate methylphosphonate, O-isobutyl S-(2-diethaminoethyl) comprises polyoxometalate nanoparticles. methylphosphothioate, Ethyl (2-bis(propan-2-yl)aminol 13. The material of claim 1, wherein the polyoxometalate ethylsulfanyl)(methyl)phosphinate (VX), O.O-diethyl-S- is disposed at a surface of the polyelectrolyte membrane. 2-(diethylamino)ethyl phosphorothioate, or a combination 14. The material of claim 1, wherein the polyoxometalate thereof. comprises a Keggin polyoxometalate. 32. The material of claim 29, wherein the G-agent com 15. The material of claim 1, wherein the polyoxometallate prises tabun, Sarin, Soman, cyclosarin, ethyl sarin, O-iso comprises a complex having the formula MO, MO. pentyl sarin, 2-(dimethylamino)ethyl N,N-dimethylphos MO, or a combination thereof, wherein M comprises a phoramidofluoridate, or a combination thereof. d-block metal. 33. The material of claim 28, wherein the chemical 16. The material of claim 15, wherein the polyoxometa warfare agent comprises, diisopropyl fluorophosphonate, late comprises a negatively charged complex having the dimethyl-methylphosphonate, malathion, or a combination formula XMO", wherein X comprises a heteroatom, thereof. M comprises a d-block metal, and n is an integer from 1 to 34. The material of claim 1, wherein an interior portion of 10. the material is configured to hydrolyze a molecule. 17. The material of claim 16, wherein the polyoxometa late comprises a compound having the formula 35. The material of claim 1, wherein an exterior portion YXMO, wherein Y comprises one or more positively of the material is configured to oxidize a molecule. charged counterions, X comprises a heteroatom, and M 36. The material of claim 1, wherein the material is comprises a d-block metal. configured to transmit water vapor through the material. 18. The material of claim 15, wherein M comprises Co or 37. The material of claim 1, further comprising a plasti W. cizer. 19. The material of claim 16, wherein X comprises V. Mo, 38. The material of claim 1, further comprising a con W. Nb, Ta, P. K, or a combination thereof. ductive material. 20. The material of claim 1, wherein the polyoxometalate 39. A self-decontaminating protective cloth comprising a comprises K. Co'W.O. K. (Fe(H2O)2),(PWO), multi-catalytic material as recited in claim 1. VMooOo. (NH4)PWOao, or a combination thereof. 40. The cloth of claim 39, wherein said multi-catalytic 21. The material of claim 1, wherein the metal oxide is material is coated on a fabric. disposed within the polyelectrolyte membrane. 41. The cloth of claim 39, wherein the cloth is configured 22. The material of claim 1, wherein the metal oxide to decompose a chemical warfare agent and transmit water comprises metal oxide nanoparticles. vapor through the clothing. 23. The material of claim 22, wherein the metal oxide 42. The cloth of claim 41, wherein the chemical warfare nanoparticles comprise clusters, alloys, core-shell particles, agent comprises a G-agent, an H-agent, a V-agent, or a or a combination thereof. combination thereof. 24. The material of claim 1, wherein the metal oxide is 43. The cloth of claim 42, wherein the H-agent comprises selected from the group consisting of Al-O, ZnO, MgO, sulfur mustard, 2-chloroethyl ethyl sulfide (CEES), or a CaO, TiO, CoO, FeOs. NiO, Ni2O. AgO, AgO, AgO, combination thereof. CoO, CoO, CoO, and combinations thereof. 44. The cloth of claim 42, wherein the V-agent comprises 25. The material of claim 1, wherein the material com S-2-(diethylamino)ethyl O-ethyl ethylphosphonothioate, prises a hydrophobic subphase, a hydrophilic Subphase, or a S-2-(diethylamino)ethyl O-ethyl methylphosphonothioate, combination thereof. 3-pyridyl 3,3,5-trimethylcyclohexyl methylphosphonate, 26. The material of claim 1, comprising a polymeric layer O-isobutyl S-(2-diethaminoethyl) methylphosphothioate, configured to overlay a Surface of the material. Ethyl ({2-bis(propan-2-yl)aminoethylsulfanyl)(methyl) 27. The material of claim 1, wherein the polyelectrolyte phosphinate (VX), O.O-diethyl-S-2-(diethylamino)ethyl membrane comprises a sulfonated tetrafluoroethylene based phosphorothioate, or a combination thereof. fluoropolymer-copolymer. 45. The cloth of claim 42, wherein the G-agent comprises 28. The material of claim 1, wherein the material is tabun, Sarin, Soman, cyclosarin, ethyl sarin, O-isopentyl configured to decompose a chemical warfare agent. Sarin, 2-(Dimethylamino)ethyl N,N-dimethylphos 29. The material of claim 28, wherein the chemical warfare agent comprises a G-agent, an H-agent, a V-agent, phoramidofluoridate, or a combination thereof. or a combination thereof. 46. The cloth of claim 41, wherein the chemical warfare 30. The material of claim 29, wherein the H-agent com agent comprises, disopropyl fluorophosphonate, dimethyl prises sulfur mustard, 2-chloroethyl ethylsulfide (CEES), or methylphosphonate, malathion, or a combination thereof. a combination thereof. k k k k k