Metal organic framework polymer based gels

Abstract

Various aspects of the instant disclosure provide a metal-organic framework- polymer composite organic-gel material. The material includes zirconium -based MOF (UiO-66) and multiple polymer components to form a gel network and exhibit multifunctionality (conductivity and piezoelectricity).

Description

METAL ORGANIC FRAMEWORK POLYMER BASED GELSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority of U.S. Provisional Patent Application Serial No. 63 / 591,837 entitled “METAL ORGANIC FRAMEWORK POLYMER BASED GELS FOR MULTIFUNCTIONAL APPLICATIONS AND METHOD OF MAKING,” filed October 20, 2023, which hereby incorporated by reference herein in its entirety.BACKGROUND

[0002] Metal organic frameworks are classes of chemical structures. They are suited for many different applications. Given their utility, it is desirable to improve methods of making metal organic frameworks and to improve their structure.SUMMARY

[0003] This disclosure provides a method to synthesize multifunctional metal-organic framework (MOF)-polymer gel materials. The gels consist of different types of polymers that can exhibit a variety of properties along with a zirconium MOF (UiO-66) which can provide ordered porosity and high surface area to the gels. Polyaniline (PANI), a conductive polymer and P(VDF-TrFE), a piezoelectric polymer are dispersed and held together by the PVA-UiO- 66 gel network to provide both the conductive and piezoelectric properties to the gel.

[0004] According to another aspect of the present disclosure, which may include any of the foregoing aspects, wherein the polymer comprises polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyacrylic acid (PAA), poly (acrylamide-co-acrylic acid), polymethyl methacrylate (PMMA), poly(acrylamide) (PAAm), poly(2-hydroxyethyl methacrylate) (PHEMA) or combinations thereof.

[0005] According to another aspect of the present disclosure, which may include any of the foregoing aspects, wherein the conductive polymer comprises polyaniline (PANI), polypyrrole (PPy), polythiophene (PTH), poly(para-phenylene) (PPP), poly(phenylenevinylene) (PPV), polyfuran (PF), poly(3,4-ethylenedi oxythiophene) (PEDOT), poly(3,4-ethylenedi oxythiophene): poly(styrene-sulfonate) (PEDOT: PSS), or combinations thereof.

[0006] According to another aspect of the present disclosure, which may include any of the foregoing aspects, wherein the piezoelectric polymer comprises of poly (vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)), poly vinylidene fluoride (PVDF), poly (vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)), polyurethane, polyamides, poly(L-lactide), polypeptides, polyesters, or combinations thereof.

[0007] According to another aspect of the present disclosure, which may include any of the foregoing aspects, wherein the metal salt is selected from the group consisting of a zirconium salt, a zinc salt, a copper salt, an aluminum salt, a titanium salt, a cobalt salt, an iron salt, a hafnium salt, a magnesium salt, a calcium salt, a manganese salt, or combinations thereof.

[0008] According to another aspect of the present disclosure, which may include any of the foregoing aspects, wherein the carboxylic acid linker is selected from the group consisting of terephthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 2- aminoterephthalic acid, 2,5-diaminoterephthalic acid, 2-sulfoterephthalic acid, 2,5- disulfoterephthalic acid, 2- methylterephthalic acid, 2,5-methylterephthalic acid, 2- phosphonoterephtahlic acid, 2,5- diphosphonoterephthalic acid, cyclohexane- 1,2, 4,- tricarboxylic acid, 1,2, 4, 5- benzenetetracarboxylic acid, cyclohexane-l,2,4,5-tetracarboxylic acid, fumaric acid, 1,4- naphthalenedicarboxylic acid, biphenyl-4,4'-di carboxylic acid, 2- amino-4,4'-biphenyldicarboxylic acid, 2-sulfo-4,4’- biphenyldicarboxylic acid, 1,3,5- benzenetri acetic acid (“trimesic acid”), 1,3,5- cyclohexanetricarboxylic acid, 2- methylimidazole, benzimidazole, 1,3,5-benzenetrisulfonic acid, 1,4-benzenedisulfonic acid, tetraethyl 4,4',4'',4'"-(pyrene-l,3,6,8-tetrayl)tetrabenzoic acid, l,3,6,8-tetrakis-(p-benzoic acid)pyrene, 4,4',4"-(triazine-2,4,6-triyl-tris(benzene-4,l- diyl))tribenzoic acid, 4, 4', 4"- (benzene-l,3,5-triyl-tris(benzene-4,l-diyl))tribenzoic acid, 4,4’,4”,4”’-(Porphine- 5,10,15,20-tetrayl)tetrakis(benzoic acid), and combinations thereof.BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1A-1C show successful gel formation of P(VDF-TrFE)-PVA-UiO-66 gel via inversion test when changing the concentration of P(VDF-TrFE).

[0010] Figure ID is an X-ray diffraction pattern of the P(VDF-TrFE)-PVA-UiO-66 gels and compared to the diffraction pattern of MOF and polymer controls.

[0011] Figure 2A shows successful gel formation of P(VDF-TrFE)-PVA-UiO-66 gels via inversion test when changing the concentration of PVA.

[0012] Figure 2B is an X-ray diffraction pattern of the P(VDF-TrFE)-PVA-UiO-66 gels shown in Figure 2A and compared to the diffraction pattern of MOF and polymer controls.

[0013] Figure 3A-3C show successful gel formation of P(VDF-TrFE)-PANI-PVA- UiO-66 gel via inversion test when changing the concentration of PANI.

[0014] Figure 3D is an X-ray diffraction pattern of P(VDF-TrFE)-PANI-PVA-UiO- 66 gels and compared to the diffraction pattern of MOF and polymer controls.

[0015] Figure 4A-4B are graphs showing that a P(VDF-TrFE)-PANI-PVA-UiO-66 gel shows both piezoelectrical and electrical properties.DETAILED DESCRIPTION

[0016] Metal-organic Frameworks (MOF) are a class of porous materials that are made up of metal ions or clusters as nodes that are connected by organic linkers to form a three-dimensional (3D) network. MOFs can exhibit high surface area and ordered porosity.

[0017] These crystalline structures generally include metal ions or clusters coordinated to organic ligands, forming intricate one-, two-, or three-dimensional networks. The resulting frameworks can be characterized by their exceptional porosity, with internal surface areas that can exceed 6,000 m2 / g, and highly tunable pore sizes ranging from, for example, microporous to mesoporous scales.

[0018] One aspect of MOFs is an ability to combine different metal nodes and organic linkers, allowing for tailoring the framework's properties to suit specific applications. This level of control can extend to control over one or more of pore size, shape, or chemical functionality, making MOFs highly adaptable to various fields of study and practical use. The synthesis of MOFs can be achieved through several methods, including solvothermal, microwave-assisted, mechanochemical, and electrochemical techniques, each offering unique advantages in terms of crystal quality, yield, and scalability.

[0019] An example of the applications of MOFs is in the field of gas storage and separation. Their high surface area and tunable pore structure make MOFs suitable candidates for hydrogen storage, carbon dioxide capture, and other gas separation processes. In the realm of catalysis, MOFs can serve as effective heterogeneous catalysts, such as offering the benefits of high surface area, tunable pore environments, and the potential for incorporating catalytically active sites within the framework structure.

[0020] Beyond energy and environmental applications, MOFs have shown great potential in biomedical fields. Their porous nature and ability to encapsulate drug molecules make them promising candidates for controlled drug delivery systems. Additionally, the chemical versatility of MOFs allows for the development of sensitive and selective chemical sensors, capable of detecting a wide range of analytes.

[0021] While MOFs can offer various aspects as discussed above, it is important to note that use or production of MOFs can present various challenges. Depending on their composition, certain MOFs may exhibit sensitivity to moisture or air, which can limit their practical applications. Ongoing research efforts are focused on improving the stability, scalability, and performance of MOFs across various applications.

[0022] A “metal-organic framework” generally refers to a coordination network with organic ligands containing potential voids. A coordination network represents a coordination compound extending, through repeating coordination entities, in one dimension, but with cross-links between two or more individual chains, loops, or spiro-links, or a coordination compound extending through repeating coordination entities in two or three dimensions. A coordination polymer represents a coordination compound with repeating coordination entities extending in one, two, or three dimensions. Most of the MOFs reported in the literature are crystalline compounds, but there are also amorphous MOFs, and other disordered phases.

[0023] In most cases for MOFs, the pores are stable during the elimination of the guest molecules (e.g., solvents) and can be refilled with other compounds. Because of this property, MOFs are of interest for the storage of gases such as hydrogen and carbon dioxide. Other possible applications of MOFs are in gas purification, in gas separation, in water remediation, in catalysis, as conducting solids and as supercapacitors. MOFs are also being considered for charge transport applications, piezoelectric applications, semiconductors, and flexible gel-like composites.

[0024] MOFs generally comprise two main components: an inorganic metal cluster (often referred to as a secondary-building unit or SBU) and an organic molecule that can be referred to as a linker. An organic molecule can refer to a molecule including an organic group. An organic group can refer to a carbon-containing functional group. Examples can include an oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group; a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group such as an alkyl and aryl sulfide group; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R)2, CN, CF3, OCF3, R, C(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, (CH2)O-2N(R)C(0)R, (CH2)O-2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR,N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, C(=NOR)R, and substituted or unsubstituted (Ci- Cioo)hydrocarbyl, wherein R can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety, and wherein the carbon-based moiety can be substituted or unsubstituted.

[0025] Organic linkers are components in the construction of metal-organic frameworks (MOFs), serving as the connective elements between metal nodes or clusters. These organic molecules play a role in determining the overall structure, properties, and functionality of MOFs. Typically composed of carbon-based compounds, organic linkers feature specific functional groups that can coordinate with metal ions, creating the three- dimensional network characteristic of MOFs. The availability of organic linkers offers a high degree of flexibility and tunability, allowing tailoring MOFs for specific applications.

[0026] The versatility of organic linkers stems from the vast array of possible molecular structures and functional groups that can be incorporated. Examples of organic linkers include carboxylates, phosphonates, and nitrogen-containing compounds such as bipyridines or imidazoles. These linkers can vary in length, rigidity, and geometry, directly influencing the pore size, shape, and chemical environment within the MOF. By selecting or synthesizing organic linkers, properties such as framework stability, guest molecule selectivity, or catalytic activity can be controlled.

[0027] Organic linkers can be functionalized, either pre- or post-synthetically. This allows for the introduction of additional chemical groups that can enhance the MOF's performance in specific applications. For example, linkers with large aromatic systems can improve gas adsorption properties, while those with chiral centers can create MOFs suitable for enantioselective catalysis. The interplay between the organic linkers and metal nodes not only defines the MOF's structure but also its chemical, thermal, and mechanical stability, making the design and selection of organic linkers a critical aspect of MOF research and development.

[0028] Given the combination of inorganic metal clusters and organic molecules, the materials are often referred to as hybrid organic-inorganic materials. The organic molecules are typically mono-, di-, tri-, or tetravalent ligands. The choice of metal and linker dictates the structure and hence properties of the MOF. For example, the metal's coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal, and in which orientation.

[0029] To describe and organize the structures of MOFs, a system of nomenclature has been developed. Subunits of a MOF, called secondary building units (SBU), can bedescribed by topologies common to several structures. Each topology, also called a net, is assigned a symbol, consisting of three lower-case letters in bold. MOF-5

[0030] Attached to the SBUs are bridging ligands, bridging ligands with rigid backbones play a role in the design and synthesis of metal-organic frameworks (MOFs) with specific structural and functional properties. These ligands are characterized by their inflexible molecular structure, which helps maintain a predetermined geometry and spacing between metal nodes in the MOF. The rigidity of these ligands contributes to the overall stability and porosity of the resulting framework, often leading to MOFs with high surface areas and well-defined pore structures.

[0031] An example of a bridging ligand with a rigid backbone is 1,4- benzenedicarboxylic acid, also known as terephthalic acid. This ligand consists of a benzene ring with carboxylic acid groups at the para positions, creating a linear and rigid structure. When used in MOF synthesis, terephthalic acid forms strong coordination bonds with metal ions, resulting in frameworks with predictable geometries and high thermal stability.

[0032] Another example is 4,4'-bipyridine, a nitrogen-containing ligand composed of two pyridine rings connected by a single bond. The rigidity of this ligand stems from the restricted rotation around the bond connecting the two aromatic rings. 4,4'-bipyridine can be used in MOF synthesis due to its ability to form linear bridges between metal centers, creating frameworks with large pores and high surface areas.

[0033] Triphenyldicarboxylic acid is a more complex example of a rigid bridging ligand. This molecule features a central benzene ring with two phenyl rings attached, each bearing a carboxylic acid group. The extended aromatic system provides rigidity, while the carboxylic acid groups offer strong coordination sites for metal ions. MOFs synthesized with this ligand often exhibit enhanced stability and interesting topologies due to the ligand's unique three-dimensional structure.

[0034] These rigid bridging ligands, among many others, allow for the design of MOFs with precise control over pore size, shape, and chemical environment. Their inflexible nature helps maintain the structural integrity of the framework under various conditions, making them valuable components in the development of MOFs for applications such as gas storage, separation, and catalysis.

[0035] Implementing MOFs in industry generally includes consideration of mechanical properties since most processing techniques (e.g., extrusion and pelletization) expose the MOFs to substantial mechanical compressive stresses. Metal-organic frameworks (MOFs) are subject to significant mechanical compressive stresses during processes likeextrusion or pelletization, which can be used to shape these materials for practical applications. These processes can, for example, involve applying high pressure to compress MOF powders into desired forms, such as pellets or extrudates. During extrusion, MOF particles can be forced through a die under pressure, causing them to deform and compact. Pelletization typically involves compressing MOF powders in a mold or die to form dense, shaped particles. The mechanical stresses experienced during these processes can lead to various structural changes in MOFs, including particle deformation, pore collapse, and in some cases, partial amorphization of the crystalline structure. The extent of these changes depends on factors such as the intrinsic mechanical properties of the MOF, the applied pressure, and the specific shaping technique used. While these processes are essential for creating MOF forms suitable for industrial applications, they can potentially alter the material's porosity, surface area, and even its chemical properties.

[0036] The mechanical response of porous structures is of interest as these structures can exhibit unusual response to high pressures. Examples of MOF systems include zeolitic imidazolate frameworks (ZIFs), Carboxylate MOFs, Zirconium -based MOFs, among others. The response of the MOF can be dependent on the linker species and the inorganic nodes.

[0037] Zirconium -based MOFs such as UIO-66 are a very robust class of MOFs(attributed to strong hexanuclear metallic nodes) with increased resistance to heat, solvents, and other harsh conditions, which makes them of interest in terms of mechanical properties. Determinations of shear modulus and pelletization have shown that the UIO-66 MOFs are very mechanically robust and have high tolerance for pore collapse when compared to ZIFs and carboxylate MOFs. Although the UIO-66 MOF shows increased stability under pelletization, the UIO-66 MOFs amorphized rapidly under ball milling conditions due to destruction of linker coordinating inorganic nodes.

[0038] MOFs are applicable in various fields such as catalysis, drug delivery, sensing, opto-electronics, tissue engineering, etc. The brittle nature of MOFs limits their applicability in many real-world applications. To address this, MOF-polymer composites can be used.Organic or hydrogels are one way of incorporating MOF and polymer together which can be applicable in biomedicine and flexible electronics. As an illustrative example, a zirconium- based MOF UiO-66 is evaluated herein. Synthesis of UiO-66 in the presence of polymer such as polyvinyl alcohol (PVA) promotes the cross linking of the polymer and results in the formation of gels.

[0039] In catalysis, MOF-polymer composites may be useful for heterogeneous catalysis applications. For instance, MOF-polymer membranes can be considered thatcombine the catalytic activity of MOFs with the processability of polymers. These composites could be used in flow reactors for continuous catalytic processes, such as the conversion of CO2 to valuable chemicals.

[0040] In the field of drug delivery, MOF-polymer hydrogels have can be created to achieve controlled release of therapeutic agents. One example involves incorporating a drug- loaded MOF into a temperature-responsive polymer hydrogel. This composite system allows for the triggered release of the drug in response to changes in body temperature, enhancing the efficacy and reducing side effects of the treatment.

[0041] Sensing applications could use MOF-polymer composites as well. For example, flexible sensors can be considered by, for example, incorporating luminescent MOFs into polymer matrices. These sensors could be used to detect various analytes, such as heavy metals or volatile organic compounds, such as while maintaining mechanical flexibility for wearable or integrated sensing devices.

[0042] In opto-electronics, MOF-polymer composites may be used in light-emitting diodes (LEDs) or photovoltaic devices. By combining the optical properties of MOFs with the processability of polymers, flexible and efficient light-emitting or light-harvesting materials can be fabricated. For example, lanthanide-based MOFs embedded in polymer films may have potential for white-light emission in flexible displays.

[0043] Tissue engineering applications can use MOF-polymer composites. For example, scaffolds made from biocompatible polymers and MOFs can be developed to promote cell growth and tissue regeneration. These composites can provide both structural support and controlled release of growth factors or other bioactive molecules to enhance tissue formation.

[0044] The present subject matter can include a method for the room temperature synthesis of an organic gel consisting of a Zr-MOF (UiO-66) and multiple polymers (PVA, polyaniline (PANI) and polyvinylidene fluoride-trifluoro ethylene (P(VDF-TrFE)) as multifunctional gels.

[0045] UiO-66, a zirconium-based metal-organic framework (MOF), can provide various aspects when used in MOF-polymer composites for flexible electronics applications. Its stability allows creating durable and robust composite materials. When combined with polymers like polyvinyl alcohol (PVA), UiO-66 promotes cross-linking, resulting in the formation of gels with enhanced mechanical properties. These MOF-polymer gels can exhibit both flexibility and functionality, addressing the brittleness issue that may otherwise limit the applicability of MOFs in real-world scenarios. The UiO-66 based composites can besynthesized at room temperature, allowing for processability and integration into flexible electronic devices. Additionally, the porosity and ordered structure of UiO-66 contribute to the composite's ability to incorporate multiple polymers with different properties, such as conductivity (from polyaniline) and piezoelectricity (from P(VDF-TrFE)), resulting in multifunctional materials suitable for various flexible electronic applications.

[0046] A Zr-based MOF-gel with incorporation of multiple polymers with different properties can be made according to any suitable method. As an example of a suitable method, 2 wt. % PVA can be dissolved in dimethyl sulfoxide (DMSO) after which the desired amount of PANI and / or P(VDF-TrFE) can be added. Then, a benzene dicarboxylic acid (BDC) linker can be added and dissolved. In a separate vial, Zr-oxo node can be prepared by adding zirconium propoxide and acetic acid in DMSO. This node solution was then added to the initial vial with the polymers and BDC can sit for 24 hrs. After 24 hrs., P(VDF-TrFE)-PVA-UiO-66 gel, PANI-PVA-UiO-66 and P(VDF-TrFE)-PANI-PVA-UiO-66 gel were ready. In these gels, PVA helps in the gel formation, PANI can provide conductivity and P(VDF-TrFE) can provide piezoelectric properties to the gel. These gels can be characterized using x-ray diffraction (XRD) to confirm the presence of UiO-66 and P(VDF- TrFE). The piezoelectric characteristics can be analyzed by measuring the voltage generated by the gel with the application of pressure. Also, electrical properties can be characterized using a four-point probe method. The inversion test and the XRD patterns in Figure 1-3 confirms the synthesis of composite gels along with crystallization of the Zr-MOF (UiO-66) along with P(VDF-TrFE). Figure 4a-4b shows that the P(VDF-TrFE)-PANI-PVA-UiO-66 gel shows both the piezoelectrical and electrical properties, hence making it a multifunctional gel material.

[0047] UiO-66-PVA gels incorporating P(VDF-TrFE) could be integrated into flexible pressure sensors. The piezoelectric properties of P(VDF-TrFE) combined with the stability and porosity of UiO-66 would allow for highly sensitive and durable pressure sensing capabilities. The gel-like nature of the composite can allow the sensor to conform to various surfaces, making it suitable for wearable electronics or smart textiles. The potential performance benefits include improved sensitivity to pressure changes, enhanced durability due to UiO-66's stability, and the ability to maintain functionality under flexing or bending conditions.

[0048] UiO-66-PVA gels with incorporated polyaniline (PANI) could be used in flexible supercapacitors. The high surface area and porosity of UiO-66, combined with theconductivity of PANI, would create a composite material with excellent charge storage capabilities

[0049] The gel-like nature of the composite can allow for the fabrication of thin, flexible supercapacitors that can be integrated into various electronic devices. Potential performance benefits include improved energy density due to the high surface area of UiO- 66, enhanced flexibility compared to traditional supercapacitors, and the ability to maintain performance under bending or stretching conditions.

[0050] By combining both P(VDF-TrFE) and PANI in the UiO-66-PVA gel, multifunctional flexible sensors can be developed. These sensors can be capable of simultaneously detecting pressure changes (via the piezoelectric effect) and electrical signals. Such devices could be integrated into smart wearables or healthcare monitoring systems. The potential performance benefits include the ability to measure multiple parameters with a single device, improved durability and stability due to the UiO-66 framework, and the flexibility to conform to complex surfaces or body contours.EXAMPLES

[0051] Materials: Dimethyl sulfoxide (DMSO, 99.8%), acetic acid, zirconium (IV) propoxide (70 % in propanol), benzene- 1,4-dicarboxylic acid (EEBDC, 98 %), polyvinylidene fluoride-trifluoro ethylene (PVDF-TrFE) (solvene 250 / P400), polyvinyl alcohol (PVA), polyaniline (emeraldine salt) (PANI, MW >15000 kDa) were purchased from Sigma Aldrich.

[0052] Method: To synthesize the Zr-oxo cluster node solution, 355 L of 70% zirconium propoxide solution in 1- propanol (0.79 mmol) was added to a mixture of 4 mL acetic acid and 7 mL DMSO in a 20 mL vial. The solution was then sonicated for 10 minutes and then placed in oven at 130 °C for 2 hours. In another vial, to 5 ml DMSO 220 mg of PVA was added and stirred at 120 °C until completely dissolved. Then, P(VDF-TrFE) or / and PANI was added and stirred until dissolved. Then, 115 mg of EEBDC was added to the polymer solution and stirred until fully dissolved. After that, 5 mL of the node solution was added to the linker + polymer solution and gently shaken to mix the node and linker solution effectively. The solution was let to sit for 24 hrs. at the end of which the formation of gels was completed. The synthesized P(VDF-TrFE)-PVA-UiO-66 gel, and PANI-PVA-UiO-66 gels were then characterized using x-ray diffraction (XRD) technique. Diffraction patterns of the films were collected using PANalytical Empyrean X-ray diffractometer. The source of the X-ray was copper anode which produced X-rays with a wavelength of 1.54 A. Samples wereanalyzed in a 2-theta range of 5 degrees to 30 degrees and the X-rays were accelerated at 45 kV and 40 mA. For piezoelectricity and conductivity measurements, thin films of gel samples were made and dried at room temperature. For piezoelectricity measurement, indium tin oxide (ITO) was used as substrate and a pressure of 10 pascal was applied and the opencircuit output voltage was measured using an oscilloscope. For conductivity measurement, glass substrate was used, and a source meter was used for a four-point method to generate a current vs. voltage (I-V) curve.Aspects of the Present Subject Matter

[0053] The following embodiments are provided by way of example but not by way of limitation, labeled as “aspects,” the numbering of which is not to be construed as designating levels of importance:

[0054] Aspect 1 provides a metal organic framework material, comprising: A metal or a salt thereof; and a plurality of polymer and linker components dispersed about the zirconium.

[0055] Aspect 2 provides the metal organic framework material of Aspect 1, wherein the plurality of polymer components independently comprises polyvinyl alcohol, polyaniline, polyvinylidene fluoride trifluoro ethylene, or a combination thereof.

[0056] Aspect 3 provides the metal organic framework material of any of Aspects 1 or 2, wherein the plurality of polymer components are crosslinked to the zirconium.

[0057] Aspect 4 provides the metal organic framework material of any of Aspects 1-3, further comprising a benzene dicarboxylic acid linker.

[0058] Aspect 5 provides the metal organic framework material of any of Aspects 1-4, wherein the material exhibits piezoelectric properties.

[0059] Aspect 6 provides the metal organic framework material of any of Aspects 1-5, wherein the material exhibits conductive properties.

[0060] Aspect 7 provides the metal organic framework material of any of Aspects 1-6, wherein the zirconium is in the form of a UiO-66 structure.

[0061] Aspect 8 provides the metal organic framework material of any of Aspects 1-7, wherein the material is suitable for use in energy storage applications.

[0062] Aspect 9 provides the metal organic framework material of any of Aspects 1-8, wherein the material is suitable for use in environmental remediation.

[0063] Aspect 10 provides the metal organic framework material of any of Aspects 1-9, wherein the material suitable for use in biomedical devices.

[0064] Aspect 11 provides the metal organic framework material of any of Aspects 1-10, wherein the material is characterized by x-ray diffraction to confirm the presence of UiO- 66.

[0065] Aspect 12 provides the metal organic framework material of any of Aspects 1-11, wherein the material is flexible and gel-like.

[0066] Aspect 13 provides the metal organic framework material of any of Aspects 1-12, wherein the material is synthesized using a zirconium propoxide precursor.

[0067] Aspect 14 provides the metal organic framework material of any of Aspects 1-13, wherien the metal or salt thereof comprises zirconium.

[0068] Aspect 15 provides a method of making the metal organic framework material of any of Aspects 1-14, the method comprising contacting the zirconium and the plurality of polymer components in solution.

[0069] Aspect 16 provides the method of Aspect 15, wherein the method is conducted at room temperature or higher.

[0070] Aspect 17 provides the method of any of Aspects 15 or 16, further comprising the step of sonication to enhance mixing.

[0071] Aspect 18 provides the method of any of Aspects 15-17, wherein the solution comprises dimethyl sulfoxide as a solvent.

[0072] Aspect 19 provides the method of any of Aspects 15-18, wherein the plurality of polymer components are added in a weight percentage ranging from 0.1% to 15% as measured in solution.

[0073] Aspect 20 provides the method of any of Aspects 15-19, further comprising drying the gel to form a thin film for characterization.

[0074] Aspect 21 provides the method of any of Aspects 15-20, wherein the polymer component includes alternative conductive polymers.

[0075] While the disclosed subject matter is described in conjunction with the enumerated claims, it is be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0076] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0077] In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. All publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0078] In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0079] The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range. The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of’ as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that about 0 wt% to about 5 wt% ofthe composition is the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than or equal to about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

Claims

CLAIMSWhat is claimed is:

1. A metal organic framework material, comprising: a metal or salt thereof; and a plurality of polymer and linker components dispersed about the zirconium.

2. The metal organic framework material of claim 1, wherein the plurality of polymer components independently comprises polyvinyl alcohol, polyaniline, polyvinylidene fluoride trifluoro ethylene, or a combination thereof.

3. The metal organic framework material of any of claims 1 or 2, wherein the plurality of polymer components are crosslinked to the zirconium, or the polymers are physically trapped in the metal organic framework crystal.

4. The metal organic framework material of any of claims 1-3, further comprising a benzene dicarboxylic acid linker.

5. The metal organic framework material of any of claims 1-4, wherein the material exhibits piezoelectric properties.

6. The metal organic framework material of any of claims 1-5, wherein the material exhibits conductive properties.

7. The metal organic framework material of any of claims 1-6, wherein the zirconium is in the form of a UiO-66 structure.

8. The metal organic framework material of any of claims 1-7, wherein the material is suitable for use in energy storage applications.

9. The metal organic framework material of any of claims 1-8, wherein the material is suitable for use in environmental remediation.

10. The metal organic framework material of any of claims 1-9, wherein the material suitable for use in biomedical devices.

11. The metal organic framework material of any of claims 1-10, wherein the material is characterized by x-ray diffraction to confirm the presence of UiO-66.

12. The metal organic framework material of any of claims 1-11, wherein the material is flexible and gel-like.

13. The metal organic framework material of any of claims 1-12, wherein the material is synthesized using a zirconium propoxide precursor.

14. The metal organic framework material of any of claims 1-13, wherien the metal or salt thereof comprises zirconium.

15. A method of making the metal organic framework material of any of claims 1-14, the method comprising contacting the zirconium and the plurality of polymer components in solution.

16. The method of claim 15, wherein the method is conducted at room temperature or higher.

17. The method of any of claims 15 or 16, further comprising the step of sonication to enhance mixing.

18. The method of any of claims 15-17, wherein the solution comprises dimethyl sulfoxide as a solvent.

19. The method of any of claims 15-18, wherein the plurality of polymer components are added in a weight percentage ranging from 0.1% to 5%.

20. The method of any of claims 15-19, further comprising drying the gel to form a thin film for characterization.

21. The method of any of claims 15-20, wherein the polymer component includes alternative conductive polymers.

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