Metal-organic backbone polytetrafluoroethylene composite structure and method for producing the same

Abstract

A method for producing structured MOF composite tapes by immobilizing metal chalcogenide particles in a polymer matrix and then in-situ converting the metal chalcogenides to MOFs. In some embodiments, the conversion is from ZnO-PTFE composites to ZIF-8-PTFE composites. ZIF-8-PTFE composites are useful materials for propylene / propane separation, oil capture, and photocatalytic disinfection against airborne bacteria. In addition to ZIF-8, structured MOF composite tapes are useful materials for chemical separation, including chemical purification, air purification, and removal of biological toxic substances, as examples. In addition, composite articles containing MOFs can be in the form of filter bags, honeycombs, columns, or other suitable forms.

Description

[Technical Field]

[0001] This disclosure relates to chemical separation materials in general, and more specifically to porous fibrillated polymer membranes, which include supported particles disposed within the fibrillated polymer membrane and can be used to separate chemical substances. [Background technology]

[0002] A composite filter can have a porous material arranged within a matrix. As a fluid moves across or through the matrix, certain components within the fluid can be separated from other components. Hybrid porous materials, such as metal-organic frameworks (MOFs), combine metal atoms with bridging organic ligands. However, the high manufacturing cost of MOFs limits their large-scale applications. In addition to the high cost, the poor processability and handling of MOF powders also hinder their widespread use in various applications. [Overview of the project] [Problems that the invention aims to solve]

[0003] Novel and improved materials, such as porous MOF composite structures, are needed to be arranged on a polymer matrix. Novel and improved methods for producing MOFs are also needed. This disclosure aims to provide such compositions and methods for producing such compositions. [Means for solving the problem]

[0004] Any or all parts of the embodiments disclosed herein may be combined with any other part of any embodiment.

[0005] In some embodiments, the method includes converting a porous metal salt polymer composite structure to a porous metal-organic skeleton (MOF) composite structure. For example, in some embodiments, the method includes in-situ conversion of a porous metal salt polymer composite structure to a porous metal-organic skeleton (MOF) composite structure. In some embodiments of the method, the porous metal salt polymer composite structure includes a metal chalcogenide polymer composite structure.

[0006] In some embodiments of the method, the porous metal chalcogenide polymer composite structure includes a metal oxide. In some embodiments of the method, the metal oxide is selected from the group consisting of transition metal oxides, group 4 metal oxides, group 5 metal oxides, group 6 metal oxides, group 7 metal oxides, group 8 metal oxides, group 9 metal oxides, group 10 metal oxides, group 11 metal oxides, group 12 metal oxides, group 13 metal oxides, and combinations thereof. In some embodiments of the method, the metal oxide is selected from the group consisting of V2O5, Fe2O3, CuO, ZnO, Al2O3, ZrO2, MgO, MnO, CoO, NiO, and combinations thereof.

[0007] In some embodiments of the method, the porous metal chalcogenide polymer composite structure comprises a metal chalcogenide. In some embodiments of the method, the metal chalcogenide comprises at least one metal atom, the at least one metal atom selected from the group consisting of transition metals, group 3 metals, group 4 metals, group 5 metals, group 6 metals, group 7 metals, group 8 metals, group 9 metals, group 10 metals, group 11 metals, group 12 metals, and combinations thereof. In some embodiments of the method, the metal chalcogenide comprises a chalcogen atom selected from the group consisting of S, Se, and Te. In some embodiments of the method, the metal chalcogenide is ZrS2, ZnS, or a combination thereof.

[0008] In some embodiments of the method, the porous metal salt polymer composite structure comprises a metal oxalate. In some embodiments of the method, the metal oxalate is selected from the group consisting of iron oxalate, copper oxalate, zirconium oxalate, aluminum oxalate, magnesium oxalate, nickel oxalate, cobalt oxalate, cerium oxalate, manganese oxalate, and chromium oxalate, but not limited to zinc oxalate.

[0009] In some embodiments of the method, the porous metal salt polymer composite structure includes a metal carbonate. In some embodiments of the method, the metal carbonate is selected from the group consisting of iron carbonate, copper carbonate, zirconium carbonate, aluminum carbonate, magnesium carbonate, nickel carbonate, cobalt carbonate, cerium carbonate, manganese carbonate, and chromium carbonate, but is not limited to zinc carbonate.

[0010] In some embodiments, the method includes producing a structural form of the porous metal salt polymer composite structure. In some embodiments of the method, the structural form includes a film, a laminate, a tube, a wound roll, a tape, a pellet, a column, a monolith, a module, a honeycomb shape, or a combination thereof.

[0011] In some embodiments of the method, the conversion from the porous metal chalcogenide polymer composite structure to the porous MOF composite structure includes a steam treatment process. In some embodiments of the method, the conversion from the porous metal chalcogenide polymer composite structure to the porous MOF composite structure includes a liquid treatment process.

[0012] In some embodiments of the method, the porous metal chalcogenide polymer composite structure includes polytetrafluoroethylene (PTFE).

[0013] In some embodiments of the method, the porous metal chalcogenide polymer composite structure comprises poly(ethylene-co-tetrafluoroethylene) (ETFE), ultra-high molecular weight polyethylene (UHMWPE), polyparaxylylene (PPX), polylactic acid, and any combination or blend thereof.

[0014] In some embodiments of the method, the porous MOF composite structure includes PTFE.

[0015] In some embodiments of the method, the porous MOF composite structure is made of ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-12, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-78, ZIF-79, ZIF-81, ZIF-82, ZIF-90, ZIF-8-90, ZIF-L, CALF-15, CALF-20, MOF-2, MOF-3, MOF-4, MOF-5, MOF-70, MOF-73, MOF-74, MOF-75, MOF-76, MOF-177, COF-1, COF-5, CO It contains at least one MOF selected from the group consisting of F-8, COF-105, COF-108, MIL-101, MIL-53, MIL-53-NH2, MIL-96, CAU-10, CAU-10-H, MOF-303, MOF-505, MOF-801, MOF-808, Al(OH) fumarate, Mg-formate, Zr-fumarate, UiO-66, UiO-66-NH2, UiO-67, UiO-68, HKUST-1, Fe-BTC, PCN-224, PCN-250, and UTSA-16, or a mixture of MOFs.

[0016] In some embodiments of the method, the porosity of the porous metal chalcogenide polymer composite ranges from about 10% to about 95%. In some embodiments of the method, at least 5% of the porosity contains pores with a diameter greater than 0.1 μm.

[0017] In some embodiments of the method, the porous metal salt polymer composite structure includes a porous ZnO-PTFE composite structure.

[0018] In some embodiments of the method, the porous MOF composite structure comprises ZIF-8-PTFE.

[0019] In some embodiments of the method, the porous metal salt polymer composite structure comprises a porous metal oxide polymer composite film.

[0020] In some embodiments of the method, the porous MOF composite structure comprises a porous MOF composite film.

[0021] In some embodiments of the method, the porous metal salt polymer composite structure comprises a metal oxide polymer composite column.

[0022] In some embodiments of the method, the porous MOF composite structure comprises a porous MOF composite column.

[0023] In some embodiments, the method further comprises forming the porous metal salt polymer composite structure.

[0024] In some embodiments, the porous MOF composite structure comprises PTFE and MOF permanently entangled in the PTFE.

[0025] In some embodiments, the porous MOF composite structure comprises ePTFE and MOF permanently entangled in the PTFE.

[0026] In some embodiments, the MOFs are ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-12, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-78, ZIF-79, ZIF-81, ZIF-82, ZIF-90, ZIF-8-90, ZIF-L, CALF-15, CALF-20, MOF-2, MOF-3, MOF-4, MOF-5, MOF-70, MOF-73, MOF-74, MOF-75, MOF-76, MOF-177, COF-1, CO The group is selected from F-5, COF-8, COF-105, COF-108, MIL-101, MIL-53, MIL-53-NH2, MIL-96, CAU-10, CAU-10-H, MOF-303, MOF-505, MOF-801, MOF-808, Al(OH) fumarate, Mg-formate, Zr-fumarate, UiO-66, UiO-66-NH2, UiO-67, UiO-68, HKUST-1, Fe-BTC, PCN-224, PCN-250, and UTSA-16.

[0027] In some embodiments of the porous MOF composite structure, the metal of the MOF is selected from the group consisting of transition metals, group 4 metals, group 5 metals, group 6 metals, group 7 metals, group 8 metals, group 9 metals, group 10 metals, group 11 metals, group 12 metals, group 13 metals, V, Fe, Cu, Zn, Al, Zr, Mg, Mn, Co, and Ni.

[0028] In some embodiments of the porous MOF composite structure, the porosity of the porous MOF composite structure ranges from about 10% to about 95%.

[0029] In some embodiments of porous MOF composite structures, the Brunauer-Emmett-Teller (BET) surface area is 20 m². 2 / g~4000m 2 It is within the range of / g.

[0030] In some embodiments of the porous MOF composite structure, the porous MOF composite structure includes a porous MOF composite film.

[0031] In some embodiments of the porous MOF composite structure, the thickness of the porous MOF composite film is approximately 0.001 mm to 5 mm.

[0032] In some embodiments, the thickness of the porous MOF composite film is approximately 0.001 mm to 0.01 mm. In some embodiments, the thickness of the porous MOF composite film is approximately 0.01 mm to 1.5 mm. In some embodiments, the thickness of the porous MOF composite film is approximately 0.01 mm to 5 mm. In some embodiments, the thickness of the porous MOF composite film is approximately 1.5 mm to 5 mm.

[0033] In some embodiments of the porous MOF composite structure, the porous MOF composite film includes an MOF layer on at least one side of the outer surface of the porous MOF composite film.

[0034] In some embodiments of the porous MOF composite structure, the thickness of the MOF layer on the outer surface is approximately 0.001 mm to approximately 5 mm.

[0035] In some embodiments of the porous MOF composite structure, the tensile strength of the porous MOF composite structure exceeds 1 pound per square inch.

[0036] In some embodiments, the method includes producing a structural form of a porous metal salt polymer composite structure and then converting the porous metal salt polymer composite structure into a porous metal-organic skeleton (MOF) composite structure.

[0037] In some embodiments, the composite article comprises a porous fibrillated polymer membrane, the porous fibrillated polymer membrane containing supported particles permanently entangled in a mesh-like manner within the porous fibrillated polymer membrane.

[0038] In some embodiments, the porous metal salt polymer composite structure is either a porous metal chalcogenide polymer composite structure or comprises a porous metal chalcogenide polymer composite structure.

[0039] In some embodiments, the porous MOF composite film includes MOF layers on at least two sides of the outer surface of the porous MOF composite film.

[0040] In some embodiments, the porous MOF composite film includes MOF layers on two opposing sides of the outer surface of the porous MOF composite film.

[0041] In some embodiments of the porous MOF composite structure, the thickness of the MOF layer on the outer surface is approximately 0.001 mm to approximately 5 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 0.001 mm to approximately 0.01 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 0.01 mm to approximately 1.5 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 0.01 mm to approximately 5 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 1.5 mm to approximately 5 mm.

[0042] In some embodiments, the method includes converting a porous metal salt polymer composite structure into a porous metal-organic skeleton (MOF) composite structure. In some embodiments of the method, the porous metal salt polymer composite structure comprises a metal chalcogenide. In some embodiments, the porous metal chalcogenide polymer composite structure comprises a metal oxide. In some embodiments, the metal oxide is selected from the group consisting of transition metal oxides, group 4 metal oxides, group 5 metal oxides, group 6 metal oxides, group 7 metal oxides, group 8 metal oxides, group 9 metal oxides, group 10 metal oxides, group 11 metal oxides, group 12 metal oxides, group 13 metal oxides, and combinations thereof. In some embodiments, the metal oxide is selected from the group consisting of V2O5, Fe2O3, CuO, ZnO, Al2O3, ZrO2, MgO, MnO, CoO, NiO, and combinations thereof. In some embodiments, the porous metal chalcogenide polymer composite structure comprises a metal chalcogenide. In some embodiments, the metal chalcogenide comprises at least one metal atom, the at least one metal atom selected from the group consisting of transition metals, group 3 metals, group 4 metals, group 5 metals, group 6 metals, group 7 metals, group 8 metals, group 9 metals, group 10 metals, group 11 metals, group 12 metals, and combinations thereof. In some embodiments, the metal chalcogenide comprises a chalcogen atom selected from the group consisting of S, Se, and Te. In some embodiments, the metal chalcogenide is ZrS2, ZnS, or a combination thereof. In some embodiments, the porous metal salt polymer composite structure comprises a metal oxalate. In some embodiments, the metal oxalate is selected from the group consisting of iron oxalate, copper oxalate, zirconium oxalate, aluminum oxalate, magnesium oxalate, nickel oxalate, cobalt oxalate, cerium oxalate, manganese oxalate, and chromium oxalate, but not limited to zinc oxalate. In some embodiments, the porous metal salt polymer composite structure includes a metal carbonate.In some embodiments, the metal carbonate is selected from the group consisting of iron carbonate, copper carbonate, zirconium carbonate, aluminum carbonate, magnesium carbonate, nickel carbonate, cobalt carbonate, cerium carbonate, manganese carbonate, and chromium carbonate, but is not limited to zinc carbonate.

[0043] In some embodiments, the method includes producing a structural form of a porous metal salt polymer composite structure and then converting the porous metal salt polymer composite structure into a porous metal-organic skeleton (MOF) composite structure. In some embodiments, the composite article includes a porous fibrillated polymer membrane, which contains supported particles permanently entangled in a mesh-like manner within the porous fibrillated polymer membrane. In some embodiments, the structural form of the composite article includes a film, a laminate, a tube, a wound roll, a tape, a pellet, a column, a monolith, a module, a honeycomb shape, or a combination thereof.

[0044] In some embodiments, the conversion from the porous metal chalcogenide polymer composite structure to the porous MOF composite structure includes a steam treatment process. In some embodiments, the conversion from the porous metal chalcogenide polymer composite structure to the porous MOF composite structure includes a liquid treatment process. In some embodiments, the porous metal chalcogenide polymer composite structure includes polytetrafluoroethylene (PTFE). In some embodiments, the porous metal chalcogenide polymer composite structure includes poly(ethylene-co-tetrafluoroethylene) (ETFE), ultra-high molecular weight polyethylene (UHMWPE), polyparaxylylene (PPX), polylactic acid, and any combination or blend thereof. In some embodiments, the porous MOF composite structure includes PTFE. In some embodiments, the porous MOF composite structure is made up of ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-12, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-78, ZIF-79, ZIF-81, ZIF-82, ZIF-90, ZIF-8-90, ZIF-L, CALF-15, CALF-20, MOF-2, MOF-3, MOF-4, MOF-5, MOF-70, MOF-73, MOF-74, MOF-75, MOF-76, MOF-177, COF-1, COF-5, COF- 8. The material comprises at least one MOF selected from the group consisting of COF-105, COF-108, MIL-101, MIL-53, MIL-53-NH2, MIL-96, CAU-10, CAU-10-H, MOF-303, MOF-505, MOF-801, MOF-808, Al(OH) fumarate, Mg-formate, Zr-fumarate, UiO-66, UiO-66-NH2, UiO-67, UiO-68, HKUST-1, Fe-BTC, PCN-224, PCN-250, and UTSA-16, or a mixture of MOFs.

[0045] In some embodiments, the porosity of the porous metal chalcogenide polymer composite ranges from about 10% to about 95%.

[0046] In some embodiments, the porous metal chalcogenide polymer composite structure includes a porous ZnO-PTFE composite structure. In some embodiments, the porous MOF composite structure includes ZIF-8-PTFE. In some embodiments, the porous metal chalcogenide polymer composite structure includes a porous metal oxide polymer composite film. In some embodiments, the porous MOF composite structure includes a porous MOF composite film. In some embodiments, the porous metal oxide polymer composite structure includes a metal oxide polymer composite column. In some embodiments, the porous MOF composite structure includes a porous MOF composite column.

[0047] In some embodiments, the porous MOF composite structure comprises PTFE and MOF permanently entangled in the PTFE. In some embodiments, the porous MOF composite structure comprises stretched polytetrafluoroethylene (ePTFE) and MOF permanently entangled in the PTFE. In some embodiments, the metal of the MOF is selected from the group consisting of transition metals, group 4 metals, group 5 metals, group 6 metals, group 7 metals, group 8 metals, group 9 metals, group 10 metals, group 11 metals, group 12 metals, group 13 metals, V, Fe, Cu, Zn, Al, Zr, Mg, Mn, Co, and Ni. In some embodiments, the Brunauer-Emmett-Teller (BET) surface area of ​​the porous MOF composite structure is 20 m². 2 / g~4000m 2 It is within the range of / g. In some embodiments, the porous MOF composite structure includes a porous MOF composite film. In some embodiments, the thickness of the porous MOF composite film is about 0.001 mm to 5 mm. In some embodiments, the thickness of the porous MOF composite film is about 0.001 mm to 0.01 mm. In some embodiments, the thickness of the porous MOF composite film is about 0.01 mm to 1.5 mm. In some embodiments, the thickness of the porous MOF composite film is about 0.01 mm to 5 mm. In some embodiments, the thickness of the porous MOF composite film is about 1.5 mm to 5 mm.

[0048] In some embodiments, the porous MOF composite film includes an MOF layer on at least one side of the outer surface of the porous MOF composite film. In some embodiments, the porous MOF composite film includes an MOF layer on at least two sides of the outer surface of the porous MOF composite film.

[0049] In some embodiments, the thickness of the MOF layer on the outer surface is approximately 0.001 mm to approximately 5 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 0.001 mm to approximately 0.01 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 0.01 mm to approximately 1.5 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 0.01 mm to approximately 5 mm. In some embodiments, the thickness of the MOF layer on the outer surface is approximately 1.5 mm to approximately 5 mm.

[0050] In some embodiments, the tensile strength of the porous MOF composite structure exceeds 1 pound per square inch. Therefore, the present invention provides a method for producing structured MOF composite tapes by immobilizing metal chalcogenide particles within a polymer matrix and then in-situ converting the metal chalcogenide to MOFs. In some embodiments, the conversion is carried out from a ZnO-PTFE composite to a ZIF-8-PTFE composite. The ZIF-8-PTFE composite is a useful material for propylene / propane separation, oil capture, and photocatalytic sterilization against airborne bacteria. Besides ZIF-8, structured MOF composite tapes are useful materials for chemical separation, including, for example, chemical purification, air purification, and removal of biologically toxic substances. In addition, composite articles containing MOFs may be in the form of filter bags, honeycombs, columns, or other appropriate forms.

[0051] Refer to the attached drawings. The drawings form part of this disclosure and illustrate examples of the systems and methods described herein. Similar reference numerals represent similar parts throughout. [Brief explanation of the drawing]

[0052] [Figure 1]Figure 1 shows an exemplary and non-limiting schematic flowchart for an exemplary method of producing a ZIF-8-PTFE composite from ZnO embedded on PTFE. [Figure 2] Figure 2 shows an example of the particle size distribution of ZnO obtained according to this non-restrictive exemplary process. [Figure 3] Figure 3 shows an example of the pore size distribution and cumulative pore volume of a ZnO-PTFE composite film based on a non-limiting embodiment. [Figure 4] Figure 4 shows the exemplary amounts of ZnO-PTFE on the surface area before and after the conversion process based on a non-limiting embodiment. [Figure 5] Figure 5 shows an example of a comparison graph based on an unrestricted exemplary process. [Figure 6] Figure 6 shows an example of cross-sectional scanning electron microscope elemental mapping based on one embodiment. [Figure 7] Figure 7 shows an example of cross-sectional scanning electron microscope elemental mapping based on one embodiment. [Figure 8] Figure 8 shows an example of a comparison graph based on an unrestricted exemplary process. [Figure 9] Figure 9 shows an example of a high-resolution scanning electron microscope image based on one embodiment. [Figure 10] Figure 10 shows an example of a high-resolution scanning electron microscope image based on one embodiment. [Figure 11] Figure 11 shows an example of a comparative chart of CO2 uptake measurements based on one embodiment. [Modes for carrying out the invention]

[0053] The cost of metal chalcogenides (e.g., metal oxides) can be several orders of magnitude lower than the cost of MOFs. Therefore, embodiments of the methods disclosed herein can produce economically feasible, large-scale, high-quality porous MOF composite structures. Furthermore, the conversion of metal chalcogenides can be performed in situ. Thus, it is not necessary to directly obtain MOF powder or particles for embedding the resulting MOF into a polymer membrane or film. In other words, this exemplary process eliminates the process of directly entangling MOF powder into a polymer membrane. Thus, some embodiments do not involve preparing or obtaining MOF powder. Furthermore, some embodiments do not involve directly entangling MOF powder into a polymer membrane or film. Non-limiting examples of embodiments are provided in more detail below.

[0054] Some embodiments of the methods disclosed herein aim to convert porous metal salt polymer composite structures into porous metal-organic framework (MOF) composite structures. In some embodiments, the porous metal salt polymer composite structure includes a metal oxide.

[0055] In some embodiments, the metal oxide is permanently entangled within the polymer membrane, and then the metal oxide is converted into a MOF while supported on the polymer membrane.

[0056] In some embodiments, the polymer membrane has at least one node-connected fibril microstructure. The fibril microstructure includes fibrils that form a network structure by interconnecting with other fibrils or nodes. Particles are placed and immobilized within this network structure. In some embodiments, the fibrillated polymer membrane forms a network structure of fibrils that immobilize and entangle for supporting particles within the fibrillated microstructure. In some embodiments, the polymer membrane is a PTFE membrane or includes a PTFE membrane having at least one node-connected fibril microstructure. In some embodiments, the polymer membrane is an ePTFE membrane or includes an ePTFE membrane having at least one node-connected fibril microstructure.

[0057] As used herein, the phrase “durably enmeshed” refers to something non-covalently immobilized within the fibrillated microstructure of a polymer membrane. For example, “catalyst particles permanently enmeshed within a polymer membrane” describes the structural relationship of catalyst particles non-covalently immobilized within the fibrillated microstructure of a polymer membrane. In some embodiments of “durably enmeshed” catalyst particles, there is no separate binder present to immobilize the catalyst particles within the membrane. In some embodiments, the catalyst particles are arranged throughout the entire thickness of the fibrillated polymer membrane.

[0058] Table 1 shows various non-limiting examples of MOF composite structures that can be produced via in-situ conversion of metal oxides. Table 1 also lists various organic linkers that can be used, as well as solvents that can be used in each process. For example, as shown in Table 1, ZnO can be converted to ZIF-8 using 2-methylimidazole as an organic linker without the use of a solvent. [Table 1] [Examples]

[0059] Example 1: Conversion of ZnO to ZIF-8 on PTFE

[0060] The following non-limiting exemplary process enables the production of economically viable, large-scale, high-quality ZnO-PTFE composites. Furthermore, the conversion from ZnO to ZIF-8 can be carried out on the ZnO-PTFE composite. Therefore, it is not necessary to directly obtain ZIF-8 powder or to embed ZIF-8 particles into PTFE. In other words, this exemplary process eliminates the process of directly entangling ZIF-8 powder into PTFE. Thus, in some embodiments, these methods do not involve obtaining ZIF-8 powder. Furthermore, in some embodiments, these methods do not involve directly entangling ZIF-8 powder into PTFE.

[0061] Figure 1 shows an embodiment of a method for forming an embodiment of a composite material. This embodiment involves forming, for example, a metal oxide PTFE composite by mixing PTFE 102 with a metal oxide. In the embodiment shown in Figure 1, the PTFE is formed first, separated from the metal oxide particles. Alternatively, the PTFE 102 is not initially formed separated from the metal oxide particles. That is, in another embodiment, the metal oxide is permanently entangled with the PTFE 102 by mixing it in during the formation of the PTFE 102. For example, to form a ZnO-PTFE composite 104, PTFE 102 is formed together with ZnO 106 particles, during which the ZnO 106 is permanently entangled inside or on the PTFE 102. Then, for example, a steam treatment process can be used to produce a ZIF-8-PTFE composite 108. The steam treatment process converts some or all of the ZnO 106 into ZIF-8 110, with the ZnO 106 permanently entangled on the PTFE 102. The resulting composite material may have a mixture of ZnO and ZIF-8 permanently entangled on the PTFE. Thus, in some embodiments, the PTFE 102 is not initially formed in a state separated from the metal oxide particles.

[0062] In some embodiments, the conversion process can control the amount of conversion from ZnO 106 to ZIF-8 110 with respect to these locations on the PTFE 102. For example, the conversion from ZnO 106 to ZIF-8 110 can be carried out on the outer thin layer of the ZnO-PTFE composite 108 by controlling the porosity of the ZnO-PTFE composite 108, for example by reducing the porosity. For example, the conversion from ZnO 102 to ZIF-8 110 can be carried out on most of the ZnO 106 of the ZnO-PTFE composite 108 by increasing the porosity of the ZnO-PTFE composite 108.

[0063] One example of a conversion process can be described as "in-situ conversion." In this case, a porous polymer film composite of metal oxide particles is converted in the liquid phase to a structured porous film composite of porous MOF particles. In some embodiments, the conversion process is carried out in a low temperature range.

[0064] Figure 2 shows the particle size distribution of ZnO obtained according to this non-limiting exemplary process. As can be seen from Figure 2, the average particle size (i.e., particle diameter) of ZnO in this example was approximately 0.5–0.6 μm, as measured by a Horiba LA-350 laser scattering particle size distribution analyzer. A composite blend of 50 wt% ZnO particles and 50 wt% PTFE was blended in the manner generally taught in Mitchell et al., U.S. Patent Application Publication 2005 / 0057888. The resulting porous fibrillated ePTFE composite film contained approximately 50 wt% ZnO particles permanently entangled and immobilized in a matrix of ePTFE nodes and fibrils.

[0065] Figure 3 shows the pore size distribution and cumulative pore volume of the ZnO-PTFE composite film. The pore size distribution and cumulative pore volume of the obtained ZnO-PTFE composite film were measured using a Micromeritics AutoPore V mercury porosimeter (Micromeritics, Norcross, Georgia, USA).

[0066] In some embodiments, the main pore size of the ZnO-PTFE composite film in this example was approximately 60 nm. In some embodiments, the porosity of the ZnO-PTFE composite film was measured to be in the range of 26–29%.

[0067] In some embodiments, high-porosity ZnO-PTFE composite films exhibited additional pores exceeding 0.1 μm. In some embodiments, the porosity of high-porosity ZnO-PTFE composite films was measured to be in the range of 59–71%. Porosity is calculated by 100*(1-bulk density / skeleton density). Bulk density was obtained on a Micromeritics AutoPore V mercury porosimeter (Micromeritics, Norcross, Georgia, USA). Skeleton density was obtained on a helium pycnometer (UltraPyc 1200e, Quantachrome instruments).

[0068] Next, the conversion process was carried out on the ZnO-PTFE composite film. The process in this example was in-situ liquid-phase conversion at a low temperature. In this example, a 10 mm diameter sample was die-cut from a 0.55 mm thick porous ZnO-PTFE film. The porous ZnO-PTFE film was converted to a porous ZIF-8-PTFE film by placing the sample in a 20 ml glass vial with 10 ml of methanol and 0.4 g of 2-methylimidazole at 20°C for 112 hours. The specific surface area of ​​the film sample was measured before and after in-situ conversion by nitrogen physicoadsorption at 77 K (Nova, Quantachrome instruments) and calculated using the Brunauer-Emmett-Teller method. The specific surface area was 2.6 m² of the ZnO-PTFE film. 2 From / g, 56m of ZnO-PTFE film treated for 112 hours 2 The amount increased to / g. Figure 4 shows a comparison chart of the amount of ZnO-PTFE on the surface before the conversion process and the amount of ZnO-PTFE on the surface after the in-situ conversion process (labeled: 112h-ZnO-PTFE(L)).

[0069] Example 2: Comparison of low-porosity and high-porosity composites

[0070] By controlling the conversion process, the resulting amount and location of the MOF in the polymer membrane can be controlled. For example, the MOF can be formed substantially on the surface of the polymer membrane (i.e., not throughout the entire polymer membrane), or the MOF can be formed throughout the polymer membrane, or any amount in between can also be formed. Thus, the conversion can be adjusted to be only on the surface or through the tape / film.

[0071] For example, FIG. 5 shows a comparative graph based on the following non-limiting exemplary process. Two 50% loading ZnO-PTFE composites were exposed to 2-methylimidazole vapor at 125° C. in a 50 ml autoclave. After treatment for 64 hours, the conversion from the ZnO-PTFE composite to the ZIF-PTFE composite increased from 4 m 2 / g to 44.1 m 2 / g for the low porosity (26 - 29%) ZnO-PTFE composite. The conversion from ZnO-PTFE to ZIF-PTFE increased to 498.8 m 2 / g for the high porosity (59 - 71%) ZnO-PTFE composite.

[0072] By further increasing the treatment time to 112 hours, for the low porosity ZnO-PTFE composite, the conversion increased to 73.1 m 2 / g. At 112 hours, the wt% of ZIF-8 produced by this conversion process was calculated to be approximately 4.2 wt%.

[0073] After 112 hours of treatment time, for the high porosity ZnO-PTFE composite, the conversion was 597.2 m 2The amount increased to / g. At 112 hours, the wt% of ZIF-8 produced by this conversion process was calculated to be approximately 34.1 wt%. The wt% of ZIF-8 in the composite is calculated by dividing the surface area of ​​the composite by the surface area of ​​the ZIF-8 powder. The surface area of ​​the ZIF-8 powder was measured at 77K by nitrogen physicoadsorption (Nova, Quantachrome instruments) and is 1753 m2 / g.

[0074] Figures 6 and 7 show cross-sectional scanning electron microscopy (SEM) elemental mapping, where the detection of nitrogen demonstrates the conversion from ZnO to ZIF-8. Cross-sectional energy-dispersive spectroscopy elemental mapping was performed on a Hitachi TM3030Plus microscope. The nitrogen signal on the outer surface of the ZnO-PTFE composite film provides evidence that ZIF-8 was converted from ZnO within the ZnO-PTFE composite film. The specific surface area of ​​the film sample was measured before and after in-situ conversion by nitrogen physicoadsorption at 77K (Nova, Quantachrome instruments) and calculated using the Brunauer-Emmett-Teller method.

[0075] The nitrogen (N) distribution shown in Figure 6 indicates that the conversion from ZnO to ZIF-8 mainly occurred on the outer surface of the low-porosity ZnO-PTFE composite. The thickness of the low-porosity ZnO-PTFE tape was approximately 0.9–1.1 mm, while the thickness of the MOF(ZIF-8) layer on the outer surface of the ZnO-PTFE tape was approximately 0.1–0.4 mm.

[0076] The uniform distribution of N shown in Figure 7 indicates that the conversion from ZnO to ZIF-8 was uniform throughout the entire composite. The thickness of the high-porosity ZnO-PTFE tape was approximately 1.0–1.4 mm, while the thickness of the MOF(ZIF-8) layer was approximately 1.0–1.4 mm.

[0077] The success of the conversion from ZnO to ZIF-8 was also confirmed by X-ray diffraction and Fourier transform infrared spectroscopy (FTIR). In some embodiments, the conversion from ZnO to ZIF-8 can also be achieved by treating the ZnO-PTFE complex in a 2-methylimidazole methanol solution at room temperature.

[0078] Example 3: Conversion of Al2O3 to MIL-53 on PTFE

[0079] The following non-limiting exemplary processes can be used to produce economically viable, large-scale, high-quality MIL-53-PTFE composites. Furthermore, the conversion from Al2O3 to MIL-53 can be carried out on the Al2O3-PTFE composite. Thus, in some embodiments, these methods do not involve obtaining MIL-53 powder. Furthermore, in some embodiments, these methods do not involve directly entangling the MIL-53 powder with PTFE.

[0080] In this embodiment, the in-situ conversion from a porous polymer film composite of metal oxide particles to a structured porous film composite of porous MOF particles is carried out in the liquid phase at a high temperature. A composite blend of 50 wt% aluminum oxide and 50 wt% PTFE was blended in the manner generally taught in Mitchell et al., U.S. Patent Application Publication 2005 / 0057888. The resulting porous fibrillated stretched PTFE (ePTFE) composite film contained 50 wt% Al2O3 particles permanently entangled and immobilized within the matrix of ePTFE nodes and fibrils. A 10 mm diameter sample was then die-cut from the 1.34 mm thick porous Al2O3-PTFE film. Porous Al2O3-PTFE film was converted to porous MIL-53-PTFE film by placing the sample in a 50 ml autoclave reactor at 220°C for 24 hours with 10 ml of DI water and 0.45 g of 1,4-benzenedicarboxylic acid. The specific surface area of ​​the film sample was measured before and after in-situ conversion by nitrogen physicoadsorption at 77 K (Nova, Quantachrome instruments), and calculated using the Brunauer-Emmett-Teller method. Figure 8 shows the comparison results. The specific surface area of ​​the Al2O3-PTFE film was 14 m². 2 From / g, 29m of 24-hour treated Al2O3-PTFE film (labeled: 24h-Al2O3-PTFE(L)) 2 The concentration increased to / g. Figure 9 shows a high-resolution scanning electron microscope image of the Al2O3-PTFE film before conversion. Figure 10 shows a high-resolution scanning electron microscope image of the Al2O3-PTFE film after in-situ liquid-phase conversion. The images in Figures 9 and 10 were obtained using a Hitachi TM3030Plus microscope. Figure 9 shows cuboidal Al2O3 crystals within the Al2O3-PTFE film, while Figure 10 shows needle-like MIL-53 crystals.

[0081] Example 4: Conversion of zinc oxalate to CALF-20 on PTFE

[0082] Generally, zinc oxalate and 1,2,4-triazole are required to form CALF-20. Typically, such reactions require 40% water, 60% methanol, and a temperature of 180°C for two days. [ka]

[0083] The following non-limiting exemplary process involves the in-situ synthesis of CALF-20 from zinc oxalate permanently embedded on PTFE. According to this process, a porous fibrillated structure is formed by mixing zinc oxalate with PTFE. The reaction is carried out using 100% MeOH to wet the PTFE. From the zinc oxalate-PTFE composite structure, the synthesis process from zinc oxalate to CALF-20 (e.g., conversion) is carried out in situ. This results in a CALF-20-PTFE composite structure. The CO2 uptake results are shown in Figure 11.

[0084] Example 5: Conversion of zinc carbonate to CALF-20 on PTFE

[0085] The following non-limiting exemplary process is an "indirect" process for producing CALF-20-PTFE composite structures. Unlike the exemplary process of Example 4, which requires obtaining zinc oxalate, this process involves obtaining zinc carbonate and oxalic acid (instead of zinc oxalate). This process may be about 1 / 20th cheaper than using zinc oxalate to produce CALF-20. According to this process, zinc oxalate is formed by reacting basic zinc carbonate with oxalic acid at 25°C. The produced zinc oxalate is then permanently entangled with PTFE, converting the zinc oxalate on the PTFE into CALF-20.

[0086] CALF-20 produced via the "indirect" method (i.e., using ZnCO3) has been shown to have slightly lower CO2 uptake characteristics than CALF-20 produced via the "direct" method (i.e., using MeOH). However, the CO2 uptake characteristics of CALF-20 produced via both the "direct" and "indirect" methods have been shown to be higher than those of BPL activated carbon. Figure 11 shows a comparative chart of CO2 uptake measurements. Table 2 shows additional tests of the "indirect" conversion of zinc carbonate to CALF-20. For a 50% ZnCO3-PTFE tape, the conversion rate to CALF-20 increased from 39% to 100% as the percentage of pores larger than 0.1 μm increased from 9.6% to 51.3% in terms of total cumulative pore volume. [Table 2]

[0087] The terms used herein are intended to describe embodiments and are not intended to be restrictive. The terms "a," "an," and "the" include the plural unless expressly otherwise. The terms "comprises" and "comprising," when used in this disclosure, specify the presence of a declared feature, integer, process, operation, element, component, or combination thereof, but do not exclude the presence or addition of one or more other features, integers, processes, operations, elements, or components.

[0088] It should be understood that modifications may be made in detail, particularly with respect to the materials used and the shape, size, and arrangement of the parts, without departing from the scope of this disclosure. This specification and the embodiments described herein are examples, and the true scope and idea of ​​the disclosure are shown by the following claims.

Claims

1. A method comprising converting a porous metal salt polymer composite structure into a porous metal-organic skeleton (MOF) composite structure, wherein the porous metal salt polymer composite structure contains a metal oxalate or a metal carbonate.

2. The method according to claim 1, wherein the metal oxalate is selected from the group consisting of iron oxalate, copper oxalate, zirconium oxalate, aluminum oxalate, magnesium oxalate, nickel oxalate, cobalt oxalate, cerium oxalate, manganese oxalate, and chromium oxalate, but is not limited to zinc oxalate.

3. The method according to claim 1, wherein the metal carbonate is selected from the group consisting of iron carbonate, copper carbonate, zirconium carbonate, aluminum carbonate, magnesium carbonate, nickel carbonate, cobalt carbonate, cerium carbonate, manganese carbonate, and chromium carbonate, but is not limited to zinc carbonate.

4. The method according to claim 1, further comprising producing the structural form of the porous metal salt polymer composite structure.

5. The aforementioned structural form includes a film, laminate, tube, wound roll, tape, pellet, column, monolith, module, honeycomb shape, or a combination thereof. The method according to claim 4.

6. The method according to any one of claims 1 to 5, wherein the conversion from the porous metal salt polymer composite structure to the porous MOF composite structure includes a steam treatment process.

7. The method according to any one of claims 1 to 5, wherein the conversion from the porous metal salt polymer composite structure to the porous MOF composite structure includes a liquid treatment process.

8. The method according to any one of claims 1 to 5, wherein the porous metal salt polymer composite structure contains polytetrafluoroethylene (PTFE).

9. The method according to any one of claims 1 to 5, wherein the porous metal salt polymer composite structure comprises poly(ethylene-co-tetrafluoroethylene) (ETFE), ultra-high molecular weight polyethylene (UHMWPE), polyparaxylylene (PPX), polylactic acid, and any combination or blend thereof.

10. The method according to any one of claims 1 to 5, wherein the porous MOF composite structure includes PTFE.

11. The porous MOF composite structure is ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-12, ZIF-67, ZIF- 68, ZIF-69, ZIF-70, ZIF-78, ZIF-79, ZIF-81, ZIF-82, ZIF-90, ZIF-8-9 0, ZIF-L, CALF-15, CALF-20, MOF-2, MOF-3, MOF-4, MOF-5, MOF-70, MOF- 73, MOF-74, MOF-75, MOF-76, MOF-177, COF-1, COF-5, COF-8, COF-105, C The method according to claim 1, comprising at least one MOF selected from the group consisting of OF-108, MIL-101, MIL-53, MIL-53-NH2, MIL-96, CAU-10, CAU-10-H, MOF-303, MOF-505, MOF-801, MOF-808, Al(OH) fumarate, Mg-formate, Zr-fumarate, UiO-66, UiO-66-NH2, UiO-67, UiO-68, HKUST-1, Fe-BTC, PCN-224, PCN-250, and UTSA-16, or a mixture of MOFs.

12. The method according to claim 1, wherein the porous MOF composite structure includes a porous MOF composite film.

13. The method according to claim 1, wherein the porous metal salt polymer composite structure includes a metal oxide polymer composite column.

14. The method according to claim 1, wherein the porous MOF composite structure includes a porous MOF composite column.

15. The method according to claim 1, further comprising forming the porous metal salt polymer composite structure.

16. A porous MOF composite structure, PTFE and, MOF permanently entangled in the aforementioned PTFE and A porous MOF composite structure characterized by containing a metal oxalate or metal carbonate.

17. A porous MOF composite structure, ePTFE and, MOF permanently entangled in the aforementioned ePTFE and A porous MOF composite structure characterized by containing a metal oxalate or metal carbonate.

18. The MOF is ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-12, ZIF-67, ZIF-68, ZIF -69, ZIF-70, ZIF-78, ZIF-79, ZIF-81, ZIF-82, ZIF-90, ZIF-8-90, ZI FL, CALF-15, CALF-20, MOF-2, MOF-3, MOF-4, MOF-5, MOF-70, MOF-73, MOF-74, MOF-75, MOF-76, MOF-177, COF-1, COF-5, COF-8, COF-105, A porous MOF composite structure according to claim 16 or 17, selected from the group consisting of COF-108, MIL-101, MIL-53, MIL-53-NH2, MIL-96, CAU-10, CAU-10-H, MOF-303, MOF-505, MOF-801, MOF-808, Al(OH) fumarate, Mg-formate, Zr-fumarate, UiO-66, UiO-66-NH2, UiO-67, UiO-68, HKUST-1, Fe-BTC, PCN-224, PCN-250, and UTSA-16.

19. The porous MOF composite structure according to claim 16 or 17, wherein the metal of the MOF is selected from the group consisting of transition metals, group 4 metals, group 5 metals, group 6 metals, group 7 metals, group 8 metals, group 9 metals, group 10 metals, group 11 metals, group 12 metals, group 13 metals, V, Fe, Cu, Zn, Al, Zr, Mg, Mn, Co, and Ni.

20. The porous MOF composite structure according to claim 16 or 17, wherein the porosity of the porous MOF composite structure is in the range of 10% to 95%.

21. The surface area of ​​the Brunauer-Emmett-Teller (BET) is 20 m². ２ / g to 4000m ２ A porous MOF composite structure according to claim 16 or 17, which is within the range of / g.

22. The porous MOF composite structure according to claim 16 or 17, wherein the porous MOF composite structure includes a porous MOF composite film.

23. The porous MOF composite structure according to claim 22, wherein the thickness of the porous MOF composite film is 0.001 mm to 5 mm.

24. The porous MOF composite structure according to claim 22, wherein the porous MOF composite film includes an MOF layer on at least one side of the outer surface of the porous MOF composite structure.

25. The porous MOF composite structure according to claim 24, wherein the thickness of the MOF layer on the outer surface is 0.001 mm to 5 mm.

26. The porous MOF composite structure according to claim 16 or 17, wherein the tensile strength of the porous MOF composite structure is greater than 1 pound per square inch.

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