Functional metal-organic framework, method for manufacturing same, and atmospheric water harvesting apparatus using same

Abstract

The method for manufacturing a functional metal-organic framework according to the present invention comprises the steps of: preparing a base metal-organic framework having a first porosity; and filling at least some of the pores of the base metal-organic framework by using a method in which the base metal-organic framework is provided with a functional oligomer, thereby manufacturing a functional metal-organic framework having a second porosity lower than the first porosity.

Description

Functional metal-organic framework, method for manufacturing the same, and atmospheric water harvesting device using the same

[0001] The present invention relates to a functional metal-organic framework, a method for producing the same, and an air water harvesting device using the same, and more particularly, to a functional metal-organic framework in which a portion of the pores of the base metal-organic framework are filled with a functional oligomer chemically bonded to a metal atom of the base metal-organic framework, a method for producing the same, and an air water harvesting device using the same.

[0002] This is the result of the research project of the present invention below.

[0003] Project Name: Development of Insulating Materials for Liquid Hydrogen Transport and Storage Tanks (Gyeonggi Province)

[0004] - Research project unique number: 202300100010001

[0005] - Project ID (Government): GRRCHanyang2020-B01

[0006] - Business-related ministry: local government

[0007] - Research Project Name: Gyeonggi Regional Cooperation Research Center Project (GRRC) / Gyeonggi Regional Cooperation Research Center Project (GRRC) / GRRC Basic Project

[0008] - Host organization: Gyeonggi Regional Cooperation Research Center

[0009] - Research Management Specialist Agency: Gyeonggi Provincial Government

[0010] Research Period: July 1, 2023 - June 30, 2024

[0011]

[0012] Metal-organic frameworks (MOFs) are polymeric structures formed by bonds between metal ions and organic ligands. These structures come in a variety of structures, such as octahedral carboxyhydrate, and are widely used in nanotechnology and in diverse applications such as molecular storage, separation, and catalysis.

[0013] For example, Korean Patent Publication No. 10-2172958 discloses a humidity sensing transistor comprising: a substrate; a gate electrode positioned on the substrate; a dielectric layer positioned over the entire surface of the substrate including the gate electrode; an organic semiconductor layer positioned over the entire surface of the dielectric layer and including a poly(3-hexylthiophene) (Poly(3-hexylthiophene); P3HT) conjugated polymer and HKUST-1 (copper benzene-1,3,5-tricarboxylate; Cu3(BTC)2) as a metal organic framework (MOF); and source and drain electrodes positioned spaced apart from each other on the organic semiconductor layer, wherein the HKUST-1 is added in an amount of 10 to 30 wt% relative to the P3HT content.

[0014] On the other hand, metal-organic frameworks (MOFs) possess the characteristic of rapidly and efficiently absorbing water at low humidity, but are vulnerable to water. Therefore, the present invention improves the water stability of MOFs by providing functional oligomers within some of the pores of the MOF.

[0015]

[0016] The technical problem to be solved by the present invention is to provide a functional metal-organic framework with improved crystal stability due to water adsorption in the air.

[0017] Another technical problem to be solved by the present invention is to provide a functional metal-organic framework that maintains the unique water adsorption level of the base metal-organic framework in the atmosphere.

[0018] Another technical problem to be solved by the present invention is to provide an atmospheric water harvesting device with improved long-term stability for water adsorption / water desorption cycles in the atmosphere.

[0019] Another technical problem that the present invention seeks to solve is to provide an atmospheric water harvesting device having improved water harvesting capacity in the atmosphere.

[0020] Another technical problem that the present invention seeks to solve is to provide a method for manufacturing a functional metal-organic framework with reduced manufacturing process costs.

[0021] Another technical problem that the present invention seeks to solve is to provide a method for manufacturing a functional metal-organic framework with a shortened manufacturing time.

[0022] Another technical problem that the present invention seeks to solve is to provide a method for manufacturing a functional metal-organic framework that is easy to mass-produce.

[0023] The technical problems to be solved by the present invention are not limited to those described above.

[0024]

[0025] To solve the above technical problem, the present invention provides a method for producing a functional metal-organic framework.

[0026] According to one embodiment, the method for producing the functional metal-organic framework may include the steps of preparing a base metal-organic framework having a first porosity, and the step of providing a functional oligomer to the base metal-organic framework, thereby filling at least a portion of the pores of the base metal-organic framework, thereby producing a functional metal-organic framework having a second porosity lower than the first porosity.

[0027] According to one embodiment, the pores of the base metal-organic framework may include a first type pore that provides a site chemically bondable with a metal atom of the base metal-organic framework, and a second type pore that does not provide a site chemically bondable with a metal atom of the base metal-organic framework, and the functional oligomer may include a first type functional oligomer and a second type functional oligomer that are filled in the first type pore and the second type pore, respectively, and the first type pore may include being filled with the first type functional oligomer chemically bonded with a metal atom of the base metal-organic framework, and the second type pore may include being filled with the second type functional oligomer that is not chemically bonded with a metal atom of the base metal-organic framework.

[0028] According to one embodiment, the method for providing the functional oligomer to the base metal-organic framework may include the steps of placing the base metal-organic framework and a source material of the functional oligomer in a reactor, and providing the functional oligomer to a portion of the pores of the base metal-organic framework by a vapor phase polymerization method of the source material, wherein the source material includes fluorophenol and paraformaldehyde, the temperature of the reactor may be controlled to 90° C., and the polymerization time of the functional oligomer may be controlled to 12 to 16 hours.

[0029] In one embodiment, the fluorophenol may include 2,3,4-trifluorophenol.

[0030] According to one embodiment, in the step of placing the base metal-organic framework and the source material in the reactor, the weight ratio of the fluorophenol to the base metal-organic framework in the reactor may be controlled to be greater than 1:0.125 and less than 1:0.25.

[0031] According to one embodiment, the second porosity of the functional metal-organic framework may be controlled to be 72% or more and less than 84% of the first porosity of the base metal-organic framework.

[0032] According to one embodiment, the step of preparing the base metal-organic framework having the first porosity may include the steps of mixing copper nitrate hydrate and an organic ligand in a solvent to prepare a mixed solution, heat-treating the mixed solution, and centrifuging and washing the heat-treated mixed solution to prepare the base metal-organic framework.

[0033] According to one embodiment, in the step of heat-treating the mixed solution, the mixed solution may be heat-treated at a temperature of 90°C for 16 to 24 hours.

[0034] In one embodiment, the solvent may comprise (CH3)2NCH, the copper nitrate hydrate may comprise Cu(NO3)2·2.5H2O, and the organic ligand may comprise 1,3,5-Benzentricarvoxylic acid.

[0035] In order to solve the above technical problem, the present invention provides a functional metal-organic framework manufactured by the above-described manufacturing method.

[0036] According to one embodiment, the functional metal-organic framework includes a base metal-organic framework and a functional oligomer filling a portion of pores of the base metal-organic framework, the pores of the base metal-organic framework include a first type pore that provides a site chemically bondable to a metal atom of the base metal-organic framework, and a second type pore that does not provide a site chemically bondable to a metal atom of the base metal-organic framework, and the functional oligomer includes a first type functional oligomer and a second type functional oligomer that are respectively filled in the first type pore and the second type pore, and a portion of the first type pore may be filled with the first type functional oligomer chemically bonded to a metal atom of the base metal-organic framework, and the second type pore may include a portion that is not entirely filled with the second type functional oligomer.

[0037] According to one embodiment, the metal atom of the base metal-organic framework may include copper (Cu), and the functional oligomer may include hydroxymethyl, fluorine, and phenol.

[0038] According to one embodiment, the porosity of the functional metal-organic framework may include a porosity of 72% or more and less than 84% of the porosity of the base metal-organic framework.

[0039] According to one embodiment, the size of the first type pore and the second type pore of the base metal-organic framework may be 13.8 Å or more.

[0040] According to one embodiment, when analyzing the functional metal-organic framework by HNMR, a peak corresponding to a methylene bridge of a hydroxymethyl group of the functional oligomer may be observed at 1.89 ppm.

[0041] According to one embodiment, when the functional metal-organic framework is analyzed by ex situ Raman spectra under conditions in which the functional metal-organic framework is exposed to a humid atmosphere for more than 120 minutes, a peak corresponding to the chemical bond between the metal atom of the base metal-organic framework and the oxygen atom of the hydroxymethyl group of the functional oligomer is observed at 169 cm -1 , and the peak corresponding to the stretching band of the metal atoms of the base metal-organic framework is observed at 229 cm -1 may include what is observed in .

[0042] According to one embodiment, under conditions of 80°C and 88%RH, the crystal structure of the functional metal-organic framework may be maintained for 47 weeks or more and less than 52 weeks.

[0043] In order to solve the above technical problem, the present invention provides an atmospheric water harvesting device using the functional metal-organic framework described above.

[0044] According to one embodiment, the atmospheric water harvesting device may include an absorbent in which the functional metal-organic framework is coated on carbon paper, water is adsorbed to the absorbent in the atmosphere, and the water adsorbed to the absorbent is desorbed by sunlight.

[0045]

[0046] A method for producing a functional metal-organic framework according to the present invention may include a step of preparing a base metal-organic framework having a first porosity, and a step of providing a functional oligomer to the base metal-organic framework, thereby filling at least a portion of the pores of the base metal-organic framework to produce the functional metal-organic framework having a second porosity lower than the first porosity.

[0047] The above functional metal-organic framework step may include a step of placing the base metal-organic framework and a source material of the functional oligomer in a reactor, and a step of providing the functional oligomer to a portion of the pores of the base metal-organic framework by a vapor phase polymerization method of the source material.

[0048] In the step of placing the base metal-organic framework and the source material of the functional oligomer in the reactor, the weight ratio of the source material, fluorophenol (e.g., 2,3,4-trifluorophenol) to the base metal-organic framework (e.g., Cu3(BTC)2) in the reactor can be controlled to be greater than 1:0.125 and less than 1:0.25.

[0049] Accordingly, the second porosity of the functional metal-organic framework can be controlled to be 72% or more and less than 84% of the first porosity of the base metal-organic framework. As a result, the functional metal-organic framework with improved crystal stability due to water adsorption in the atmosphere can be provided.

[0050] The functional metal-organic framework manufactured by the above-described manufacturing method may include the base metal-organic framework and the functional oligomer (e.g., 2,3,4-trifluoro-6-hydroxymethyl-phenol) that fills a portion of the pores of the base metal-organic framework.

[0051] The pores of the base metal-organic framework may include a first type pore provided with a site chemically bondable to a metal atom (e.g., Cu) of the base metal-organic framework, a second type pore provided without a site chemically bondable to a metal atom of the base metal-organic framework, and a third type pore.

[0052] And, the functional oligomer may include the first type functional oligomer provided in the first type pore of the base metal-organic framework and chemically bonded with the metal atom of the base metal-organic framework, and the second type functional oligomer provided in the second type pore and / or the third type pore of the base metal-organic framework and connected to the first type functional oligomer. For example, the first type pore of the base metal-organic framework of the functional metal-organic framework may be partially filled with the first type possible oligomer, and the second type pore and the third type pore of the base metal-organic framework may be empty and not filled with the second type functional oligomer. Accordingly, the second porosity of the functional metal-organic framework may be 72% or more and less than 84% of the first porosity of the base metal-organic framework. Accordingly, the metal atoms of the base metal-organic framework of the functional metal-organic framework can be protected from water by the functional oligomer in the atmosphere. In addition, the inherent water adsorption level of the base metal-organic framework can be maintained within the functional metal-organic framework. As a result, hydrolysis of the base metal-organic framework of the functional metal-organic framework due to water adsorption in the atmosphere can be minimized. Accordingly, the problem of the base metal-organic framework being vulnerable to water adsorption in the atmosphere can be solved. Therefore, the functional metal-organic framework can be applied to an atmospheric water harvesting device.

[0053]

[0054] FIG. 1 is a flowchart illustrating a method for manufacturing a functional metal-organic framework according to an embodiment of the present invention.

[0055] FIG. 2 is a flowchart illustrating a method for manufacturing a base metal-organic framework according to an embodiment of the present invention.

[0056] FIG. 3 is a drawing for explaining a method for producing a mixed solution, which is a source material of a base metal-organic framework according to an embodiment of the present invention.

[0057] Figure 4 is a drawing for explaining a heat treatment method of a mixed solution according to an embodiment of the present invention.

[0058] FIG. 5 is a drawing for explaining a method for obtaining a base metal-organic framework from a heat-treated mixed solution according to an embodiment of the present invention.

[0059] FIG. 6 is a drawing for explaining the pores of a base metal-organic framework according to an embodiment of the present invention.

[0060] FIG. 7 is a flowchart illustrating a method for providing a functional oligomer to the pores of a base metal-organic framework according to an embodiment of the present invention.

[0061] FIG. 8 is a drawing for explaining a method of placing a base metal-organic framework and a source material of a functional oligomer in a reactor according to an embodiment of the present invention.

[0062] FIG. 9 is a drawing for explaining a method of vapor-phase polymerizing a source material into pores of a base metal-organic framework according to an embodiment of the present invention.

[0063] FIG. 10 is a drawing for explaining a functional metal-organic framework according to an embodiment of the present invention.

[0064] Figure 11 is a drawing showing a physicochemical analysis of a metal-organic framework according to Comparative Example 1 of the present invention and a functional metal-organic framework according to experimental examples.

[0065] FIG. 12 is a drawing specifically explaining a vapor phase polymerization method in a method for manufacturing a functional metal-organic framework according to experimental examples of the present invention.

[0066] FIG. 13 is a diagram for comparing the dynamic vapor sorption (DVS) levels under various humidity conditions of metal-organic frameworks according to comparative examples of the present invention and functional metal-organic frameworks according to experimental example 3-3.

[0067] FIG. 14 is a drawing for explaining the performance of an indoor water harvesting device to which a functional metal-organic framework according to Experimental Example 3-3 of the present invention is applied.

[0068] FIG. 15 is a drawing for explaining the performance of an outdoor water harvesting device to which a functional metal-organic framework according to Experimental Example 3-3 of the present invention is applied.

[0069] Figure 16 is an SEM photograph of a metal-organic framework according to Comparative Example 1 of the present invention.

[0070] Figure 17 is a graph analyzing the physicochemical properties of a metal-organic framework according to Comparative Example 1 of the present invention and a functional metal-organic framework according to experimental examples.

[0071] Figure 18 is a graph analyzing the physicochemical properties of a metal-organic framework according to Comparative Example 1 of the present invention and a functional metal-organic framework according to experimental examples.

[0072] Figure 19 is an SEM photograph of a functional metal-organic framework according to Experimental Examples 3-1 and 3-2 of the present invention.

[0073] Figure 20 is a drawing showing a physicochemical analysis of a functional metal-organic framework according to Experimental Examples 3-2 and 3-3 of the present invention.

[0074] FIG. 21 is a drawing for comparing the PXRD analysis results of a metal-organic framework according to Comparative Example 1 of the present invention and functional metal-organic frameworks according to Experimental Examples 1-2, 2-2, and 3-2.

[0075] Figure 22 is a drawing for explaining the pores of the base metal-organic framework according to experimental examples of the present invention.

[0076] FIG. 23 is a drawing for comparing the absorption wavelengths of a metal-organic framework according to Comparative Example 1 of the present invention, a functional metal-organic framework according to Experimental Example 3-3, and an absorbent to which a functional metal-organic framework according to Experimental Example 3-3 is applied.

[0077] FIG. 24 is a drawing for comparing the performance of an indoor water harvesting device to which a functional metal-organic composite according to Experimental Examples 3-3 and 3-4 of the present invention is applied.

[0078]

[0079] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the technical concept of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the spirit of the present invention to those skilled in the art.

[0080] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. In addition, in the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents.

[0081] Also, although terms such as first, second, and third have been used to describe various components in various embodiments of this specification, these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiments. Also, the term "and / or" has been used herein to mean including at least one of the components listed before and after.

[0082] In the specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to specify the presence of a feature, number, step, component, or combination thereof described in the specification, and should not be construed as excluding the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. In addition, the term "connection" is used in the present specification to mean both indirectly connecting multiple components and directly connecting them.

[0083] In addition, when describing the present invention below, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

[0084]

[0085] FIG. 1 is a flowchart for explaining a method for producing a functional metal-organic framework according to an embodiment of the present invention, FIG. 2 is a flowchart for explaining a method for producing a base metal-organic framework according to an embodiment of the present invention, FIG. 3 is a drawing for explaining a method for producing a mixed solution as a source material of a base metal-organic framework according to an embodiment of the present invention, FIG. 4 is a drawing for explaining a method for heat treating a mixed solution according to an embodiment of the present invention, FIG. 5 is a drawing for explaining a method for obtaining a base metal-organic framework from a heat-treated mixed solution according to an embodiment of the present invention, FIG. 6 is a drawing for explaining pores of a base metal-organic framework according to an embodiment of the present invention, FIG. 7 is a flowchart for explaining a method for providing a functional oligomer to the pores of a base metal-organic framework according to an embodiment of the present invention, FIG. 8 is a drawing for explaining a method for arranging a base metal-organic framework and a source material of a functional oligomer in a reactor according to an embodiment of the present invention, and FIG. 9 is a drawing for explaining a method for arranging a base metal-organic framework and a source material of a functional oligomer in a reactor according to an embodiment of the present invention, and FIG. This is a drawing for explaining a method for vapor-phase polymerization of a source material in a pore, and FIG. 10 is a drawing for explaining a functional metal-organic framework according to an embodiment of the present invention.

[0086] Referring to FIG. 1 and FIG. 2 to FIG. 5, a base metal-organic framework (100) having a first porosity is prepared (S100).

[0087] The method for producing the above base metal-organic framework (100) may include a step (S101) of producing a mixed solution (140) by mixing copper nitrate hydrate (120) and an organic ligand (130) in a solvent (110), a step (S102) of heat-treating the mixed solution (140), and a step (S103) of centrifuging and washing the heat-treated mixed solution (140) to produce the base metal-organic framework (100).

[0088] In the step of preparing the above mixed solution (140), for example, the solvent (110) may be (CH3)2NCH. For example, the copper nitrate hydrate (120) may be Cu(NO3)2·2.5H2O. For example, the organic ligand may be 1,3,5-Benzentricarvoxylic acid. In addition, in the step of heat-treating the above mixed solution (140), the above mixed solution (140) may be heat-treated at a temperature of 90°C for 16 to 24 hours. Accordingly, the base metal-organic framework (100) may be easily formed. For example, the base metal-organic framework (10) may be Cu3(BTC)2.

[0089] Referring to FIG. 6, the pores of the base metal-organic framework (100) are described.

[0090] As illustrated in FIG. 6, the pores of the base metal-organic framework (100) may include first type pores (101) that provide sites chemically bondable with metal atoms of the base metal-organic framework (100), second type pores (102) and third type pores (103) that do not provide sites chemically bondable with metal atoms of the base metal-organic framework (100). For example, the sizes of the first type pores (101) and the second type pores (102) may be 13.8 Å or more. For example, the size of the third type pores (103) may be smaller than the sizes of the first type pores (101) and the second type pores (102). For example, the base metal-organic framework (100) may include metal (10) and oxygen (20). For example, the metal atom of the base metal-organic framework (100) may be copper. For example, the base metal-organic framework (100) may be Cu3(BTC)2.

[0091] Accordingly, since the first type pore (101) of the base metal-organic framework (100) has a site that can chemically bond with the metal atoms of the base metal-organic framework (100), the metal atoms of the base metal-organic framework (100) and the source material of the functional oligomer described below can be chemically bonded. As a result, the problem of the crystal structure of the base metal-organic framework (100) collapsing due to the metal atoms of the base metal-organic framework (100) and the oxygen atoms of water molecules being chemically bonded to the first type pore (101) of the base metal-organic framework (100) in the air can be solved. That is, by providing the functional oligomer having strength against water to a part of the first type pore (101) of the base metal-organic framework (100) in the atmosphere, the sites where the metal atoms of the base metal-organic framework (100) in the first type pore (101) can come into contact with water molecules are reduced, so that the problem of the crystal structure of the base metal-organic framework (100) collapsing due to water adsorption in the atmosphere can be solved.

[0092] Referring to FIG. 1 and FIGS. 7 to 9, a method of providing the functional oligomer to the base metal-organic framework (100) fills at least a portion of the pores of the base metal-organic framework (100), thereby producing a functional metal-organic framework (300) having a second porosity lower than the first porosity (S200).

[0093] The method for manufacturing the functional metal-organic framework (300) may include a step (S201) of placing the base metal-organic framework (100) and the source material of the functional oligomer in a reactor (1), and a step (S202) of providing the functional oligomer to a portion of the pores of the base metal-organic framework (100) by a vapor phase polymerization method using the source material.

[0094] In the step of placing the base metal-organic framework (100) and the source material of the functional oligomer in the reactor (1), the source material may include fluorophenol (210) and paraformaldehyde (220). For example, the fluorophenol (210) may be trifluorophenol (2,3,4-trifluorophenol).

[0095] And, as the amount of the fluorophenol (210) and the paraformaldehyde (220) provided to the reactor (1) increases, the amount of the functional oligomer filled in the pores of the base metal-organic framework (100) increases, so that the second porosity of the functional metal-organic framework (300) can be reduced.

[0096] According to one embodiment, the weight ratio of the fluorophenol (210) to the base metal-organic framework (100) in the reactor (1) can be controlled to be greater than 1:0.125 and less than 1:0.25. Accordingly, the second porosity of the functional metal-organic framework (300) can be controlled to be greater than 72% and less than 84% of the first porosity of the base metal-organic framework (100). As a result, the crystal stability of the functional metal-organic framework (300) due to water adsorption in the air can be improved.

[0097] In contrast, when the weight ratio of the fluorophenol (210) to the base metal-organic framework (100) in the reactor (1) is controlled to 1:0.125 or less, the second porosity of the functional metal-organic framework (300) can be controlled to 84% or more of the first porosity of the base metal-organic framework (100). Accordingly, the crystal stability of the functional metal-organic framework (300) due to water adsorption in the air can be reduced.

[0098] And, when the weight ratio of the fluorophenol (210) to the base metal-organic framework (100) in the reactor (1) is controlled to exceed 1:0.25, the second porosity of the functional metal-organic framework (300) can be controlled to be less than 72% of the first porosity of the base metal-organic framework (100). Accordingly, the water adsorption level of the functional metal-organic framework (300) in the air can be significantly reduced.

[0099] Therefore, according to an embodiment of the present application, the weight ratio of the fluorophenol (210) to the base metal-organic framework (100) in the reactor (1) can be controlled to be greater than 1:0.125 and less than 1:0.25. Accordingly, the second porosity of the functional metal-organic framework (300) can be controlled to be greater than 72% and less than 84% of the first porosity of the base metal-organic framework (100). As a result, the functional metal-organic framework (300) with improved crystal stability due to water adsorption in the air can be provided.

[0100] In the step of providing the functional oligomer to a portion of the pores of the base metal-organic framework (100) by using the source material (210, 220) in the base metal-organic framework (100) by a vapor phase polymerization method, as illustrated in FIG. 9, the fluorophenol (210) and formaldehyde (222) of the paraformaldehyde (220) can be provided to the metal atoms of the base metal-organic framework (100) in the pores of the base metal-organic framework (100). Accordingly, the metal atom of the base metal-organic framework (100) and the oxygen atom of the hydroxyl group of the fluorophenol (210) are chemically coordinated, and a hydroxymethyl functional group is formed on the fluorophenol (210) coordinated with the metal atom of the base metal-organic framework (100) by the formaldehyde (222), so that the functional oligomer including hydroxymethyl, fluorine, and phenol can be formed. In addition, by the fluorophenol (210) additionally provided to the functional oligomer, the fluorophenol (210) of the functional oligomer and the additionally provided fluorophenol (210) are condensation-polymerized, so that the functional oligomer can be additionally connected to the functional oligomer coordinated with the metal atom of the base metal-organic framework (100). Accordingly, a portion of the pores of the base metal-organic framework (100) may be filled with the functional oligomer, so that the functional metal-organic framework (300) having the second porosity lower than the first porosity of the base metal-organic framework (100) may be manufactured. For example, when the source material (210, 220) is subjected to vapor phase polymerization in the base metal-organic framework (100), the temperature of the reactor (1) may be controlled to 90°C, and the polymerization time may be controlled to 12 to 16 hours. For example, the functional oligomer may include 2,3,4-trifluoro-6-hydroxymethyl-phenol.For example, for the functional metal-organic framework (300), it can be seen that, upon HNMR analysis, a peak corresponding to the methylene bridge of the hydroxymethyl group of the functional oligomer is observed at 1.89 ppm.

[0101] As described above, the pores of the base metal-organic framework (100) may include the first type pore (101) provided with a site chemically bondable to the metal atom of the base metal-organic framework (100), the second type pore (102) and the third type pore (103) provided with no site chemically bondable to the metal atom of the base metal-organic framework (100).

[0102] In the present application specification, in order to specifically describe the functional metal-organic framework (300), the functional oligomer provided in the first type pore (101) of the base metal-organic framework (100) and chemically bonded with the metal atom of the base metal-organic framework (100) is defined as a first type functional oligomer, and an additional functional oligomer provided in the second type pore (102) and / or the third type pore (103) of the base metal-organic framework (100) and not bonded with the metal atom of the base metal-organic framework (100) and connected with the first type functional oligomer is defined as a second type functional oligomer.

[0103] In conclusion, the method for manufacturing the functional metal-organic framework (300) according to an embodiment of the present application may include a step of preparing the base metal-organic framework (100) having the first porosity, and a step of providing the functional oligomer to the base metal-organic framework (100) to fill at least a portion of the pores of the base metal-organic framework (100) to manufacture the functional metal-organic framework (300) having the second porosity lower than the first porosity.

[0104] The step of forming the functional metal-organic framework (300) may include a step of placing the base metal-organic framework (100) and the source material of the functional oligomer in the reactor (1), and a step of providing the functional oligomer to a portion of the pores of the base metal-organic framework (100) by a vapor phase polymerization method.

[0105] In the step of placing the base metal-organic framework (100) and the source material of the functional oligomer in the reactor (1), the weight ratio of the fluorophenol (210) to the base metal-organic framework (100) in the reactor (1) can be controlled to be greater than 1:0.125 and less than 1:0.25. Accordingly, the second porosity of the functional metal-organic framework (300) can be controlled to be greater than 72% and less than 84% of the first porosity of the base metal-organic framework (100). Accordingly, the functional metal-organic framework (300) with improved crystal stability due to water adsorption in the air can be provided.

[0106] Referring to FIG. 10, the functional metal-organic framework (300) is described.

[0107] As illustrated in FIG. 10, the functional metal-organic framework (300) may include the base metal-organic framework (100) and the functional oligomer that fills a portion of the pores of the base metal-organic framework (100).

[0108] As described above, the pores of the base metal-organic framework (100) may include the first type pore (101) provided with a site chemically bondable to the metal atom of the base metal-organic framework (100), the second type pore (102) not provided with a site chemically bondable to the metal atom of the base metal-organic framework (100), and the third type pore (103).

[0109] And, as described above, the functional oligomer may include the first type functional oligomer (310) provided in the first type pore (101) of the base metal-organic framework (100) and chemically bonded with the metal atom of the base metal-organic framework (100), and the second type functional oligomer (320) provided in the second type pore (102) and / or the third type pore (103) of the base metal-organic framework (100) and connected with the first type functional oligomer (310).

[0110] In summary, the functional metal-organic framework (300) may include a portion of the first type pores (101) of the base metal-organic framework (100) filled with the first type functional oligomer (310), and may include a portion of the second type pores (102) and / or the third type pores (103) of the base metal-organic framework (100) not being completely filled with the second type functional oligomer (320).

[0111] According to one embodiment, the functional metal-organic framework (300) may be in a state where the first type pores (101) of the base metal-organic framework (100) are partially filled with the first type functional oligomer (310), and the second type pores (102) and the third type pores (103) of the base metal-organic framework (100) are not filled with the second type functional oligomer (320). In this case, the second porosity of the functional metal-organic framework (300) may be 72% or more and less than 84% of the first porosity of the base metal-organic framework (100). Accordingly, the metal atoms of the base metal-organic framework (100) of the functional metal-organic framework (300) may be protected from water by the functional oligomer in the air. In addition, the inherent water adsorption level of the base metal-organic framework (100) can be maintained within the functional metal-organic framework (300). As a result, hydrolysis of the base metal-organic framework (100) of the functional metal-organic framework (300) due to water adsorption in the air can be minimized. Accordingly, the problem of the base metal-organic framework (100) being vulnerable to water adsorption can be solved. Therefore, the functional metal-organic framework (300) can be applied to an atmospheric water harvesting device.

[0112] In contrast, when the first type pores (101) of the base metal-organic framework (100) of the functional metal-organic framework (300) are completely filled with the first type potential oligomer (310), and the second type pores (102) and / or the third type pores (103) are partially or completely filled with the second type functional oligomer (320), in other words, when the second porosity of the functional metal-organic framework (300) is less than 72% of the first porosity of the base metal-organic framework (100), the inherent water adsorption level of the base metal-organic framework (100) of the functional metal-organic framework (300) may be significantly reduced. Accordingly, the functional metal-organic framework (300) cannot be applied to an atmospheric water harvesting device.

[0113] And, when the first type pore (101) of the base metal-organic framework (100) of the functional metal-organic framework (300) is hardly filled with the first type potential oligomer (310), and the second type pore (102) and / or the third type pore (103) are not filled with the second type functional oligomer (320) and are in an empty state, in other words, when the second porosity of the functional metal-organic framework (300) is 84% ​​or more of the first porosity of the base metal-organic framework (100), the sites where water molecules in the air can chemically bond with the metal atoms of the base metal-organic framework (100) may increase. Accordingly, hydrolysis of the base metal-organic framework (100) of the functional metal-organic framework (300) due to water adsorption in the air may be accelerated. Accordingly, the functional metal-organic framework (300) cannot be applied to an atmospheric water harvesting device.

[0114] Therefore, according to the present application embodiment, the second porosity of the functional metal-organic framework (300) may be 72% or more and less than 84% of the first porosity of the base metal-organic framework (100). Accordingly, the metal atoms of the base metal-organic framework (100) of the functional metal-organic framework (300) in the air may be protected from water by the functional oligomer. In addition, the unique water adsorption level of the base metal-organic framework (100) may be maintained within the functional metal-organic framework (300). As a result, hydrolysis of the base metal-organic framework (100) due to water adsorption in the air may be minimized. Accordingly, the problem of the base metal-organic framework (100) being vulnerable to water adsorption may be solved. Therefore, the functional metal-organic framework (300) may be applied to an atmospheric water harvesting device. For example, under conditions of 80°C and 88%RH, the crystal structure of the base metal-organic framework (100, for example, Cu3(BTC)2) of the functional metal-organic framework (300) can be maintained for 47 weeks or more and less than 52 weeks. For example, when the functional metal-organic framework (300) is exposed to a humid atmosphere for 120 minutes or more, when an ex situ Raman spectra analysis is performed, a peak corresponding to a chemical bond between a metal atom (for example, Cu) of the base metal-organic framework (100) and an oxygen atom of a hydroxymethyl group of the functional oligomer is observed at 169 cm -1 , and the peak corresponding to the stretching band of the metal atom (e.g., Cu) of the base metal-organic framework (100) is 229 cm -1 can be observed in .

[0115] In conclusion, the functional metal-organic framework (300) according to an embodiment of the present application may include the base metal-organic framework (100) and the functional oligomer that fills a portion of the pores of the base metal-organic framework (100).

[0116] The pores of the base metal-organic framework (100) may include the first type pore (101) provided with a site chemically bondable to the metal atom of the base metal-organic framework (100), the second type pore (102) not provided with a site chemically bondable to the metal atom of the base metal-organic framework (100), and the third type pore (103).

[0117] And, the functional oligomer may include the first type functional oligomer (310) provided in the first type pore (101) of the base metal-organic framework (100) and chemically bonded to the metal atom of the base metal-organic framework (100), and the second type functional oligomer (320) provided in the second type pore (102) and / or the third type pore (103) of the base metal-organic framework (100) and connected to the first type functional oligomer (310). For example, the first type pore (101) of the base metal-organic framework (100) of the functional metal-organic framework (300) may be partially filled with the first type potential oligomer (310), and the second type pore (102) and the third type pore (103) of the base metal-organic framework (100) may be empty and not filled with the second type functional oligomer (320). Accordingly, the second porosity of the functional metal-organic framework (300) may be 72% or more and less than 84% of the first porosity of the base metal-organic framework (100). Accordingly, the metal atoms of the base metal-organic framework (100) of the functional metal-organic framework (300) may be protected from water by the functional oligomer in the air. In addition, the inherent water adsorption level of the base metal-organic framework (100) can be maintained within the functional metal-organic framework (300). As a result, hydrolysis of the base metal-organic framework (100) due to water adsorption can be minimized. Accordingly, the problem of the base metal-organic framework (100) being vulnerable to water adsorption in the atmosphere can be solved. Therefore, the functional metal-organic framework (300) can be applied to an atmospheric water harvesting device.

[0118] The above-described atmospheric water harvesting device may include an absorbent coated with the functional metal-organic framework (300) on carbon paper. For example, the absorbent may be manufactured by mixing the functional metal-organic framework (300) and a solvent (e.g., Acetonitrile) to manufacture an absorbent source, and then dip-coating the carbon paper onto the absorbent source.

[0119] And, when the above-described atmospheric water harvesting device including the absorbent is placed in a place where sunlight is not provided in the atmosphere, water can be easily adsorbed by the base metal-organic framework (100) of the functional metal-organic framework (300) of the absorbent. Then, when the above-described atmospheric water harvesting device including the absorbent with water adsorbed thereon is placed in a place where sunlight is provided, the absorbent with water adsorbed thereon can easily desorb the water adsorbed thereon by absorbing sunlight. Accordingly, the above-described atmospheric water harvesting device can harvest water by capturing the desorbed water. For example, water harvested by the above-described atmospheric water harvesting device can be used as drinking water.

[0120] In addition, the absorbent can have stability against water adsorption by the functional oligomer provided in a part of the pores of the base metal-organic framework (100) of the functional metal-organic framework (300) of the absorbent within the atmospheric water harvesting device. As a result, not only can the long-term stability of the water adsorption / water desorption cycle of the atmospheric water harvesting device be improved, but also the water harvesting amount of the atmospheric water harvesting device can be improved.

[0121]

[0122] Hereinafter, specific experimental examples and characteristic evaluation results of functional metal-organic frameworks according to embodiments of the present invention are described.

[0123]

[0124] Metal-organic framework (Pristine-HK) according to comparative example 1

[0125] Copper nitrate hydrate (Cu(NO3)22.5H2O, 5 g) and organic ligand (1,3,5-BTC(1,3,5-benzentricarvoxylic acid), 3 g) were added to a solvent (DMF(dimethylformamide, (CH3)2NCH), 150 mL) and mixed until transparent, thereby preparing a mixed solution.

[0126] Then, the mixed solution was sealed and provided to a convection oven, and reacted at 90°C for 16 hours to produce a metal-organic framework (Cu3(BTC)2). The produced metal-organic framework was obtained through centrifugation and washing (DMF and Acetonirile, washed three times).

[0127]

[0128] Functional metal-organic frameworks according to experimental examples

[0129] As a base metal-organic framework, the metal-organic framework (Pristine-HK, Cu3(BTC)2) according to Comparative Example 1 was prepared by activating it in a vacuum oven (at 100°C), and phenol (3-fluorophenol, 2,3,4-trifluorophenol) and paraformaldehyde were prepared as source materials of functional oligomers.

[0130] The base metal-organic framework and the source material were each placed in a 500 mL glass reactor, and vapor phase polymerization (VPP) was performed in a convection oven at 90°C for 12 to 16 hours to produce a functional metal-organic framework. The produced functional metal-organic framework was obtained through centrifugation and washing (DMF and acetonitrile, 3 washes). The obtained functional metal-organic framework was provided to a vacuum oven and dried at 70°C for 6 hours.

[0131] Classification Base Metal Organic Framework Phenol 3-fluorophenol 2,3,4-trifluorophenol Paraformaldehyde Remarks Experimental Example 1-1200mg 5.16--2.5F0 @HK_95 Experimental Example 1-2200mg 15.5--7.5F0 @HK_85 Experimental Example 1-3200mg 31--15F0 @HK_70 Experimental Example 1-4200mg 93--45F0 @HK_0 Experimental Example 2-1200mg-6.3-2.5F1 @HK_95 Experimental Example 2-2200mg-19-7.5F1 @HK_85 Experimental Example 2-3200mg-38-15F1 @HK_70 Experimental Example 2-4200mg-114-45F1 @HK_0 Experimental Example 3-1200mg--3.62.5F3@HK_95Experimental Example 3-2200mg--257.5F3@HK_85Experimental Example 3-3200mg--5015F3@HK_70Experimental Example 3-4200mg--10022.5F3@HK_50Experimental Example 3-5200mg--15045F3@HK_0

[0132]

[0133] Figure 11 is a drawing showing a physicochemical analysis of a metal-organic framework according to Comparative Example 1 of the present invention and a functional metal-organic framework according to experimental examples.

[0134] Referring to (a) of Fig. 11, water adsorption isotherms were measured for the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Example 3-3 at 298 K conditions.

[0135] As can be seen in (a) of Fig. 11, under low relative pressure conditions, the functional metal-organic framework according to Experimental Example 3-3 and the metal-organic framework according to Comparative Example 1 can be seen to exhibit substantially similar water adsorption levels.

[0136] Referring to (b) and (c) of FIG. 11, in the method for manufacturing the functional metal-organic framework according to Experimental Example 3-3, a base metal-organic framework (HKUST-1; Cu3(BTC)2), fluorophenol (2,3,4-Trifluorophenol), and paraformaldehyde are provided in a glass reactor, and a functional oligomer (fluorophenyl oligomer) bonded to the copper atoms of the base metal-organic framework (HKUST-1) is provided in the pores of the base metal-organic framework (HKUST-1) by a vapor phase polymerization (VPP) method.

[0137] As can be seen in (b) and (c) of FIG. 11, since the copper atoms of the base metal-organic framework and the oxygen atoms of the hydroxyl groups of the fluorophenol are dynamically coordinated, not only are the copper atoms of the base metal-organic framework protected in the functional metal-organic framework according to Experimental Example 3-3, but also the inherent water adsorption level of the base metal-organic framework is maintained. Accordingly, even under dry conditions, the water adsorption level is improved, and hydrolysis of the base metal-organic framework due to water adsorption can be minimized, so the functional metal-organic framework according to Experimental Example 3-3 can be used as an absorbent in an air water harvesting device.

[0138] Referring to (d) of Fig. 11, nitrogen adsorption isotherms were measured for the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 3-1, 3-2, and 3-3, and the results are summarized in below.

[0139] As can be seen in (d) of FIG. 11 and , the porosity of the metal-organic framework according to Comparative Example 1 is 100%, the porosity of the functional metal-organic framework according to Experimental Example 3-1 is 96%, the porosity of the functional metal-organic framework according to Experimental Example 3-2 is 84%, and the porosity of the functional metal-organic framework according to Experimental Example 3-3 is 72%.

[0140] Therefore, in the method for providing a functional oligomer to a base metal-organic framework according to an embodiment of the present invention, it can be seen that as the amount of the source material of the functional oligomer increases, the porosity of the functional metal-organic framework decreases.

[0141] Classification S BET (m 2 g -1 )V tot (cm 3 g -1 )V micro (cm 3 g -1 )Remainingmicropore volume(% of V micro ) Comparison Example 11,3580.530.53100 Experimental Example 3-11,3050.520.5196 Experimental Example 3-21,1880.490.4584 Experimental Example 3-38420.390.3972

[0142]

[0143] Referring to (e) of FIG. 11, the functional metal-organic framework according to Experimental Example 3-3 was photographed using SEM, and referring to (f) of FIG. 11, PXRD analysis was performed on the metal-organic framework according to Comparative Example 1 and the functional metal-organic frameworks according to Experimental Examples 3-1, 3-2, and 3-3. As can be seen from (e) and (f) of FIG. 11, the morphological characteristics and crystal structures of the metal-organic framework according to Comparative Example 1 and the functional metal-organic frameworks according to Experimental Examples 3-1, 3-2, and 3-3 are substantially the same.

[0144] Therefore, in the method for providing a functional oligomer to a base metal-organic framework according to an embodiment of the present invention, it can be seen that the morphological characteristics and crystal structure of the base metal-organic framework are substantially maintained after the vapor phase polymerization process.

[0145] Referring to (g) of Fig. 11, the crystals of the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 3-3 and 3-5 were completely decomposed with DMSO-d6 (with D2SO4), and then HNMR analysis was performed.

[0146] As can be seen in (g) of Fig. 11, the functional metal-organic framework according to Experimental Example 3-5 can be seen to have a peak corresponding to a methylene ether bridge between fluorophenols observed at 2.78 ppm, and a peak corresponding to a methylene bridge between fluorophenols observed at 2.61 ppm.

[0147] On the other hand, it can be seen that peaks corresponding to the methylene ether bridge and methylene bridge were not observed in the metal-organic framework according to Comparison 1.

[0148] And, it can be seen that the peaks corresponding to the methylene ether bridge and the methylene bridge in the functional metal-organic framework according to Experimental Example 3-3 are reduced compared to the functional metal-organic framework according to Experimental Example 3-5. In addition, it can be seen that, unlike the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Example 3-5, a peak corresponding to the methylene bridge of the hydroxymethyl group was observed at 1.89 pmm. Therefore, it can be seen that, in the vapor phase polymerization process of the functional metal-organic framework according to Experimental Example 3-3, after the functional oligomer is chemically bonded to the copper atom of the base metal-organic framework, the functional oligomer that is not condensation polymerized with the fluorophenol exists.

[0149] Referring to (h) of Fig. 11, the functional metal-organic framework according to Experiment 3-3 was photographed using HAADF and then mapped for the F element.

[0150] As can be seen in (h) of Fig. 11, the functional oligomer of the functional metal-organic framework according to Experimental Example 3-3 is uniformly distributed within the pores (type 1 pores) rather than on the crystal surface of the functional metal-organic framework.

[0151] Referring to (i) of Fig. 11, the functional metal-organic framework according to Experimental Example 3-3 was left for 3 weeks (3w), 19 weeks (19w), 38 weeks (38w), 47 weeks (47w), and 56 weeks (56w) at 88°C, and then the change in crystal structure was analyzed by PXRD.

[0152] As can be seen from (i) of Fig. 11, it can be seen that the crystal structure of the functional metal-organic framework according to Experimental Example 3-3 is maintained for 47 weeks or more and less than 56 weeks under high temperature / high humidity conditions (at 88°C).

[0153] Therefore, it can be seen that the method of providing a functional oligomer to the pores of a base metal-organic framework using a vapor phase polymerization method according to an embodiment of the present application is a method of significantly improving stability against water, i.e. stability against hydrolysis, under high temperature / high humidity conditions.

[0154]

[0155] FIG. 12 is a drawing specifically explaining a vapor phase polymerization method in a method for manufacturing a functional metal-organic framework according to experimental examples of the present invention.

[0156] Referring to (a) and (b) of FIG. 12, the functional metal-organic frameworks according to Experimental Examples 3-2 and 3-3 were dried at 70°C for 6 hours and activated. Then, the activated functional metal-organic frameworks according to Experimental Examples 3-2 (Act_F3@HK_85) and 3-3 (Act_F3@HK_70) were exposed to a humid atmosphere, and in order to confirm the temporal changes of the functional metal-organic frameworks with respect to the humid atmosphere, in situ Raman spectra analysis was performed on the functional metal-organic frameworks according to Experimental Examples 3-2 (H2O_F3@HK_85) and 3-3 (H2O_F3@HK_70) at 5 and 30 minutes per hour. Referring to (c) of Fig. 12, the results measured in (a) and (b) of Fig. 12 are illustrated in a figure.

[0157] As can be seen from (a) to (c) of Fig. 12, the functional metal-organic framework according to the activated experimental example 3-2 and experimental example 3-3 has a 169 cm -1 In , a peak corresponding to the chemical bond (coordination bond) between the copper atom of the base metal-organic framework and the oxygen atom of the hydroxyl group of the functional oligomer was observed at 229 cm -1 It can be seen that a peak corresponding to the copper atom-copper atom stretching band of the base metal-organic framework is observed.

[0158] And, when the functional metal-organic framework according to Experimental Example 3-2 was exposed to a humid atmosphere for 20 minutes, the peak corresponding to the chemical bond between the copper atom of the base metal-organic framework and the oxygen atom of the functional oligomer was 169 cm -1 173cm at -1 It can be seen that the peak corresponding to the copper atom-copper atom stretching of the base metal-organic framework was not observed. This factor is interpreted to be due to the dissociation of the hydroxyl group of the functional oligomer in the humid atmosphere, resulting in the bonding of the copper atom of the base metal-organic framework with water molecules in the humid atmosphere.

[0159] In contrast, when the functional metal-organic framework according to Experimental Example 3-3 activated in a humid atmosphere was exposed for 120 minutes, it can be seen that the peak corresponding to the chemical bonding of the copper atom of the base metal-organic framework and the oxygen atom of the functional oligomer and the peak corresponding to the copper atom-copper atom stretching of the base metal-organic framework were observed at substantially the same wavelength and at similar levels compared to before the functional metal-organic framework according to Experimental Example 3-3 was exposed to the humid atmosphere. Accordingly, it can be seen that under humid atmospheric conditions, the chemical bonding between the copper of the base metal-organic framework and the oxygen of the hydroxyl group of the functional oligomer is more stably maintained in the functional metal-organic framework according to Experimental Example 3-3 than in the functional metal-organic framework according to Experimental Example 3-2.

[0160] Referring to (d) of FIG. 12, in the process of manufacturing a functional metal-organic framework according to Experimental Examples 3-2, 3-3, and 3-5, the functional oligomers filled in the first type pore (type I), the second type pore (type II), and the third type pore (type III) of the base metal-organic framework are illustrated.

[0161] As can be seen in (d) of FIG. 12, the functional metal-organic framework according to Experimental Example 3-3 has a greater amount of functional oligomers filled in the first type pores than the functional metal-organic framework according to Experimental Example 3-2, and thus the effects described above in (a) to (c) of FIG. 12 can be seen to have occurred. In addition, it can be seen that the functional oligomers are filled in the first type pores of the base metal-organic framework, and then the second type pores and the third type pores are filled with the functional oligomers.

[0162]

[0163] FIG. 13 is a diagram for comparing the dynamic vapor sorption (DVS) levels under various humidity conditions of metal-organic frameworks according to comparative examples of the present invention and functional metal-organic frameworks according to experimental example 3-3.

[0164] Referring to Fig. 13 (a), dynamic vapor adsorption for the functional metal-organic framework according to Experimental Example 3-3 was measured under conditions of 10%RH, 20%RH, and 30%RH.

[0165] As can be seen in (a) of Fig. 13, the functional metal-organic framework according to Experimental Example 3-3 has an excellent vapor adsorption level under 10%RH, 20%RH, and 30%RH conditions.

[0166] Referring to (b) of Fig. 13, the water uptake and vapor sorption rate according to time (1 min, 2 min, 5 min) were measured for the functional metal-organic framework according to Experimental Example 3-3 under conditions of 10%RH, 20%RH, and 30%RH.

[0167] Referring to (b) of Fig. 13, under the conditions of 10%RH, 20%RH, and 30%RH, the functional metal-organic framework according to Experimental Example 3-3, within 5 minutes, each, 0.084gg -1, 0.177gg -1 , and 0.249gg -1 It can be seen that it has a vapor adsorption capacity of .

[0168] And, it can be seen that the functional metal-organic framework according to Experimental Example 3-3 has an adsorption capacity of 70% or more within 1 minute under conditions of 10%RH, 20%RH, and 30%RH.

[0169] In addition, the functional metal-organic framework according to Experimental Example 3-3 was, for 1 minute, 3.84 Lkg under the conditions of 10%RH, 20%RH, and 30%RH, respectively. -1 h -1 , 8.04Lkg -1 h -1 , and 11.76Lkg -1 h -1 has a vapor adsorption rate of 2.37Lkg for 2 minutes, respectively. -1 h -1 , 4.92Lkg -1 h -1 , 7.02Lkg -1 h -1 It can be seen that it has a vapor adsorption rate of .

[0170] Referring to Fig. 13 (c), under conditions of 30% RH or less, the vapor adsorption rates of the metal-organic frameworks according to comparative examples (L-SNF, NC, HS-700-LiCl, LiCl@rGO, POG, PAM-LiCl. SHPF, MIL-101, TUN-1 SA, MOF-801, MOF-301) which are conventional metal-organic frameworks, and the functional metal-organic framework (This work) according to Experimental Example 3-3 were compared. And, the results are summarized in below.

[0171] As can be seen in (c) of Fig. 13 and , under conditions of 30% RH or less, the functional metal-organic framework according to Experimental Example 3-3 has a significantly higher vapor adsorption rate compared to the metal-organic framework according to the comparative examples.

[0172] Water uptake (gg) -1 )Vapor sorption rate(L kg -1 h -1 )Experiment example 3-3300.196 @ 1 min0.234 @ 2 min11.767.02200.134 @ 1 min0.164 @ 2 min8.044.92100.064 @ 1 min0.079 @ 2 min3.842.37Mesoporous silica nanofiber (L-SNF)300.125 @ 20 min0.375MOF-derived nanoporous carbon30200.19 @ 23 min0.13 @ 19 min0.50.41HS-700_LiCl (Hollow silica: LiCl = 3:7)201.21 @ 87 min0.834LiCl@rGO-SA301.52 @ 3.3 h0.9Photothermal organogel (POG)300.048 @ 3 h0.055Polyarcylamide hydrogel (PAM-LiCl)301.5 @ 2h0.75Super hygroscopic polymer films (SHPF)300.96 @ 70 min1.65LiCl@-MIL-101(Cr)_51300.6 @ 2 h0.3TUN-1 SA200.22 @ 70 min0.37MOF-801300.25 @ 35 min0.43MOF-30330200.4 @ 5 min0.38 @ 10 min4.82.28

[0173]

[0174] Referring to (d) of Fig. 13, a vapor adsorption / desorption cycle (adsorption (25°C, 88%RH), desorption (25°C, pressure swing of nitrogen gas)) was performed on the metal-organic framework according to Comparative Example 1, and referring to (e) of Fig. 13, a vapor adsorption / desorption cycle (adsorption (25°C, 88RH%), desorption (25°C, pressure swing of nitrogen gas)) was performed on the functional metal-organic framework according to Experiment 3-3.

[0175] As can be seen in (d) and (e) of FIG. 13, the metal-organic framework according to Comparative Example 1 shows that the vapor adsorption capacity gradually decreases as the number of vapor adsorption / desorption cycles increases. In contrast, the functional metal-organic framework according to Experimental Example 3-3 shows that the vapor adsorption capacity is stably maintained for 76 cycles (approximately 300 hours).

[0176]

[0177] FIG. 14 is a drawing for explaining the performance of an indoor water harvesting device to which a functional metal-organic framework according to Experimental Example 3-3 of the present invention is applied.

[0178] Referring to (a) of Fig. 14, an indoor water harvesting device to which a functional metal-organic framework according to Experimental Example 3-3 is applied is illustrated in a drawing, and referring to (b) of Fig. 14, an actual photograph of the indoor water harvesting device is taken.

[0179] As can be seen in (a) and (b) of FIG. 14, an acrylic box is placed in the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 is applied, and a holder made of Styrofoam and polytetrafluoroethylene is placed inside the acrylic box, and 10 absorbents coated with the functional metal-organic framework according to Experimental Example 3-3 on carbon paper are embedded in the holder. Specifically, the absorbent was prepared by mixing the functional metal-organic framework according to Experimental Example 3-3 with Acetonitrile to prepare an absorbent source (0.5 g of functional metal-organic framework / 1 mL of Acetonitrile), and then dip-coating the carbon paper (diameter 2 cm, thickness 0.16 mm, Sigracet 29AA carbon paper) on the absorbent source and drying it at 90°C.

[0180] Referring to Fig. 14(c), the water adsorption capacity and water desorption capacity of the indoor water harvesting device were measured over time. Specifically, the indoor water harvesting device was placed in a chamber under conditions of 25°C and 25%RH, and the water adsorption capacity was measured using a scale. Afterwards, the indoor water harvesting device was placed in a dark room, and the absorbent of the water harvesting device was irradiated with sunlight (1 sun condition), and the water desorption capacity was measured using a scale.

[0181] As can be seen in (c) of Fig. 14, the water adsorption capacity of the indoor water harvesting device is 0.23gg -1 It can be seen that water adsorption was completed within 10 minutes. And, it can be seen that more than 90% of the water was desorbed within 20 minutes.

[0182] Referring to (d) of Fig. 14, during the water desorption process of the indoor water harvesting device, the temperature change of the absorbent due to sunlight was measured over time using an infrared camera.

[0183] As can be seen in (d) of Fig. 14, the temperature of the absorbent of the indoor water harvesting device rises to about 54°C within 10 minutes and is then maintained at a constant temperature of about 54°C. Referring to the inset of Fig. 14 (b), when the indoor water harvesting device is placed in a dark room and exposed to sunlight for 20 minutes, water droplets are observed on the absorbent of the indoor water harvesting device. Therefore, it can be seen that the water adsorbed on the absorbent of the indoor water harvesting device is easily desorbed by the heat of the sunlight being exposed.

[0184] Referring to (e) of Fig. 14, the dissolved copper ion concentration of water collected from an indoor water harvesting device using a metal-organic framework according to Comparative Example 1 and an indoor water harvesting device using the functional metal-organic framework according to Experimental Example 3-3 was measured.

[0185] As can be seen in (e) of FIG. 14, the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 was applied has a lower dissolved copper ion concentration in the collected water than the indoor water harvesting device to which the metal skeleton according to Comparative Example 1 was applied. In addition, the dissolved copper ion concentration in the collected water from the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 was applied is lower than the standard dissolved copper ion concentration for drinking water according to the U.S. Environmental Protection Agency (EPA) and the World Health Organization (WHO). Therefore, the water harvested from the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 was applied can be used as drinking water.

[0186] Referring to (f) of Fig. 14, for the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 was applied, water adsorption (25°C and 25%RH chamber, maintained for 10 min) / desorption (dark room, 1 sun condition, maintained for 20 min) cycles were performed 48 times.

[0187] As can be seen in (f) of Fig. 14, the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 is applied produces 10.08 Lkg per day (24 hours). -1 It can be seen that drinking water can be produced.

[0188]

[0189] FIG. 15 is a drawing for explaining the performance of an outdoor water harvesting device to which a functional metal-organic framework according to Experimental Example 3-3 of the present invention is applied.

[0190] Referring to Fig. 15 (a), a photograph was taken of an outdoor water harvesting device to which a functional metal-organic framework according to Experimental Example 3-3 was applied.

[0191] As can be seen in (a) of Fig. 15, in the outdoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 is applied, a Styrofoam holder having an upper surface opened by five holes is placed, and 20 absorbents coated with the functional metal-organic framework according to Experimental Example 3-3 on carbon paper are laminated and embedded inside the holder, and the upper surface of the absorbents placed at the top is exposed by the five holes of the holder, and the holder is provided in a transparent glass box. Then, when natural light is irradiated on the outdoor water harvesting device for 20 minutes, it can be seen that water droplets form on the upper surface and side surfaces of the transparent glass box.

[0192] Referring to Figure 15(b), the outdoor water harvesting device was placed on the rooftop at 7:00 AM, and the amount of water adsorption and desorption over time was measured. Specifically, the outdoor water harvesting device was placed in the shade, and the amount of water adsorption was measured using a scale. Thereafter, the outdoor water harvesting device was placed under natural light, and the amount of water desorption was measured using a scale.

[0193] As can be seen in (b) of Fig. 15, under conditions of about 53% RH, about 0.23gg is produced in the absorbent of the outdoor water harvesting device within 10 minutes. -1 It can be seen that water is adsorbed. And, it can be seen that more than 90% of the water adsorbed on the absorbent is desorbed within about 20 minutes starting from 7:10 AM.

[0194] Referring to (c) of Fig. 15, after exposing the absorbent of the outdoor water harvesting device to natural light for 10 minutes, the temperature change of the absorbent was measured using an infrared camera.

[0195] As can be seen in (c) of Fig. 15, the temperature of the absorbent exposed to natural light for 10 minutes is 56.5°C.

[0196] Referring to (d) of Fig. 15, for the outdoor water harvesting device, a total of 22 cycles were performed with a 30-minute water adsorption (10 min) / desorption (20 min) cycle from 7:30 AM to 6:30 PM, and the ambient temperature (Ambient temp.), the temperature of the absorbent (adsorbent temp.), humidity (Humidity), and the intensity of natural light (Solar flux) of the outdoor water harvesting device over time were measured. Referring to (e) of Fig. 15, the water harvesting amount of the outdoor water harvesting device was graphically represented while performing the water adsorption / desorption cycle described in (d) of Fig. 15.

[0197] As can be seen in (d) and (e) of Fig. 15, when the outdoor water harvesting device is operated for 22 water adsorption / desorption cycles (11 hours), 4.40 Lkg -1 You can see that water (drinking water) can be harvested.

[0198]

[0199] Figure 16 is an SEM photograph of a metal-organic framework according to Comparative Example 1 of the present invention.

[0200] Referring to Fig. 16, the metal-organic framework according to Comparative Example 1 was photographed using SEM.

[0201] As can be seen in Fig. 16, the metal-organic framework according to Comparative Example 1 has an octahedral shape.

[0202]

[0203] Figure 17 is a graph analyzing the physicochemical properties of a metal-organic framework according to Comparative Example 1 of the present invention and a functional metal-organic framework according to experimental examples.

[0204] Referring to Fig. 17 (a), nitrogen adsorption isotherms were measured for the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 1-1, 1-2, 1-3, and 1-4. The results are summarized in below.

[0205] As can be seen in FIG. 17 and , the porosity of the metal-organic framework according to Comparative Example 1 is 100%, the porosity of the functional metal-organic framework according to Experimental Example 1-1 is 95%, the porosity of the functional metal-organic framework according to Experimental Example 1-2 is 83%, the porosity of the functional metal-organic framework according to Experimental Example 1-3 is 70%, and the porosity of the functional metal-organic framework according to Experimental Example 1-4 is 0%.

[0206] Class S BET (m 2 g -1 )V tot (cm 3 g -1 )V micro (cm 3 g -1 )Remainingmicropore volume(% of V micro ) Comparison Example 11,3580.530.53100 Experimental Example 1-11,3190.510.595 Experimental Example 1-21,1400.440.4483 Experimental Example 1-37870.380.3770 Experimental Example 1-41.80.010.0010

[0207]

[0208] Referring to (b) of Fig. 17, PXRD analysis was performed on the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 1-1, 1-2, 1-3, and 1-4.

[0209] As can be seen in (b) of Fig. 17, it can be seen that the crystal structures of the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 1-1 to 1-4 are substantially the same.

[0210] Referring to (c) of FIG. 17, the functional metal-organic framework according to Experimental Example 1-1 was photographed using SEM, and referring to (d) of FIG. 17, the functional metal-organic framework according to Experimental Example 1-2 was photographed using SEM, and referring to (e) of FIG. 17, the functional metal-organic framework according to Experimental Example 1-3 was photographed using SEM, and referring to (f) of FIG. 17, the functional metal-organic framework according to Experimental Example 1-4 was photographed using SEM.

[0211] As can be seen from (c) to (f) of Fig. 17, the surface morphology of the functional metal-organic frameworks according to Experimental Examples 1-1 to 1-4 is substantially the same.

[0212]

[0213] Figure 18 is a graph analyzing the physicochemical properties of a metal-organic framework according to Comparative Example 1 of the present invention and a functional metal-organic framework according to experimental examples.

[0214] Referring to Fig. 18 (a), nitrogen adsorption isotherms of the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 2-1, 2-2, and 2-3 were measured. The results are summarized in below.

[0215] As can be seen in FIG. 18 and , the porosity of the metal-organic framework according to Comparative Example 1 is 100%, the porosity of the functional metal-organic framework according to Experimental Example 2-1 is 96%, the porosity of the functional metal-organic framework according to Experimental Example 2-2 is 83%, and the porosity of the functional metal-organic framework according to Experimental Example 2-3 is 71%.

[0216] SampleS BET (m 2 g -1 )V tot (cm 3 g -1 )V micro (cm 3 g -1 )Remaining micropore volume(% of V micro ) Comparison Example 11,3580.530.53100 Experimental Example 2-11,2950.520.5196 Experimental Example 2-31,1540.440.4483 Experimental Example 2-48230.390.3871

[0217]

[0218] Referring to (b) of Fig. 18, PXRD analysis was performed on the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 2-1, 2-2, and 2-3. As can be seen from (b) of Fig. 18, the crystal structures of the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Examples 2-1 to 2-3 are substantially the same.

[0219] Referring to (c) of FIG. 18, the functional metal-organic framework according to Experimental Example 2-1 was photographed using SEM, and referring to (d) of FIG. 17, the functional metal-organic framework according to Experimental Example 2-2 was photographed using SEM, and referring to (e) of FIG. 17, the functional metal-organic framework according to Experimental Example 2-3 was photographed using SEM.

[0220] As can be seen from (c) to (e) of FIG. 18, the surface morphology of the functional metal-organic frameworks according to Experimental Examples 2-1 to 2-3 is substantially the same.

[0221]

[0222] Figure 19 is an SEM photograph of a functional metal-organic framework according to Experimental Examples 3-1 and 3-2 of the present invention.

[0223] Referring to (a) of Fig. 19, a functional metal-organic framework according to Experimental Example 3-1 was photographed using SEM, and referring to (b) of Fig. 19, a functional metal-organic framework according to Experimental Example 3-2 was photographed using SEM.

[0224] As can be seen from (a) and (b) of FIG. 19, the surface morphology of the functional metal-organic frameworks according to Experimental Examples 3-1 and 3-2 is substantially the same.

[0225]

[0226] Figure 20 is a drawing showing a physicochemical analysis of a functional metal-organic framework according to Experimental Examples 3-2 and 3-3 of the present invention.

[0227] Referring to (a) of Fig. 20, the functional metal-organic framework according to Experimental Example 3-2 was photographed using SEM, and the photographed photograph was analyzed using EDX. Referring to (b) of Fig. 20, the functional metal-organic framework according to Experimental Example 3-3 was photographed using SEM, and the photographed photograph was analyzed using EDX, and the results are summarized in below.

[0228] As can be seen in (a), (b) of FIG. 20, and , the content of fluorine atoms in the functional metal-organic framework according to Experimental Example 3-2 is 3.8 at%, and the content of fluorine atoms in the functional metal-organic framework according to Experimental Example 3-3 is 6.3 at%.

[0229] Classification C(Weight / Atom %) O(Weight / Atom %) F(Weight / Atom %) Cu(Weight / Atom %) Total(Weight / Atom %) Experimental Example 3 - 235.6 / 47.9 44.9 / 44.4 4.4 / 3.8 15.1 / 3.9 100 / 100 Experimental Example 3 - 336.3 / 48.0 42.6 / 42.3 7.5 / 6.3 13.5 / 3.4 100 / 100

[0230]

[0231] FIG. 21 is a drawing for comparing the PXRD analysis results of a metal-organic framework according to Comparative Example 1 of the present invention and functional metal-organic frameworks according to Experimental Examples 1-2, 2-2, and 3-2.

[0232] Referring to (a) of FIG. 21, under conditions of 88°C, the metal-organic framework according to Comparative Example 1 was left for 6 hours (6h), 12 hours (12h), and 18 hours (18h), and then the change in crystal structure was analyzed by PXRD. Referring to (b) of FIG. 21, under conditions of 88°C, the functional metal-organic framework according to Experimental Example 1-2 was left for 1 day (1d), 1 week (1w), and 3 weeks (3w), and then the change in crystal structure was analyzed by PXRD. Referring to (c) of FIG. 21, under conditions of 88°C, the functional metal-organic framework according to Experimental Example 2-2 was left for 1 day (1d), 3 days (3d), 1 week (1w), 3 weeks (3w), 5 weeks (5w), and 7 weeks (7w), and then the change in crystal structure was analyzed by PXRD. Referring to (d) of FIG. 21, under conditions of 88°C, the functional metal-organic framework according to Experimental Example 2-2 was left for 1 day (1d), 3 days (3d), 1 week (1w), 3 weeks (3w), 5 weeks (5w), and 7 weeks (7w), and then the change in crystal structure was analyzed by PXRD. The functional metal-organic framework according to 3-2 was left for 1 day (1d), 3 days (3d), 1 week (1w), 3 weeks (3w), 5 weeks (5w), 7 weeks (7w), and 9 weeks (9w), and then the changes in crystal structure were analyzed by PXRD.

[0233] As can be seen from (a) to (d) of FIG. 21, under high temperature / high humidity conditions (at 88°C), the crystal structure of the metal-organic framework according to Comparative Example 1 changed in 18 hours, the crystal structure of the functional metal-organic framework according to Experimental Example 1-2 changed in 3 weeks, the crystal structure of the functional metal-organic framework according to Experimental Example 2-2 changed in 7 weeks, and the crystal structure of the functional metal-organic framework according to Experimental Example 3-2 changed in 9 weeks.

[0234] Therefore, it can be seen that when the functional oligomer provided in the pores of the base metal-organic framework contains fluorine, the stability of the crystal structure of the functional metal-organic framework is improved, thereby improving stability against hydrolysis. Furthermore, it can be seen that as the number of fluorine groups in the functional oligomer increases, the stability of the crystal structure of the functional metal-organic framework is significantly improved, thereby significantly improving stability against hydrolysis.

[0235]

[0236] Figure 22 is a drawing for explaining the pores of the base metal-organic framework according to experimental examples of the present invention.

[0237] Referring to FIG. 22, the first type pore (type-I), the second type pore (type-II), and the third type pore (type-III) of the base metal-organic framework (HKUST-1; Cu3(BTC)2) according to experimental examples are described.

[0238] As can be seen in Fig. 22, the first type pore and the second type pore of the base metal-organic framework can be seen to have a cage structure of a truncated cubic shape, and the third type pore can be seen to have a cage structure of a truncated octahedral shape.

[0239] And, it can be seen that the second type pores are arranged between a plurality of the first type pores, and the third type pores are arranged between the first type pores and the second type pores. In addition, it can be seen that the sizes of the first type pores and the second type pores are 13.8 Å, and the size of the third type pores is smaller than the sizes of the first type pores and the second type pores.

[0240] It can be seen that the first type pores are different from the first type pores in that a site to which the copper atoms of the base metal-organic framework can be chemically bonded is provided, but the second type pores are not provided with a site to which the copper atoms of the base metal-organic framework can be chemically bonded. Accordingly, since the copper atoms of the base metal-organic framework and the source material of the provided functional oligomer undergo vapor phase polymerization in the first type pores, as described above in (c) of FIG. 11, it can be seen that the copper atoms of the base metal-organic framework and the oxygen of the hydroxyl group of the source material are chemically bonded, thereby forming the functional oligomer within the first type pores of the base metal-organic framework.

[0241] Additionally, considering that the PXRD results for the functional metal-organic framework according to Experimental Examples 3-2 and 3-3 described in FIG. 12, the sizes of the first type pores to the third type pores, the size of the functional oligomer (2,3,4-trifluoro-6-hydroxymethyl-phenol), and the amount of the provided source material and the amount of the generated functional oligomer are similar, a simulation was performed on the functional metal-organic framework according to Experimental Example 3-3, and it was found that the first type pores of the functional metal-organic framework according to Experimental Example 3-3 were almost filled with the functional oligomer, and the second type pores and the third type pores were empty. Accordingly, when the base metal-organic framework including the first type pore to the third type pore and the source material of the functional oligomer are subjected to vapor phase polymerization, it can be seen that the first type pore is preferentially filled with the functional oligomer, and then the second type pore and the third type pore are filled with the functional oligomer.

[0242] And, referring to FIG. 22 together with FIG. 12 described above, when the functional metal-organic frameworks according to Experimental Examples 3-2 and 3-3 are exposed to a humid atmosphere, it can be seen that the functional metal-organic framework according to Experimental Example 3-3 has a larger amount of functional oligomers filled in the first type pores of the base metal-organic framework than the functional metal-organic framework according to Experimental Example 3-2. Accordingly, it can be seen that the functional metal-organic framework according to Experimental Example 3-3 has lower porosity than the functional metal-organic framework according to Experimental Example 3-2. Therefore, it can be seen that the functional metal-organic framework according to Experimental Example 3-2 has more sites in the first type pores where the copper atoms of the base metal-organic framework can chemically bond (coordinate bond) with oxygen of water than the functional metal-organic framework according to Experimental Example 3-3, and thus the stability of the crystal structure in a humid atmosphere is lower. In contrast, it can be seen that the functional metal-organic framework according to Experimental Example 3-3 has fewer sites in the first type pores where the copper atoms of the base metal-organic framework can chemically bond with oxygen of water than the functional metal-organic framework according to Experimental Example 3-2.

[0243] In summary, in the method for manufacturing a functional metal-organic framework according to an embodiment of the present invention, it can be seen that the method of controlling the weight ratio of fluorophenol to the base metal-organic framework to exceed 1:0.125 and controlling the porosity of the functional metal-organic framework to less than 84% (upper limit) of the porosity of the base metal-organic framework is a method for improving the stability of the crystal structure of the functional metal-organic framework and its stability against hydrolysis in the air.

[0244]

[0245] FIG. 23 is a drawing for comparing the absorption wavelengths of a metal-organic framework according to Comparative Example 1 of the present invention, a functional metal-organic framework according to Experimental Example 3-3, and an absorbent to which a functional metal-organic framework according to Experimental Example 3-3 is applied.

[0246] Referring to Fig. 23, the metal-organic framework according to Comparative Example 1, the functional metal-organic framework according to Experimental Example 3-3, and the absorbent coated with the functional metal-organic framework according to Experimental Example 3-3 on carbon paper were irradiated with sunlight (1-sun condition).

[0247] As can be seen in Fig. 23, the metal-organic framework according to Comparative Example 1 and the functional metal-organic framework according to Experimental Example 3-3 can be seen to selectively absorb wavelengths of 550 nm and 1,100 nm. In contrast, the absorbent to which the functional metal-organic framework according to Experimental Example 3-3 is applied can be seen to absorb wavelengths of 200 nm to 2,500 nm.

[0248]

[0249] FIG. 24 is a drawing for comparing the performance of an indoor water harvesting device to which a functional metal-organic composite according to Experimental Examples 3-3 and 3-4 of the present invention is applied.

[0250] Referring to (a) of Fig. 24, an indoor water harvesting device was manufactured by applying the functional metal-organic composite according to Experimental Example 3-3 as described above in Fig. 14, and the water adsorption capacity and water desorption capacity of the indoor water harvesting device were measured over time. Specifically, the indoor water harvesting device was placed in a chamber under conditions of 25°C and 25%RH, and the water adsorption capacity was measured using a scale. Afterwards, the indoor water harvesting device was placed in a dark room, and the absorbent of the water harvesting device was irradiated with sunlight (1 sun condition), and the water desorption capacity was measured using a scale. Referring to (b) of Fig. 24, an indoor water harvesting device was manufactured by applying the functional metal-organic composite according to Experimental Example 3-4 as described above in Fig. 14, and the water adsorption capacity and water desorption capacity of the indoor water harvesting device were measured over time using the same method as described above in (a) of Fig. 24.

[0251] As can be seen in (a) and (b) of FIG. 24, the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-3 was applied has a greater water adsorption amount than the indoor water harvesting device to which the functional metal-organic framework according to Experimental Example 3-4 was applied. This is interpreted as being due to the fact that the functional metal-organic framework according to Experimental Example 3-3 has a higher porosity than the functional metal-organic framework according to Experimental Example 3-4.

[0252] Therefore, in the method for manufacturing a functional metal-organic framework according to an embodiment of the present invention, it can be seen that the method of controlling the weight ratio of fluorophenol to the base metal-organic framework to 1:0.25 or less and controlling the porosity of the functional metal-organic framework to 72% or more (lower limit) of the porosity of the base metal-organic framework is a method for improving water adsorption capacity.

[0253] In conclusion, in the method for manufacturing a functional metal-organic framework according to an embodiment of the present invention, it can be seen that the method of controlling the porosity of the functional metal-organic framework to be 72% or more (lower limit) and less than 84% (upper limit) of the porosity of the base metal-organic framework is a method for improving the stability of the crystal structure of the functional metal-organic framework and increasing the amount of water harvested from the atmosphere.

[0254]

[0255] While the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to the specific embodiments described above, and should be interpreted in accordance with the appended claims. Furthermore, those skilled in the art will appreciate that numerous modifications and variations are possible without departing from the scope of the present invention.

Claims

1. A step of preparing a base metal-organic framework having a first porosity; and A method for producing a functional metal-organic framework, comprising the step of providing a functional oligomer to the base metal-organic framework, thereby filling at least a portion of the pores of the base metal-organic framework to produce a functional metal-organic framework having a second porosity lower than the first porosity.

2. In paragraph 1, The pores of the above base metal-organic framework are: A first type pore providing a site chemically bondable with a metal atom of the base metal-organic framework; and Including a second type pore that does not provide a site chemically bondable with the metal atom of the base metal-organic framework, The above functional oligomer includes a first type functional oligomer and a second type functional oligomer that are filled in the first type pore and the second type pore, respectively, The above first type pores include those filled with the first type functional oligomer chemically bonded to the metal atoms of the base metal-organic framework, A method for producing a functional metal-organic framework, comprising filling the second type pores with a second type functional oligomer that is not chemically bonded to the metal atoms of the base metal-organic framework.

3. In paragraph 2, A method for providing the functional oligomer to the base metal-organic framework comprises: A step of placing the base metal-organic framework and the source material of the functional oligomer in a reactor; and A step of providing the functional oligomer to a portion of the pores of the base metal-organic framework by vapor phase polymerization of the source material to the base metal-organic framework, The above source material contains fluorophenol and paraformaldehyde, The temperature of the above reactor is controlled at 90℃, A method for producing a functional metal-organic framework, comprising controlling the polymerization time of the functional oligomer to be 12 to 16 hours.

4. In paragraph 3, The above fluorophenol is a method for producing a functional metal-organic framework containing trifluorophenol (2,3,4-trifluorophenol).

5. In paragraph 4, In the step of placing the base metal-organic framework and the source material in the reactor, A method for producing a functional metal-organic framework, comprising controlling the weight ratio of the fluorophenol to the base metal-organic framework in the reactor to be greater than 1:0.125 and less than 1:0.

25.

6. In paragraph 5, A method for producing a metal-organic framework, comprising controlling the second porosity of the functional metal-organic framework to be 72% or more and less than 84% of the first porosity of the base metal-organic framework.

7. In paragraph 1, The step of preparing the base metal-organic framework having the first porosity is as follows: A step of preparing a mixed solution by mixing copper nitrate hydrate and an organic ligand in a solvent; A step of heat treating the above mixed solution; and A method for producing a metal-organic framework, comprising the step of centrifuging and washing the heat-treated mixed solution to produce the base metal-organic framework.

8. In paragraph 7, A method for producing a metal-organic framework, comprising: in the step of heat-treating the mixed solution, the mixed solution is heat-treated at a temperature of 90°C for 16 to 24 hours.

9. In paragraph 8, The solvent contains (CH3)2NCH, The above copper nitrate hydrate contains Cu(NO3)2·2.5H2O, A method for producing a metal organic framework, wherein the organic ligand comprises 1,3,5-Benzentricarvoxylic acid.

10. A functional metal-organic framework comprising a base metal-organic framework and a functional oligomer filling a portion of the pores of the base metal-organic framework, The pores of the above base metal-organic framework are: A first type pore providing a site chemically bondable with a metal atom of the base metal-organic framework; and Including a second type pore that does not provide a site chemically bondable with the metal atom of the base metal-organic framework, The functional oligomer comprises a first type functional oligomer and a second type functional oligomer, which are filled in the first type pore and the second type pore, respectively. A part of the first type pores is filled with the first type functional oligomer chemically bonded to the metal atoms of the base metal-organic framework, A functional metal-organic framework, wherein the second type pores are not completely filled with the second type functional oligomer.

11. In paragraph 10, The metal atoms of the above base metal-organic framework include copper (Cu), The above functional oligomer is a functional metal-organic framework comprising hydroxymethyl, fluorine, and phenol.

12. In paragraph 11, A functional metal-organic framework, wherein the porosity of the functional metal-organic framework is 72% or more and less than 84% of the porosity of the base metal-organic framework.

13. In paragraph 12, A functional metal-organic framework, wherein the sizes of the first type pores and the second type pores of the base metal-organic framework are 13.8 Å or more.

14. In paragraph 13, When analyzing the above functional metal-organic framework by HNMR, A functional metal-organic framework comprising a peak corresponding to a methylene bridge of a hydroxymethyl group of the functional oligomer at 1.89 ppm.

15. In paragraph 13, When the functional metal-organic framework was exposed to a humid atmosphere for more than 120 minutes, ex situ Raman spectra were analyzed. The peak corresponding to the chemical bond between the metal atom of the base metal-organic framework and the oxygen atom of the hydroxymethyl group of the functional oligomer is 169 cm -1 is observed in, The peak corresponding to the stretching band of the metal atoms of the above base metal-organic framework is 229 cm -1 A functional metal-organic framework comprising what is observed in .

16. In paragraph 13, A functional metal-organic framework, wherein the crystal structure of the functional metal-organic framework is maintained for 47 weeks or more and less than 52 weeks under conditions of 80°C and 88%RH.

17. An absorbent comprising the functional metal-organic framework according to Article 10 coated on carbon paper, An atmospheric water harvesting device comprising water adsorbed on an absorbent in the atmosphere and the water adsorbed on the absorbent being desorbed by sunlight.

Images