Polyaniline-containing metal-organic framework for atmospheric water harvesting using open coordination sites

Abstract

The present invention provides a functional metal-organic framework (MOF) comprising a base metal-organic framework and a polymer formed within pores of the base metal-organic framework, wherein the base metal-organic framework comprises a metal having open coordination sites (OCS) and the polymer is formed by polymerization of an unsubstituted aniline; an aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof.

Description

Polyaniline-containing metal-organic frameworks for atmospheric water harvesting utilizing open coordination sites

[0001] The present invention relates to a metal-organic framework (MOF) for atmospheric water harvesting. The present invention provides a metal-organic framework having open coordination sites and a functional metal-organic framework comprising a polymer within the pores of the metal-organic framework. Furthermore, the present invention provides a method for producing the functional metal-organic framework and an atmospheric water harvesting device comprising the same.

[0002] Recently, metal-organic frameworks (MOFs) with excellent water vapor capture and storage capabilities have been attracting attention as adsorbents for atmospheric water harvesting devices. MOFs are a type of crystalline material composed of metal ions or clusters linked to organic ligands. Due to their high surface area and high degree of chemical and structural controllability, MOFs can be utilized for atmospheric water harvesting. For example, Yaghi and co-workers used Zr-based MOF-801 to produce 2.8 L kg / day at a low relative humidity of 20% using only sunlight, without external energy input. -1 Water was harvested from air (Kim, Hyunho, et al. "Water harvesting from air with metal-organic frameworks powered by natural sunlight." Science 356.6336 (2017): 430-434.).

[0003] An ideal adsorbent for atmospheric water harvesting requires the following: (1) high hydrolytic stability to maintain water capacity even after multiple water adsorption / desorption cycles; (2) high water adsorption capacity in dry environments (<20% relative humidity); (3) / (4) fast adsorption / desorption kinetics; and (5) high photo-to-thermal conversion for water desorption using sunlight.

[0004] Meanwhile, among MOFs, MOFs with open coordination sites are known to have excellent water adsorption capacity, as they can provide sites for water molecules to coordinate. Due to their high water adsorption capacity, many researchers have considered MOFs with open coordination sites as adsorbents for atmospheric water harvesting devices. However, most MOFs with open coordination sites have poor water stability and require high thermal energy for water desorption, hindering their practical application. Therefore, Zr-based structures without open coordination sites have been primarily utilized, and researchers have conducted research on modifying the structures to make them hydrophilic or to increase water capacity at low relative humidity. However, there is a limit to increasing the maximum water capacity of MOFs. Therefore, research on atmospheric water harvesting, including multicycles, has become important to increase the number of adsorption / desorption cycles per unit time. To this end, the development of MOFs with faster adsorption / desorption kinetics is still required.

[0005] Against this backdrop, the inventors of the present invention have made extensive research efforts to develop an atmospheric water harvesting device that utilizes the high water adsorption capacity of MOFs having open coordination sites, while also exhibiting high water stability and fast adsorption / desorption kinetics, and have thus completed the present invention.

[0006] [Prior Art Literature]

[0007] [Non-patent literature]

[0008] Kim, Hyunho, et al. “Water harvesting from air with metal-organic frameworks powered by natural sunlight.” Science 356.6336 (2017): 430-434

[0009] The primary purpose of the present invention is to provide a functional metal-organic framework comprising a polymer within the pores of the metal-organic framework and a method for preparing the same. Furthermore, the present invention aims to provide an atmospheric water harvesting device comprising the functional metal-organic framework. The present invention also aims to provide an adsorbent for an adsorption cooling system and an adsorption cooling device comprising the functional metal-organic framework.

[0010] As one aspect for achieving the above object, the present invention provides a functional metal-organic framework. Specifically, the functional metal-organic framework comprises a base metal-organic framework and a polymer formed within pores of the base metal-organic framework, wherein the base metal-organic framework comprises a metal having open coordination sites (OCS), and the polymer is a polymer formed by a polymerization reaction of unsubstituted aniline; aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof.

[0011] Figure 1 shows a method for synthesizing HKUST-1 containing polyaniline.

[0012] Figure 2a shows the hydrophobic effect and PIC effect of HKUST-1 containing polyaniline.

[0013] Figure 2b shows the mechanism of water desorption from HKUST-1 containing polyaniline.

[0014] Figure 3a shows optical micrographs of Pri-HK, Ani-HK, tAni-Hk, and pAni-HK samples. From left to right, Pri-HK, Ani-HK, tAni-Hk, and pAni-HK are shown.

[0015] Figure 3b shows SEM images of Pri-HK, Ani-HK, tAni-Hk, and pAni-HK samples. From left to right, Pri-HK, Ani-HK, tAni-Hk, and pAni-HK are shown.

[0016] Figure 4a shows the Ani-HK, tAni-Hk, and pAni-HK samples. 1 This is the H NMR result.

[0017] Figure 4b shows the results of measurements after decomposition of Ani-HK, tAni-Hk, and pAni-HK with HCl. 1 This is the H NMR result.

[0018] Figure 5 shows the FT-IR spectrum values ​​of pAni-HK and Pri-HK.

[0019] Figure 6 shows the N X-ray photoelectron spectrometry (XPS) results for Pri-HK, tAni-Hk, and pAni-HK samples.

[0020] Figure 7 shows Cu XPS results for Pri-HK, tAni-Hk, and pAni-HK samples.

[0021] Figure 8 shows Cu XANENS (X-ray absorption near-edge structure) results for Pri-HK and pAni-HK samples.

[0022] Figure 9 shows the powder X-ray diffraction (PXRD) patterns for Pri-HK, Ani-HK, tAni-Hk, and pAni-HK samples.

[0023] Figure 10 shows N2 adsorption / desorption isotherms for Pri-HK, tAni-Hk, and pAni-HK samples.

[0024] Figure 11 shows the results of pore size distribution analysis based on density functional theory (DFT).

[0025] Figure 12 is a thermogravimetric analysis (TGA) profile for Pri-HK, Ani-HK, tAni-Hk, and pAni-HK samples.

[0026] Figure 13a shows the PXRD results for Pri-HK and pAni-HK samples under conditions of 88°C and 88% relative humidity.

[0027] Figure 13b is a specific data result for pAni-HK in Figure 13a.

[0028] Figure 13c shows the N2 isotherm results for Pri-HK and pAni-HK samples under conditions of 88°C and 88% relative humidity.

[0029] Figure 14a shows PXRD results under different temperature and pH conditions for Pri-HK and pAni-HK samples.

[0030] Figure 14b is a specific data result for pAni-HK in Figure 14a.

[0031] Figure 14c shows the N2 isotherm results for the pAni-HK sample under different temperature and pH conditions.

[0032] Figure 15 shows water adsorption isotherms at 25°C for Pri-HK and pAni-HK samples.

[0033] Figures 16a and 16b show the temperature changes of Pri-HK and pAni-HK samples over time under 1 sun conditions.

[0034] Figure 17 shows the wavelengths of light that polyaniline, Pri-HK, Ani-HK, tAni-Hk, and pAni-HK samples can absorb.

[0035] Figure 18 shows the results of a water adsorption experiment over time of pAni-HK in a chamber under conditions of 25°C and 25% RH and the results of a water desorption experiment under 1 sun conditions.

[0036] Figure 19 shows the multi-cycle atmospheric water collection results of pAni-HK at 25°C, 25% RH, 1 sun.

[0037] Figure 20a shows the water adsorption and desorption results over time of pAni-HK under outdoor conditions.

[0038] Figure 20b shows the experimental device and results of Figure 20a.

[0039] Figure 20c shows outdoor conditions for multi-cycle atmospheric water collection.

[0040] Figure 21 shows the multi-cycle atmospheric water collection results of pAni-HK under the conditions of Figure 20c.

[0041] Figure 22 shows the operating principle of an adsorption cooler.

[0042] Hereinafter, embodiments are described in detail with reference to the attached drawings. However, the embodiments may be modified in various ways, and the scope of the patent application is not limited or restricted by these embodiments. It should be understood that all modifications, equivalents, or alternatives to the embodiments are included within the scope of the patent application.

[0043] The terms used in the examples are for illustrative purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise" or "have" are intended to indicate the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but should be understood to not preclude the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0044] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiments pertain. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and shall not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0045] In addition, when describing with reference to the attached drawings, identical components will be assigned the same reference numerals regardless of the drawing numbers, and redundant descriptions thereof will be omitted. When describing embodiments, if a detailed description of a related known technology is judged to unnecessarily obscure the gist of the embodiment, the detailed description will be omitted.

[0046] Additionally, terms such as first, second, A, B, (a), (b), etc. may be used to describe components of the embodiment. These terms are only intended to distinguish the components from other components, and the nature, order, or sequence of the components are not limited by the terms.

[0047] Components included in one embodiment and components with common functions will be described using the same names in other embodiments. Unless otherwise stated, the descriptions given in one embodiment can be applied to other embodiments, and detailed descriptions will be omitted to the extent of overlap.

[0048] The term “about” is understood to refer to a range of numbers that one of ordinary skill in the art would consider equivalent to the stated value in terms of achieving the same function or result.

[0049] Throughout this specification, "%" used to indicate the concentration of a particular substance is (weight / weight) % for solid / solid, (weight / volume) % for solid / liquid, and (volume / volume) % for liquid / liquid, unless otherwise noted.

[0050] As used herein, "C 1-3 "Alkyl" refers to a hydrocarbon having 1 to 3 carbon atoms. Here, "C 1-3 " is C1, C2, C 3, C 1-2, C 1-3, C 2-3 Contains alkyl. For example, C 1-3 Alkyl includes, but is not limited to, methyl, ethyl, n-propyl, iso-propyl, etc.

[0051] As used herein, "C 1-3 "Alkoxy" refers to -OR, where R is substituted or unsubstituted C 1-3 It is alkyl. For example, C 1-3 Alkyl includes, but is not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, etc.

[0052] As used herein, the term "halo" refers to fluoro (F), chloro (Cl), bromo (Br), and iodo (I). In some embodiments, halo refers to F, Cl, or Br. In some embodiments, halo refers to F or Cl. In some embodiments, halo refers to F.

[0053] The term "C" as used herein 1-3 "Haloalkyl" means the above "C 1-3 "Alkyl" refers to one or more substituted halo groups. For example, haloalkyl includes, but is not limited to, -CF3, -CH2F, -CHF2, -CHFCH2F, -CH2CHF2, -CF2CF3, -CCl3, -CH2Cl, -CHCl2, etc.

[0054] The term "HK" or "Pri-HK" used herein refers to HKUST-1 or synthesized HKUST-1. Here, HKUST-1 is Cu3(BTC)2, where BTC is benzene-1,3,5-tricarboxylate. In this specification, a material in which aniline monomer is coordinated to HKUST-1 is referred to as "Ani-HK", and a crystal obtained by heating Ani-HK and undergoing an oxidative polymerization reaction is referred to as "tAni-HK". And a crystal obtained by washing tAni-HK is referred to as "pAni-HK".

[0055] The term "1 sun" as used herein means 90 to 110 mW / cm 2 refers to the conditions under which light is incident. Preferably, "1 sun" is 100 mW / cm 2 Refers to the conditions under which light is emitted.

[0056] The term 'RH (relative humidity)' used in this specification refers to relative humidity.

[0057]

[0058] As a first aspect of the present invention, a functional metal-organic framework (MOF) is provided, wherein the functional metal-organic framework comprises a base metal-organic framework and a polymer formed within a pore of the base metal-organic framework, wherein the base metal-organic framework comprises an open coordination site metal, and the polymer is a polymer formed by a polymerization reaction of unsubstituted aniline; aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof.

[0059]

[0060] In one aspect of the present invention, the open coordination site metal is Cu 2+ am.

[0061]

[0062] In one aspect of the present invention, the base metal-organic framework is HKUST-1 (Cu3(BTC)2; BTC = benzene-1,3,5-tricarboxylate).

[0063]

[0064] In one aspect of the present invention, the polymer is formed by polymerization of unsubstituted aniline.

[0065]

[0066] In one aspect of the present invention, the polymer comprises an emeralinde base form, pernigraniline, or leucoemeraldine base form. Preferably, the polymer comprises a leucoemeraldine base form.

[0067]

[0068] In one aspect of the present invention, the pore volume of the functional metal-organic framework is 70% to 80% of the pore volume of the base metal-organic framework. Preferably, the pore volume of the functional metal-organic framework is 72% to 78% of the pore volume of the base metal-organic framework. Preferably, the pore volume of the functional metal-organic framework is 76% of the pore volume of the base metal-organic framework.

[0069]

[0070] In one embodiment of the present invention, under conditions of a temperature of 85°C to 95°C and a relative humidity of 85% to 95%, the functional metal-organic framework maintains at least 95% of the pore volume for at least 4 weeks. In one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 95% of the pore volume for at least 4 weeks. Preferably, in one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 97% of the pore volume for at least 4 weeks. In one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 98% of the pore volume for at least 4 weeks.

[0071]

[0072] In one embodiment of the present invention, under conditions of a temperature of 85°C to 95°C and a relative humidity of 85% to 95%, the functional metal-organic framework maintains at least 60% of the pore volume for at least 6 months. In one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 60% of the pore volume for at least 6 months. Preferably, in one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 70% of the pore volume for at least 6 months. In one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 80% of the pore volume for at least 6 months.

[0073]

[0074] In one embodiment of the present invention, under conditions of a temperature of 85°C to 95°C and a relative humidity of 85% to 95%, the functional metal-organic framework maintains at least 40% of the pore volume for at least 12 months. In one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 40% of the pore volume for at least 12 months. Preferably, in one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 50% of the pore volume for at least 12 months. In one embodiment of the present invention, under conditions of a temperature of 88°C and a relative humidity of 88%, the functional metal-organic framework maintains at least 60% of the pore volume for at least 12 months.

[0075]

[0076] In one embodiment of the present invention, when the functional metal-organic framework is exposed to water at 25°C or 100°C, it maintains at least 60% of its pore volume for at least 3 months. Preferably, in one embodiment of the present invention, when the functional metal-organic framework is exposed to water at 25°C or 100°C, it maintains at least 70% of its pore volume for at least 3 months. In one embodiment of the present invention, when the functional metal-organic framework is exposed to water at 25°C or 100°C, it maintains at least 80% of its pore volume for at least 3 months.

[0077]

[0078] In one embodiment of the present invention, when the functional metal-organic framework is exposed to a pH of 3 or 11, at least 60% of the pore volume is maintained for at least 3 months. Preferably, in one embodiment of the present invention, when the functional metal-organic framework is exposed to a pH of 3 or 11, at least 70% of the pore volume is maintained for at least 3 months. In one embodiment of the present invention, when the functional metal-organic framework is exposed to a pH of 3 or 11, at least 80% of the pore volume is maintained for at least 3 months.

[0079]

[0080] In one aspect of the present invention, the functional metal-organic framework is irradiated with 100 mW / cm for 10 minutes. 2 When exposed to, the temperature of the functional metal-organic framework becomes 65°C to 75°C. In one embodiment of the present invention, the functional metal-organic framework is exposed to 100 mW / cm for 10 minutes. 2 When exposed to, the temperature of the functional metal-organic framework becomes 65°C to 70°C. Preferably, in one embodiment of the present invention, the functional metal-organic framework is exposed to 100 mW / cm for 10 minutes. 2 When exposed to , the temperature of the functional metal-organic framework becomes 69°C.

[0081]

[0082] In one aspect of the present invention, the functional metal-organic framework is in powder form.

[0083]

[0084] As a second aspect of the present invention, a method for producing a functional metal-organic framework is provided, wherein the functional metal-organic framework comprises a base metal-organic framework and a polymer formed within the pores of the base metal-organic framework, and the method for producing the functional metal-organic framework comprises:

[0085] A step of preparing a base metal-organic framework comprising an open coordination site metal;

[0086] A step of preparing a monomer solution, wherein the monomer solution comprises an organic solvent, and the monomer solution comprises unsubstituted aniline; aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof;

[0087] A step of adding the base metal-organic framework to the monomer solution at room temperature to coordinate the monomer to the open coordination site metal of the base metal-organic framework; and

[0088] A method for producing a metal-organic framework, comprising: heating a metal-organic framework in which a monomer is coordinated to an open coordination site metal in air containing O2, thereby forming a polymer within the pores of the base metal-organic framework through oxidative polymerization of the monomer.

[0089]

[0090] At this time, O2 acts as an oxidizing agent for deprotonation and the base metal-organic framework acts as a catalyst.

[0091]

[0092] In one aspect of the present invention, the organic solvent of the monomer solution comprises TCM. Preferably, in one aspect of the present invention, the organic solvent of the monomer solution comprises purified TCM.

[0093]

[0094] In one aspect of the present invention, the manufacturing method further comprises a step of washing the functional metal-organic framework. In one aspect of the present invention, the manufacturing method further comprises a step of washing the functional metal-organic framework with a TCM solvent.

[0095]

[0096] In one aspect of the present invention, heating the metal-organic framework in which the monomer is coordinated to the open coordination site metal is performed at 70°C to 100°C for 10 to 14 hours. Preferably, in one aspect of the present invention, heating the metal-organic framework in which the monomer is coordinated to the open coordination site metal is performed at 90°C for 12 hours.

[0097]

[0098] In one aspect of the present invention, the method further comprises a step of determining the concentration of the monomer solution such that the monomer is 0.8 to 1.2 equivalents per equivalent of the open-coordination site metal of the base metal-organic framework. Preferably, in one aspect of the present invention, the method further comprises a step of determining the concentration of the monomer solution such that the monomer is 1 equivalent per equivalent of the open-coordination site metal of the base metal-organic framework.

[0099]

[0100] In one aspect of the present invention, the open coordination metal in the manufacturing method is Cu 2+ am.

[0101]

[0102] In one aspect of the present invention, the base metal-organic framework in the manufacturing method is HKUST-1 (Cu3(BTC)2; BTC = benzene-1,3,5-tricarboxylate).

[0103]

[0104] In one aspect of the present invention, the monomer solution in the above manufacturing method contains unsubstituted aniline.

[0105]

[0106] In one aspect of the present invention, the oxidation number of the open coordination site metal in the functional metal-organic framework is the same as the oxidation number of the open coordination site metal in the base metal-organic framework to which the monomer is not coordinated.

[0107]

[0108] In one aspect of the present invention, the functional metal-organic framework manufactured by the above manufacturing method is in powder form.

[0109]

[0110] As a third aspect of the present invention, an atmospheric water harvesting device is provided, wherein the atmospheric water harvesting device includes a water absorbent comprising the functional metal-organic framework of the first and second aspects of the present invention.

[0111]

[0112] In one aspect of the present invention, the atmospheric water harvesting device includes a water absorbent that adsorbs atmospheric water and the adsorbed water is desorbed by sunlight.

[0113]

[0114] In one aspect of the present invention, a functional metal-organic framework is provided in which a polymer is synthesized within a base metal-organic framework. While HKUST-1 containing polyaniline is illustrated in FIG. 1, the present invention is not limited thereto.

[0115]

[0116] In the functional metal-organic framework of the present invention, the polymer located in the pores can improve the moisture stability of the functional metal-organic framework. This may be due to (1) the hydrophobic effect or (2) the pin-in-channel (PIC) effect of the polymer. First, in the case of a hydrophobic polymer, it may hinder the access of water molecules to the open coordination sites of the functional metal-organic framework. On the other hand, when a water molecule forms a coordination bond to a metal center, the water molecule can typically dissociate the metal-ligand coordination bond through a “push through” or “twist” mechanism, and may damage the crystal or induce a crystalline phase transformation into a non-porous crystal due to modification of the coordination bond geometry or coordination bond mode (e.g., bonding with another ligand molecule). At this time, the polymer contained in the pores may help the dissociated ligand to recombine with the dissociated metal through the PIC effect, which prevents the dissociated metal from undergoing a change in its coordination mode. Figure 2a illustrates the mechanisms of the hydrophobic effect and the PIC effect.

[0117]

[0118] In addition, the functional metal-organic framework of the present invention has a high photon-to-thermal conversion effect. In particular, the polymer used in the present invention has a narrow gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), so it absorbs light energy in the visible light range, and most of the absorbed light energy is converted into heat energy. This high photon-to-thermal conversion and the dynamic bonding of the polymer will help water desorption from the functional metal-organic framework. Due to the high photon-to-thermal conversion, the functional metal-organic framework of the present invention maintains a high temperature under sunlight, and dynamic bonding occurs more actively. For example, as shown in Fig. 2b, when water temporarily dissociates from Cu(II), the hydrophobic polyaniline repels the water, thereby assisting complete dissociation. Although Figs. 2a and 2b are described based on HKUST-1 containing polyaniline, the present invention is not limited thereto.

[0119]

[0120] Meanwhile, in one aspect of the present invention, the oxidation number of the open coordination site metal in the functional metal-organic framework is the same as the oxidation number of the open coordination site metal in the base metal-organic framework to which the monomer is not coordinated. In other words, the open coordination site metal acts as a catalyst for the polymer reaction.

[0121]

[0122] The functional metal-organic framework of the present invention maintains a similar level of water adsorption capacity compared to a base metal-organic framework that does not include a polymer. In one embodiment of the present invention, the functional metal-organic framework maintains at least 80% of the water adsorption capacity of the base metal-organic framework. In one embodiment of the present invention, the functional metal-organic framework maintains at least 85% of the water adsorption capacity of the base metal-organic framework. Preferably, in one embodiment of the present invention, the functional metal-organic framework maintains at least 88% of the water adsorption capacity of the base metal-organic framework.

[0123]

[0124] In one aspect of the present invention, the functional metal-organic framework has a water adsorption amount of 0.2 to 0.35 g·g at 25°C and 25% relative humidity. -1 In one aspect of the present invention, the functional metal-organic framework has a water adsorption amount of 0.20 to 0.30 g·g at 25°C and 25% relative humidity. -1 Preferably, in one aspect of the present invention, the functional metal-organic framework has a water adsorption amount of 0.21 g·g at 25°C and 25% relative humidity. -1 Preferably, in one aspect of the present invention, the functional metal-organic framework has a water adsorption amount of 0.27 g·g at 25°C and 25% relative humidity. -1 am.

[0125]

[0126] In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water adsorption is completed within 50 minutes at 25°C and 25% relative humidity. Preferably, in one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water adsorption is completed within 40 minutes at 25°C and 25% relative humidity.

[0127]

[0128] In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water desorption is completed within 30 minutes under 1 sun condition. Preferably, in one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water desorption is completed within 20 minutes under 1 sun condition.

[0129]

[0130] What is even more surprising is that, in the case of the atmospheric water harvesting device including the functional metal-organic framework of the present invention, water can be completely desorbed under sunlight using only the functional metal-organic framework itself, without a solar absorbent such as carbon paper or graphene oxide.

[0131]

[0132] In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 50 times a day at 25°C, 25% RH, 1 sun. In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 45 times a day at 25°C, 25% RH, 1 sun. Preferably, in one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 41 times a day at 25°C, 25% RH, 1 sun. In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 30 times a day at 25°C, 25% RH, 1 sun.

[0133]

[0134] In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, 5 to 10 L·kg per day at 25°C, 25% RH, 1 sun -1In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, 7 to 9 L·kg per day at 25°C, 25% RH, 1 sun -1 Water can be obtained. Preferably, in one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, 8.22 L·kg per day at 25°C, 25% RH, 1 sun -1 You can get water from it.

[0135]

[0136] In one embodiment of the air water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 30 times a day in an outdoor environment (ambient temperature, ambient relative humidity). In one embodiment of the air water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 25 times a day in an outdoor environment (ambient temperature, ambient relative humidity). Preferably, in one embodiment of the air water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 20 times a day in an outdoor environment (ambient temperature, ambient relative humidity). In one embodiment of the air water harvesting device comprising the functional metal-organic framework of the present invention, water can be harvested up to 15 times a day in an outdoor environment (ambient temperature, ambient relative humidity).

[0137]

[0138] In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, 2.0 to 5.0 L·kg per day in an outdoor environment (ambient temperature, ambient relative humidity) -1 In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, 3.0 to 4.0 L·kg per day in an outdoor environment (ambient temperature, ambient relative humidity) -1In one embodiment of the atmospheric water harvesting device comprising the functional metal-organic framework of the present invention, 3.783 L·kg per day in an outdoor environment (ambient temperature, ambient relative humidity) -1 You can harvest water from it.

[0139]

[0140] As a fourth aspect of the present invention, an adsorbent for an adsorption cooling system is provided, wherein the adsorbent for the adsorption cooling system comprises a water absorbent comprising the functional metal-organic framework of the first and second aspects of the present invention.

[0141]

[0142] As a fifth aspect of the present invention, an adsorption cooling device is provided, wherein the adsorption cooling device comprises:

[0143] refrigerant;

[0144] Coolant; and

[0145] Contains an adsorbent,

[0146] The above refrigerant is water,

[0147] The above adsorbent comprises a water absorbent comprising the functional metal-organic framework of the first aspect and the second aspect of the present invention.

[0148]

[0149] The operating principle of an adsorption chiller is as follows:

[0150] 1) Evaporation stage: A pipe through which cooling water flows passes inside an evaporator containing water as the refrigerant. The interior of the evaporator is maintained in a vacuum, and the refrigerant water evaporates at a low temperature (5 to 15°C). As the water converts to water vapor, it absorbs surrounding heat, producing a cooling effect. This cooling effect cools the cooling water, which is used in air conditioning devices, etc. (see 1) Evaporation in Figure 22).

[0151] 2) Adsorption stage: The connecting valve between the adsorber and the evaporator is opened to move the water vapor generated in the evaporator to the adsorber. There is an adsorbent inside the adsorber, and this adsorbent adsorbs the water vapor generated in the evaporator. Therefore, the water vapor concentration inside the evaporator can be maintained low. As a result, a low vapor pressure is continuously maintained inside the evaporator, and the refrigerant water can continuously evaporate to produce a cooling effect. In other words, in an adsorption chiller, the adsorbent acts as a pump that induces refrigerant circulation (see adsorber 1 of 2) adsorption in Fig. 22).

[0152] 3) Desorption stage: After the adsorbent has sufficiently adsorbed water vapor, the connection valve between the adsorber and the evaporator is closed, and the connection valve between the adsorber and the condenser is opened. The adsorbent is heated to desorb the water vapor adsorbed on the adsorbent, and the desorbed water vapor is moved to the condenser (see Adsorber 1 of Desorption, 3) in Fig. 22).

[0153] 4) Condensation stage: The desorbed water vapor is condensed into water by cooling water. The condensed water is supplied to the evaporator again and goes through the evaporation stage. In other words, the condenser operates as a circulation system (see 4) Condensation in Fig. 22).

[0154]

[0155] In adsorption cooling systems, the performance of the adsorbent directly affects cooling efficiency and system stability, and an ideal adsorbent should have the following characteristics:

[0156] 1) Moisture stability: Excellent adsorption performance must be maintained even during repeated adsorption and desorption processes;

[0157] 2) High moisture adsorption capacity at low humidity: Since the inside of the evaporator is in a vacuum state, excellent adsorption performance is required even at low water vapor pressure (P / P0 = 0.1~0.3);

[0158] 3) Fast adsorption rate: Fast adsorption rate is required to increase the efficiency of the cooling system;

[0159] 4) Fast desorption speed: The cycle efficiency increases when the desorption process is smooth; and

[0160] 5) Low-temperature desorption capability: To reduce energy consumption, it must be possible to regenerate using low-temperature heat sources such as waste heat or solar heat at a temperature of 60 to 90°C.

[0161]

[0162] The above five properties are all similar to the properties of an ideal adsorbent for atmospheric water harvesting, and it was confirmed that these properties are all possessed by the functional metal-organic framework (e.g., pAni-HK) of the first and second aspects of the present invention. The functional metal-organic framework of the first and second aspects of the present invention can be utilized as a high-performance adsorbent in an adsorption cooling device.

[0163]

[0164] In one embodiment, an adsorption refrigeration device includes two adsorbers, each of which can operate alternately (Fig. 22). For example, while adsorber 1 adsorbs water vapor, adsorber 2 is heated and desorbs the water vapor. Conversely, while adsorber 1 is heated and desorbs the water vapor, adsorber 2 adsorbs the water vapor. In this way, by alternately performing adsorption and desorption in each adsorber, continuous refrigerant circulation and a cooling effect can be maintained.

[0165]

[0166] Below, examples of manufacturing functional metal-organic frameworks of the present invention and examples of verifying their characteristics are described. These manufacturing examples and examples are merely illustrative and do not limit the present invention.

[0167]

[0168] Manufacturing example: Synthesis of polyaniline inside HKUST-1

[0169]

[0170] Synthesis of HKUST-1

[0171]

[0172] In a 20 mL vial, Cu(NO3)2·2.5H2O (98%, Aldrich) (0.87 g, 3.6 mmol) was dissolved in 10 mL of DDW. Then, using a separate vial, H3BTC (1,3,5-benzenetricarboxylic acid; 98%, alfa) (0.22 g, 1.0 mmol) was dissolved in 10 mL of EtOH (94.5%, Daejung). Then, the Cu(NO3)2 solution was quickly added to the vial containing the H3BTC solution. The mixed solution was continuously stirred at room temperature for 10 minutes, and then 1 mL of DMF (99.5% Daejung) was added to the mixture. Then, the vial was sealed with polytetrafluoroethylene (PTFE) tape and placed in an oven at 80°C for 20 hours to allow the mixture to react. After the product was cooled to room temperature, the crystals (Pri-HK) were collected and washed with a mixed solvent of H2O and EtOH.

[0173]

[0174] Synthesis of pAni-HK

[0175]

[0176] Before aniline treatment of HKUST-1, the H2O and EtOH solvents coordinated to Pri-HK were removed by thermal activation. The Pri-HK sample was placed in a glass vacuum tube. Then, vacuum (~ 10 -3 The tube was heated at 180°C for 20 h under 10 Torr conditions. After activation, the glass vacuum tube was transferred to a glove box with a moisture-free Ar atmosphere.

[0177]

[0178] Refined TCM (CHCl 3,Aniline (99.5%, Aldrich) (450 μL) was dissolved in 20 mL of trichloromethane (99.0%, Alfa) in a vial, and then 0.50 g of activated Pri-HK was added to the vial. The crystals were left at room temperature for 12 h to allow aniline to coordinate to the HKUST-1 Cu site. Afterwards, the crystals were washed with purified TCM solvent to remove aniline on the crystal surface. Finally, the obtained Ani-HK crystals were dried under vacuum before use. This process was performed in a glove box under a moisture-free Ar atmosphere.

[0179]

[0180] For in-situ polymerization of aniline monomer, Ani-HK was heated in air in an oven at 90°C for 12 h. Both oxygen and MOF are essential for the polymerization process, as the reaction will not occur if either oxygen or MOF in the air is lacking. Here, O2 acts as an oxidizing agent for deprotonation, and HKUST-1 acts as a catalyst. The resulting black crystals (tAni-HK) were washed five times with purified TCM solvent to remove unreacted substances and byproducts (azobenzene) (pAni-HK). Finally, the obtained pAni-HK crystals were activated by heating at 180°C for 20 h under vacuum before use.

[0181]

[0182] Example 1: Characterization of pAni-HK

[0183]

[0184] Optical microscope and SEM images

[0185]

[0186] Optical microscope photographs and SEM images of Pri-HK, Ani-HK, tAni-Hk, and pAni-HK samples are shown in Figs. 3a and 3b, respectively. Nikon's SMZ800N was used as the optical microscope, and the SEM images were obtained using Hitachi's S-4800. Figs. 3a and 3b show images of Pri-HK, Ani-HK, tAni-Hk, and pAni-HK, in that order from left to right.

[0187]

[0188] Looking at Fig. 3a, we can see that the color of the HKUST-1 crystals changes at each step. In particular, tAni-HK and pAni-HK after the polymerization reaction are black in contrast to Pri-HK, which is blue. Meanwhile, Fig. 3b shows that Pri-HK, tAni-HK, and pAni-HK all have smooth surfaces, indicating that the polymers are synthesized within the pores of HKUST-1.

[0189]

[0190] 1 H NMR analysis

[0191]

[0192] To determine the product after polymerization of aniline monomer, each sample was washed with CDCl3. 1 H NMR measurements were performed. A small amount of Ani-HK sample was placed in 1 mL of CDCl3 solvent and sonicated. Then, the CDCl3 supernatant was transferred to an NMR tube and analyzed. For the tAni-HK and pAni-HK samples, the CDCl3 supernatant was washed in the same manner as before, and the CDCl3 supernatant solution was 1 H-NMR spectra were measured.

[0193]

[0194] As confirmed in Fig. 3a, even in the case of pAni-HK with azobenzene removed, the black color still appears, suggesting that there is a polymer synthesized inside the pores through the ship-in-a-bottle strategy. To verify this, the structure of each sample was decomposed using acid. 1 H NMR was measured. 20 mg of Ani-HK sample was dissolved in 10 ml of HCl solution at pH -0.56. Then, the solution was evaporated through a rotary evaporator, and the obtained powder was dissolved in DMSO-d6 solvent and transferred to an NMR tube. The tAni-HK and pAni-HK samples were also decomposed in the same manner and then dissolved in DMSO-d6 solution. 1 H-NMR spectra were measured.

[0195]

[0196] The upper layer of CDCl3 solution and the solution of DMSO-d6 1 H-NMR was measured using an AVANCE III HD 400 MHZ instrument from Brucker.

[0197]

[0198] Looking at Fig. 4a, first, a peak corresponding to aniline can be confirmed in Ani-HK, which means that the aniline monomer is well coordinated to the Cu(II) center. In the tAni-HK sample heated in air, the peak corresponding to aniline disappears and a peak corresponding to azobenzene appears. This means that after the reaction, the aniline monomer dimerizes to produce azobenzene. In pAni-HK, the azobenzene inside the pores is removed, so no corresponding peak appears, which means that azobenzene is removed during the washing process of tAni-HK.

[0199]

[0200] Looking at Fig. 4b, the characteristic NH peak of polyaniline can be confirmed in tAni-HK and pAni-HK. This confirms that polyaniline, which cannot escape through the window of HKUST-1, was synthesized within the pores of HKUST-1.

[0201]

[0202] Fourier transform infrared spectroscopy (FT-IR) and nitrogen X-ray photoelectron spectra (XPS) analysis

[0203]

[0204] To determine the morphology of polyaniline synthesized through the intra-pore injection strategy, FT-IR and nitrogen XPS measurements were performed. FT-IR and nitrogen XPS were performed using Perkin Elmer's Spectrum Two and Thermo Scientific's ESCALAB 250Xi instruments, respectively.

[0205]

[0206] As shown in Fig. 5, in the FT-IR spectrum, pAni-HK showed higher peaks at 1615, 1243, and 1190 cm compared to Pri-HK. -1 Three new absorption bands are observed in pAni-HK, which correspond to the NH plane bending, benzenoid-N stretching, and CH bending of polyaniline, respectively. In addition, pAni-HK exhibits a band at 1483 cm -1 The absence of the corresponding quinonoid-N stretching band indicates that polyaniline exists in the leucoemeraldine base form inside the HKUST-1 pores.

[0207]

[0208] As shown in Fig. 6, in the N XPS spectrum, no N 1s band is observed in Pri-HK, but in tAni-HK and pAni-HK after the polymerization reaction, an N 1s band is formed at 399.6 ev, which corresponds to benzenoid-N (-NH-).

[0209]

[0210] Based on these FT-IR and nitrogen XPS analyses, pAni-HK reveals that polyaniline exists in the form of leucoemeraldine base inside HKUST-1.

[0211]

[0212] Cu XPS and XANES analysis

[0213]

[0214] To confirm the oxidation number of the Cu center of pAni-HK, X-ray photoelectron analysis (XPS) was performed and the results are shown in Fig. 7. An ESCALAB 250Xi instrument from Thermo Scientific was used for the X-ray photoelectron analysis.

[0215]

[0216] For comparison, the Pri-HK sample was also analyzed by XPS. The XPS spectrum of the Cu(2p) region shows two main peaks corresponding to spin-orbit coupled energy states, J = 3 / 2 and 1 / 2, and two shake-up satellite peaks for the main peaks. The chemical shifts of the main peaks for Pri-HK, tAni-HK, and pAni-HK are at 932.6 and 952.7 eV, respectively, which correspond to the 2p state of Cu(II). 3 / 2 and Cu 2p 1 / 2 This indicates the energy state. In addition, since no peaks appear at 934.6 and 954.3 eV corresponding to Cu(I), it can be seen that only Cu(II) exists in pAni-HK.

[0217]

[0218] Furthermore, X-ray absorption near-edge structure (XANES) analysis was performed on the Pri-HK and pAni-HK samples using the 7D beamline at Pohang Accelerator Laboratory. The results are shown in Fig. 8, and it can be confirmed that both the Pri-HK and pAni-HK samples exhibit only a shoulder peak for Cu(II) at 8986 eV, which corresponds to the electronic transition from the 1s orbital to the 4s orbital.

[0219]

[0220] Cu XPS and XANES spectra show that the oxidation number of Cu node of HKUST-1 does not change before and after polymerization reaction, which indicates that polyaniline synthesis reaction is Cu 2+ It indicates that it is a catalytic reaction.

[0221]

[0222] Example 2. Phase purity analysis

[0223]

[0224] To confirm the phase purity of the HKUST-1 sample before and after the polymerization reaction, powder X-ray diffraction (PXRD) and N2 adsorption / desorption isotherms were measured. An Empyrean instrument from PANalytical and a Max instrument from Belsorp were used for these measurements, and the results are shown in Figs. 9 and 10, respectively.

[0225]

[0226] As shown in Fig. 9, the PXRD results confirm that the structure of HKUST-1 was maintained before and after the polymerization reaction.

[0227]

[0228] As shown in Fig. 10, in the N2 adsorption / desorption isotherm, Pri-HK has an internal surface area and pore volume of 1946 m 2 ·g -1 and 545 cm 3 ·g -1 While tAni-HK has a high internal surface area and pore volume of 81 m 2 ·g -1 and 43 cm 3 ·g -1 The internal surface area and pore volume decreased sharply. This is because polyaniline and azobenzene fill 90% of the total pore volume of HKUST-1. When azobenzene is removed through washing, the internal surface area and pore volume increased to 1570 m 2 ·g -1 and 413 cm 3 ·g -1 In the case of pAni-HK, it has a relatively lower value than Pri-HK because polyaniline exists inside the pores, and polyaniline fills about 24% of the pore volume of HKUST-1 (i.e., the pore volume of pAni-Hk is about 76% of the pore volume of Pri-Hk).

[0229]

[0230] Figure 11 shows the results of pore size distribution analysis based on density functional theory (DFT). The pore size distribution analysis was performed using BELMaster software from MicrotracBEL. It can be seen that tAni-HK has almost no pores due to polyaniline and azobenzene, and pAni-HK has a reduced pore size due to the presence of polyaniline within the pores.

[0231]

[0232] Also, Fig. 12 shows the thermogravimetric analysis (TGA) profiles of the samples. The Auto Q500 from TA Instruments was used for the TGA. In HKUST-1, the weight loss below 250°C is due to the removal of guest molecules inside the pores, and the temperature change from 250°C to 400°C is caused by the decomposition of the structure. The weight loss of pAni-HK below 250°C is less than that of Pri-HK due to the polyaniline incorporated into the pores. In addition, the weight loss of tAni-HK below 250°C is less than that of pAni-HK due to the increase in the total weight due to the polyaniline and azobenzene present inside the pores.

[0233]

[0234] Example 3. Confirmation of moisture stability

[0235]

[0236] The polyaniline within HKUST-1 is expected to exhibit superior moisture stability compared to conventional metal-organic frameworks, due to the hydrophobic and PIC effects. To demonstrate this, samples were placed in a chamber at 88°C and 88% relative humidity to test their moisture stability. PXRD and N2 isotherm measurements were performed using the same equipment as in Example 2.

[0237]

[0238] Figure 13a shows the PXRD results, and Figure 13b shows more specific PXRD results for pAni-HK. Under humid conditions, Pri-HK turned into a non-porous solid within a day, whereas pAni-HK remained the same even after one year.

[0239]

[0240] These results were consistent with the N2 isotherm results shown in Fig. 13c. Pri-HK left for one day under humid conditions had a pore volume of almost 0, whereas pAni-HK had a pore volume of 410 cm even after one month. 3 ·g -1 400 cm from 3 ·g -1 It only decreased slightly. Even after 6 months, it was 295 cm 3 ·g -1 The pore volume was reduced by only about 30% after 12 months, and then decreased to about 50% after 12 months.

[0241]

[0242] In addition, Figs. 14a to 14c show the PXRD (Figs. 14a, 14b) and N2 isotherm results (Fig. 14c) when pAni-HK was soaked in water at 25°C and 100°C for 3 months, and the PXRD (Figs. 14a, 14b) and N2 isotherm results (Fig. 14c) when the pH was 3 (acidic) and 11 (basic). pAni-HK retained its structure well even after soaking in water at 25°C and 100°C for 3 months, and its pore volume only decreased by about 30%. In addition, pAni-HK showed improved hydrolytic stability under acidic (pH 3) and basic (pH 11) conditions over 3 months, and its pore volume decreased by about 30%.

[0243]

[0244] Through these results, it can be confirmed that the pAni-HK of the present invention has excellent moisture stability.

[0245]

[0246] Example 4. Water adsorption / desorption characteristics

[0247]

[0248] To confirm the water adsorption ability of pAni-HK, water adsorption isotherm was measured at 25℃ using Jeio Tech's TH-ME-025 device. In the water adsorption isotherm, Pri-HK has a type-I conformation due to the presence of open coordination sites. According to "Crystalline hydrogen bonding of water molecules confined in a metal-organic framework." Communications Chemistry 5 (2022): 51, Pri-HK has 0.09 g·g -1 The point is due to water coordinating to the open coordination site, 0.27 g·g -1 This is due to the water inside the pores forming hydrogen bonds with the water coordinated by the branch.

[0249]

[0250] As shown in Fig. 15, pAni-HK also has the same type-I morphology, and the inflection point shifted toward the hydrophobic direction due to the integrated polyaniline. In the case of pAni-HK, the inflection point shifted to 0.08 g·g due to the increase in the weight of the MOF caused by polyaniline and the decrease in the amount of water filling the pores. -1 , 0.23 g·g -1 Although it was changed to , it can be seen that the open coordination metal is still used for water adsorption. As a result, pAni-HK has 0.20, 0.29, and 0.44 g·g at 10, 20, and 30% RH, respectively. -1 , it can be seen that it has a high water adsorption capacity at low humidity.

[0251]

[0252] To evaluate the photon-to-thermal conversion capability, an infrared camera (FLIR) was used to measure the temperature change of the sample over time under 1 sun conditions. In this example, "1 sun" is 100 mW / cm 2The light conditions are as follows. Samples for UV-visible absorption spectra were prepared as follows. Before measuring the UV-visible absorption spectra, aniline-treated HKUST-1 samples were transferred to a glove box under a moisture-free Ar atmosphere. Then, the crystals were placed in a disk-shaped quartz cell (Starna, Type 37GS Cylindrical Cells with Quartz to Borofloat graded seal). The quartz cell was sealed with a glass cork and grease (Apiezon, H high-temperature Vacuum Greases) before measurement.

[0253]

[0254] As shown in FIGS. 16a and 16b, Pri-HK rose to about 55°C within 10 minutes, while pAni-HK rose to about 69°C, demonstrating a higher photon-to-heat conversion capability. This is because the black color of pAni-HK can absorb most of the light in the visible light range. In particular, polyaniline has a narrow gap between its HOMO and LUMO, so it can absorb light energy in the visible light range and convert the absorbed light energy into heat energy. In other words, these characteristics of polyaniline provide an advantage that makes the functional metal-organic framework of the present invention advantageous for use in an atmospheric water harvesting device.

[0255]

[0256] Furthermore, as shown in Fig. 17, the UV-visible spectrum results show that Pri-HK does not absorb light well in the 300-500 nm range of the visible light range, whereas pAni-HK can absorb most of the visible light due to polyaniline. This provides pAni-HK with an advantageous advantage in harvesting atmospheric water using sunlight.

[0257]

[0258] Meanwhile, due to the high photon-to-thermal conversion, the functionalized metal-organic framework of the present invention will maintain a high temperature under sunlight, and dynamic bonding will occur more actively. Furthermore, when water temporarily dissociates from the Cu(II) node, the hydrophobic polyaniline repels the water, thereby facilitating complete dissociation. Water adsorption experiments over time of pAni-HK and water desorption experiments under 1 sun were performed in a chamber under conditions of 25°C and 25% RH. 2.85 g of pAni-HK was compressed to a thickness of 200 μm on a 5x5 cm square plate. The adsorbent was wrapped in Styrofoam to effectively prevent temperature rise and heat loss, and placed in an acrylic box for the experiment. The device with the adsorbent was placed in a chamber controlled at 25°C and 25% RH, and the top cover was left open for adsorption. After 20 minutes, the amount of adsorbed water was measured using a scale, then the top cover was closed, and the device was moved to a dark room equipped with a solar simulator, where it underwent a desorption process for 15 minutes under 1 sun conditions. The amount of desorbed water was also measured using a scale. The solar simulator used here was Abet's 1050 device.

[0259]

[0260] As shown in Fig. 18, the adsorption amount of pAni-HK after 20 minutes in the adsorption step was 0.2026 g·g -1 and finally, within 40 minutes, about 0.27 g·g -1 The adsorption was completed, and the desorption step showed high adsorption / desorption kinetics, with all water being desorbed within 20 minutes. What is even more surprising is that all water was desorbed under sunlight using only the MOF itself, without any solar adsorbents such as carbon paper or graphene oxide.

[0261]

[0262] Example 5. Experimental study on indoor solar energy-based atmospheric water harvesting.

[0263]

[0264] Before measuring the indoor solar energy-based atmospheric water harvesting efficiency, 2.85 g of pAni-HK was compressed into a 5x5 cm square plate with a thickness of 200 μm. The adsorbent was wrapped with Styrofoam to prevent effective temperature rise and heat loss, and the experiment was conducted inside an acrylic box. To increase the water harvesting efficiency, the adsorption was performed for 20 min (0.2026 g g -1 ) during which the desorption was carried out for 15 minutes under 1 sun conditions.

[0265]

[0266] The device with the adsorbent was placed in a chamber controlled at 25°C and 25% relative humidity, and the top cover was left open for adsorption. After 20 minutes, the amount of adsorbed water was measured using a scale, and then the top cover was closed. The device was moved to a dark room equipped with a solar simulator and subjected to a desorption process under 1 sun condition for 15 minutes. In this example, "1 sun" is 100 mW / cm 2 The light conditions are as follows. The amount of water desorbed was also measured using a scale. This process was repeated 41 times to determine the accumulated adsorption and desorption amounts. The solar simulator used here was Abet's 1050 device.

[0267]

[0268] The results of multi-cycle atmospheric water absorption under indoor conditions are shown in Fig. 19. pAni-HK can harvest water up to 41 times a day in an indoor environment, and the experimental results show a total of 8.22 L·kg -1 It was possible to obtain water. In addition, Fig. 19 shows that pAni-HK maintains a constant water adsorption and desorption capacity over 41 cycles, which is a result of the high water stability of pAni-HK.

[0269]

[0270] Example 6. Outdoor solar energy-based atmospheric water harvesting experiment

[0271]

[0272] To verify the feasibility under outdoor conditions, water harvesting was tested at Hanyang University in Korea (37°17'55.6"N; 126°50'09.2"E). Before verifying multi-cycle water harvesting, water harvesting was performed at 4 p.m. under ambient conditions (29°C, 33% RH, 0.71 kW m -2 ) was performed to conduct water adsorption / desorption experiments over time on pAni-HK. The adsorption amount of pAni-HK during the adsorption stage was approximately 0.21 g·g -1 Adsorption was completed within 20 minutes, and all water was desorbed within 20 minutes in the desorption step, as shown in Fig. 20a.

[0273]

[0274] During the desorption process, rapid desorption was observed, with water droplets forming on the ceiling after only one minute of the experiment. As shown in Fig. 20b, the temperature of the adsorbent measured by an infrared camera rose to 71.7°C in just 10 minutes, and a photograph taken from the ceiling 15 minutes later confirmed that many water droplets had formed on the surface.

[0275]

[0276] Based on the above data, multi-cycle atmospheric water harvesting was performed in an outdoor environment, with each cycle consisting of 35-minute adsorption-desorption cycles from 7:30 AM to 6:40 PM. The daily temperature (adsorbent and ambient), relative humidity, and solar flux are shown in Figure 20c.

[0277]

[0278] The outdoor solar energy-based atmospheric water harvesting experiment was conducted on September 9, 2023, using the same device used in the indoor solar energy-based atmospheric water harvesting experiment, installed on the rooftop of Hanyang University (37°17'55.6"N; 126°50'09.2"E). The cover was opened in a shaded area to allow adsorption, and the amount of adsorbed water was measured using a scale after 20 minutes. After that, the cover was closed and exposed to sunlight for 15 minutes to proceed with the desorption process, and the desorbed water was obtained and measured using a scale. This process was conducted under an irradiance of 0.4 kW / m 2 The experiment was repeated from 7:00 a.m. to 6:40 p.m. to maintain the ideal, and the accumulated water desorption amount was measured through a total of 20 repetitions. The solar irradiance was measured using a pyranometer (SR05-D2A2, Hukseflux), and the ambient temperature, sample temperature, and humidity were measured using a thermometer, an infrared camera (FLIR), and a hygrometer, respectively. Due to the characteristics of early autumn in Korea, the humidity is higher than 30% RH, and the solar irradiance from 7:00 a.m. to 9:00 a.m. and from 5:00 p.m. to 7:00 p.m. was 0.63 to 0.32 kW m -2 It goes down to .

[0279]

[0280] As shown in Fig. 21, 20 cycles of atmospheric water harvesting could be performed during the day, producing 3.783 L·kg per day without additional energy input. -1 We were able to harvest water.

[0281]

[0282] Although the embodiments described above have been described with limited drawings, those skilled in the art will appreciate that various technical modifications and variations can be applied based on the above. For example, appropriate results can be achieved even if the described techniques are performed in a different order than described, and / or components of the described systems, structures, devices, circuits, etc. are combined or combined in a different manner than described, or are replaced or substituted with other components or equivalents. Therefore, other implementations, other embodiments, and equivalents of the claims also fall within the scope of the claims described below.

[0283]

[0284] The present disclosure provides the following aspects:

[0285]

[0286] Embodiment 1: A functional metal-organic framework (MOF), wherein the functional metal-organic framework comprises a base metal-organic framework and a polymer formed within pores of the base metal-organic framework,

[0287] The above base metal-organic framework comprises a metal with open coordination sites (OCS),

[0288] A functional metal-organic framework, wherein the polymer is a polymer formed by a polymerization reaction of an unsubstituted aniline; an aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof.

[0289]

[0290] Embodiment 2: In Embodiment 1, the open coordination site metal is Cu 2+ A functional metal-organic framework.

[0291]

[0292] Embodiment 3: A functional metal-organic framework in any one of the aforementioned embodiments, wherein the base metal-organic framework is HKUST-1 (Cu3(BTC)2; BTC = benzene-1,3,5-tricarboxylate).

[0293]

[0294] Embodiment 4: A functional metal-organic framework, wherein the polymer in any one of the aforementioned embodiments is a polymer formed by polymerization of unsubstituted aniline.

[0295]

[0296] Embodiment 5: A functional metal-organic framework according to any one of the aforementioned embodiments, wherein the polymer comprises a leucoemeraldine base form.

[0297]

[0298] Embodiment 6: A functional metal-organic framework in any one of the aforementioned embodiments, wherein the pore volume of the functional metal-organic framework is 70% to 80% of the pore volume of the base metal-organic framework.

[0299]

[0300] Embodiment 7: A functional metal-organic framework according to any one of the aforementioned embodiments, wherein under conditions of a temperature of 85°C to 95°C and a relative humidity of 85% to 95%, the functional metal-organic framework maintains a pore volume of at least 95% for at least 4 weeks.

[0301]

[0302] Embodiment 8: In any one of the aforementioned embodiments, the functional metal-organic framework is exposed to 100 mW / cm for 10 minutes. 2 A functional metal-organic framework, wherein when exposed to a temperature of 65°C to 75°C.

[0303]

[0304] Embodiment 9: A functional metal-organic framework according to any one of the aforementioned embodiments, wherein the functional metal-organic framework is in powder form.

[0305]

[0306] Embodiment 10: A method for producing a functional metal-organic framework, wherein the functional metal-organic framework comprises a base metal-organic framework and a polymer formed within the pores of the base metal-organic framework, wherein the method comprises:

[0307] A step of preparing a base metal-organic framework comprising an open coordination site metal;

[0308] A step of preparing a monomer solution, wherein the monomer solution comprises an organic solvent, and the monomer solution comprises unsubstituted aniline; aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof;

[0309] A step of adding the base metal-organic framework to the monomer solution at room temperature to coordinate the monomer to the open coordination site metal of the base metal-organic framework; and

[0310] A step of heating a metal-organic framework in which a monomer is coordinated to an open coordination site metal in air containing O2 to form a polymer within the pores of the base metal-organic framework through oxidative polymerization of the monomer;

[0311] A manufacturing method comprising:

[0312]

[0313] Embodiment 11: A method of manufacturing in any one of the aforementioned embodiments, wherein the method further comprises a step of washing the functional metal-organic framework.

[0314]

[0315] Embodiment 12: A manufacturing method in any one of the aforementioned embodiments, wherein heating the metal-organic framework in which the monomer is coordinated to the open coordination site metal is performed at 70°C to 100°C for 10 to 14 hours.

[0316]

[0317] Embodiment 13: A manufacturing method further comprising the step of determining the concentration of the monomer solution so that the monomer is 0.8 to 1.2 equivalents per 1 equivalent of the open coordination site metal of the base metal-organic framework, in any one of the aforementioned embodiments.

[0318]

[0319] Embodiment 14: In any one of the aforementioned embodiments, the open coordination site metal is Cu 2+ The manufacturing method.

[0320]

[0321] Embodiment 15: A manufacturing method in any one of the aforementioned embodiments, wherein the base metal-organic framework is HKUST-1 (Cu3(BTC)2; BTC = benzene-1,3,5-tricarboxylate).

[0322]

[0323] Embodiment 16: A manufacturing method in any one of the aforementioned embodiments, wherein the monomer solution contains unsubstituted aniline.

[0324]

[0325] Embodiment 17: A manufacturing method in any one of the aforementioned embodiments, wherein the oxidation number of the open coordination site metal in the functional metal-organic framework is the same as the oxidation number of the open coordination site metal in the base metal-organic framework to which the monomer is not coordinated.

[0326]

[0327] Embodiment 18: A manufacturing method according to any one of the aforementioned embodiments, wherein the functional metal-organic framework is in powder form.

[0328]

[0329] Embodiment 19: An atmospheric water harvesting device comprising a water absorbent comprising a functional metal-organic framework as described in any one of the aforementioned embodiments.

[0330]

[0331] Embodiment 20: In any one of the aforementioned embodiments, the atmospheric water harvesting device is an atmospheric water harvesting device, wherein the water absorbent adsorbs atmospheric water and the adsorbed water is desorbed by sunlight.

[0332]

[0333] Embodiment 21: An adsorbent for an adsorptive cooling system comprising a functional metal-organic framework as described in any one of the aforementioned embodiments.

[0334]

[0335] Aspect 22: Refrigerant;

[0336] Coolant; and

[0337] An adsorption cooling device comprising an adsorbent,

[0338] The above refrigerant is water,

[0339] An adsorption cooling device, wherein the adsorbent comprises a functional metal-organic framework as described in any one of the aforementioned embodiments.

Claims

1. A functional metal-organic framework (MOF), wherein the functional metal-organic framework comprises a base metal-organic framework and a polymer formed within pores of the base metal-organic framework, The above base metal-organic framework comprises a metal with open coordination sites (OCS), A functional metal-organic framework, wherein the polymer is a polymer formed by a polymerization reaction of an unsubstituted aniline; an aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof.

2. In the first paragraph, the open coordination metal is Cu 2+ A functional metal-organic framework.

3. A functional metal-organic framework according to claim 1, wherein the base metal-organic framework is HKUST-1 (Cu3(BTC)2; BTC = benzene-1,3,5-tricarboxylate).

4. A functional metal-organic framework according to claim 1, wherein the polymer is a polymer formed by a polymerization reaction of unsubstituted aniline.

5. A functional metal-organic framework according to claim 1, wherein the polymer comprises a leucoemeraldine base form.

6. A functional metal-organic framework according to claim 1, wherein the pore volume of the functional metal-organic framework is 70% to 80% of the pore volume of the base metal-organic framework.

7. A functional metal-organic framework according to claim 1, wherein, under conditions of a temperature of 85°C to 95°C and a relative humidity of 85% to 95%, the functional metal-organic framework maintains a pore volume of at least 95% for at least 4 weeks.

8. In the first paragraph, the functional metal-organic framework is exposed to 100 mW / cm for 10 minutes. 2 A functional metal-organic framework, wherein when exposed to a temperature of 65°C to 75°C.

9. A functional metal-organic framework according to claim 1, wherein the functional metal-organic framework is in powder form.

10. A method for producing a functional metal-organic framework, wherein the functional metal-organic framework comprises a base metal-organic framework and a polymer formed within the pores of the base metal-organic framework, and the method for producing the functional metal-organic framework comprises: A step of preparing a base metal-organic framework comprising an open coordination site metal; A step of preparing a monomer solution, wherein the monomer solution comprises an organic solvent, and the monomer solution comprises unsubstituted aniline; aniline substituted with at least one substituent selected from the group consisting of halo, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and hydroxy; or a combination thereof; A step of adding the base metal-organic framework to the monomer solution at room temperature to coordinate the monomer to the open coordination site metal of the base metal-organic framework; and A step of heating a metal-organic framework in which a monomer is coordinated to an open coordination site metal in air containing O2 to form a polymer within the pores of the base metal-organic framework through oxidative polymerization of the monomer; A manufacturing method comprising:

11. A manufacturing method according to claim 10, wherein the manufacturing method further comprises a step of washing the functional metal-organic framework.

12. A manufacturing method in claim 10, wherein heating the metal-organic framework in which the monomer is coordinated to the open coordination site metal is performed at 70°C to 100°C for 10 to 14 hours.

13. A manufacturing method, further comprising a step of determining the concentration of the monomer solution so that the monomer is 0.8 to 1.2 equivalents per 1 equivalent of the open coordination site metal of the base metal-organic framework in the 10th paragraph.

14. In the 10th paragraph, the open coordination metal is Cu 2+ The manufacturing method.

15. A manufacturing method according to claim 10, wherein the base metal-organic framework is HKUST-1 (Cu3(BTC)2; BTC = benzene-1,3,5-tricarboxylate).

16. A manufacturing method according to claim 10, wherein the monomer solution contains unsubstituted aniline.

17. A manufacturing method in claim 10, wherein the oxidation number of the open coordination site metal in the functional metal-organic framework is the same as the oxidation number of the open coordination site metal in the base metal-organic framework to which the monomer is not coordinated.

18. A manufacturing method according to claim 10, wherein the functional metal-organic framework is in powder form.

19. An atmospheric water harvesting device comprising a water absorbent comprising the functional metal-organic framework described in paragraph 1.

20. In the 19th paragraph, the atmospheric water harvesting device is an atmospheric water harvesting device in which the water absorbent absorbs atmospheric water and the absorbed water is desorbed by sunlight.

21. An adsorbent for an adsorption cooling system comprising the functional metal-organic framework described in paragraph 1.

22. Refrigerant; Coolant; and An adsorption cooling device comprising an adsorbent, The above refrigerant is water, An adsorption cooling device, wherein the adsorbent comprises the functional metal-organic framework described in claim 1.

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