KR102287864B1 - Method for preparation of MOF with improved stability against moisture, MOF prepared by the same and use thereof - Google Patents

Abstract

The present invention is a first step of modifying some or all of the unsaturated metal sites in the MOF with a nucleophilic compound, blocking the unsaturated (coordinatevely unsaturated) metals or defective sites from moisture; and optionally, a second step of additionally supporting a compound capable of adsorption or catalysis on the modified MOF from the first step; MOF prepared according to the present invention and its use as an adsorbent.

Description

Method for preparing MOF with improved moisture stability, MOF prepared accordingly, and uses thereof

The present invention is a first step of modifying some or all of the unsaturated metal sites in the MOF with a nucleophilic compound, blocking the unsaturated (coordinatevely unsaturated) metals or defective sites from moisture; and optionally, a second step of additionally supporting a compound capable of adsorption or catalysis on the modified MOF from the first step; MOF prepared according to the present invention and its use as an adsorbent.

In addition to the presence of threats against traditional chemical warfare agents (CWAs), there is an increasing risk of toxic industrial chemicals (TICs) such as chlorine and ammonia and radioactive gases (organic iodine, iodine). As can be seen from the recent explosion of the Fukushima nuclear power plant, the leaked radioactive gaseous material can cause contamination and damage to people in a very wide area. In particular, radioactive iodine is a major nuclide of radioactive gas, and when inhaled into the human body, it accumulates in the thyroid gland and is highly harmful to the human body, so it is necessary to effectively remove it. In addition, representative compounds among gaseous radioactive iodine are elemental iodine and methyl iodine (organic iodine). Elemental iodine is easily removed by an activated carbon adsorbent. The adsorption amount is small, and there is a phenomenon of desorption over time, and the adsorption amount rapidly drops at high humidity due to the large influence on humidity.

Looking at the current state of technology in Korea, activated carbon-based radioactive iodine adsorbents have been used since the 1980s. In particular, the demand for impregnated activated carbon containing KI or TEDA is increasing in industry and overall life due to its excellent adsorption capacity for harmful gases. is becoming However, impregnated activated carbon is very expensive, and its efficiency is lowered due to natural deterioration during the overseas import period, and the adsorption capacity and life of the adsorbent are greatly affected by organic matter, nitrogen oxides, carbon dioxide, etc. present in the gas phase.

In US Patent No. 5,063,196, in the case of ASZM-TEDA activated carbon containing silver (Ag), copper (Cu), zinc (Zn) and molybdenum (Mo), the ratio of metal precursor and organic amine is adjusted to approximately 5% copper , presented a method for preparing activated carbon in which activated carbon was impregnated with 0.05% silver, 5% zinc, 2% molybdenum, and 3% TEDA.

However, in the case of the metal-TEDA-containing activated carbon manufacturing method using the impregnation method, when the porous carbon carrier is impregnated with transition metals such as copper, zinc, molybdenum, silver, vanadium and organic amines, which are active metals, it can be dispersed or dissolved in a solution phase. The amounts of metals and organic amines are limited, and in particular, since activated carbon has micropores due to the characteristics of activated carbon, when the content of the metal precursor is large, it is difficult to support a large amount of metal active material in the pores by blocking the micropore entrance of the carrier.

On the other hand, iodine can be removed by reacting with an adsorbent containing metals such as Cu, Cd, Mn, Pb, Mn, Hg and Ag, but Ag is known to be the most effective. Therefore, there is a limit in increasing the content of active metal materials such as copper, zinc, which are metal active materials, and chromium (Cr), tungsten (W), and molybdenum (Mo), which are group 6B elements, so that a high content of metal is dispersed and heat And the development of a new porous composite material with excellent chemical stability is required.

Metal-organic frameworks (MOFs) are generally referred to as 'porous coordination polymers' or 'porous organic-inorganic hybrids', and have the advantage of providing a large surface area with nano-sized pores. Therefore, it is used as an adsorbent, a gas storage material, a sensor, a membrane, a functional thin film, a drug delivery material, a catalyst and a catalyst carrier, etc. for the purpose of adsorbing and removing the material or carrying the composition in the pores to deliver it, as well as a guest smaller than the pore size. It is being actively studied because it is used to trap molecules or separate molecules according to their size using pores, and can be applied to catalysis using various active metals present in the structure of the metal-organic framework. Meanwhile, recently, various studies have been conducted to remove chemical agents and toxic industrial substances using metal-organic frameworks [Angew. Chem. Int. Ed. 54, 6795-6799 (2015), J. Am. Chem. Soc. 133, 4178-4181 (2011), Angew. Chem. Int. Ed. 55, 13224-13228 (20160), PNAS 105, 11623-11627 (2008), Chem. Eng. Sci 124, 118-124 (2015)].

Korean Patent Registration No. 10-0148793; US Patent No. 5,063,196.

J. Am. Chem. Soc. 2014, 136, 4369-4381.

As a result of intensive research efforts to discover a method capable of improving the moisture stability of MOF and imparting additional functionality by post-synthesis modification, the present inventors introduced a nucleophilic compound to introduce an unsaturated metal site or defect that is easy to hydrolyze due to its high reactivity By selectively modifying some or all of the sites with a nucleophilic compound, it is possible to improve stability by blocking access to moisture, as well as by additionally supporting a functional compound capable of performing adsorption or catalysis in its mesopores. It was confirmed that harmful substances such as iodine can be effectively adsorbed, and the present invention was completed.

A first aspect of the present invention is a method for producing a metal-organic framework (MOF) with improved moisture stability, by modifying some or all of the unsaturated metal sites in the MOF with a nucleophilic compound, a first step of blocking the unsaturated) metal or defect sites from moisture; and optionally, a second step of additionally supporting a compound capable of performing adsorption or catalysis on the modified MOF from the first step;

The second aspect of the present invention provides a MOF with improved moisture stability compared to the MOF before modification, in which some or all of the unsaturated metal sites in the MOF are modified with a nucleophilic compound, and hydrolysis at the unsaturated metal or defect site is blocked. .

A third aspect of the present invention provides a composition for adsorption, comprising the MOF having improved water stability of the second aspect.

A fourth aspect of the present invention provides a method of using the MOF having improved water stability of the second aspect as an adsorbent in a wet condition with a relative humidity of 0.01% or more or in a water-containing medium.

Hereinafter, the present invention will be described in detail.

The present invention maintains the structure of MOF, which is a basic framework, by post-synthetic modification (PSM) while maintaining high reactivity, such as unsaturated metal sites or defect sites contained therein, selectively at sites that are easily hydrolyzed in the presence of moisture. By introducing a nucleophilic compound to make it hydrophobic, it is possible to improve water stability by blocking the access of water molecules, and by additionally introducing a functional compound that can perform adsorption or catalytic reaction in its mesopores, an additional function is given. It is based on the discovery that it can be used as an adsorbent for adsorbing and separating carbon dioxide or removing harmful substances such as organic iodine and formaldehyde.

A metal-organic framework (MOF) is a porous organic-inorganic high molecular compound formed by combining a central metal ion with an organic ligand through molecular coordination bonds, and includes both organic and inorganic materials in the framework structure and has a molecular or nano-sized pore structure. It is a crystalline compound having The organic ligand is also referred to as a linker, and any organic compound having a functional group capable of coordinating is possible. For example, the organic ligand is a carboxyl group (-COOH), a carboxylate anion group (-COO-), an amine group (-NH ₂ ) and imino group (=NH), nitro group (-NO ₂ ), hydroxyl group (-OH), halogen group (-X) and _{sulfonic acid group (-SO 3} H), sulfonic acid anion group (-SO ₃ -), a compound having at least one functional group selected from the group consisting of a methanedithioic acid group (-CS ₂ H), a methanedithioic acid ion group (-CS ₂ -), a pyridine group and a pyrazine group, or a mixture thereof may be used. .

The framework of the MOF is formed by a covalent bond between a metal cluster, which is a secondary building unit (SBU), and organic ligands, and the metal cluster may become a node in the framework of the MOF. MOFs are composed of various coordination geometries, polytopic linkers, and ancillary ligands (F-, OH-, H ₂ O among others). Therefore, MOF design starts with the selection of appropriate metal ions and appropriate organic ligands. For example, when metal ions (eg, Zn ^{2 +} ) react with various acetates, Zn ₄ O(CH ₃ COO) ₆ clusters are formed, and when these clusters are combined with an organic ligand, a MOF structure is created. In this case, the organic ligand portion of the benzene structure may be a spacer, and the Zn ₄ O(CH ₃ COO) ₆ cluster portion may be a node.

However, these MOFs are difficult to have complete crystallinity and contain unsaturated metal sites and/or defect sites to which ligands are not bound. On the other hand, these unsaturated metal sites and defect sites have relatively high reactivity, so that they can be easily hydrolyzed in the presence of water molecules, thereby indicating vulnerability to moisture. Therefore, it is possible to improve the stability to moisture by preventing the water molecules from approaching these sites.

To this end, the present invention provides a method for producing a MOF with improved moisture stability, wherein the production method of the present invention modifies a part or all of the unsaturated metal sites in the MOF with a nucleophilic compound, thereby providing an unsaturated (coordinatevely unsaturated) metal or defect. (defect) a first step of blocking the sites from moisture; and optionally (optionally), a second step of further supporting a compound capable of performing adsorption or catalysis on the modified MOF from the first step.

For example, the MOF to be modified in the first step used in the manufacturing method of the present invention is characterized in that it has a defect site that acts as a Lewis acid during MOF synthesis.

For example, in the manufacturing method of the present invention, through the first step, a nucleophilic compound smaller than the pore size of the MOF to be modified may be selectively modified at the unsaturated metal site, which is the Lewis acid site of the MOF.

For example, in the preparation method of the present invention, the compound used for modification in the first step is C _1-12 alkylamine, C _1-12 haloalkylamine, C _1-4 haloalkyl-aryl-C _1-4 alkylamine , NHR ₁ -C _n H _2n -NHR ₂ , SH-C _n' H _{2n '} -SH or R _3-5 PC _n" H _2n" N-PR _6-8 (wherein n, n' and n" are each independently an integer of 1 to 12, and R ₁ to R ₈ are each independently H, C _1-12 alkylene).

Furthermore, the compound additionally supported in the second step may be triethylenediamine (TEDA) or quinuclidine, but is not limited thereto.

In addition, the compound additionally supported in the second step may be a metal ion or a metal nanoparticle, but is not limited thereto.

For example, in the manufacturing method of the present invention, the second step is (i) the MOF modified from the first step and the compound to be further supported is left in an oven, or (ii) the MOF modified from the first step by vapor deposition It can be achieved by a method of supporting the compound to be supported in addition to, but is not limited thereto.

For example, when a vapor deposition method is used in the second step, a compound capable of adsorption or catalysis is added while some of the nucleophilic compound supported on the MOF modified from the first step is partially removed due to the nature of the reaction performed at vacuum and high temperature. can be loaded with

Furthermore, the present invention provides a MOF with improved moisture stability compared to the pre-modification MOF, in which some or all of the unsaturated metal sites in the MOF are modified with a nucleophilic compound, and hydrolysis at the unsaturated metal or defect site is blocked.

For example, the MOF with improved water stability of the present invention is characterized in that a nucleophilic compound smaller than the pore size of the MOF is selectively modified at an unsaturated metal site, which is a Lewis acid site formed during MOF synthesis.

For example, the MOF with improved water stability of the present invention may have increased hydrophobicity compared to the MOF before modification due to modification with a nucleophilic compound. A specific principle for this will be described later.

For example, the MOF with improved moisture stability of the present invention may be based on a mesoporous MOF including both micropores and mesopores, and in this case, modification by a nucleophilic compound may be preferentially made within the mesopores rather than the micropores. there is.

Modification target MOF that can be used to provide the MOF with improved moisture stability of the present invention is not limited to the type as long as it has mesopores in its structure. That is, the MOF to be modified preferably has a window size capable of supporting metal-organic clusters, for example, a window size of 1 nm or more, but is not limited to the type as long as it satisfies this. For example, the modified MOF that can be used to provide the MOF with improved moisture stability of the present invention is NU-1000, MIL-100, MIL-101, extended MOF-74, PCN-222, DUT-32, Al-BDC ( Benzene dicarboxylate; benzene dicarboxylate), Fe-BDC, Cr-BDC, V-BDC, Al-BTC, Cr-BTC, Fe-BTC, Al-BDC, Cr-BDC, Zr-BPDC, Cu-BTC ( L1) (L1 is 5-nitro-1,3-dicarboxylate, 5-cyanide-1,3-dicarboxylate, 5-hydroxyl-1,3-dicarboxylate, or pyridine-3 ,5-dicarboxylate), UiO-67, UiO-68, MOF-808, DUT-37, HKUST-1(Cu ₃ (btc) ₂ , btc; benzene-1,3,5-tricarboxylate) (tbo ), MOF-14(Cu ₃ (btb) ₂ , btb; benzene-1,3,5-tribenzoate)(pto), DUT-34(Cu ₃ (btb) ₂ ), DUT-23([Cu ₂ (bipy) )] ₃ (btb) ₄ ), MOF-14, DUT-34, DUT-33, MOF-74(CPO-27), UMCM-1, UMCM-2, DUT-6(MOF-205), UMCM-3 , UMCM-4, UMCM-5, MOF-210, DUT-32(Zn ₄ O(bpdc)(btctb) _{4 /3} , btctb; 4,4',4"-[benzene-1,3,5-triyltris (carbonylimino)]trisbenzoate, bpdc; 4,4'-biphenylendicarboxylate), DUT-6, PCN-21, DUT-68, MOP-1, DUT-49, UMCM-1, DUT-7, DUT-28 (Co ₂₂ (BTB) ₁₂ (NO ₃ ) ₈ (DEF) _x (H ₂ O) _y ) (where x and y are rational numbers greater than 0 and less than 50, respectively), NU-109, NU-110, DUT-13 (Zn ₄ O-(BenzTB) _3/2 , BenzTB;N,N,N',N'-benzidinetetr abenzoate), PCN-69, HKUST-1, MIL-101 (Cr), or UMCM-1.

For example, in the MOF with improved water stability of the present invention, the MOF before modification may be a material in which the ligand of the MOF as exemplified above is functionalized. For example, the MOF before modification may be one in which an amino group is substituted with a ligand constituting the same, but is not limited thereto.

Specifically, the pre-modification MOF constituting the MOF with improved moisture stability of the present invention may be MIL-101, MIL-100, or MIL-101-NH ₂ , but is not limited thereto.

For example, the MOF with improved moisture stability of the present invention is a nucleophilic compound, C _1-12 alkylamine, C _1-12 haloalkylamine, C _1-4 haloalkyl-aryl-C _1-4 alkylamine, NHR ₁ -C _n H _2n -NHR ₂ , SH-C _n' H _2n' -SH or R _3-5 PC _n" H _2n" N-PR _6-8 (Wherein, n, n' and n" are each independently 1 to may be an integer of 12, and R ₁ to R ₈ are each independently H, C _1-12 alkylene.) The nucleophilic compound includes an amine, thiol or phosphine as a reactive functional group, and Since the main chain includes a hydrophobic hydrocarbon chain, it is possible to exhibit the effect of improving the hydrophobicity of the MOF to be modified compared to before the modification through modification using the same.

Specifically, the nucleophilic compound may be amylamine, heptylamine, 4-(trifluoromethyl)benzylamine, or 2,2,3,3,4,4,4-heptafluorobutylamine, but not limited

For example, the nucleophilic compound may be included in an amount of 1 to 70 parts by weight, specifically 10 to 60 parts by weight, based on 100 parts by weight of the MOF used.

Furthermore, the MOF with improved moisture stability of the present invention can exhibit two or more functions by additionally supporting a compound capable of performing adsorption or catalysis on the MOF modified with a nucleophilic compound.

In this case, the additionally supported compound may be TEDA or quinuclidine, but is not limited thereto. These compounds are characterized by having nucleophilicity by including at least one tertiary amine having a lone pair of electrons in the molecule, and may exhibit adsorption performance for toxic gases based on such nucleophilicity.

For example, the additionally supported compound may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the MOF used. For example, it may be included in 3 to 20 parts by weight, but is not limited thereto. In addition, the amount of the supported compound can be adjusted to a desired level by adjusting the amount of the reacted compound.

The MOF with improved water stability of the present invention is characterized in that the access of water molecules to its adsorption site is blocked. As described above, the MOF with improved water stability of the present invention is modified with a compound having a hydrophobic hydrocarbon chain in the main chain to exhibit additional hydrophobicity, thereby blocking the access of water molecules.

For example, the MOF modified with the nucleophilic compound according to the present invention and/or the MOF additionally supported with a compound capable of performing adsorption or catalysis on the modified MOF has reduced moisture by at least 10% compared to the unmodified MOF. adsorption capacity may be exhibited. Specifically, the MOF of the present invention may be a MOF having a moisture adsorption amount reduced by 20% or more, 30% or more, and further 50% or more compared to an unmodified MOF, but is not limited thereto.

In a specific embodiment of the present invention, the moisture adsorption amount of MIL-101 additionally supported with TFM-BA and optionally quinuclidine for MIL-101 was compared, and the same temperature and It was confirmed that the amount of moisture adsorption was reduced to less than half under the pressure condition (FIG. 9).

As described above, the MOF with improved water stability of the present invention can be modified with a hydrophobic compound to block the access of water molecules, so that hydrolysis is inhibited even in wet conditions of at least 0.01% relative humidity, for example, at least 15% or in a water-containing medium. It is characterized in that it can be used as an adsorbent or catalyst.

The MOF with improved water stability of the present invention may be prepared by the method according to the first aspect of the present invention, but is not limited thereto.

Furthermore, the present invention may provide a composition for adsorption, including the MOF having improved moisture stability.

As described above, the MOF having improved moisture stability of the present invention can be used as an adsorbent for these substances because it has an adsorbing power to a toxic gas by being modified with a nucleophilic compound.

For example, the adsorption composition of the present invention may adsorb toxic gas, radioactive gas, carbon dioxide, semiconductor waste gas, or waste gas present in a secondary battery, but is not limited thereto.

In addition, the composition for adsorption of the present invention, as described above, contains a MOF having improved water stability by increasing hydrophobicity through modification, and thus, a relative humidity of 0.01% or more, for example, 15% or more, in a wet condition or in a water-containing medium. It is a feature that can be used.

Furthermore, the present invention provides a method of using the MOF with improved moisture stability of the second aspect as an adsorbent in a wet condition of 0.01% or more, for example, 15% or more, or in a moisture-containing medium. Its working principle is as described above.

The MOF with improved moisture stability of the present invention is a particle having a size of about 150 to 500 nm, and when used as an adsorbent, it may be molded into a pellet form and used, but is not limited thereto.

The production method of the present invention introduces a nucleophilic compound into the MOF by post-synthesis modification and selectively modifies some or all of the unsaturated metal sites or defect sites, which are easily hydrolyzed due to high reactivity, with a nucleophilic compound, thereby accessing moisture. In addition to being able to improve stability by blocking Since the MOF provided with additional functionality is provided, the modified MOF prepared as described above can be usefully used as an adsorbent for toxic gases.

1 is a diagram showing the structure of MIL-101. Green indicates Cr atoms, red indicates O atoms, gray indicates C atoms, and H atoms are omitted.
2 shows a primary nucleophilic compound in MIL-101, such as trifluoromethylbenzylamine (TFM-BA), heptafluorobutylamine (HF-ButA), amylamine (C5A) or Heptylamine (C7A), and as a secondary functional organic material is a diagram schematically showing a process of supporting triethylenediamine (TEDA) or quinuclidine (quinuclidine).
3 is a diagram showing a powder X-ray diffraction (PXRD) pattern of MIL-101, TFM-BA-supported MIL-101, and MIL-101 additionally supported with quinuclidine.
4 is (a) N ₂ physisorption isotherms and ( b) A diagram showing the pore size distribution.
5 is a view showing a scanning electron microscope image of MIL-101, MIL-101 on which TFM-BA is supported, and MIL-101 on which quinuclidine is additionally supported.
6 is a diagram showing infrared spectroscopy (FT-IR) spectra of MIL-101, TFM-BA-supported MIL-101, and MIL-101 further supported thereon with quinuclidine under He flow.
7 is a view showing the PXRD pattern of MIL-101, TFM-BA-supported MIL-101, and MIL-101 additionally supported with quinuclidine by two different methods, for example, oven and vapor deposition.
_{8 is (a) N 2} physisorption isotherms and (b) pores of MIL-101, TFM-BA-supported MIL-101 at 77K, and MIL-101 additionally supported with quinuclidine by oven and vapor deposition thereon; It is a diagram showing the size distribution diagram.
9 is a diagram showing the moisture adsorption isotherms of MIL-101, TFM-BA-supported MIL-101, and MIL-101 additionally supported with quinuclidine at 303K.
10 is a view showing the PXRD pattern of MIL-101, each of (a) amylamine and (b) heptylamine-supported MIL-101, and MIL-101 on which quinuclidine is additionally supported.
_{11 is a diagram showing (a) N 2} physisorption isotherms and (b) pore size distributions of MIL-101 and MIL-101 supported with amylamine and heptylamine at 77K, respectively.
12 is a diagram showing the PXRD pattern of the _{MIL-101-NH 2, TFM} -BA supporting the MIL-101-NH _2, and hence the quinuclidine the MIL-101-NH ₂ further supported.
13 is a view showing the PXRD pattern of MIL-100, TFM-BA-supported MIL-100, and MIL-100 on which quinuclidine is additionally supported.
14 is a diagram showing a schematic diagram of an organic iodine breakthrough device.
15 is a diagram showing a log-type breakthrough curve obtained using ASZM-TEDA, a commercial carbon-based adsorbent, under a wet condition of 95% relative humidity and 303K.
Figure 16 is under a wet condition of 95% relative humidity and 303K, TFM-BA-supported MIL-101, and MIL-101 additionally loaded with quinuclidine by oven and vapor deposition thereon for organic iodine (a) Linear Breakthrough curves and (b) are diagrams showing logarithmic breakthrough curves.
17 is a diagram showing a log-type breakthrough curve for organic iodine of _{TFM-BA-supported MIL-101-NH 2} under a wet condition of 95% relative humidity and 303K.
18 is a diagram showing a log breakthrough curve for organic iodine of TFM-BA-supported MIL-100 under a wet condition of 95% relative humidity and 303K.
19 is a diagram showing a schematic diagram of a DMMP breakthrough device.
20 is a diagram showing a linear breakthrough curve for DMMP obtained by using ASZM-TEDA, TFM-BA, and MIL-101 additionally supported therewith with quinuclidine under a wet condition of 15% relative humidity and 297K.
21 is a diagram showing a log breakthrough curve for formaldehyde of a commercial carbon-based adsorbent SGC-100 under a wet condition of 80% relative humidity and 298K.
22 is a log breakthrough curve for formaldehyde of MIL-101, TFM-BA-supported MIL-101, and MIL-101 additionally supported therewith with quinuclidine under a wet condition of 80% relative humidity and 298 K It is also

Hereinafter, the present invention will be described in more detail through examples. These Examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by these Examples.

Preparation Example 1: Preparation of MIL-101

MIL-101 was prepared using a hydrothermal method. Specifically, a 1L Teflon-lined autoclave _{was mixed with Cr(NO 3} ) ₃ ·9H ₂ O, TPA (terephthalic acid) and water in a molar ratio of 1:1:267 to prepare a synthetic solution, and at 220°C for 8 hours After the reaction, the _{mixture was washed with water, ethanol and NH 4} F aqueous solution, filtered and dried. MIL-101 synthesized as described above _{has a chemical formula of [Cr 3} (OH)(H ₂ O) ₂ O(C ₆ H ₄ (CO ₂ ) ₂ ) ₃ ]·H ₂ O, and a pentagonal window with a size of 12 Å (pentagonal window), having a hexagonal window of 16 × 14.5 Å size and a mesoporous cage of 29 × 34 Å size, having the framework structure of Figure 1 .

Preparation Example 2: MIL-101-NH ₂ manufacture of

After synthesizing MIL-101-NO ₂ using a hydrothermal method, a reduction reaction was performed to prepare _{MIL-101-NH 2 . Specifically, a synthetic solution was prepared by mixing CrCl 3} .6H ₂ O, nitro-TPA (nitroterephthalic acid) and water in a 1L Teflon-lined autoclave in a molar ratio of 1:1:268, and reacted at 200°C for 4 days. Then, washed with water, ethanol and NH ₄ F aqueous solution, filtered and dried to obtain MIL-101-NO ₂ . The obtained MIL-101-NO ₂ was refluxed for 6 hours with an ethanol solvent of 20 mol of SnCl ₂ and 4000 molar ratio relative to 1 equivalent, cooled to room temperature, hydrochloric acid was added, stirred for 6 hours or more, and washed with water and ethanol was filtered and dried.

Preparation Example 3: Preparation of MIL-100

MIL-100 was prepared using the hydrothermal method. _{Specifically, a synthetic solution was prepared by mixing Fe(NO 3} ) ₃ ·9H ₂ O, TPA and water in a molar ratio of 1:0.7:56 in a 1L Teflon-lined autoclave, and after reacting at 160°C for 8 hours, Washed with water and ethanol, filtered and dried.

Example 1: Preparation of lipophilic surface-modified MOF

The MOF prepared according to Preparation Examples 1 to 3 was impregnated with hydrophobic amines to impart hydrophobicity. The hydrophobic amines include alkylamines amylamine (C5-A) and heptylamine (C7-A) and amines including F trifluoromethylbenzylamine (TFM-BA) and heptafluoro Heptafluorobutylamine (HF-ButA) was used, and the MOF prepared according to the above preparation example was pretreated at vacuum and high temperature of 150° C. for 12 hours to remove moisture or residual impurities bound to unsaturated metal sites. . Specifically, 3 mmol of an amine and 60 mL of anhydrous toluene were added per 1 g of MOF, followed by reflux reaction for 24 hours. After the reaction was completed, cooled, washed with ethanol and distilled water, and dried at 100° C. to recover the adsorbed powder.

Example 2: Secondary as a functional organic material modified Manufacturing of MOFs

In order to effectively support the functional organic material of amines in the pores of the lipophilic surface-modified MOF according to Example 1, the process was carried out in two ways, and the reactivity was compared. First, by using a supporting method using an oven, 1 g of the surface-treated MOF prepared according to Example 1 was mixed with a solid amine corresponding to 10% by weight, put in an oven at 80° C., and supported for 4 hours. Next, an amine was selectively supported in the pores of the MOF using a vapor deposition method. Specifically, 1 g of the surface-modified MOF prepared according to Example 1 was mounted in a reactor, and then pretreated for 12 hours at a high temperature of 150° C. under a helium atmosphere. When the pre-treatment is finished, 10% by weight of the functional organic material to be loaded is placed in another container connected to the reactor, made in a vacuum, and then slowly heated to 150° C. to sublimate the functional organic material and react, and when the reaction is completed, the sample is cooled recovered.

Experimental example 1: Structural and compositional analysis

Characteristics of MOF modified with hydrophobic and functional organic materials synthesized according to Preparation Examples and Examples with improved lipophilicity and stability were analyzed.

First, MIL-101 is a porous nanostructure represented by the formula _{of [Cr 3} (OH)(H ₂ O) ₂ O(C ₆ H ₄ (CO ₂ ) ₂ ) ₃ ] H _{2 O, and} Since it has a large number of highly reactive coordinatively unsaturated metal sites (CUS) (about 1.7 mmol/g), it is suitable for selectively functionalizing amine compounds.

Among the materials prepared according to Examples 1 and 2, MIL-101 was used as a basic framework, and TFM-BA, an amine containing F, and quinuclidine as a functional organic material were used to react in an oven. The crystal structure was analyzed by powder X-ray diffraction (PXRD), and the results are shown in FIG. 3 . As shown in FIG. 3 , as a result of XRD analysis, XRD was measured before and after loading a hydrophobic organic material such as TFM-BA or HF-ButA and/or a functional organic material, quinuclidine, which was previously reported MIL-101 Compared with the XRD pattern for MIL-101, it was confirmed that the characteristic XRD pattern of MIL-101 itself was maintained even after modification.

Furthermore, nitrogen adsorption isotherms and pore size distributions were derived using the nitrogen physisorption method, and the results are shown in FIG. 4 . The BET surface area value calculated from the nitrogen adsorption isotherm shown in FIG. 4a ^{decreased from 2980 m 2} /g to 1915 m ² /g after TFM-BA loading compared with MIL-101, and after additional loading of quinuclidine, reduced to 1769 m ² /g. The total pore volume of MIL-101 was also reduced from 1.52 mL/g to 0.88 mL/g after TFM-BA loading. On the other hand, the pore distribution shown in FIG. 4b showed a pore size reduction of about 1 to 2 nm due to the loading of TFM-BA and quinuclidine, which prevented the mesopores of MIL-101 by TFM-BA and quinuclidine. This is due to the reduction in surface area and total pore volume due to some pore clogging that occurs. In particular, the decrease in the amount of nitrogen adsorption in the low pressure region (mesopores) between _{P/P 0 =0.1 and 0.2 indicates that the introduced amine is preferentially supported in the mesopores.} From this, it was confirmed that micropores capable of adsorbing gas still remained even after amines were supported. On the other hand, when HF-ButA was supported, the surface area of MIL-101 ^{decreased from 2980 m 2} /g to 2647 m ² /g, and the total pore volume decreased from 1.52 mL/g to 1.21 mL/g. This indicates that, unlike the case of supporting TFM-BA, a relatively small amount of HF-ButArk is supported, so that the decrease in surface area and/or pore volume is small. The decrease in the pore distribution also decreased to 0.5 to 1 nm.

In addition, the shape and size changes of the particles after modification were confirmed through scanning electron microscopy analysis, and the results are shown in FIG. 5 . As shown in FIG. 5 , in all cases, the size of the particles was about 150 to 500 nm, and there was no visible change in the surface according to the amine loading.

In addition, through Fourier Transform infrared spectroscopy (FT-IR), it was checked whether TFM-BA and HF-ButA, which are hydrophobic organic materials used for MOF modification, and quinuclidine, a functional organic material, were loaded. is shown in FIG. 6 . As shown in FIG. 6 , after TFM-BA loading on MIL-101, 1141 cm ^-1 _{corresponding to CF 3} stretching vibration, a characteristic peak of TFM-BA, increased rapidly, indicating that TFM-BA was successfully loaded. will be. ^{On the other hand, the peak intensity in the 3000 to 3500 cm −1} region caused by moisture in the structure was relatively decreased, which indirectly suggests that the TFM-BA support has made it relatively hydrophobic.

The specific loading amount of each component was measured using an elemental analyzer. As a result of elemental analysis, in the case of the MIL-101 sample supporting TFM-BA, an increase in the amount of nitrogen by 2.3% by weight based on 100% by weight of MIL-101 was observed, which corresponds to 28% by weight. Furthermore, after loading quinuclidine using an oven, an increase in nitrogen content by 0.8% by weight was confirmed, indicating that 6.7% by weight of quinuclidine was supported in addition to TFM-BA. On the other hand, when quinuclidine was additionally supported by the vapor deposition method, it was confirmed that 14.5% by weight of quinuclidine was supported, which exceeds the target 10% by weight, and is not suitable for vacuum and high temperature conditions used for vapor deposition. It was found that the amount of quinuclidine supported by TFM-BA was increased as some of the TFM-BA loaded in advance was removed. On the other hand, when modified with HF-ButA, an increase in the amount of nitrogen by 0.4% by weight based on 100% by weight of MIL-101 was confirmed, and the loading amount was significantly lower than that of the TFM-BA treatment, which is a relatively large molecule appeared to be due to size.

In addition, the crystal structure of the MOF powder additionally supported with quinuclidine by the above two methods was analyzed by XRD, and the results are shown in FIG. 7 . As shown in FIG. 7 , there was no difference in the crystal structure according to the quinuclidine loading method. That is, the introduction of quinuclidine could be induced without crystallinity disruption in the MIL-101 framework structure regardless of the loading method.

Furthermore, the surface area change according to the quinuclidine introduction method was confirmed, and the results are shown in FIG. 8 . As shown in FIG. 8a , the BET surface area value calculated from the nitrogen adsorption isotherm ^{decreased from 2980 m 2} /g to 1915 m ² /g after TFM-BA loading, and then quinuclidine was treated using an oven and vapor phase deposition method. When introduced, it ^{was further reduced to 1769 m 2} /g and 1798 m ² /g, respectively. At this time, the total pore volume was from 1.52 mL/g to 0.88 mL/g when TFM-BA was loaded from MIL-101, and when quinuclidine was additionally introduced using an oven and vapor deposition method, 0.83 mL/g and It further decreased to 0.82 mL/g. On the other hand, as shown in FIG. 8b , the measured pore distribution at this time was confirmed to be reduced by about 1 to 2 nm when TFM-BA and/or additional quinuclidine was loaded, but no difference was confirmed depending on the quinuclidine loading method. . This indicates that TFM-BA, which is partially lost during vapor phase loading, is offset by further loading of quinuclidine at the corresponding binding site.

Experimental example 2: amine to compound to reform change in characteristics

In order to confirm the change in the properties of MIL-101 according to the TFM-BA and/or quinuclidine loading, moisture adsorption isotherms were measured at 303K, and the results are shown in FIG. 9 . As shown in FIG. 9 , after loading with TFM-BA and/or quinuclidine, the amount of moisture adsorbed by 1 g of the adsorbent was reduced to less than half. This indicates that the adsorbent is hydrophobized by the TFM-BA and/or quinuclidine loading.

Experimental example 3: amine Analysis of structure and properties according to the use of alkylamines as compounds

Furthermore, after loading on MIL-101 in a similar manner using an alkylamine such as amylalkyl (C5-A) and heptylamine (C7-A) instead of the amines containing F, hydrophobization degree and stability improvement It was checked whether When C5-A and C7-A were supported, an increase in nitrogen content of 2.8 wt% and 2.7 wt%, respectively, based on 100 wt% of MIL-101 was confirmed, which corresponds to 17 wt% and 22 wt%, respectively. Furthermore, quinuclidine was additionally supported on MIL-101 carrying C5-A and C7-A using an oven, and elemental analysis was performed to confirm that additional loading of 5.6 wt% and 7.1 wt%, respectively, was made. . In addition, in order to confirm the change in the crystal structure according to the use of these alkylamines, the crystal structure of MIL-101 powder additionally supported with quinuclidine after C5-A and C7-A as described above was analyzed by XRD, The results are shown in FIG. 10 . As shown in FIG. 10 , there was no change in the intensity of the characteristic peak according to the addition of alkylamine and/or additional quinuclidine, indicating that amines can be introduced without crystallinity collapse even when alkylamine is used.

In addition, the nitrogen adsorption isotherm of MIL-101 loaded with quinuclidine after C5-A and C7-A loading was measured and shown in FIG. 11 . ^{The calculated BET surface area value decreased from 3598 m 2} /g calculated for MIL-101 itself to ^{2561 m 2} /g and 2260 m ² /g, respectively. At this time, the measured total pore volume of MIL-101 decreased from 1.7 mL/g to 1.20 mL/g and 1.1 mL/g, respectively. In addition, the pore distribution diagram shown in FIG. 11b showed that the pore size distribution of C5-A and C7-A-supported MOF was decreased by 1 to 2 nm from the pore size distribution of MIL-101.

Experimental example 4: aminated Analysis of structure and properties according to the use of MOF

_{MIL-101-NH 2} ([Cr ₃ (OH)(H ₂ O) ₂ O(C ₆ H ₃ (CO) synthesized according to Preparation Example 2) instead of MIL-101 synthesized according to Preparation Example 1 as a basic framework ₂ ) ₂ (NH ₂ )) ₃ ]·H ₂ O) was supported by the method of Examples 1 and 2, except that hydrophobic amines were supported, and quinuclidine was additionally supported as a functional organic material. A tea-modified MOF was prepared and its structure and properties were analyzed.

First, as a result of analyzing the components by conducting elemental analysis on the synthesized MOF, the amount of nitrogen increased by 1.2% by weight based on 100% by weight _{of MIL-101-NH 2 when TFM-BA was supported, which corresponds to 7.0% by weight} do. Furthermore, the nitrogen content was increased by 0.7 wt% after additionally supporting quinuclidine using an oven, indicating that quinuclidine was supported in addition to TFM-BA by 2.8 wt%.

In addition, in order to confirm the change in the crystal structure, XRD analysis was performed, and the results are shown in FIG. 12 . Even when MIL-101-NH ₂ was used as a basic framework, as in MIL-101, there was no change in the XRD characteristic peak due to TFM-BA and/or additional quinuclidine loading, i.e., no change in crystal structure. , showed the same pattern as previously reported MIL-101-NH _{2 .} This indicates that MIL-101-NH ₂ is also not accompanied by crystallinity decay according to the loading of amines.

Experimental example 5: Analysis of structure and properties according to the use of MIL-100

MIL-100 synthesized according to Preparation Example 3 instead of MIL-101 synthesized according to Preparation Example 1 as a basic framework ([Fe ₃ (OH)(H ₂ O) ₂ O(C ₆ H ₃ (CO ₂ ) _{3 )} ) ₂ ]·nH ₂ O) was supported by the method of Examples 1 and 2, except that hydrophobic amines were supported, and quinuclidine was additionally supported as a functional organic material to prepare a second modified MOF, , its structure and properties were analyzed.

First, as a result of analyzing the components by conducting elemental analysis on the synthesized MOF, the amount of nitrogen increased by 0.1% by weight based on 100% by weight of MIL-100 when TFM-BA was supported, which corresponds to 1.8% by weight. This indicates that the MIL-101 confirmed in Experimental Example 1 was supported in a significantly smaller amount compared to the case of using it as a framework, indicating that additional modification is difficult due to the inclusion of Fe filled with d orbital as a central metal. In addition, the nitrogen content was increased by 1.1% by weight after additionally supporting quinuclidine using an oven, indicating that 8.9% by weight of quinuclidine was additionally supported in addition to TFM-BA.

In addition, in order to confirm the change in the crystal structure, XRD analysis was performed, and the result is shown in FIG. 13 . Even when MIL-100 is used as a basic framework, as in MIL-101, there was no change in the XRD characteristic peak due to TFM-BA and/or additional quinuclidine loading, that is, no change in crystal structure. It showed the same pattern as reported MIL-100. This indicates that MIL-100 is also not accompanied by crystallinity degradation due to the loading of amines.

Experimental example 6: non-radioactive Organic Iodine Adsorption Experiment

All of the samples were used to select particles of a certain size by molding the adsorbent in powder form into pellets, then pulverizing them. The molded adsorbent particles were selected to have a size of 500 to 707 μm (#25 to #35 mesh), which was calculated to minimize the pressure drop in the adsorption reactor. The molded adsorbent provided as described above was sufficiently dried in an oven to remove moisture contained in the adsorbent by physical adsorption, and then the bulk density was measured and used. An apparatus schematic diagram of the breakthrough test system used in the present invention is shown in FIG. 14 .

The organic iodine test concentration, 1.75 mg/m ³ (0.306 ppm) according to the standard, was prepared by mixing 2.25 mL/min of 20 ppm CH ₃ I/N ₂ and 150 mL/min of N ₂ (99.999%). The adsorption reactor used a 1/4" quartz tube reactor with an inner diameter of 4 mm, and the measured bulk density of the adsorbent pre-humidified for 16 hours in a saturator of 90 to 95% relative humidity. , and ^{filled with 25 mm 3.} At this time, the pressure of the reactor was maintained at 1 atm and the temperature was maintained at 30° C. In addition, the organic iodine mixed gas was bypassed before supplying the adsorbent to the reactor filled with gas chromatography ( gas chromatography;. GC) analysis confirmed the initial concentration (C ₀₎ of the organic iodine stabilized when the concentration of the organic iodine by using a four-position valve supplying the organic iodine mixed gas into the reactor was carried out organic iodine breakthrough experiment (Retention time 0.12 sec) A breakthrough curve was created by measuring the concentration (C) of organic iodine that passed through the adsorbent in real time _{and calculating C/C 0 over time.} Analyzed in units of 3 minutes DB-624 was used as a GC column, and an electron capture detector (ECD) was used to detect the concentration of organic iodine.As a control, ASZM-, a commercial carbon-based adsorbent, was used. TEDA was used, under a wet condition of 95% relative humidity and 303 K, ASZM-TEDA; use and a MIL-100 carrying the quinuclidine to TFM-BA and / or added to the adsorbent; BA supporting the MIL-101-NH _2, and / or adding a MIL-101-NH ₂ bearing the quinuclidine to The linear and/or logarithmic breakthrough curves for the measured organic iodine are shown in FIGS. 15 to 18, respectively.

As shown in FIG. 15 , ASZM-TEDA, a commercial carbon-based adsorbent, maintained a removal performance of 99.99% for about 10 minutes, and exhibited a removal performance of 99.9% after breaking through.

16 is a result for MIL-101 and modified MIL-101, in which the moisture retained in the pores during the moisture pretreatment process during TFM-BA loading escapes during the organic iodine adsorption experiment and rolls up in the breakthrough curve The results are shown. On the other hand, when quinuclidine was additionally supported using an oven, organic iodine removal performance of 99.99% or more was shown up to 400 minutes or longer, whereas when quinuclidine was supported by vapor deposition, it exceeded 99.99% by about 40 minutes. The organic iodine removal performance was exhibited, and thereafter, the level was maintained at 99.99%. This indicates that, as described above, TFM-BA previously supported in high temperature and vacuum conditions for vapor deposition was partially removed, indicating that the removal performance was somewhat reduced in wet conditions.

17 is a TFM-BA and further, as a result of a MIL-101-NH ₂ bearing the quinuclidine to, 2 the MIL-101-NH ₂ modified into as described above removes organic yocho 99.99% DE to 350 minutes performance, and thereafter, the removal performance gradually decreased to a level of 99.99% or less. These results indicate a rather low removal performance compared to the modified MIL-101, which indicates that the amount of TFM-BA supported is relatively small, indicating that the TFM-BA is broken through at a faster time.

Finally, FIG. 18 shows the results for MIL-100 loaded with TFM-BA and additionally quinuclidine. In the case of MIl-100, TFM-BA is hardly supported, indicating very poor performance from the beginning of breakthrough under wet conditions. It was. However, the removal of some organic iodine is thought to be due to quinuclidine, which is additionally supported with TFM-BA and has organic iodine removal performance on its own.

Experimental example 7: DMMP adsorption experiment

Furthermore, the adsorption performance of dimethyl methylphosphonate (DMMP), a kind of chemical agent, was analyzed in real time using gas chromatography (GC). The GC was equipped with a dual FPD detector capable of simultaneously analyzing sulfur compounds and phosphorus compounds, and an Agilent HP-1ms was used as the column. A schematic diagram of the DMMP breakthrough device used in the present invention is shown in FIG. 19 . Specifically, the relative humidity was adjusted to maintain the 15% level by passing air through a water-saturator. DMMP and moisture-containing air were ^{uniformly mixed in a gas-mixing chamber to a concentration of 3000 mg/m 3} , and then supplied to the adsorbent in the reactor through a multi-position valve. The adsorption reactor used a 1/4" quartz tube reactor with an inner diameter of 4 mm, and the adsorbent previously humidified at 15% relative humidity for 2 hours was calculated by the measured bulk density and ^{filled with 50 mm 3} (retention in the adsorbent) time 0.34 sec) At this time, the reactor pressure was maintained at 1 atm and the temperature was maintained at 24° C. In addition, before the breakthrough test, the DMMP mixed gas was bypassed before being supplied to the reactor filled with the adsorbent and subjected to GC analysis to determine the initial concentration of DMMP (C _{0 ) was confirmed.A breakthrough curve was prepared by calculating the C/C 0} over time by measuring the concentration (C) of DMMP that passed through the adsorbent in real time.As a control, AZSM-TEDA, a commercial carbon adsorbent, and the The results measured for MIL-101 carrying TFM-BA and additional quinuclidine are shown in Fig. 20. As shown in Fig. 20, TEDA, an amine contained in ASZM-TEDA, is a P=O group of DMMP. Since it can act as an adsorption site for , it exhibited high removal performance up to 300 minutes, but since the adsorbent of the present invention contains quinuclidine having a higher nucleophilicity than TEDA, it exhibited higher removal performance up to about 400 minutes.

Experimental example 8: Formaldehyde Adsorption Experiment

The adsorption performance for another toxic substance, formaldehyde (HCHO), was analyzed in real time using a formaldehyde detector, Airwell+ 707. The detector is a device capable of analyzing a low concentration of 0.01 to 20 ppm of formaldehyde with an accuracy of 0.01 ppm. In the formaldehyde breakthrough experiment of the present invention, the same system as the DMMP breakthrough device disclosed in FIG. 19 was used. Specifically, the relative humidity was controlled to maintain the 80% level by passing air through a water-saturator. Air containing formaldehyde and moisture was uniformly mixed in a gas mixing chamber to a concentration of 20 ppm, and then supplied to the adsorbent in the reactor through a multi-position valve. The adsorption reactor used a 1/4" quartz tube reactor with an inner diameter of 4 mm, and the adsorbent previously humidified at 80% relative humidity for 2 hours was calculated by the measured bulk density and ^{filled with 50 mm 3} (retention in the adsorbent) time 0.34 sec) At this time, the pressure of the reactor was maintained at 1 atm and the temperature was maintained at 25 ° C. In addition, before the breakthrough test, the formaldehyde mixed gas was bypassed before feeding the adsorbent-filled reactor to the initial concentration of formaldehyde (C ₀ ) was checked.The concentration (C) of formaldehyde passed through the adsorbent was measured in real time, and C/C ₀ was calculated over time to create a breakthrough curve. As a control, a commercial carbon adsorbent SGC-100 was used. A breakthrough curve is shown in Fig. 21, and the results measured for the TFM-BA of the present invention and MIL-101 further loaded with quinuclidine are shown in Fig. 22. As shown in Fig. 22, MIL-101 It broke through after removing more than 99% of formaldehyde by 170 minutes, which is due to the fact that it contains a large amount (about 1.7 mmol/g) of highly reactive CUS that can act as an adsorption site for HCHO. After BA loading, more than 99.9% of formaldehyde was removed up to about 2200 minutes, which became hydrophobic by reforming with TFM-BA. In addition, when quinuclidine was additionally supported, more than 99.9% of formaldehyde was removed by 2500 minutes, which means that the additionally supported quinuclidine acted as another adsorption site. it indicates that

Claims (24)

In the manufacturing method of MOF with improved moisture stability,
A first step of modifying some or all of the unsaturated metal sites that are Lewis acid sites in the MOF with a nucleophilic compound to block the unsaturated (coordinatevely unsaturated) metals or defective sites from moisture; and
A second step of additionally supporting triethylenediamine (TEDA) or quinuclidine, which can perform adsorption or catalysis on the modified MOF from the first step,
The nucleophilic compound is C _1-12 alkylamine, C _1-12 haloalkylamine, C _1-4 haloalkyl-aryl-C _1-4 alkylamine, NHR ₁ -C _n H _2n -NHR ₂ , SH-C _n' H _2n' -SH and R _3-5 PC _n" H _2n" N-PR _6-8 (Wherein, n, n' and n" are each independently an integer of 1 to 12, and R ₁ to R ₈ each independently comprises at least one selected from the group consisting of H, or C _{1-12 alkylene;}
The MOF includes mesopores and micropores, and in the first step, the unsaturated metal site of the MOF is modified with the nucleophilic compound, and in the second step, triethylenediamine is formed in the mesopores of the MOF. ; TEDA) or quinuclidine is supported,
In the first step, a nucleophilic compound smaller than the pore size of the MOF to be modified is selectively modified at the unsaturated metal site, which is the Lewis acid site of the MOF, a method for producing a moisture-stable MOF.
delete delete delete delete According to claim 1,
In the second step, (i) the MOF modified from the first step and the compound to be further supported are left in an oven, or (ii) the compound to be further supported is supported on the MOF modified from the first step by vapor deposition. A method for producing a moisture-stable MOF, characterized in that.
7. The method of claim 6,
In the second step, a compound capable of performing adsorption or catalysis is additionally supported while a part of the nucleophilic compound supported on the modified MOF from the first step is removed.
It is a MOF with improved moisture stability compared to the MOF before modification, in which some or all of the unsaturated metal sites, which are Lewis acid sites in the MOF, are modified with a nucleophilic compound, and hydrolysis at the unsaturated metal or defect site is blocked,
The nucleophilic compound is C _1-12 alkylamine, C _1-12 haloalkylamine, C _1-4 haloalkyl-aryl-C _1-4 alkylamine, NHR ₁ -C _n H _2n -NHR ₂ , SH-C _n' H _2n' -SH and R _3-5 PC _n" H _2n" N-PR _6-8 (Wherein, n, n' and n" are each independently an integer of 1 to 12, and R ₁ to R ₈ each independently comprises at least one selected from the group consisting of H, or C _{1-12 alkylene;}
The MOF includes mesopores and micropores, the unsaturated metal site of the MOF is modified with the nucleophilic compound, and triethylenediamine (TEDA) or quinuclidine in the mesopores of the MOF This is loaded,
A nucleophilic compound smaller than the pore size of the MOF is selectively modified at the unsaturated metal site, which is a Lewis acid site formed during MOF synthesis, MOF.
delete 9. The method of claim 8,
MOF with improved water stability, characterized in that hydrophobicity is increased compared to the MOF before modification due to modification with a nucleophilic compound.
delete 9. The method of claim 8,
MOF before modification is characterized in that an amino group is substituted with a ligand constituting it, MOF with improved water stability.
delete delete 9. The method of claim 8,
wherein the nucleophilic compound is selected from the group consisting of amylamine, heptylamine, 4-(trifluoromethyl)benzylamine, and 2,2,3,3,4,4,4-heptafluorobutylamine. , MOF with improved moisture stability.
delete delete 9. The method of claim 8,
MOF with improved moisture stability, characterized by blocking the access of water molecules to the adsorption site of the MOF.
9. The method of claim 8,
MOF with improved moisture stability, characterized in that it can be used as an adsorbent or catalyst because hydrolysis is inhibited in a wet condition with a relative humidity of 0.01% or more or in a water-containing medium.
delete A composition for adsorption comprising the MOF having improved moisture stability according to claim 8.
22. The method of claim 21,
A composition for adsorption, characterized in that it adsorbs toxic gas, radioactive gas, carbon dioxide, semiconductor waste gas or secondary battery waste liquid.
22. The method of claim 21,
A composition for adsorption, characterized in that it is used in a wet condition with a relative humidity of 0.01% or more or in a water-containing medium.
A method of using the MOF having improved water stability according to claim 8 as an adsorbent in a wet condition of 0.01% or more of relative humidity or in a water-containing medium.

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