WO2018190672A1

WO2018190672A1 - Method for producing metal-organic complex comprising group 4b element

Info

Publication number: WO2018190672A1
Application number: PCT/KR2018/004338
Authority: WO
Inventors: 류삼곤; 이해완; 황영규; 홍도영; 조경호; 장종산; 이우황; 차가영
Original assignee: 국방과학연구소
Priority date: 2017-04-13
Filing date: 2018-04-13
Publication date: 2018-10-18
Also published as: KR20180115503A; KR101911173B1

Abstract

The present invention relates to a method for producing a metal-organic complex comprising a Group 4B element, and more specifically, to a method for producing a metal-organic complex exhibiting an excellent function of removing chemical warfare agents, the method comprising: a first step for preparing a metal-organic framework comprising any one Group 4B element among zirconium (Zr), titanium (Ti) and hafnium (Hf); and a second step for producing a metal-organic complex by depositing organic amine in pores of the metal-organic framework by means of a vapor-vacuum deposition method.

Description

Method for preparing metal-organic composite containing group 4B element

The present invention relates to a method for preparing a metal-organic composite having excellent performance in removing a chemical agent based on a metal-organic framework (MOF), which is a porous material.

Activated carbon used in gas masks in the seventh and eighties was mainly ASC impregnated activated carbon containing hexavalent chromium, which caused problems with disposal methods and environmental hazards due to the toxicity of hexavalent chromium. In Korean Patent No. 10-0148793, ASZM-TEDA activated carbon containing triethylenediamine (TEDA), an organic amine that does not contain chromium, has been developed and used until recently to solve this problem.

U.S. Patent No. 5,063,196 discloses about 5% copper by controlling the ratio of metal precursor and organic amine in the case of ASZM-TEDA activated carbon including silver (Ag), copper (Cu), zinc (Zn) and molybdenum (Mo). , 0.05% silver, impregnated with 5% zinc, 2% molybdenum and 3% TEDA to propose an activated carbon manufacturing method supported on activated carbon.

However, in the method of manufacturing metal-TEDA-containing activated carbon by impregnation, when the porous carbon carrier is impregnated with a transition metal such as copper, zinc, molybdenum, silver, vanadium, and organic amine, it can be dispersed or dissolved in solution. The amount of the metal and the organic amine is limited, and in particular, because of the nature of the activated carbon has a fine pores, when the content of the metal precursor is large, it is difficult to support a large amount of the metal active material in the pores by blocking the inlet of the micropores of the carrier. In addition, since expensive silver is used, it is difficult to secure economic feasibility.

Therefore, there is a limit to increase the content of active metal materials such as copper, zinc, and 6B elements, metals such as chromium (Cr), tungsten (W), and molybdenum (Mo), which are high content metals and organic amines. There is a need for the development of highly dispersed new porous composite materials.

Metal-organic frameworks (MOFs) are also commonly referred to as 'porous coordination polymers' or 'porous organic-inorganic hybrids'. They have the advantage of providing a large surface area with nano-sized pores. It is used in adsorbents, gas storage materials, sensors, membranes, functional thin films, drug delivery materials, catalysts and catalyst carriers, and is used for adsorption and removal of substances by carrying the composition in the pores. It has been actively studied because it can be used to capture molecules or use pores to separate molecules according to size, and can also be applied to catalysis using various active metals present in the structure of the metal-organic framework.

Various metal-organic framework materials for the removal of chemical agents have been reported, but it is difficult to deposit more than 10% by weight of the organic amine for chemical agent removal in the basic metal-organic framework structure due to the reduction of the active surface area of the pores. . Accordingly, there is a need for a method of preparing a metal-organic composite that can minimize the reduction of the area of the active surface of the pores of the metal-organic framework and maximize the removal performance of the chemical agent.

The present invention is to solve the problems as described above by a vapor-vacuum deposition method in the pores of the metal-organic skeleton containing elements of group 4B based on the periodic table (IUPAC inorganic chemical nomenclature revised edition, 1989) as a metal element It is an object to provide a method for preparing a metal-organic composite having at least 10% by weight of organic amine deposited to have excellent performance in removing chemical agents.

Metal-organic composite manufacturing method of the present invention for achieving the above object is the first step (S100) to prepare a metal-organic framework and the organic amine by vapor-vacuum deposition method in the pores of the metal-organic framework And depositing a second step (S200), which is performed as shown in the flowchart shown in FIG.

First, the first step (S100) is a step for preparing a metal-organic framework containing an element of Group 4B based on the periodic table (IUPAC Inorganic Chemistry Nomenclature, 1989), and a solvent with a metal precursor and an organic ligand. Preparing a precursor solution by mixing in a step (S110), heating the prepared precursor solution at a crystallization temperature to synthesize a metal-organic framework (S120), and purifying to obtain a synthesized metal-organic framework. It may be made, including (S130).

In the preparing of the precursor solution (S110), the metal precursor is a compound containing any one metal of zirconium (Zr), titanium (Ti), and hafnium (Hf) as an element of Group 4B. Each independently may be any one or more selected from chloride, nitrate, sulfate and acetate compounds of each metal.

For example, the metal precursor is a zirconium precursor, a titanium precursor and a hafnium precursor, preferably a metal oxyhydroxide material, such as titanium oxyhydroxide, zirconium oxyhydroxide and zirconium oxyhydroxide. Hafnium oxyhydroxide may be used, but is not limited thereto.

The organic ligand, which is another component of the metal-organic framework, is also called a linker, and any organic compound having a coordinating functional group can be used. For example, the organic ligand may be a carboxyl group (-COOH), carboxylic acid anion group (-COO ^-), an amine group (-NH _2), and an imino group (-NH), a nitro group (-NO _2), a hydroxy group (-OH), a halogen group (-X) and seulpon acid ( -SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^-), one selected from the group consisting of a pyridine group and a pyrazine Compounds or mixtures thereof having the above functional groups can be used.

In the present invention, organic ligands include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalenetricarboxylic acid, benzenetribenzoic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, and formic acid. (formic acid), oxalic acid, malonic acid, succinic acid, glutamic acid, hexanedioic acid, heptanedioic acid and cyclohexyldicarboxylic acid may be used, and more preferably, the chemical formula of FIG. Benzene-1,3,5-tricarboxylic acid (BTC), such as 1 ').

In the case of the metal-organic skeleton having a hydroxide functional group, such as the acid (HCl), which is a decomposition product of cyanide chloride (CK) having a molecular formula of CNCl, the metal used in the present invention- It is preferable that the organic skeleton uses what contains a hydroxide functional group.

The solvent used to prepare the precursor solution may be used without limitation as long as it is a solvent capable of dissolving both a metal component and an organic ligand. For example, water, N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc), ethylene glycol, glycerol, polyethylene Glycol, acetone, methyl ethyl ketone, hexane, heptane, octane, acetonitrile, dioxane, chlorobenzene, pyridine, N-methyl pyrrolidone (NMP), sulfolane, tetrahydrofuran (THF), gamma-butyrolactone , Cyclohexanol and alcohols such as methanol, ethanol, and propanol may be used, and two or more solvents may be mixed, and most preferably N, N-dimethylformamide (DMF) may be used. have.

In the step of synthesizing the metal-organic framework (S120), a solvent heat synthesis or microwave synthesis for synthesizing the metal-organic framework is performed by performing a crystallization reaction by heating a predetermined time by heating solvent heat, microwaves or ultrasonic waves. Metal-organic frameworks can be synthesized.

Next, in the step of obtaining a metal-organic skeleton by the process (S130), the synthesized metal-organic skeleton is purified for a predetermined time in the presence of a solution (solvent) for a predetermined time to obtain a synthesized metal-organic skeleton. In this case, the purification method may be performed by a conventional centrifugation method and the like, but is not limited thereto.

The metal-organic framework of the present invention synthesized in this manner may be represented by the following Chemical Formula 2 as a non-limiting example.

[Formula 2]

M (μ ₃ -O) ₄ (μ ₃ -OH) ₄ (L) ₂ (HCOO) ₆

In Formula 2, M is any one metal selected from Ti ⁴ ⁺ , Zr ⁴ ^+, and Hf ⁴ ⁺ , and L is a carboxyl group (-COOH), a carboxylic acid anion group (-COO ⁻ ), or an amine group (-NH ₂₎ and the imino group (-NH), a nitro group (-NO _2), a hydroxy group (-OH), a halogen group (-X) and seulpon acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), Osan methane dithiol group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^-), a compound or a mixture thereof is an organic ligand having at least one functional group selected from the group consisting of pyridine group and pyrazinyl group. Μ ₃ in Formula 2 means a structure in which oxygen (O) is bonded to three zirconiums (Zr).

The second step (S200) is a metal-deposited organic amine of 1 to 30% by weight based on 100% by weight of the total metal-organic framework in the pores of the metal-organic framework prepared in the first step (S100)- It is a step of preparing an organic complex.

Specifically, the second step (S200) is an activation step (S210) for activating the metal-organic framework by placing the metal-organic framework in a reactor and heating to a predetermined temperature under vacuum reduced pressure conditions, the organic amine powder by vacuum decompression Vacuum drying step (S220) for removing excess water present in the amine powder, and the dried organic amine is heated to a certain temperature under vacuum decompression conditions to form a gaseous organic amine, and activated the formed gaseous organic amine It can be made by including a deposition step (S230) to be injected into the reactor having a metal-organic skeleton at a constant rate and deposited in the pores of the activated metal-organic framework.

The organic amine may be any one selected from triethylenediamine, triethylamine and pyridine-4-carboxylic acid, or a mixture thereof, preferably Triethylenediamine can be used.

The activation step (S210) is to put the metal-organic skeleton in the reactor and heated the reactor to a temperature of 110 to 150 ℃ under vacuum reduced pressure conditions of 1 × 10 ^-1 to 1 × 10 ^-5 torr, the metal-organic skeleton It can be activated by removing the moisture and impurities present in the pores of the sieve. If the pressure and the temperature ranges below the water and impurities in the pores of the metal-organic framework is not properly removed, the activation of the metal-organic framework is not properly made, there is a problem that the production of metal-organic complex is difficult, If the range exceeds, there is a problem in that excess energy is consumed in terms of energy efficiency compared to the activation reaction.

In the vacuum drying step (S220), the organic amine powder is vacuum-reduced to 1 × 10 ⁻¹ to 1 × 10 ⁻⁵ torr at a temperature of 15 to 30 ° C. to remove moisture, and the temperature and pressure presented in the vacuum drying step. Outside the range, since the water removal of the organic amine is not made properly, it is difficult to form a gaseous organic amine in a later step, it is preferable to satisfy the conditions presented.

In the deposition step (S230), the dried organic amine may be heated to a temperature of 110 to 150 ° C. under a vacuum decompression condition of 1 × 10 ⁻¹ to 1 × 10 ⁻⁵ torr to form an organic amine in a gaseous state. When the organic amine in the gaseous state is less than the pressure and temperature ranges described above, it is difficult to deposit in the pores of the activated metal-organic framework because the organic amines in the gaseous state are not properly changed, and when the pressure and temperature ranges are exceeded. Metal-Organic Frameworks Due to the rather high temperature, the deposition of organic amines in the pores of activated metal-organic frameworks is difficult.

As such, the crystal size of the metal-organic composite prepared by the above-described manufacturing method is preferably 100 nm or more on average.

Meanwhile, in the present specification, the "metal-organic complex" means a metal-organic framework in which organic amine is deposited or supported on pores of the metal-organic framework.

The metal-organic composite including the Group 4B element prepared through the production method of the present invention has a crystal size of 100 nm or more and is excellent in crystallinity, and the metal-organic composite is prepared through the vapor-vapor deposition method. At least 10% by weight of organic amine is deposited in the pores of the metal-organic framework with respect to 100% by weight of the organic framework, which minimizes the reduction of the area of the active surface of the pores and has an excellent effect on the removal of chemical agents.

1 is a flowchart illustrating a method for preparing a metal-organic composite of the present invention.

2 is a chemical formula of benzene-1,3,5-tricarboxylic acid (BTC).

3 is X of a metal-organic framework (MOF-808) including zirconium (Zr) having a crystal size of 100 nm or more prepared through microwave synthesis (a) and solvent thermal synthesis (b) according to an embodiment of the present invention. The result of the line diffraction analysis.

4 is a photograph of a zirconium (Zr) -based metal-organic framework (MOF-808) synthesized by microwave synthesis according to an embodiment of the present invention with a scanning electron microscope (SEM).

FIG. 5 is a photograph of a zirconium (Zr) -based metal-organic framework (MOF-808) synthesized by solvent thermal synthesis according to an embodiment of the present invention with a scanning electron microscope (SEM).

Figure 6 shows a system for producing a metal-organic composite according to the present invention.

7 is an X-ray diffraction (XRD) before and after deposition of triethylenediamine (TEDA) on a zirconium (Zr) -based metal-organic framework (MOF-808) according to an embodiment of the present invention. The analysis results are shown.

FIG. 8 is a graph showing nitrogen adsorption results and BET specific surface areas before and after deposition of triethylenediamine (TEDA) on a zirconium (Zr) -based metal-organic framework (MOF-808) according to an embodiment of the present invention.

9 is a result of comparing the removal performance of cyanogen chloride (CK) according to the amount of triethylenediamine (TEDA) deposition in the metal-organic composite prepared according to the embodiment of the present invention.

10 is a result of comparing the removal performance of cyanogen chloride (CK) of the metal-organic composite and ASZM-TEDA activated carbon prepared according to an embodiment of the present invention.

The number of repetitions of each step described in the method for producing a metal-organic composite of the present invention, process conditions such as reaction temperature, and the like are not particularly limited as long as they do not depart from the object of the present invention, and are considered to be optimal for the purpose of the present invention. Indicates the conditions.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, these Examples and Comparative Examples are only one example and the scope of the present invention is not limited to these Examples and Comparative Examples, and can be implemented by variously modified and changed by those skilled in the art. Therefore, it is not limited to what is described here.

Example 1 synthesized a metal-organic composite named MOF-808 in Preparation Example 1 below as a method for preparing a metal-organic composite of the present invention.

Preparation Example 1 relates to a method for producing a metal-organic skeleton containing zirconium (Zr), and a method for producing MOF-808 as a metal-organic framework containing zirconium (Zr). Chem. Soc. 2014, 136, 4369-4381).

Specifically, the preparation of the metal-organic framework of the present invention includes zirconium oxyhydroxide including zirconium (Zr) as a metal precursor and benzene-1,3,5-tricarboxylic acid (benzene-1) as an organic ligand. Precursor solution was prepared using N, N-dimethylformamide (DMF) as a solvent using 3,5-tricarbozylic acid (BTC) and formic acid. As shown in Table 1 below, the mixture is controlled to have a ratio of metal precursor: organic ligand: DMF: formic acid = 1: 1: 246: 521 based on the molar ratio.

Then, the prepared precursor solution was heated at a crystallization temperature for a predetermined time to proceed with the synthesis of the metal-organic framework, in which the synthesis was performed by dissolution heat synthesis or microwave synthesis to shorten the reaction time.

Dissolution heat synthesis synthesized the metal-organic framework by injecting the precursor solution into the tube through a micro metering pump and passing the heated section to a temperature of about 100 ° C. The synthesized metal-organic framework was called 'MOF- It is also indicated as 808-R '.

In the microwave synthesis, a microwave was heated to a precursor solution at a temperature of 100 ° C. for 3 hours to form a metal-organic framework. The metal-organic framework synthesized by the microwave synthesis method is 'MOF-808-M'. Also referred to as.

In the purification process, the metal-organic frameworks synthesized from the reaction solution after the reaction were sufficiently washed with N, N-dimethylformamide (DMF) and ethanol, and then the metal-organic framework crystals were recovered by centrifugation. It was then dried at a temperature of 100 ℃.

Table 1 summarizes the reaction conditions for preparing MOF-808.

In the molar ratio of Table 1, M represents a metal precursor, L * represents an organic ligand, DMF represents N, N-dimethylformamide, and FA ** represents formic acid.

구분division	금속-유기 골격체 합성 방법Metal-organic framework synthesis method	몰비(M:L:DMF:FA)Molar ratio (M: L : DMF: FA **)	Reactor scaleReactor scale
MOF-808-RMOF-808-R	용해열 합성(3일, 100℃)Heat of dissolution synthesis (3 days, 100 ℃)	1:1:246:5211: 1: 246: 521	100 ml100 ml
MOF-808-MMOF-808-M	마이크로파 합성(3시간, 100℃)Microwave Synthesis (3 hours, 100 ° C)	1:1:246:5211: 1: 246: 521	100 ml100 ml

MOF-808, a metal-organic framework containing zirconium (Zr) as its core metal, is a porous nanostructure with a Zr ₆ O ₄ (OH) ₄ (OOCH) ₆ (BTC) ₂ structure and has pores with sizes of 0.48 nm and 1.82 nm. It has a cage and its surface area is between 1300 and 2000 m ² / g according to the synthesis method of MOF-808, and includes various zirconium (Zr) active sites such as metal hydroxides including acid / base functional groups. It is included.

The metal-organic framework thus synthesized was analyzed by X-ray diffraction (XRD) analysis of the crystal structure of the powder after drying, as shown in FIG. 3, as shown in MOF-808-R and MOF-808. -M was confirmed to be consistent with the structure of the MOF-808 previously reported.

In addition, the synthesized metal-organic framework was confirmed crystal size through a scanning electron microscope.

As a result, as shown in Fig. 4 and 5, in the case of MOF-808-M, a metal-organic framework synthesized by the method of microwave synthesis, the crystal size was 500 to 600 nm on average, and the metal synthesized by the heat of melting synthesis method- In the case of MOF-808-R which is an organic skeleton, it was confirmed that it has a particle size of 200-400 nm on average. All of them have a crystal size of 100 nm or more, so the crystallinity is excellent.

In addition, since the active surface of the metal-organic framework is generally almost inside the pores of the metal-organic framework, it is necessary to secure the surface pore volume for quick and easy access to the interior of the pores during the deposition or adsorption of organic amines. Importantly, the surface area of the metal-organic framework synthesized as described above is about 1300 ~ 2000 m ² / g, it can be seen that the deposition of the organic amine is easy.

Preparation Example 2 relates to a method of preparing a metal-organic composite by depositing an organic amine on the metal-organic framework prepared in Preparation Example 1, and a metal by vapor-vacuum deposition through a system as shown in FIG. 6. Organic complexes were prepared.

As shown in FIG. 6, the production system for manufacturing the metal-organic composite of the present invention is a quartz tubular reactor in which a furnace is formed in which a furnace is formed for depositing an organic amine in the pores of the metal-organic framework. And a mass flow controller (MFC) for controlling the flow rate of an inert gas such as a helium (He) gas and an organic amine supply bulb which is prepared by heating the organic amine to form a gaseous organic amine and then supplied to the reactor. Is configured to include a supply pipe for supplying an inert gas.

Referring to Figure 6 looks at the manufacturing method of the metal-organic composite of the present invention.

The pores in the reduced pressure of ⁵ ^torr-metal prepared in Preparative Example 1 to an organic backbone chain MOF-808 frit disc (Fritted disk) is installed quartz temperature and 10 ^-1 to 10 into a 150 ℃ (quartz) tube reactor It activates by removing existing water and impurities. A bulb containing a certain amount of solid triethylenediamine (TEDA) as an organic amine was treated at room temperature and under reduced pressure (1 × 10 ⁻¹ to 1 × 10 ⁻⁵ torr) to obtain a bulb and a tree. After removing the water present in ethylenediamine (TEDA), it is connected to a quartz reactor containing an activated metal-organic framework. Slowly increasing the temperature of the bulb under reduced pressure to control the sublimation rate of triethylenediamine (TEDA) to control the partial pressure of gaseous triethylenediamine (TEDA) in the system. It is selectively deposited on the inner pore wall. Finally, when all of the solid triethylenediamine (TEDA) in the bulb is sublimated, helium (He) gas is used to remove the remaining gaseous triethylenediamine (TEDA), thereby reducing the amount of triethylenediamine (TEDA) deposited. An organic framework, a metal-organic complex, was prepared, and the metal-organic complex thus prepared was designated as 'TEDA-MOF-808'.

7 is X-ray diffraction (X-) before and after deposition of triethylenediamine (TEDA) on a zirconium (Zr) -based metal-organic framework (MOF-808) as a metal-organic composite synthesized according to an embodiment of the present invention. ray diffraction (XRD) analysis results, in the graph of Figure 6 (a) is the X-ray diffraction pattern of the metal-organic framework MOF-808 before the deposition of triethylenediamine (TEDA), (b) is a tree X-ray diffraction pattern of the metal-organic framework after ethylenediamine (TEDA) deposition is shown.

Although the crystallinity of the metal-organic framework is relatively low after triethylenediamine (TEDA) deposition as shown in FIG. 7, the characteristic X-ray diffraction pattern having the same crystal structure as MOF-808 is maintained. It could be confirmed.

Example 1 prepared a metal-organic composite by the same method as Preparation Example 2, except that the amount of triethylenediamine (TEDA) deposited, 8.4 wt%, 10 wt%, 14 wt%, 22 wt% and 23 A metal-organic composite was prepared in which wt% triethylenediamine (TEDA) was deposited.

According to the amount of triethylenediamine (TEDA) deposited on the metal-organic framework in Example 1 of the present invention, the deposition amount is indicated before 'TEDA-MOF-808', for example, 8.4 wt% of triethylenediamine (TEDA) was deposited in the form of "8.4 wt% TEDA-MOF-808" or "8.4 wt% TEDA-MOF-808".

FIG. 8 shows nitrogen adsorption isotherms before and after the deposition of triethylenediamine (TEDA) on a zirconium (Zr) -based metal-organic framework (MOF-808), and a metal obtained by applying a BET equation to the measured nitrogen adsorption isotherms. The BET surface area value (cm ³ / g) per weight before and after triethylenediamine (TEDA) deposition on the organic framework was measured.

In Figure 8 (a) is the nitrogen adsorption curve of the metal-organic framework MOF-808 prior to the deposition of triethylenediamine (TEDA), (b) is a metal-organic deposition of 23% by weight of triethylenediamine (TEDA) The nitrogen adsorption curve of the framework is shown.

Looking at the nitrogen adsorption curve of Figure 8, the zirconium (Zr) -based metal-organic framework (MOF-808) BET surface area of 1733 m ² / g, pore volume of about 0.74 ml / g, but 23% by weight of triethylene The BET surface area of diamine (TEDA) -deposited metal-organic ear was 1092m ² / g, the pore volume was 0.49 ml / g, and the BET surface area and the pore volume were confirmed to be small.

The breakthrough experiment of cyanogen chloride (CK), which is one of the chemical agents, was performed on the metal-organic complex prepared in Example 1, and the specific method is as follows.

CK cyanide breakthrough experiment uses a 4 mm inner diameter glass tube as the adsorption reactor, and the adsorption reactor was filled with a metal-organic composite of 0.1 ml and a filling height of about 8 cm. Do this. Here, the metal-organic composite is formed by pulverizing the metal-organic composite in powder form in order to evaluate the adsorption performance, and then pulverized, and has a particle size in which the pressure drop in the adsorption reactor can be minimized. 70 mesh) size particles were used.

After the pretreatment was carried out through a humid air of 20 ° C. and a relative humidity of 60% for 2 hours in a adsorption reactor filled with a metal-organic complex with an adsorbent, a mixture containing cyan chloride (CK) concentration of 4,000 mg / m ³ Destruction experiments were carried out by passing air (20 ° C., relative humidity 60%) through an adsorption reactor at a linear speed of 2.65 cm / s. Analyze the concentration of cyan chloride (CK) by sampling the air injected into the inlet and outlet of the adsorption reactor in real time at the front and rear ends of the adsorption reactor filled with the metal-organic complex, and measuring the outlet concentration (C). Divided by the concentration (Co), the results are expressed as a function of the experiment time, the results are as shown in FIG.

As can be seen in Figure 9, as the deposition amount of triethylenediamine (TEDA) increases, the time for the cyanogen chloride (CK) to stay inside the metal-organic complex is gradually increased, the metal-organic complex of the present invention is chloride As the deposition amount of organotriethylenediamine (TEDA) increased, it was confirmed that the removal efficiency was increased due to the good adsorption to cyanogen chloride (CK).

Example 2 was 29 wt% by the same method as Preparation Example 2, except that the BET surface area of MOF-808, a metal-organic framework on which triethylenediamine (TEDA) was deposited, was 1610 m ² / g. And 29 wt% TEDA-MOF-808 and 30 wt% TEDA-MOF-808 with 30 wt% triethylenediamine (TEDA) deposited.

For comparison, a breakthrough experiment of cyanogen chloride (CK), one of chemical agents, was performed using ASZM-TEDA activated carbon, a commercial product having a surface area of about 1000 m ² / g, which is used in conventional military gas masks.

As can be seen in Figure 10 it can be seen that the TEDA-MOF-808 produced by the vapor-vacuum deposition method according to the present invention is up to three times more than the CK removal performance of the conventional ASZM-TEDA activated carbon.

As described above, the metal-organic composite prepared by the vapor-vacuum deposition method according to the metal-organic composite manufacturing method of the present invention is a tree which is an organic amine substance having high decomposition activity to chemical agents in the pores of the metal-organic framework. Ethylenediamine (TEDA) was confirmed to be deposited at 10 to 30% by weight.

In addition, although the pore size is measured in the present specification, although not shown in the drawings of the present invention, when the metal-organic composite is prepared using the vapor-vacuum vapor deposition method of the present invention, it is included in the structure of the MOF-808. According to the definition of the International Union of Pureand Applied Chemistry (UPUPAC), the volume of mesoporous cells with a range of 2-50 nm is maintained at about 50%, indicating that the active surface, which is an adsorption site for the removal of chemical agents, is activated. I could confirm it.

Therefore, the metal-organic composite prepared according to the production method of the present invention can minimize the pore volume and surface area of the metal-organic framework, which is a porous material, to deposit an organic amine material at 1 to 30% by weight, in particular, As deposited as 10-30% by weight or more, it has excellent performance in removing chemical agents including cyanide chloride (CK).

The above-described embodiment is not only limited to the above-described embodiment but is a preferred embodiment that can be easily carried out by those of ordinary skill in the art to which the present invention pertains because of this the scope of the present invention Is not limited. Therefore, it will be apparent to those skilled in the art that various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention, and it is obvious that parts easily changed by those skilled in the art are included in the scope of the present invention.

Claims

Preparing a metal-organic framework including any one of zirconium (Zr), titanium (Ti), and hafnium (Hf) as a Group 4B element; And

And depositing an organic amine in the pores of the metal-organic framework by a vapor-vacuum deposition method to produce a metal-organic composite.
The method of claim 1,

The organic amine is characterized in that any one or a mixture thereof selected from triethylenediamine, triethylamine and pyridine-4-carboxylic acid (pyridine-4-carboxylic acid) Method for preparing metal-organic composite.
The method of claim 1,

The second step,

An activation step of activating the metal-organic framework by placing the metal-organic framework into a reactor and heating to a constant temperature under vacuum reduced pressure;

Vacuum drying the organic amine powder under vacuum to remove excess moisture present in the organic amine powder;

The dried organic amine is heated to a constant temperature under vacuum decompression conditions to form a gaseous organic amine, and the formed gaseous organic amine is injected at a constant rate into a reactor having an activated metal-organic framework to activate the metal-organic Deposition step of depositing in the pores of the skeleton; Metal-organic composite manufacturing method comprising a.
The method of claim 3,

In the activation step, the metal-organic framework is placed in a reactor, and the reactor is heated to a temperature of 110 to 150 ° C. under a vacuum decompression condition of 1 × 10 −1 to 1 × 10 −5 torr, so that the pores of the metal-organic framework are Method for producing a metal-organic composite, characterized in that to activate by removing the water and impurities present in the.
The method of claim 3,

The vacuum drying step is a method for producing a metal-organic composite, characterized in that to remove the water by vacuum decompression of the organic amine powder to 1 × 10 -1 to 1 × 10 -5 torr at a temperature of 15 to 30 ℃.
The method of claim 3,

In the deposition step, the dried organic amine is heated to a temperature of 110 to 150 ° C. under a vacuum reduced pressure of 1 × 10 −1 to 1 × 10 −5 torr to form a gaseous organic amine. Manufacturing method.
The method of claim 1,

In the second step, a metal-organic composite manufacturing method comprising preparing a metal-organic composite in which 1 to 30% by weight of organic amine is deposited based on 100% by weight of the total metal-organic framework.
The method of claim 1,

The first step,

Mixing the metal precursor and the organic ligand together in a solvent to prepare a precursor solution;

Heating the prepared precursor solution at a crystallization temperature to synthesize a metal-organic framework; And

Purifying for a predetermined time at a predetermined temperature in the presence of a solution (solvent) to obtain a metal-organic framework; metal-organic composite manufacturing method comprising a.
The method of claim 8,

The metal precursor is a compound containing any one metal selected from zirconium (Zr), titanium (Ti) and hafnium (Hf), and selected from chloride, nitrate, sulfate and acetate compounds of the metal. Method for producing a metal-organic composite, characterized in that any one or more.
The method of claim 8,

The organic ligands include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalenetricarboxylic acid, benzenetribenzoic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, Method of producing a metal-organic composite, characterized in that any one or more selected from malonic acid, succinic acid, glutamic acid, hexanedioic acid, heptanedioic acid and cyclohexyldicarboxylic acid.
The method of claim 8,

The solvent may be water, methanol, ethanol, propanol, acetone, N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc), acetonitrile, chlorobenzene, pyridine, N-methyl pyrrolidone (NMP) and tetrahydrofuran (THF) Method for producing a metal-organic composite, characterized in that at least one.