KR101911173B1 - Method for preparing metal-organic composite of containing 4b group metal elements - Google Patents
Method for preparing metal-organic composite of containing 4b group metal elements Download PDFInfo
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- KR101911173B1 KR101911173B1 KR1020170047896A KR20170047896A KR101911173B1 KR 101911173 B1 KR101911173 B1 KR 101911173B1 KR 1020170047896 A KR1020170047896 A KR 1020170047896A KR 20170047896 A KR20170047896 A KR 20170047896A KR 101911173 B1 KR101911173 B1 KR 101911173B1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/12—Organic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
Abstract
The present invention relates to a method for preparing a metal-organic composite containing a Group 4B element, and more particularly, to a method for preparing a metal-organic composite containing a metal- A first step of preparing an organic skeleton and a second step of depositing an organic amine on the pores of the metal-organic skeleton by a vapor-vacuum deposition method to produce a metal-organic complex, ≪ RTI ID = 0.0 > metal-organic < / RTI >
Description
The present invention relates to a method for producing 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 7th ~ 80th years is ASC-impregnated activated carbon mainly containing hexavalent chromium. Due to the toxicity of hexavalent chromium, post-use disposal method and environmental hazard have become a problem. In Korean Patent No. 10-0148793, ASZM-TEDA activated carbon containing triethylenediamine (TEDA), which is an organic amine containing no chromium, has been developed and used until recently.
U.S. Patent No. 5,063,196 discloses that 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 about 5% , 0.05% was impregnated with 5% zinc, 2% molybdenum and 3% TEDA, and supported on activated carbon.
However, in the case of the metal-TEDA-containing activated carbon manufacturing method using the impregnation method, the porous carbon carrier can be dispersed or dissolved in the solution state when impregnating the transition metal such as copper, zinc, molybdenum, silver, vanadium and organic amine, The amount of metal and organic amine is limited. Especially, when the content of metal precursor is large due to the nature of activated carbon, it is difficult to deposit a large amount of metal active material in the pores by blocking the micropores of the carrier. In addition, since expensive silver is used, it is difficult to secure economical efficiency.
Therefore, there is a limitation in increasing the content of active metal materials such as copper, zinc and 6B group elements such as chromium (Cr), tungsten (W), and molybdenum (Mo), which are metal active materials and high amounts of metals and organic amines The development of highly dispersed new porous composite materials is required.
Metal-organic frameworks (MOFs) are also commonly referred to as 'porous coordination polymers' or 'porous organic-inorganic hybrid materials'. They have nanoscale pores to provide a large surface area A gas storage material, a sensor, a membrane, a functional thin film, a drug delivery material, a catalyst, a catalyst carrier, etc., for the purpose of adsorbing and removing a substance or carrying the composition in pores, Is being actively studied because it can be applied to catalytic reactions using various active metals present in the structure of the metal-organic skeleton, which are used for collecting molecules or separating molecules by size using pores.
A variety of metal-organic skeleton materials for removing chemical agents have been reported, but it is difficult to deposit more than 10% by weight of organic amine for removing chemical agents in the basic metal-organic skeleton structure due to reduction of the active surface area of pores and the like . Accordingly, there is a need for a method for producing a metal-organic composite capable of minimizing the reduction of the area of the active surface area of the pores of the metal-organic skeleton and maximizing the removal performance of the chemical agent.
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a metal-organic vacuum vapor deposition method for metal-organic pores of a metal-organic skeleton containing elements of Group 4B based on the periodic table (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989) Organic amine is deposited in an amount of 10% by weight or more to provide a method for producing a metal-organic composite having excellent performance in removing a chemical agent.
According to another aspect of the present invention, there is provided a method for preparing a metal-organic composite, comprising the steps of: preparing a metal-organic skeleton (S100) (S200), which is performed as shown in the flowchart of FIG.
The first step S100 is a step for preparing a metal-organic skeleton containing an element of Group 4B on the basis of the periodic table (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), wherein a metal precursor and an organic ligand together with a solvent (S120) of synthesizing a metal-organic skeleton by heating the prepared precursor solution at a crystallization temperature, and a step (S120) of obtaining a metal-organic skeleton synthesized through purification to obtain a precursor solution (S130).
In the step of producing the precursor solution (S110), the metal precursor is a compound containing any one metal of zirconium (Zr), titanium (Ti) and hafnium (Hf) as a group 4B element, Each may be independently selected from the group consisting of chloride, nitrate, sulfate and acetate compounds of each metal.
For example, the metal precursor may be a zirconium precursor, a titanium precursor, and a hafnium precursor, preferably a metal oxyhydroxide material, such as titanium oxyhydroxide, zirconium oxyhydroxide, Hafnium oxyhydroxide may be used, but is not limited thereto.
The organic ligand, which is another component of the metal-organic skeleton, is also referred to as a linker, and any organic compound having a functional group capable of coordinating bonds is possible. 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 - ), a methanedithioic acid group (-CS 2 H), a methanedithioic acid anion group (-CS 2 - ), a pyridine group and a pyrazine group A compound having the above functional groups or a mixture thereof may be used.
As the organic ligand in the present invention, there may be mentioned benzene dicarboxylic acid, naphthalene dicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, benzene tribenzoic acid, pyridine dicarboxylic acid, bipyridyl dicarboxylic acid, at least one selected from the group consisting of formic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, hexanedioic acid, heptanedioic acid and cyclohexyldicarboxylic acid, 1,3,5-tricarboxylic acid (BTC) may be used.
In the case of a metal-organic skeleton having a hydroxid functional group, it is possible to effectively remove acid (HCl), which is a decomposition product of cyanide chloride (CK) having a molecular formula of CNCl, The organic skeleton is preferably one containing a hydroxide functional group.
[Chemical Formula 1]
The solvent used for preparing the precursor solution can be used without limitation as long as it is a solvent capable of dissolving both the metal component and the organic ligand. For example, water, N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc), ethylene glycol, glycerol, polyethylene (N-methylpyrrolidone), sulfolane, tetrahydrofuran (THF), gamma-butyrolactone (NMP), tetrahydrofuran , Cyclohexanol and alcohols such as methanol, ethanol and propanol. Among them, two or more kinds of solvents can be used, and most preferred is N, N-dimethylformamide (DMF) have.
In the step of synthesizing the metal-organic skeleton (S120), the solvent is thermally or microwave-synthesized to synthesize a metal-organic skeleton by performing a crystallization reaction by heating for a predetermined time by irradiating with solvent heat, microwave or ultrasonic wave A metal-organic skeleton can be synthesized.
In the next step (S130) of obtaining a metal-organic skeleton, the synthesized metal-organic skeleton is purified at a predetermined temperature for a predetermined time in the presence of a solvent to obtain a synthesized metal-organic skeleton Here, the purification method may be performed by a conventional method such as a centrifugal separation method and the like, but is not limited thereto.
The metal-organic skeleton of the present invention synthesized by such a method may be represented by the following general formula (2) as a non-limiting example.
(2)
M (μ 3 -O) 4 (μ 3 -OH) 4 (L) 2 (HCOO) 6
In the
In the second step S200, the metal-organic skeleton prepared through the first step S100 is coated with a metal-organic skeleton having 10 to 30 wt% of organic amine based on 100 wt% Organic complexes.
Specifically, the second step (S200) includes an activation step (S210) of activating the metal-organic skeleton by heating the metal-organic skeleton in a reactor under a vacuum-reduced condition at a predetermined temperature, Vacuum drying step (S220) for removing excess water present in the amine powder, and drying the dried organic amine to a predetermined temperature under vacuum decompression conditions to form an organic amine in a gaseous state, And a deposition step (S230) of depositing the metal-organic skeleton on the activated metal-organic skeleton by injecting the metal-organic skeleton into the reactor at a constant rate.
The organic amine may be any one selected from the group consisting of triethylenediamine, triethylamine and pyridine-4-carboxylic acid, or a mixture thereof. Triethylenediamine may be used.
In the activation step (S210), the metal-organic skeleton is placed in a reactor, and the reactor is heated to a temperature of 110 to 150 ° C under a reduced pressure of 1 × 10 -1 to 1 × 10 -5 torr, Water and impurities present in the pores of the sieve can be removed and activated. If the pressure and the temperature are lower than the above-mentioned ranges, water and impurities in the pores of the metal-organic skeleton are not properly removed, and the metal-organic skeleton is not activated properly. In the case of exceeding the range, there is a problem that excessive energy is consumed in terms of energy efficiency versus activation reaction.
In the vacuum drying step (S220), it is preferable that the organic amine powder is vacuum-depressurized at a temperature of 15 to 30 ° C at a pressure of 1 × 10 -1 to 1 × 10 -5 torr to remove moisture, and the temperature and pressure If the amount of the organic amine is outside the range, it is difficult to remove the water of the organic amine and it is difficult to form a gaseous organic amine in the subsequent step.
The deposition step (S230) may be by heating the dried organic amine to 1 × 10 -1 to 1 × 10 -5 torr in a vacuum reduced pressure of 110 to 150 ℃ temperature to form an organic amine in the gas state. When the pressure and the temperature are lower than the above-mentioned range, the organic amine in the gaseous state is not properly changed into the gaseous state, which makes it difficult to deposit on the pores of the activated metal-organic skeleton. It is difficult to deposit organic amines in the pores of the activated metal-organic skeleton due to the rather high temperature of the metal-organic skeleton.
The crystal size of the metal-organic composite produced by the above-described production method is preferably 100 nm or more on average.
In the present specification, the term "metal-organic composite" means a metal-organic skeleton in which organic amine is deposited or supported on the pores of the metal-organic skeleton.
The metal-organic composites prepared by the method of the present invention have excellent crystallinity since they have a crystal size of 100 nm or more. Further, the metal-organic composites are produced by the vapor-vapor deposition method, Organic skeleton having more than 10% by weight of organic amine is deposited in the pores of the metal-organic skeleton with respect to 100% by weight of the organic skeleton, thereby minimizing the reduction of the area of the active surface of the pores and exhibiting an excellent effect of removing chemical agents.
1 is a flowchart of a method for producing a metal-organic composite of the present invention.
FIG. 2 is a graph showing the X-ray diffraction patterns of a metal-organic skeleton (MOF-808) containing zirconium (Zr) having a crystal size of 100 nm or more, prepared by a microwave synthesis method (a) Ray diffraction analysis.
FIG. 3 is a photograph of a zirconium (Zr) based metal-organic skeleton (MOF-808) synthesized by microwave synthesis according to an embodiment of the present invention by scanning electron microscope (SEM).
4 is a photograph of a zirconium (Zr) based metal-organic skeleton (MOF-808) synthesized by a solvent thermal synthesis method according to an embodiment of the present invention with a scanning electron microscope (SEM).
5 shows a system for manufacturing a metal-organic composite according to the present invention.
6 is a graph showing X-ray diffraction (XRD) before and after deposition of triethylenediamine (TEDA) on a zirconium (Zr) based metal-organic skeleton (MOF-808) The results of the analysis are shown.
7 is a graph showing the results of nitrogen adsorption and BET specific surface area before and after deposition of triethylenediamine (TEDA) on a zirconium (Zr) based metal-organic skeleton (MOF-808) according to an embodiment of the present invention.
FIG. 8 is a graph illustrating the removal performance of cyanogen chloride (CK) according to the deposition amount of triethylenediamine (TEDA) in a metal-organic composite prepared according to an embodiment of the present invention.
9 is a graph illustrating the removal performance of cyanogen chloride (CK) of ASZM-TEDA activated carbon prepared according to an embodiment of the present invention.
The process conditions such as the number of repetitions of each step and the reaction temperature described in the method for producing a metal-organic composite of the present invention are not particularly limited as long as they do not deviate from the object of the present invention and are considered to be optimum for the purpose of the present invention Is a conditional description.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, these examples and comparative examples are merely examples, and the scope of the present invention is not limited to these examples and comparative examples, and various modifications and changes may be made by those skilled in the art. Therefore, the present invention is not limited to what is described herein.
Example 1 is a method for producing a metal-organic complex of the present invention, and a metal-organic complex named MOF-808 in the following Production Example 1 was synthesized.
Production Example 1 relates to a process for producing a metal-organic skeleton containing zirconium (Zr), and a process for producing MOF-808 as a metal-organic skeleton containing zirconium (Zr) Chem. Soc. 2014, 136, 4369-4381).
Specifically, the preparation of the metal-organic skeleton of the present invention is carried out by using zirconium oxyhydroxide containing zirconium (Zr) as a metal precursor and benzene-1,3,5-tricarboxylic acid , 3,5-tricarbozylic acid (BTC) and formic acid as solvents, N, N-dimethylformamide (DMF) was used to prepare the precursor solution, The mixture was adjusted to a metal precursor: organic ligand: DMF: formic acid = 1: 1: 246: 521 ratio based on the molar ratio as shown in Table 1 below.
The precursor solution prepared was heated at the crystallization temperature for a certain period of time to synthesize the metal-organic skeleton. In order to shorten the reaction time, the synthesis was performed by dissolving heat or microwave synthesis.
The dissolution heat synthesis was carried out by injecting the precursor solution through a micro-metering pump and passing through a heated zone at a temperature of about 100 ° C. to synthesize a metal-organic skeleton. The thus-synthesized metal- 808-R '.
The microwave synthesis was performed by heating a microwave in a precursor solution at a temperature of 100 ° C. for 3 hours to obtain a metal-organic skeleton. The metal-organic skeleton synthesized by the microwave synthesis method was 'MOF-808-M' .
In the purification process, the metal-organic skeleton synthesized from the reaction solution in which the reaction was completed was thoroughly washed with N, N-dimethylformamide (DMF) and ethanol, and the metal-organic skeleton crystals were recovered by centrifugation Followed by drying at a temperature of 100 ° C.
Table 1 below summarizes the reaction conditions for preparing MOF-808.
(M: L *: DMF: FA **)
(3 days, 100 < 0 > C)
(3 hours, 100 < 0 > C)
MOF-808, a metal-organic skeleton containing zirconium (Zr) as a central metal, is a porous nanostructure having the structural formula of Zr 6 O 4 (OH) 4 (OOCH) 6 (BTC) 2 and has pore sizes of 0.48 nm and 1.82 nm Cage and has a surface area ranging from 1300 to 2000 m 2 / g depending on the method of synthesis of MOF-808 and has various zirconium (Zr) active sites such as metal hydroxides including acid / base functional groups .
The thus-synthesized metal-organic skeleton was analyzed by X-ray diffraction (XRD) analysis of the crystal structure of the powder after drying. As a result, it was found that MOF-808-R and MOF-808- -M are all consistent with the structure of MOF-808 reported in the past.
In addition, the synthesized metal-organic skeleton was confirmed to have a crystal size through a scanning electron microscope.
As a result, as shown in FIGS. 3 and 4, MOF-808-M, which is a metal-organic skeleton synthesized by a microwave synthesis method, had an average crystal size of 500 to 600 nm, In the case of the organic skeleton chain MOF-808-R, it was confirmed that the average particle size was 200 to 400 nm. All of these have a crystal size of 100 nm or more, and thus have excellent crystallinity.
In general, since the active surface of the metal-organic skeleton is mostly present in the pores of the metal-organic skeleton, the surface pore volume is secured so that the organic amine is quickly or easily accessible to the interior of the pores during the deposition or adsorption. Importantly, as described above, the surface area of the synthesized metal-organic skeleton is about 1,300 to 2,000 m 2 / g, which is easy to deposit organic amine.
Production Example 2 relates to a method for producing a metal-organic composite by depositing an organic amine on the metal-organic skeleton prepared in Preparation Example 1, and a method for producing a metal-organic composite by vapor-vacuum deposition Metal-organic complexes were prepared.
As shown in FIG. 5, the production system for producing the metal-organic composite of the present invention is a reactor in which a furnace for depositing organic amine is formed in the pores of the metal-organic skeleton, and a quartz tubular reactor A bulb which is an organic amine feeder which is prepared by heating organic amines in the form of gaseous organic amines and supplies the organic amines to the reactor, a mass flow controller (MFC) which regulates the flow rate of an inert gas such as helium (He) And a supply pipe for supplying an inert gas.
The method for producing the metal-organic composite of the present invention will be described with reference to FIG.
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 Removing existing moisture and impurities to activate. A bulb containing a certain amount of triethylenediamine (TEDA) as an organic amine was treated at room temperature and under reduced pressure (1 × 10 -1 to 1 × 10 -5 torr) to form a bulb and a tree After removing the water present in the ethylenediamine (TEDA), it is connected to a quartz reactor containing the activated metal-organic skeleton. The temperature of the bulb is slowly increased under reduced pressure to control the rate of sublimation of triethylenediamine (TEDA) to control the concentration of triethylenediamine (TEDA) present in the pores of the activated metal-organic skeleton through controlled partial pressure of gaseous triethylenediamine (TEDA) And selectively deposited on the inner pore walls. Finally, when all of the solid triethylenediamine (TEDA) in the bulb is sublimed, the residual gaseous triethylenediamine (TEDA) is removed using helium (He) gas, Organic skeleton chain metal-organic complexes were prepared and the metal-organic complexes thus prepared were designated 'TEDA-MOF-808'.
6 shows X-ray diffraction (X-ray diffraction) before and after deposition of triethylenediamine (TEDA) on a zirconium (Zr) based metal-organic skeleton (MOF-808) ray diffraction (XRD) analysis. FIG. 6 (a) is an X-ray diffraction pattern of the metal-organic skeleton MOF-808 before the deposition of triethylenediamine (TEDA) Ray diffraction pattern of the metal-organic skeleton after deposition of ethylenediamine (TEDA).
As shown in FIG. 6, although the crystallinity of the metal-organic skeleton after the deposition of triethylenediamine (TEDA) was relatively low, the characteristic X-ray diffraction pattern having the same crystal structure as MOF-808 remained .
The metal-organic complexes were prepared in the same manner as in Preparation Example 2, except that the amount of triethylenediamine (TEDA) was changed to 8.4 wt%, 10 wt%, 14 wt%, 22 wt%, and 23 wt% A metal-organic composite on which the weight% triethylenediamine (TEDA) was deposited was prepared.
According to the amount of triethylenediamine (TEDA) deposited on the metal-organic skeleton in Example 1 of the present invention, the deposition amount is indicated in front of '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. 7 shows the nitrogen adsorption isotherms before and after the deposition of triethylenediamine (TEDA) on a zirconium (Zr) based metal-organic skeleton (MOF-808). The BET equation was applied to the measured nitrogen adsorption isotherm - The BET surface area value (cm 3 / g) per weight before and after the deposition of triethylenediamine (TEDA) in the organic skeleton was measured.
FIG. 7A is a nitrogen adsorption curve of the metal-organic skeleton MOF-808 before the deposition of triethylenediamine (TEDA), FIG. 7B is a graph showing the nitrogen adsorption curve of the metal-organic skeleton MOF-808 with 23 wt.% Of triethylenediamine (TEDA) The nitrogen adsorption curve of the skeleton is shown.
7, the BET surface area of the zirconium (Zr) based metal-organic skeleton (MOF-808) was 1733 m 2 / g and the pore volume was about 0.74 ml / The BET surface area and the pore volume of the metal - organic layer on which the diamine (TEDA) was deposited were 1092 m 2 / g and the pore volume was 0.49 ml / g.
The metal-organic complexes prepared in Example 1 were tested for cyanogen chloride (CK) as one of the chemical agents.
The CK breakthrough was carried out using a 4 mm ID glass tube as the adsorption reactor. The charge of the metal-organic complex was 0.1 ml and the charge height was about 8 cm. . In order to evaluate the adsorption performance of the metal-organic complexes, the metal-organic complexes were shaped into pellets and then pulverized to obtain particles having a particle size ranging from 212 μm to 250 μm (60 - 70 mesh) size particles were selected and used.
This metal in the adsorbent - 20 ℃ for 2 hours in the adsorption reactor to charge the organic complex, after passing the opponent moist air humidity of 60% subjected to the pretreatment, mixed chloride cyan (CK) concentration is included as 4,000 mg / m 3 Air (20 ° C, relative humidity 60%) was passed through the adsorption reactor at a linear velocity of 2.65 cm / s to perform a fracture test. The concentration of chlorinated cyanide (CK) is sampled by injecting air into the inlet of the adsorption reactor at the front end and the rear end of the adsorption reactor filled with the metal-organic complex, Concentration (Co), and the result is shown as a function according to the experiment time, and the result is as shown in FIG.
As can be seen from FIG. 8, as the deposition amount of triethylenediamine (TEDA) increases, the time for cyanogen chloride (CK) to stay in the metal-organic complex gradually increases. As a result, the metal- As the amount of organic phosphorus triethylenediamine (TEDA) was increased, the adsorption of cyanogen chloride (CK) was improved and the removal efficiency was increased.
Example 2 shows that the metal-organic skeleton MOF-808 on which triethylenediamine (TEDA) is deposited has a BET surface area of 1610 m 2 / g and 29% by weight in the same manner as in Example 2. And 29 wt% TEDA-MOF-808 and 30 wt% TEDA-MOF-808 deposited with 30 wt% triethylenediamine (TEDA).
For comparison, a breakthrough experiment of cyanogen chloride (CK), one of the chemical agents, was conducted using ASZM-TEDA activated carbon, which is a commercially available product with a surface area of about 1000 m 2 / g, which is conventionally used for military respirators.
As can be seen from FIG. 9, it was confirmed that the TEDA-MOF-808 produced by the vapor-phase vacuum deposition according to the present invention exhibited a maximum three times improvement in the CK removal performance of the conventional ASZM-TEDA activated carbon.
As described above, the metal-organic composite prepared by the vapor-phase vacuum deposition method according to the method for producing a metal-organic composite of the present invention is a tri-organosilane compound having a high decomposition activity in a pore of a metal- It was confirmed that 10 to 30% by weight of ethylene diamine (TEDA) was deposited.
In addition, although the results of measuring the pore size in this specification are not shown in the drawings of the present invention, when the metal-organic composite is produced by using the vapor-vacuum deposition method of the present invention, it is included in the structure of MOF-808 According to the definition of IUPAC (International Union of Pure and Applied Chemistry), the mesoporous volume in the range of 2 to 50 nm is maintained at 50%, so that the active surface, which is the adsorption site for the removal of chemical agents, is activated I could confirm.
Accordingly, the metal-organic composite prepared according to the present invention can minimize the pore volume and surface area of the metal-organic skeleton, which is a porous material, so that the organic amine material can be deposited in an amount of 1 to 30 wt% And 10 to 30 wt% as 10 wt.% Or more. Thus, it has excellent performance in removing chemical agents including cyanide chloride (CK).
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, Is not limited. It will be apparent to those skilled in the art that various changes, substitutions, and alterations can be made hereto without departing from the spirit of the present invention, and it is obvious that those parts easily changeable by those skilled in the art are included in the scope of the present invention.
Claims (11)
And a second step of depositing an organic amine on the pores of the metal-organic skeleton by a vapor-vacuum deposition method to produce a metal-organic composite,
The second step comprises:
The metal-organic skeleton is placed in a reactor and the reactor is heated to a temperature of 110 to 150 ° C under a vacuum-reduced condition of 1 × 10 -1 to 1 × 10 -5 torr to remove moisture present in the pores of the metal-organic skeleton And an activation step of removing the impurities to activate the metal-organic skeleton;
A vacuum drying step of vacuum-depressurizing the organic amine powder to remove excess water present in the organic amine powder;
The dried organic amine is heated to a temperature of 110 to 150 ° C under a reduced pressure of 1 × 10 -1 to 1 × 10 -5 torr to form an organic amine in a gaseous state, And a deposition step of injecting the metal complex into the reactor having the organic skeleton at a constant rate to deposit the pores on the pores of the activated metal-organic skeleton.
Wherein the organic amine is any one selected from the group consisting of triethylenediamine, triethylamine, and pyridine-4-carboxylic acid, or a mixture thereof. ≪ / RTI >
Wherein the vacuum drying step is a step of vacuum-depressurizing the organic amine powder at a temperature of 15 to 30 DEG C to 1 x 10 < -1 > to 1 x 10 < -5 > torr to remove water.
Wherein the metal-organic complex is prepared by depositing 10 to 30% by weight of an organic amine based on 100% by weight of the total metal-organic skeleton in the second step.
In the first step,
Preparing a precursor solution by mixing a metal precursor and an organic ligand together in a solvent;
Heating the prepared precursor solution at a crystallization temperature to synthesize a metal-organic skeleton; And
Organic complex is obtained by purifying the metal-organic skeleton at a predetermined temperature for a predetermined time in the presence of a solvent.
The metal precursor is a compound containing any one metal selected from zirconium (Zr), titanium (Ti) and hafnium (Hf), and is selected from chloride, nitrate, sulfate and acetate compounds Wherein the metal-organic complex is at least one selected from the group consisting of a metal and a metal.
Wherein the organic ligand is selected from the group consisting of benzene dicarboxylic acid, naphthalene dicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, benzene tribenzoic acid, pyridine dicarboxylic acid, bipyridyl dicarboxylic acid, formic acid, Wherein the metal-organic complex is at least one selected from the group consisting of malonic acid, succinic acid, glutamic acid, hexanedioic acid, heptanedioic acid, and cyclohexyldicarboxylic acid.
The solvent may be selected from the group consisting of water, methanol, ethanol, propanol, acetone, N, N-dimethylformamide, N, N-diethylformamide, (N-dimethylacetamide, DMAc), acetonitrile, chlorobenzene, pyridine, N-methyl pyrrolidone (NMP) and tetrahydrofuran Wherein the metal-organic composite is at least one metal-organic composite.
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| KR1020170047896A KR101911173B1 (en) | 2017-04-13 | 2017-04-13 | Method for preparing metal-organic composite of containing 4b group metal elements |
| PCT/KR2018/004338 WO2018190672A1 (en) | 2017-04-13 | 2018-04-13 | Method for producing metal-organic complex comprising group 4b element |
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