KR102538233B1 - Mass manufacturing method of metal-organic polyhedra and metal-organic polyhedra manufactured using the same - Google Patents

Abstract

The present invention relates to a method for mass-producing metal-organic polyhedrons and a metal-organic polyhedron manufactured using the same. One aspect of the present invention relates to a trinuclear metal cluster precursor; organic linking ligand precursors; And a solvent; preparing a reaction mixture comprising; Stirring the reaction mixture at room temperature in a sealed state; heating the reaction mixture stirred at room temperature at a temperature of 30° C. to 100° C. for 10 hours to 20 hours, and then cooling the reaction mixture at room temperature to obtain a reaction product; washing the reaction product with an organic solvent; and performing a cation exchange reaction by adding the washed reaction product to a cation solution.

Description

Mass manufacturing method of metal-organic polyhedron and metal-organic polyhedron manufactured using the same

The present invention relates to a method for mass-producing metal-organic polyhedrons and metal-organic polyhedrons manufactured using the same.

MOF (metal-organic framework) is a porous organic-inorganic high molecular compound formed by combining a central metal with an organic linking ligand. it means. MOFs are being utilized for fabrication of forms with a wide range of functions by simple methods such as self-assembly using metal nodes and organic linkers.

Recently, synthesis of high-order metal-organic materials has been performed using nano-scale building blocks such as metal-organic polyhydra (MOP) by self-assembly, and MOP and research on the synthesis of cage-based structures using MOFs as building blocks for porous materials.

As described above, metal-organic polyhedrons are actively studied based on their porous properties and excellent stability, but most studies are conducted on a small scale and mass synthesis methods have not yet been reported. In particular, synthesis on a large scale has a limitation in that purity is lowered as impurities are generated.

Therefore, it is necessary to develop a synthesis process of metal-organic polyhedra capable of securing high purity and yield on a large scale.

The above background art is possessed or acquired by the inventor in the process of deriving the disclosure of the present application, and cannot necessarily be said to be known art disclosed to the general public prior to the present application.

The present invention is to solve the above problems, and an object of the present invention is to provide a method for mass-producing metal-organic polyhedrons capable of securing high yield and purity during mass synthesis.

However, the problem to be solved by the present invention is not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

One aspect of the present invention, a trinuclear metal cluster precursor; organic linking ligand precursors; And a solvent; preparing a reaction mixture comprising; Stirring the reaction mixture at room temperature in a sealed state; heating the reaction mixture stirred at room temperature at a temperature of 30° C. to 100° C. for 10 hours to 20 hours, and then cooling the reaction mixture at room temperature to obtain a reaction product; washing the reaction product with an organic solvent; and performing a cation exchange reaction by adding the washed reaction product to a cation solution.

According to one embodiment, the trinuclear metal cluster precursor may include one or more selected from the group consisting of Cp ₂ ZrCl ₂ , Cp ₂ ZrH ₂ , Cp ₂ ZrClH and Cp ₂ ZrBr ₂ .

According to one embodiment, the organic linking ligand precursor may include a compound represented by Formula 1 below.

[Formula 1]

Here, R ¹ to R ⁴ are, respectively, hydrogen, halogen, a hydroxy group (-OH), an alkyl group having 1 to 50 carbon atoms, an alkenyl group having 2 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, a carboxyl group (-COOH), An ether group (-CH ₂ OR, R is an alkyl group having 1 to 50 carbon atoms or an alkenyl group having 2 to 30 carbon atoms), an amine group (-NRR', R and R' are hydrogen or an alkyl group having 1 to 50 carbon atoms, respectively) , nitro group (-NO ₂ ), sulfonic acid group (-SO ₃ H), azide group (-N ₃ ), alcohol group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, heterocyclo having 3 to 30 carbon atoms It is an alkyl group, a C5-C30 aryl group, or a C5-C30 heteroaryl group.

According to one embodiment, the solvent is an organic solvent; or a mixed solvent containing an organic solvent and distilled water; wherein the organic solvent is N,N-dimethylacetamide (DMA), N,N'-dimethylformamide (DMF), N,N-diethylform Amides (DEF), alcohols of 1 to 10 carbon atoms, ethylene glycol, glycerol, cyclohexanol, ketones of 2 to 10 carbon atoms, acetonitrile, dioxane, chlorobenzene, pyridine, N-methylpyrrolidone (NMP), sulfonyl containing at least one selected from forran, tetrahydrofuran (THF), gamma-butyrolactone, alkylamines having 1 to 12 carbon atoms, hexane, heptane, octane, toluene, acetone, methyl ethyl ketone, chloroform and dichloromethane can

According to one embodiment, the molar ratio of the trinuclear metal cluster precursor and the organic linking ligand precursor may be 1:0.1 to 1:1.

According to one embodiment, washing the reaction product with an organic solvent; may be performed 3 to 8 times.

According to one embodiment, the cationic solution is dimethylammonium chloride, diethylammonium chloride, bis(3-chloro-2-hydroxypropyl)dimethylammonium chloride, bis(2,3-epoxypropyl)dimethylammonium chloride, bis (2,3-dihydroxypropyl) at least one selected from the group consisting of dimethylammonium chloride, acryloxyethyl trimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, diallyldiethylammonium chloride and diallyldimethylammonium chloride may include

According to one embodiment, the concentration of the cation solution may be 0.01 M to 1 M.

According to one embodiment, performing the cation exchange; may be performed 1 to 5 times.

According to one embodiment, performing the cation exchange reaction; Thereafter, washing and drying the reaction product in which the cation exchange reaction has been performed; further comprising, wherein the washing is performed three times using at least one organic solvent selected from the group consisting of chloroform, dichloromethane, and acetone. It may be performed up to 8 times.

According to one embodiment, the yield of the metal-organic polyhedron may be 50% or more.

According to one embodiment, the final production amount of the metal-organic polyhedron may be 90 mg to 3,000 mg.

Another aspect of the present invention provides a metal-organic polyhedron prepared by the above preparation method and comprising a compound represented by Formula 2 below.

[Formula 2]

는,

이고,here, above

Is,

ego,

R is an organic linking ligand.

Another aspect of the present invention provides a gas adsorption material comprising the metal-organic polyhedron.

The method for mass-producing metal-organic polyhedrons according to the present invention has an effect of mass-producing metal-organic polyhedrons in high yield by controlling the solvent and temperature during the solvothermal reaction.

The metal-organic polyhedron mass-produced according to the present invention is structurally and chemically stable, has high porosity, and exhibits excellent gas collection performance, and thus has the advantage of being applicable to sensors, catalysts, drug delivery, adsorption, and separation membranes.

1 shows the structure of a metal-organic polyhedron (UMOP-1-H) prepared according to an embodiment of the present invention.
2 is an X-ray diffraction pattern of a metal-organic polyhedron prepared according to an embodiment of the present invention.
3 is a pore size distribution graph of metal-organic polyhedrons prepared according to an embodiment of the present invention.
4 is a nitrogen adsorption graph (77K) of a metal-organic polyhedron (UMOP-1-H) prepared according to an embodiment of the present invention.
5 is a carbon dioxide adsorption graph (273K, 298K) of a metal-organic polyhedron (UMOP-1-H) prepared according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes can be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents or substitutes to the embodiments are included within the scope of rights.

Terms used in the examples are used only for descriptive purposes and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

In addition, in the description with reference to the accompanying drawings, the same reference numerals are given to the same components regardless of reference numerals, and overlapping descriptions thereof will be omitted. In describing the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description will be omitted.

In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the corresponding component is not limited by the term. When an element is described as being “connected,” “coupled to,” or “connected” to another element, that element may be directly connected or connected to the other element, but there may be another element between the elements. It should be understood that may be "connected", "coupled" or "connected".

Components included in one embodiment and components having common functions will be described using the same names in other embodiments. Unless stated to the contrary, descriptions described in one embodiment may be applied to other embodiments, and detailed descriptions will be omitted to the extent of overlap.

One aspect of the present invention, a trinuclear metal cluster precursor; organic linking ligand precursors; And a solvent; preparing a reaction mixture comprising; Stirring the reaction mixture at room temperature in a sealed state; heating the reaction mixture stirred at room temperature at a temperature of 30° C. to 100° C. for 10 hours to 20 hours, and then cooling the reaction mixture at room temperature to obtain a reaction product; washing the reaction product with an organic solvent; and performing a cation exchange reaction by adding the washed reaction product to a cation solution.

The mass production method of metal-organic polyhedrons according to the present invention has an effect of producing metal-organic polyhedrons in high yield on a large scale using solvothermal reaction.

Hereinafter, a method for mass-producing metal-organic polyhedrons according to the present invention will be described step by step in detail.

Reaction mixture preparation step

In the method for mass-producing metal-organic polyhedrons according to the present invention, the first step is to prepare a reaction mixture.

The metal-organic polyhedron prepared according to the present invention includes trinuclear metal clusters and organic linking ligands connecting them.

In order to prepare the metal-organic polyhedron, first, a trinuclear metal cluster precursor as a reactant; organic linking ligand precursors; Prepare a reaction mixture comprising; and a solvent.

The trinuclear metal cluster precursor and the organic linking ligand precursor are added to and dissolved in the solvent in a predetermined amount. As a container used for the dissolution, a round bottom flask can be used.

According to one embodiment, the trinuclear metal cluster precursor may contain at least one selected from the group consisting of sulfates, nitrates, hydrochlorides, carbonates, halogen salts, phosphates, hydrides, and hydroxides of metal metallocenes. .

According to one embodiment, the trinuclear metal cluster precursor may include a trinuclear zirconium cluster precursor.

According to one embodiment, the trinuclear metal cluster precursor may include one or more selected from the group consisting of Cp ₂ ZrCl ₂ , Cp ₂ ZrH ₂ , Cp ₂ ZrClH and Cp ₂ ZrBr ₂ .

The trinuclear metal cluster precursor forms a trinuclear metal cluster included in a metal-organic polyhedron, and is connected by an organic linking ligand to form a polyhedral network.

According to one embodiment, the trinuclear metal cluster may include Cp ₃ Zr ₃ O(OH) ₃ (RCO ₂ ) ₃ .

According to one embodiment, the organic linking ligand precursor may include a compound represented by Formula 1 below.

[Formula 1]

Here, R ¹ to R ⁴ are, respectively, hydrogen, halogen, a hydroxy group (-OH), an alkyl group having 1 to 50 carbon atoms, an alkenyl group having 2 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, a carboxyl group (-COOH), An ether group (-CH ₂ OR, R is an alkyl group having 1 to 50 carbon atoms or an alkenyl group having 2 to 30 carbon atoms), an amine group (-NRR', R and R' are hydrogen or an alkyl group having 1 to 50 carbon atoms, respectively) , nitro group (-NO ₂ ), sulfonic acid group (-SO ₃ H), azide group (-N ₃ ), alcohol group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, heterocyclo having 3 to 30 carbon atoms It is an alkyl group, a C5-C30 aryl group, or a C5-C30 heteroaryl group.

Preferably, R ¹ to R ⁴ are each selected from hydrogen, halogen, a hydroxy group (-OH), an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carboxyl group (- COOH), an ether group (-CH ₂ OR, R is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms), an amine group (-NRR', R and R' are each hydrogen or 1 to 10 carbon atoms alkyl group), a nitro group (-NO ₂ ), a sulfonic acid group (-SO ₃ H), an azide group (-N ₃ ), or an alcohol group having 1 to 10 carbon atoms.

The organic linking ligand precursor forms an organic linking ligand included in the metal-organic polyhedron, and forms a polyhedral network by connecting trinuclear metal clusters of the metal-organic polyhedron.

According to one embodiment, the organic linking ligand precursor may include terephthalic acid.

According to one embodiment, the solvent is an organic solvent; or a mixed solvent containing an organic solvent and distilled water; wherein the organic solvent is N,N-dimethylacetamide (DMA), N,N'-dimethylformamide (DMF), N,N-diethylform Amides (DEF), alcohols of 1 to 10 carbon atoms, ethylene glycol, glycerol, cyclohexanol, ketones of 2 to 10 carbon atoms, acetonitrile, dioxane, chlorobenzene, pyridine, N-methylpyrrolidone (NMP), sulfonyl containing at least one selected from forran, tetrahydrofuran (THF), gamma-butyrolactone, alkylamines having 1 to 12 carbon atoms, hexane, heptane, octane, toluene, acetone, methyl ethyl ketone, chloroform and dichloromethane can

The organic solvent may act to induce self-assembly of metal-organic polyhedrons.

According to one embodiment, the volume ratio of the organic solvent and the distilled water may be 1:0.1 to 1:1.

Preferably, the volume ratio of the organic solvent and the distilled water may be 1:0.1 to 1:0.1, more preferably, 1:0.1 to 1:0.3, and even more preferably, 1 : 0.1 to 1: may be 0.2.

According to one embodiment, the molar ratio of the trinuclear metal cluster precursor and the organic linking ligand precursor may be 1:0.1 to 1:1.

Preferably, the molar ratio of the trinuclear metal cluster precursor and the organic linking ligand precursor may be 1: 0.3 to 1: 0.8, more preferably, 1: 0.4 to 1: 0.6.

Stirring the reaction mixture at room temperature

In the mass production method of the metal-organic polyhedron according to the present invention, the next step is to stir the prepared reaction mixture at room temperature in a sealed state.

At this time, the stirring may be performed until the color of the reaction mixture becomes transparent, which may be for sufficiently dissolving the trinuclear metal cluster precursor and the organic linking ligand precursor in a solvent.

Obtaining a Reaction Product

This step is a step of obtaining a reaction product by reacting the reaction mixture stirred at room temperature through a solvothermal reaction.

The reaction mixture stirred at room temperature may be heated at a temperature of 30 °C to 100 °C for 10 hours to 20 hours.

Preferably, it can be heated at a temperature of 50 °C to 100 °C for 10 hours to 15 hours, more preferably, it can be heated at a temperature of 50 °C to 80 °C for 12 hours to 15 hours.

If, when heating at a temperature less than the above temperature range or for a time less than the above time range, the reaction may not proceed sufficiently and the yield of the product may be lowered.

On the other hand, when heating at a temperature exceeding the above temperature range or for a time exceeding the above range, process efficiency may decrease, and a different crystal structure or non-crystalline impurities may be formed.

The heating may be performed using a hot plate, an oil bath, an oven or a water bath, but is not limited thereto.

For example, heating using a hot plate and an oil bath can improve the yield of a product on a large scale by allowing the synthesis reaction to proceed sufficiently at a uniform temperature.

A reaction product is finally obtained by cooling the product formed through heating of the reaction mixture at room temperature.

According to one embodiment, the cooling may be performed for 1 hour to 5 hours.

Reaction product washing step

The reaction product obtained above is washed with an organic solvent.

The washing may be performed to remove impurities prior to the cation exchange step.

According to one embodiment, washing the reaction product with an organic solvent; may be performed 3 to 8 times.

Preferably, the washing step may be performed 4 to 7 times.

If the number of times the washing step is performed is less than the above range, impurities may not be sufficiently removed, resulting in a decrease in purity, and if the number exceeds the above range, process efficiency may be reduced.

According to one embodiment, the organic solvent used in the washing is N,N-dimethylacetamide (DMA), N,N'-dimethylformamide (DMF), N,N-diethylformamide (DEF), Alcohols having 1 to 10 carbon atoms, ethylene glycol, glycerol, cyclohexanol, ketones having 2 to 10 carbon atoms, acetonitrile, dioxane, chlorobenzene, pyridine, N-methylpyrrolidone (NMP), sulfolane, tetrahydrofuran (THF), gamma-butyrolactone, alkylamine having 1 to 12 carbon atoms, hexane, heptane, octane, toluene, acetone, methyl ethyl ketone, chloroform, and dichloromethane.

Steps for carrying out the cation exchange reaction

The washed reaction product may be added to a cation solution to proceed with a cation exchange reaction.

The cation exchange reaction may be performed for the purpose of increasing the porosity of the metal-organic polyhedron.

The method for mass-producing metal-organic polyhedrons according to the present invention is characterized in that porosity of finally obtained metal-organic polyhedrons can be increased through a cation exchange reaction using a specific cation solution.

According to one embodiment, the cationic solution is dimethylammonium chloride, diethylammonium chloride, bis(3-chloro-2-hydroxypropyl)dimethylammonium chloride, bis(2,3-epoxypropyl)dimethylammonium chloride, bis (2,3-dihydroxypropyl) at least one selected from the group consisting of dimethylammonium chloride, acryloxyethyl trimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, diallyldiethylammonium chloride and diallyldimethylammonium chloride may include

The cation solution may be a cation solution capable of increasing the porosity of the metal-organic polyhedron.

The metal-organic polyhedron obtained through the cation exchange reaction has a characteristic in that gas trapping performance improves as porosity increases.

That is, the metal-organic polyhedron prepared by the manufacturing method according to the present invention not only has excellent structural and chemical stability, but also has high porosity, so it exhibits excellent gas collection performance and can be used in sensors, catalysts, drug delivery, adsorption, separation membranes, etc. It may have applicable advantages.

According to one embodiment, the concentration of the cation solution may be 0.01 M to 1 M.

Preferably, the concentration of the cationic solution may be 0.05 M to 1 M, more preferably, 0.05 M to 0.5 M, and even more preferably, 0.08 M to 0.2 M. there is.

If the concentration of the cation solution is less than the above range, the cation exchange reaction may not be sufficiently performed and the porosity of the metal-organic polyhedron may be reduced. If the concentration exceeds the above range, structural stability may be deteriorated.

According to one embodiment, performing the cation exchange; may be performed 1 to 5 times.

Preferably, performing the cation exchange; may be performed 3 to 5 times. This may be to secure high porosity through sufficient exchange of cations.

According to one embodiment, performing the cation exchange reaction; Thereafter, washing and drying the reaction product in which the cation exchange reaction has been performed; further comprising, wherein the washing is performed three times using at least one organic solvent selected from the group consisting of chloroform, dichloromethane, and acetone. It may be performed up to 8 times.

The washing and drying steps may be performed to remove impurities present in the reaction product.

According to one embodiment, the yield of the metal-organic polyhedron may be 50% or more.

Preferably, the yield of the metal-organic polyhedron may be 55% or more, more preferably 60% or more, and still more preferably 65% or more.

The method for producing metal-organic polyhedrons according to the present invention has an effect of securing a high yield even in mass production.

According to one embodiment, the final production amount of the metal-organic polyhedron may be 90 mg to 3,000 mg.

According to one embodiment, the final production amount of the metal-organic polyhedron may be 500 mg to 3,000 mg.

According to one embodiment, the metal-organic polyhedron may include an inner cavity having a size ranging from 15 Å to 20 Å.

An inner cavity of the metal-organic polyhedron may be in a range optimized for adsorbing gases such as nitrogen and carbon dioxide.

Another aspect of the present invention provides a metal-organic polyhedron prepared by the above preparation method and comprising a compound represented by Formula 2 below.

[Formula 2]

는,

이고,here, above

Is,

ego,

R is an organic linking ligand.

According to one embodiment, the organic coupling ligand may include a compound represented by Formula 3 below.

[Formula 3]

Here, M is a linking site with a metal of a trinuclear metal cluster, and R ¹ to R ⁴ are, respectively, hydrogen, halogen, a hydroxyl group (-OH), an alkyl group having 1 to 50 carbon atoms, an alkenyl group having 2 to 50 carbon atoms, An alkoxyl group having 1 to 50 carbon atoms, a carboxyl group (-COOH), an ether group (-CH ₂ OR, R is an alkyl group having 1 to 50 carbon atoms or an alkenyl group having 2 to 30 carbon atoms), an amine group (-NRR', R and R ' is, respectively, hydrogen or an alkyl group having 1 to 50 carbon atoms), a nitro group (-NO ₂ ), a sulfonic acid group (-SO ₃ H), an azide group (-N ₃ ), an alcohol group having 1 to 30 carbon atoms, and a carbon number 3 to a cycloalkyl group having 30 carbon atoms, a heterocycloalkyl group having 3 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, or a heteroaryl group having 5 to 30 carbon atoms.

Another aspect of the present invention provides a gas adsorption material comprising the metal-organic polyhedron.

The gas adsorbent may adsorb one gas selected from the group consisting of hydrocarbons, moisture, volatile organic compounds, nitrogen, and carbon dioxide.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

<Example> Synthesis of metal-organic polyhedron (UMOP-1-H)

Zirconocene dichloride (Cp ₂ ZrCl ₂ ) and terephthalic acid (H ₂ BDC) were weighed into a 500 mL round bottom flask, and dissolved using dimethylacetamide (DMA) and distilled water.

After sealing the round bottom flask using a rubber septum, the lysate was stirred at room temperature until the color of the lysate became transparent.

After stirring, the mixture was reacted at 60 °C for 12 hours using a hot plate and an oil bath, and then cooled at room temperature.

Then, it was washed 6 times with dimethylacetamide, cation exchanged 4 times with 0.1 M dimethylammonium cation solution prepared from dimethylamine hydrochloride and chloroform, washed 4 times with chloroform, and dried.

The content and yield of the reactants used in the synthesis are shown in Table 1.

Example 1
(10x) Example 2
(50x) Example 3
(100x) Example 4
(200x) Example 5
(500x) Cp ₂ ZrCl ₂ 175 mg
(0.6 mmol) 857mg
(3 mmol) 1753.9 mg
(6 mmol) 3507.7mg
(12 mmol) 8.7693g
(30 mmol) _H2BDC 50 mg
(0.3 mmol) 250mg
(1.5 mmol) 90mg
(3 mmol) 1297.2mg
(6 mmol) 2.4920g
(15 mmol) DMA 10 mL 50 mL 100 mL 50 mL 125 mL H ₂ O 1.5 mL 7.5 mL 15 mL 7.5 mL 18.75 mL yield
(Yield) 90.6mg
(52.8%) 503.3mg
(58.6%) 1161.7mg
(68%) 2268.6mg
(66%) 3.3559g
(39%)

Referring to Table 1, when the method for preparing metal-organic polyhedrons according to the present invention is used, when the amount of reactants used in conventional synthesis is increased by 10 to 500 times, metal-organic polyhedrons (UMOP-1-H ) was successfully synthesized.

In particular, it can be seen that the yield was secured up to 68% when the scale was increased 100 times.

<Experimental Example 1> Confirmation of structural characteristics of metal-organic polyhedra

In order to confirm the structure of the synthesized metal-organic polyhedron, the finally synthesized powder in Example 5 was analyzed using X-ray diffraction. In addition, the pore size distribution of the synthesized metal-organic polyhedra was measured.

1 shows the structure of a metal-organic polyhedron (UMOP-1-H) prepared according to an embodiment of the present invention.

2 is an X-ray diffraction pattern of a metal-organic polyhedron prepared according to an embodiment of the present invention.

Referring to FIG. 2 , it can be confirmed that UMOP-1-H was successfully synthesized by the manufacturing method according to the present invention.

3 is a pore size distribution graph of metal-organic polyhedrons prepared according to an embodiment of the present invention.

Referring to FIG. 3, it can be seen that the UMOP-1-H manufactured by the manufacturing method according to the present invention has the largest number of pores having a size of 15 Å to 20 Å.

<Experimental Example 2> Confirmation of Gas Adsorption Characteristics of Metal-Organic Polyhedrons

In order to confirm the gas trapping performance of the prepared metal-organic polyhedron, the adsorption amount of nitrogen and carbon dioxide of the metal-organic polyhedron (UMOP-1-H) finally obtained in Example 5 was measured.

4 is a nitrogen adsorption graph (77K) of a metal-organic polyhedron (UMOP-1-H) prepared according to an embodiment of the present invention.

5 is a carbon dioxide adsorption graph (273K, 298K) of a metal-organic polyhedron (UMOP-1-H) prepared according to an embodiment of the present invention.

Referring to FIGS. 4 and 5 , it can be confirmed that the metal-organic polyhedron (UMOP-1-H) prepared according to an embodiment of the present invention has excellent nitrogen and carbon dioxide adsorption characteristics.

As described above, although the embodiments have been described with limited drawings, those skilled in the art can apply various technical modifications and variations based on the above. For example, the described techniques may be performed in an order different from the method described, and/or components of the described system, structure, device, circuit, etc. may be combined or combined in a different form than the method described, or other components may be used. Or even if it is replaced or substituted by equivalents, appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents of the claims are within the scope of the following claims.

Claims (14)

trinuclear metal cluster precursor; organic linking ligand precursors; And a solvent; preparing a reaction mixture comprising;
Stirring the reaction mixture at room temperature in a sealed state;
heating the reaction mixture stirred at room temperature at a temperature of 30° C. to 100° C. for 10 hours to 20 hours, and then cooling the reaction mixture at room temperature to obtain a reaction product;
washing the reaction product with an organic solvent; and
Adding the washed reaction product to a cation solution to perform a cation exchange reaction;
A method for mass production of metal-organic polyhedrons.
According to claim 1,
The trinuclear metal cluster precursor,
Cp ₂ ZrCl ₂ , Cp ₂ ZrH ₂ , Cp ₂ ZrClH and Cp ₂ ZrBr ₂ To include one or more selected from the group consisting of,
A method for mass production of metal-organic polyhedrons.
According to claim 1,
The organic linking ligand precursor,
To include a compound represented by Formula 1,
Method for Mass Production of Metal-Organic Polyhedrons:
[Formula 1]

Here, R ¹ to R ⁴ are, respectively, hydrogen, halogen, a hydroxy group (-OH), an alkyl group having 1 to 50 carbon atoms, an alkenyl group having 2 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, a carboxyl group (-COOH), An ether group (-CH ₂ OR, R is an alkyl group having 1 to 50 carbon atoms or an alkenyl group having 2 to 30 carbon atoms), an amine group (-NRR', R and R' are hydrogen or an alkyl group having 1 to 50 carbon atoms, respectively) , nitro group (-NO ₂ ), sulfonic acid group (-SO ₃ H), azide group (-N ₃ ), alcohol group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, heterocyclo having 3 to 30 carbon atoms It is an alkyl group, a C5-C30 aryl group, or a C5-C30 heteroaryl group.
According to claim 1,
The solvent is
organic solvent; Or a mixed solvent containing an organic solvent and distilled water;
The organic solvent is N,N-dimethylacetamide (DMA), N,N'-dimethylformamide (DMF), N,N-diethylformamide (DEF), alcohol having 1 to 10 carbon atoms, ethylene glycol, Glycerol, cyclohexanol, ketones having 2 to 10 carbon atoms, acetonitrile, dioxane, chlorobenzene, pyridine, N-methylpyrrolidone (NMP), sulfolane, tetrahydrofuran (THF), gamma-butyrolactone, It contains at least one selected from alkylamines having 1 to 12 carbon atoms, hexane, heptane, octane, toluene, acetone, methyl ethyl ketone, chloroform and dichloromethane,
A method for mass production of metal-organic polyhedrons.
According to claim 1,
The molar ratio of the trinuclear metal cluster precursor and the organic linking ligand precursor,
1: 0.1 to 1: 1,
A method for mass production of metal-organic polyhedrons.
According to claim 1,
Washing the reaction product with an organic solvent;
Which is performed 3 to 8 times,
A method for mass production of metal-organic polyhedrons.
According to claim 1,
The cation solution,
Dimethylammonium Chloride, Diethylammonium Chloride, Bis(3-chloro-2-hydroxypropyl)dimethylammonium Chloride, Bis(2,3-epoxypropyl)dimethylammonium Chloride, Bis(2,3-dihydroxypropyl)dimethyl containing at least one selected from the group consisting of ammonium chloride, acryloxyethyl trimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, diallyldiethylammonium chloride and diallyldimethylammonium chloride,
Mass production method of metal-organic polyhedra.
According to claim 1,
The concentration of the cation solution is,
0.01 M to 1 M,
A method for mass production of metal-organic polyhedrons.
According to claim 1,
Performing the cation exchange; is,
Which is performed 1 to 5 times,
A method for mass production of metal-organic polyhedrons.
According to claim 1,
performing the cation exchange reaction; Since the,
Further comprising washing and drying the reaction product in which the cation exchange reaction has been performed,
The washing is performed 3 to 8 times using at least one organic solvent selected from the group consisting of chloroform, dichloromethane and acetone.
A method for mass production of metal-organic polyhedrons.
According to claim 1,
The yield of the metal-organic polyhedron is 50% or more,
A method for mass production of metal-organic polyhedrons.
According to claim 1,
The final production amount of the metal-organic polyhedron is 90 mg to 3,000 mg,
A method for mass production of metal-organic polyhedrons.
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