KR20190074374A - Mothod for preparation of metal-organic-framework and metal-organic-framework prepared by the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a metal organic framework having excellent performance in adsorption/separation of carbon dioxide, and a metal organic framework manufactured thereby. The method for manufacturing a metal organic framework of the present invention comprises the steps of: preparing an organic linker solution; adding a glycidyl-based compound to the organic linker solution; and adding a metal precursor to a resultant of the above step to allow reaction to occur.

Description

METHOD FOR PREPARING METAL ORGANIC FRAMEWORK AND METAL-ORGANIC-FRAMEWORK PREPARED BY THE SAME Technical Field [1] The present invention relates to a metal organic skeleton,

The present invention relates to a method for producing metal-organic-frameworks (MOF) and a metal organic skeleton produced thereby, and it is possible to produce metal organic skeletons of various sizes, By preparing the metal organic skeleton, it is possible to improve the dispersibility in mixing with the medium in the production of the gas / liquid separation membrane, and thus to form the metal organic skeleton having various sizes of sub-micron size, And a metal organic skeleton produced thereby.

Metal-organic framework (MOF) is a porous material in which metal ions or clusters and organic ligands are connected by coordination bonds to form a three-dimensional structure.

Basically, MOF not only has a very large surface area, but also has an open pore structure, so that it can move a large amount of molecules or solvents compared to other known porous materials. One of the outstanding values of MOF, represented by a large surface area material, is that it can change the frame or the constituent of the formed central metal-organic ligand, as well as the pore size (volume).

The pore size and physical / chemical properties of this material can be easily controlled by selection of suitable metal atoms and organic linkages. Because of this particular nature, the potential applications for gas storage and / or absorption, catalysis, and separation membranes have been demonstrated.

However, such a metal organic skeleton is produced in a micrometer size, and when applied to a separation membrane, there is a problem that the dispersibility is poor.

Accordingly, there is a demand for a method of manufacturing a metal organic skeleton that can be freely controlled in size, such as the size of a micrometer unit, the size of a nanometer unit, and the like, while still having a simple process.

[Patent Document 1] Korean Patent Registration No. 10-108283 [Patent Document 2] Korean Patent Publication No. 10-2015-0117535

DISCLOSURE Technical Problem The present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a metal organic skeleton having various sizes, It is an object of the present invention to provide a method for producing a metal organic skeleton in which the dispersibility is improved when mixed with a medium at the time of production, and thereby a mixed medium film or a thin film coating can be properly performed.

A specific object of the present invention is to provide a catalyst having superior adsorption / separation and catalytic properties for a specific molecule compared to a MOF having the same crystal structure by using an organic linker having an amine group. Particularly, And a method for manufacturing a small MOF.

It is another object of the present invention to provide a metal organic skeleton having a nanometer size, which is excellent in the function of adsorbing / separating carbon dioxide produced by the method for producing a metal organic skeleton according to the present invention.

In order to accomplish the above object, a method for producing a metal organic skeleton of the present invention may include the following steps:

(1) dissolving an organic linker having an amine group in a solvent to prepare an organic linker solution;

(2) adding a glycidyl compound to the organic linker solution of step (1); And

(3) adding a metal precursor to the result of step (2) and reacting.

In the above step (1), the organic linker having an amine group may be selected from the group consisting of 2-aminoterephthalic acid, 4-aminophthalic acid, 4-aminoisophthalic acid, 5-aminoisophthalic acid, 2,5-diaminoterephthalic acid, 4,4'-stilbene dicarboxylic acid, 5-cyano-1,3-benzenedicarboxylic acid, 2-methylimidazole and 4,4 ', 4 " , 4,6-triyl-tribenzoic acid, and the like.

In the step (1), the solvent is selected from methanol, ethanol, butanol, dimethylformamide, diethylformamide, dimethylsulfoxide, deionized water, N-methyl-2-pyrrolidone (NMP) and dimethylacetamide More than one kind can be used every day.

In the step (1), the content of the organic linker in the organic linker solution may be 0.3 to 10 wt%.

In the step (2), the glycidyl compound may be glycidyl diglycidyl ether, diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , Polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, polyethylene glycol-epoxide, epoxy (2-hydroxy) propoxypolyethylene glycol glycidyl ether and dodecyloxypolyethylene glycol glycidyl Dicyclohexylcarbodiimide and diallyl ether.

In the step (2), the molar ratio of the organic linker: glycidyl compound may be 1: 0.01 to 1.0.

In the step (2), adding the glycidyl compound to the organic linker solution may further include performing the reaction at 40 to 90 ° C for 5 to 10 hours.

In the step (3), the molar ratio of the organic linker to the metal precursor may be 40:60 to 90:10.

In the step (3), the reaction may be carried out at 80 to 200 ° C for 5 hours to 96 hours.

The metal precursor may be at least one selected from the group consisting of a titanium precursor, an iron precursor, an aluminum precursor, a copper precursor, and a magnesium precursor.

The titanium precursor may be at least one selected from the group consisting of titanium butoxide, titanium isopropoxide, titanium chloride, and titanium propoxide.

The iron precursor tetrachloro ferrite (FeCl _4), ferric chloride (FeCl _3), citric acid, ferric _{(FeC 6 H 5 O 7)} , citric acid iron (III) hydrate _{(FeC 6 H 5 O 7 ·} nH 2 O ), Ferrous sulfate heptahydrate (FeSO ₄ .H ₂ O), iron oxalate dihydrate (FeC ₂ O ₄ .H ₂ O), iron acetylacetonate (Fe (C ₅ H ₇ O ₂ ) ₃ ) At least one selected from the group consisting of ferric dihydrate (FePO ₄ .H ₂ O), ferric hydroxide (FeO (OH)), ferric nitrate, and iron acetate.

The aluminum precursor may be at least one selected from the group consisting of aluminum hydroxide, aluminum acetate, alumina trihydrate and aluminum chloride.

The copper precursor may be at least one selected from the group consisting of copper acetate, copper acetate hydrate, copper acetylacetonate, copper isobutyrate, copper carbonate, copper chloride, copper chloride hydrate, copper ethyl acetoacetate, copper 2-ethylhexanoate, copper fluoride, Copper hexachloroacetylacetonate, copper hexafluoroacetylacetonate hydrate, copper methoxide, copper neodecanoate, copper nitrate copper hydrate, copper nitrate, copper perchlorate, copper sulfate, copper sulfate hydrate, copper tartrate copper hydrate , Copper triflouro acetylacetonate, copper triflouromethane sulfonate, and tetraamine copper sulfate hydrate.

The magnesium precursor may be at least one selected from the group consisting of magnesium nitrate hexahydrate, magnesium sulfate, magnesium chloride, and magnesium acetate.

In the step (3), the metal precursor is a titanium precursor,

In the step (1), the content of the organic linker in the organic linker solution is 3 to 7% by weight,

In the step (2), the molar ratio of the organic linker: glycidyl compound is 1: 0.01 to 0.5,

In step (3), the molar ratio of the organic linker to the metal precursor is 70:30 to 90:10, and the reaction in step (3) may be performed at 100 to 200 ° C for 2 to 4 days. have.

In the step (3), the metal precursor is an iron precursor,

In the step (1), the content of the organic linker in the organic linker solution is 0.3 to 1.0 wt%

In the step (2), the molar ratio of the organic linker: glycidyl compound is 1: 0.05 to 1.0,

In step (3), the molar ratio of the organic linker to the metal precursor is 60:40 to 40:60, and the reaction in step (3) may be performed at 80 to 150 ° C for 5 to 20 hours have.

The metal organic skeleton according to the present invention may be a metal organic skeleton having a nanometer size produced by the method of producing the metal organic skeleton according to the present invention.

According to the present invention, by using an organic linker having an amine group, it is possible to obtain excellent adsorption / separation and catalytic properties for a specific molecule compared to a MOF having the same crystal structure. In particular, a metal organic skeleton having excellent performance for carbon dioxide adsorption / .

In addition, according to the method for producing a metal organic skeleton of the present invention, metal organic skeletons of various sizes can be produced, and a nano-sized metal organic skeleton can be prepared thereby to prepare a gas / The dispersibility is improved, and thus the effect of the mixing medium film or the thin film coating can be achieved.

1 is an SEM image of titanium organic skeleton particles of Examples 1 to 3 and Comparative Example 1. Fig.
FIG. 2 is a graph showing the results of X-ray diffraction analysis of titanium organic skeleton particles of Examples 1 to 3 and Comparative Example 1. FIG.
3 is an SEM image of titanium organic skeleton particles of Comparative Example 2. Fig.
4 is an SEM image of the titanium organic skeleton particles of Comparative Example 3. Fig.
5 is an SEM image of the iron organic skeleton particles of Examples 4 to 5 and Comparative Example 4. Fig.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to achieve them, will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art. It is to be understood by one of ordinary skill in the art that the scope of the invention is to be fully understood and the invention is only defined by the scope of the claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

Hereinafter, a method for producing a metal organic skeleton according to the present invention and a metal organic skeleton produced thereby will be described in detail.

The method of making a metal organic skeleton according to the present invention may comprise the following steps:

(1) dissolving an organic linker having an amine group in a solvent to prepare an organic linker solution;

(2) adding a glycidyl compound to the organic linker solution of step (1); And

(3) adding a metal precursor to the result of step (2) and reacting.

In the above step (1), the organic linker having an amine group may be selected from the group consisting of 2-aminoterephthalic acid, 4-aminophthalic acid, 4-aminoisophthalic acid, 5-aminoisophthalic acid, 2,5-diaminoterephthalic acid, 4,4'-stilbene dicarboxylic acid, 5-cyano-1,3-benzenedicarboxylic acid, 2-methylimidazole and 4,4 ', 4 " , 4,6-triyl-tribenzoic acid. In the case of an organic linker having an amine group, it is excellent in thermal stability, and the structure of MOF using various metal precursors due to the amine group is controlled So that the produced MOF has excellent performance for carbon dioxide adsorption / separation.

In the step (1), the solvent is selected from methanol, ethanol, butanol, dimethylformamide, diethylformamide, dimethylsulfoxide, deionized water, N-methyl-2-pyrrolidone (NMP) and dimethylacetamide In the case of producing a metal organic skeleton containing titanium, preferably, the solvent may be a mixture of dimethylformamide and methanol, and the mixing ratio by weight of dimethylformamide and methanol is 9 to 5: 1. Further, when a metal organic skeleton containing iron is produced, methanol may be used alone as the solvent.

In the step (1), the content of the organic linker in the organic linker solution may be 0.3 to 10 wt%. If the amount of the organic linker is less than 0.3 wt%, it is difficult to obtain the final product, There is such a problem that the organic linker is not dissolved in the solvent, which is not preferable.

In the step (2), the glycidyl compound may be glycidyl diglycidyl ether, diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , Polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, polyethylene glycol-epoxide, epoxy (2-hydroxy) propoxypolyethylene glycol glycidyl ether and dodecyloxypolyethylene glycol glycidyl Dicyclohexylcarbodiimide and diallyl ether.

In the above step (2), it is preferable that the molar ratio of the organic linker: glycidyl compound is 1: 0.01 to 1.0. If the molar ratio of the glycidyl compound is less than 0.01, If it exceeds 1.0, the metal organic skeleton may not be produced, which is not preferable.

In step (2), the method may further include adding a glycidyl compound to the organic linker solution, and then performing the reaction at 40 to 90 ° C for 5 to 10 hours. If the amount is outside the above range, Or a sufficient primary reaction does not proceed, which makes it difficult to control the shape and size of the metal organic skeleton, which is not preferable.

In step (3), it is preferable that the molar ratio of the organic linker: metal precursor is 40:60 to 90:10, or 60:40 to 80:20. If the ratio is out of the above range, the remaining unreacted organic linker By-products are generated by the metal precursor or excessive organic linkers remain, which is not preferable.

In the step (3), the reaction may be carried out at 80 to 200 ° C for 5 to 96 hours. At a temperature lower than the above temperature and a short reaction time, the metal organic skeleton is not produced. The crystal structure may collapse upon reaction for a longer period of time.

The metal precursor may be at least one selected from the group consisting of a titanium precursor, an iron precursor, an aluminum precursor, a copper precursor, and a magnesium precursor, but is not limited thereto.

The titanium precursor may be at least one selected from the group consisting of titanium butoxide, titanium isopropoxide, titanium chloride, and titanium propoxide.

The iron precursor tetrachloro ferrite (FeCl _4), ferric chloride (FeCl _3), citric acid, ferric _{(FeC 6 H 5 O 7)} , citric acid iron (III) hydrate _{(FeC 6 H 5 O 7 ·} nH 2 O ), Ferrous sulfate heptahydrate (FeSO ₄ .H ₂ O), iron oxalate dihydrate (FeC ₂ O ₄ .H ₂ O), iron acetylacetonate (Fe (C ₅ H ₇ O ₂ ) ₃ ) (FePO ₄ .H ₂ O), ferric hydroxide (FeO (OH)), ferric nitrate, and iron acetate, and preferably at least one selected from the group consisting of tetrachloroferrite FeCl ₄ ) or ferric chloride (FeCl ₃ ).

The aluminum precursor may be at least one selected from the group consisting of aluminum hydroxide, aluminum acetate, alumina trihydrate and aluminum chloride.

The copper precursor may be at least one selected from the group consisting of copper acetate, copper acetate hydrate, copper acetylacetonate, copper isobutyrate, copper carbonate, copper chloride, copper chloride hydrate, copper ethyl acetoacetate, copper 2-ethylhexanoate, copper fluoride, Copper hexachloroacetylacetonate, copper hexafluoroacetylacetonate hydrate, copper methoxide, copper neodecanoate, copper nitrate copper hydrate, copper nitrate, copper perchlorate, copper sulfate, copper sulfate hydrate, copper tartrate copper hydrate , Copper triflouro acetylacetonate, copper triflouromethane sulfonate, and tetraamine copper sulfate hydrate.

The magnesium precursor may be at least one selected from the group consisting of magnesium nitrate hexahydrate, magnesium sulfate, magnesium chloride, and magnesium acetate.

In the step (3), when the metal precursor is a titanium precursor,

In step (1), the content of the organic linker in the organic linker solution is 3 to 10% by weight, preferably 5 to 7% by weight. When the amount is less than 3% by weight, the organic linker is too small, , And if it exceeds 10% by weight, the organic linker is not dissolved in the solvent and the like, which is not preferable;

In the above step (2), the molar ratio of the organic linker: glycidyl compound is preferably 1: 0.01 to 0.5, more preferably 1: 0.1 to 0.5, wherein the molar ratio of the glycidyl compound is less than 0.01 It is not preferable because control of the backside size is not easy, and if it exceeds 1.0, the metal organic skeleton may not be produced, which is not preferable;

In step (3), it is preferable that the molar ratio of the organic linker: metal precursor is 70:30 to 90:10. If the metal linker is out of the above range, Lt; / RTI > of the linker is not preferred;

The reaction in the step (3) may be carried out preferably at 100 to 200 캜, more preferably at 140 to 160 캜, preferably for 2 to 4 days, more preferably for 60 to 75 hours , A metal organic skeleton can not be produced at a temperature lower than the above-mentioned temperature and a short reaction time, and the crystal structure may collapse at a temperature higher than the above-mentioned temperature for a longer time.

In the step (3), when the metal precursor is a titanium precursor, the reaction scheme of the titanium organic skeleton to be produced may be represented by the following reaction formula (1).

[Reaction Scheme 1]

In the step (3), when the metal precursor is an iron precursor,

(1) In the step, the amount of the organic linker, the linker of the organic solution is 0.3~ 1.0% by weight is preferred, 0.5 to 0.8 together more preferably from wt.%, Less than 0.3 wt% when the organic linker is too It is difficult to obtain the final product, and if it exceeds 1.0% by weight, the organic linker is not dissolved in the solvent, which is not preferable;

In the step (2), the molar ratio of the organic linker to the glycidyl compound is preferably 1: 0.05 to 1.0, more preferably 1: 0.5 to 1.0, wherein the molar ratio of the glycidyl compound is less than 0.01 It is not preferable because control of the backside size is not easy, and if it exceeds 1.0, the metal organic skeleton may not be produced, which is not preferable;

In step (3), the molar ratio of the organic linker to the metal precursor may be 60:40 to 40:60. If the metal precursor is out of the above range, byproducts may be generated by residual metal precursors not reacted with the organic linker, Undesirable due to the presence of an organic linker ;

The reaction in the step (3) may be carried out preferably at 80 to 150 캜, more preferably at 90 to 110 캜, preferably for 5 to 20 hours, more preferably for 7 to 12 hours However, the metal organic skeleton is not produced at a temperature lower than the above-mentioned temperature and a short reaction time, and the crystal structure may collapse at a temperature higher than the above temperature for a longer time, which is not preferable.

In the above step (3), when the metal precursor is an iron precursor, the reaction formula of the produced iron organic skeleton may be represented by the following reaction formula (2).

[Reaction Scheme 2]

The metal organic skeleton according to the present invention can be manufactured in a nanometer size by the method of producing the metal organic skeleton according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Examples and Comparative Examples

[material]

2-aminoterephthalic acid, dimethylformamide, methanol, polyethylene glycol diglycidyl ether, titanium butoxide, ferric chloride and terephthalic acid used in the following examples and comparative examples were purchased from Sigma-Aldrich and used without purification Respectively.

Examples 1 to 3 and Comparative Example 1

2-aminoterephthalic acid (NH ₂ -BDC) was dissolved in DMF / MeOH (9/1, v / v) as a solvent as an organic linker and then poly (ethylene glycol) diglycidyl Diester (PEGDE) was added, and then stirred at 60 占 폚 for 7 hours. Subsequently, titanium butoxide as a titanium precursor was added to the resulting NH ₂ -BDC-PEGDE solution, stirred for 30 minutes, and then reacted at 150 ° C for 72 hours using an autoclave to obtain a titanium organic skeleton. Are shown in Table 1 below. SEM images of the titanium organic skeleton are shown in FIG. 1, and the results of X-ray diffraction analysis showing the crystal structure of the skeleton are shown in FIG.

Comparative Example 2

2-aminoterephthalic acid (NH ₂ -BDC), poly (ethylene glycol) diglycidyl ether (PEGDE) as an organic linker and titanium butoxide as a titanium precursor were added to the solvent at once, stirred for 30 minutes, And the reaction was carried out at 150 ° C for 24 hours to obtain a titanium organic skeleton. The particle size of the titanium organic skeleton is shown in Table 1 below, and an SEM image is shown in FIG.

Comparative Example 3

A titanium organic skeleton was obtained in the same manner as in Example 1, except that terephthalic acid was used as the organic linker, and the particle sizes of the titanium organic skeleton were also shown in Table 1 below.

Titanium precursor
(g) NH ₂ -BDC (g) Terephthalic acid PEGDED (g) NH ₂ -BDC:
The molar ratio of PEGDE Solvent (ml) MOF
Particle size
(diameter) Example 1 One 2.5 - 3.50 1: 0.5 DMF / MeOH 45/5 100 nm Example 2 One 2.5 - 1.80 1: 0.25 DMF / MeOH 45/5 300 nm Example 3 One 2.5 - 0.86 1: 0.13 DMF / MeOH 45/5 700 nm Comparative Example 1 One 2.5 - 0 1: 0 DMF / MeOH 45/5 1.5 탆 Comparative Example 2 One 2.5 - 3.50 1: 0.5 DMF / MeOH 45/5 Inability to control Comparative Example 3 One - 2.5 3.50 1: 0.5 DMF / MeOH 45/5 1 탆

As shown in Table 1 and FIG. 1, the spherical nanometer-sized titanium organic skeleton was prepared in Examples 1 to 3, whereas the comparative example 1 shows that the titanium organic skeleton having an octahedral structure of 1 μm or more was prepared. Further, as shown in FIG. 1, it can be seen that in Examples 1 to 3, the size of the metal organic skeleton can be controlled according to the molar ratio of the organic linker and the glycidyl compound. Referring to FIG. 2, it can be seen that Examples 1 to 3 and Comparative Example 1 are titanium organic structure structures.

However, in the case of Comparative Example 2 in which the organic linker, the glycidyl compound and the titanium precursor were simultaneously added and mixed, since the epoxy group of the poly (ethylene glycol) diglycidyl ether interacts with the amine functional group of the organic linker, Control of the size and structure of the skeleton was not possible, and large particles of micron size were produced.

On the other hand, in Examples 1 to 3, after the epoxy group of the poly (ethylene glycol) diglycidyl ether reacts with the amine functional group of the organic linker first and then the metal precursor is added, the size and structure can be controlled. Sub-micron particles were produced.

In addition, as shown in Table 1 and FIG. 4, in Comparative Example 3 where a phthalate compound free of an amine functional group was used as an organic linker, particles having a ten-sided structure were produced. However, Unlike the linker, the size of the prepared particles was about 1 탆, and the size was not controlled by the nano-sized small particles.

Examples 4 to 5 and Comparative Example 4

(Ethylene glycol) diglycidyl ether (PEGDE) was added after dissolving ₂ -aminoterephthalic acid (NH ₂ -BDC) in methanol (MeOH) as an organic linker as shown in the following Table 2, Then, the mixture was stirred at 60 ° C for 7 hours. Then, ferric chloride (FeCl ₃ ) was added as an iron precursor to the resulting NH ₂ -BDC-PEGDE solution, stirred for 30 minutes, and reacted at 100 ° C. for 10 hours using an autoclave to obtain an iron organic skeleton , And an SEM image thereof is shown in Fig.

iron
Precursor
(g)
NH ₂ -BDC (g)
PEGDED (g)
NH ₂ -BDC: mole ratio of PEGDE
Solvent (ml)
MOF
Particle size Length diameter Example 4 0.6 0.4 0.56 1: 1 MeOH 60 300 nm 100 nm Example 5 0.6 0.4 0.23 1.0.5 MeOH 60 700 nm 200 nm Comparative Example 4 0.6 0.4 0 1: 0 MeOH 60 1.5 탆 400 nm

As shown in Fig. 5, the iron organic skeletons of Examples 4 to 5 were bar-shaped iron organic skeletons, and iron organic skeletons having a length and diameter of nanometer size were prepared. In Comparative Example 4, It can be seen that a micrometer-sized iron organic skeleton was prepared. Further, as shown in FIG. 5, it can be seen that in Examples 4 to 5, the size of the metal organic skeleton can be controlled according to the molar ratio of the organic linker and the glycidyl compound.

Claims (18)

A process for preparing a metal organic skeleton comprising the steps of:
(1) dissolving an organic linker having an amine group in a solvent to prepare an organic linker solution;
(2) adding a glycidyl compound to the organic linker solution of step (1); And
(3) adding a metal precursor to the result of step (2) and reacting. The method according to claim 1,
In the above step (1), the organic linker having an amine group may be selected from the group consisting of 2-aminoterephthalic acid, 4-aminophthalic acid, 4-aminoisophthalic acid, 5-aminoisophthalic acid, 2,5-diaminoterephthalic acid, 4,4'-stilbene dicarboxylic acid, 5-cyano-1,3-benzenedicarboxylic acid, 2-methylimidazole and 4,4 ', 4 " , 4,6-triyl-tribenzoic acid, and the like. The method according to claim 1,
In the step (1), the solvent is selected from methanol, ethanol, butanol, dimethylformamide, diethylformamide, dimethylsulfoxide, deionized water, N-methyl-2-pyrrolidone (NMP) and dimethylacetamide Lt; RTI ID = 0.0 > 1, < / RTI > The method according to claim 1,
In the step (1), the content of the organic linker in the organic linker solution is 0.3 to 10% by weight. The method according to claim 1,
In the step (2), the glycidyl compound may be glycidyl diglycidyl ether, diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , Polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, polyethylene glycol-epoxide, epoxy (2-hydroxy) propoxypolyethylene glycol glycidyl ether and dodecyloxypolyethylene glycol glycidyl Wherein the metal organic skeleton is at least one selected from the group consisting of dibutyl ether and dibutyl ether. The method according to claim 1,
In the step (2), the molar ratio of the organic linker: glycidyl compound is 1: 0.01 to 1.0. The method according to claim 1,
The method for producing a metal organic skeleton according to claim 1, further comprising, in the step (2), adding a glycidyl compound to the organic linker solution and then conducting a reaction at 40 to 90 ° C for 5 to 10 hours. The method according to claim 1,
In the step (3), the molar ratio of the organic linker: the metal precursor is 40:60 to 90:10. The method according to claim 1,
In the step (3), the reaction is performed at 80 to 200 ° C for 5 hours to 96 hours. The method according to claim 1,
Wherein the metal precursor is at least one selected from the group consisting of a titanium precursor, an iron precursor, an aluminum precursor, a copper precursor, and a magnesium precursor. 11. The method of claim 10,
Wherein the titanium precursor is at least one selected from the group consisting of titanium butoxide, titanium isopropoxide, titanium chloride, and titanium propoxide. 11. The method of claim 10,
The iron precursor tetrachloro ferrite (FeCl _4), ferric chloride (FeCl _3), citric acid, ferric _{(FeC 6 H 5 O 7)} , citric acid iron (III) hydrate _{(FeC 6 H 5 O 7 ·} nH 2 O ), Ferrous sulfate heptahydrate (FeSO ₄ .H ₂ O), iron oxalate dihydrate (FeC ₂ O ₄ .H ₂ O), iron acetylacetonate (Fe (C ₅ H ₇ O ₂ ) ₃ ) Wherein the metal organic skeleton is at least one selected from the group consisting of ferric dihydrate (FePO ₄ .H ₂ O), ferric hydroxide (FeO (OH)), ferric nitrate and iron acetate. 11. The method of claim 10,
Wherein the aluminum precursor is at least one selected from the group consisting of aluminum hydroxide, aluminum acetate, alumina trihydrate, and aluminum chloride. 11. The method of claim 10,
The copper precursor may be at least one selected from the group consisting of copper acetate, copper acetate hydrate, copper acetylacetonate, copper isobutyrate, copper carbonate, copper chloride, copper chloride hydrate, copper ethyl acetoacetate, copper 2-ethylhexanoate, copper fluoride, Copper hexachloroacetylacetonate, copper hexafluoroacetylacetonate hydrate, copper methoxide, copper neodecanoate, copper nitrate copper hydrate, copper nitrate, copper perchlorate, copper sulfate, copper sulfate hydrate, copper tartrate copper hydrate , Copper triflouro acetylacetonate, copper triflouromethane sulfonate, and tetraamine copper sulfate hydrate. 2. A method for producing a metal organic skeleton according to claim 1, 11. The method of claim 10,
Wherein the magnesium precursor is at least one selected from the group consisting of magnesium nitrate hexahydrate, magnesium sulfate, magnesium chloride, and magnesium acetate. The method according to claim 1,
Wherein the metal precursor in the step (3) is a titanium precursor,
In the step (1), the content of the organic linker in the organic linker solution is 3 to 7% by weight,
In the step (2), the molar ratio of the organic linker: glycidyl compound is 1: 0.01 to 0.5,
In the step (3), the molar ratio of the organic linker: the metal precursor is 70:30 to 90:10, and the reaction in the step (3) is performed at 100-200 ° C for 2 days to 4 days. A method for producing an organic skeleton. The method according to claim 1,
Wherein the metal precursor in the step (3) is an iron precursor,
In the step (1), the content of the organic linker in the organic linker solution is 0.3 to 1.0 wt%
In the step (2), the molar ratio of the organic linker: glycidyl compound is 1: 0.05 to 1.0,
In the step (3), the molar ratio of the organic linker to the metal precursor is 60:40 to 40:60, and the reaction in the step (3) is performed at a temperature of 80 to 150 ° C for 5 to 20 hours A method for producing an organic skeleton. 18. A nanoscale-sized metal organic framework according to any one of claims 1 to 17, which is produced by a process for the preparation of a metal-organic framework.

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