KR102358489B1 - Method of preparing sparsely pillared organic-inorganic hybrid compound - Google Patents

Abstract

Disclosed is a method for preparing an organic-inorganic hybrid compound having a low-density columnar structure. The disclosed method for producing an organic-inorganic hybrid compound having a low-density columnar structure includes the steps of preparing a compound having a gibbsite structure by a method other than hydrothermal synthesis using a trivalent metal cation source, an alkali imparting agent, and a first solvent (S10), and and preparing an organic-inorganic hybrid compound by a method other than hydrothermal synthesis using the compound having the gibbsite structure, a divalent metal cation source, dicarboxylic acid, and a second solvent (S20).

Description

Method of preparing sparsely pillared organic-inorganic hybrid compound of low-density columnar structure

Disclosed is a method for preparing an organic-inorganic hybrid compound having a low-density columnar structure. More specifically, a method for preparing an organic-inorganic hybrid compound having a low-density columnar structure having excellent structural stability while having extremely low column density as dicarboxylic acid ions are inserted in a columnar form between inorganic material layers having a layered structure is disclosed.

Although gibbsite (γ-Al(OH) ₃ ) or other layered materials (eg, hydrotalcite), an experiment of intercalation (intercalation: insertion) of various organic materials has been previously conducted (Prior Art Document 1 and 2), when organic matter is inserted between the layers, it generally tends to fill up with few vacancies. Therefore, in the case of the conventional organic-inorganic hybrid compound, there is not much room to effectively use the interlayer space for adsorption of other materials or gas collection.

Conventionally, activated carbon or aluminum oxide powder has been used as a material used to adsorb harmful substances or store various gases in factories and homes (see Prior Art Documents 3 and 4).

Activated carbon has a large specific surface area and micro-pores, so it is widely used to remove harmful gases such as odors or to purify water. However, activated carbon has a problem in that the size of pores is too fine, the total pore volume is small, there is a limit to the material that can be adsorbed, and the gas adsorption efficiency is sharply decreased in a high humidity situation (Prior Art Document 4) Reference).

In the case of aluminum oxide, it has an excellent property of adsorbing harmful substances on the surface of the powder. However, aluminum oxide (or a similar hydrotalcite structure material) has a problem in that the specific surface area capable of adsorbing other materials and the total volume of pores are relatively small (see Prior Art Documents 4 and 5).

1. A. V. Besserguenev et al., Chem. Mater. 1997, 9, 241-247 2. J. R. Rees et al., J. Solid State Chem. 2015, 224, 36 3. https://en.wikipedia.org/wiki/Activated_carbon 4. C. Nedez et al., Langmuir 1996, 12, 3927-3931 5. M. E. Perez-Bernal et al., J. Solid State Chem. 2009, 182, 1593-1601

One embodiment of the present invention provides a method for preparing an organic-inorganic hybrid compound having a low-density columnar structure having an extremely low columnar density and excellent structural stability.

One aspect of the present invention is

preparing a compound having a gibbsite structure by a method other than hydrothermal synthesis using a trivalent metal cation source, an alkali imparting agent, and a first solvent (S10); and

The organic-inorganic hybrid compound comprising the step (S20) of preparing an organic-inorganic hybrid compound by a method other than hydrothermal synthesis using the compound of the gibbsite structure, a divalent metal cation source, dicarboxylic acid, and a second solvent A manufacturing method is provided.

The trivalent metal cation source may be a source of trivalent metal cations including Al ³⁺ , Fe ³⁺ , Cr ³⁺ , B ³⁺ , Ga ³⁺ , In ³⁺ , Y ³⁺ , or a combination thereof. .

The alkali-imparting agent is NaOH, LiOH, KOH, LiBH ₄ , NaBH ₄ , KBH ₄ , LiH, NaH, LiAlH ₄ , NaAlH ₄ , KAlH ₄ , ( i -Bu ₂ AlH) ₂ , LiHCO ₃ , NaHCO ₃ , KHCO _{3 ,} Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , NH ₄ OH, or a combination thereof.

The first solvent or the second solvent may include water.

The compound having the gibbsite structure may appear amorphous in the XRD analysis result.

The divalent metal cation source is 2 including Zn ²⁺ , Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ or a combination thereof It may be a source of valent metal cations.

The dicarboxylic acid is terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, unde Candiic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethyl glutaric acid, maleic acid, acetylenedicarboxylic acid, glutaconic acid, 2-disenedioic acid, traumatic acid, muconic acid, Glutinic acid, citraconic acid, mesaconic acid, itaconic acid, tartronic acid, mesosalic acid, malic acid, tartaric acid, oxaloacetic acid, aspartic acid, glutamic acid, diaminopimelic acid, saccharic acid and 2,6-naphthalene dicarboxylic acids or combinations thereof.

The organic-inorganic hybrid compound has the ability to adsorb and store volatile organic compounds, liquid environmental hazardous substances, polycyclic aromatic hydrocarbons, exhaust gas-based environmental pollutants, greenhouse gases, radioactive substances, hazardous heavy metals, toxic chemicals, or hydrogen gas. can

The step (S10) comprises dissolving the trivalent metal cation source in the first solvent to prepare a first metal salt solution (S10-1), dissolving the alkali imparting agent in the first solvent to prepare an alkali solution It may include preparing (S10-2), and synthesizing a compound having a gibbsite structure by contacting the first metal salt solution and the alkali solution at room temperature (S10-3).

The step (S20) is a step (S20-1) of obtaining a mixture by mixing the compound of the gibbsite structure, the divalent metal cation source, the dicarboxylic acid and the second solvent (S20-1), and 50~ After heating to 90 ℃ may include the step of synthesizing the organic-inorganic hybrid compound by maintaining it for 3 to 72 hours (S20-2).

Another aspect of the present invention is

two inorganic material layers extending in one direction to face each other; and

An organic material layer disposed between the two inorganic material layers,

Each inorganic layer has a gibbsite structure in which a divalent cation metal is doped at an octahedral site,

The organic material layer is chemically bonded to each of the inorganic material layers to provide an organic-inorganic hybrid compound including a plurality of pillars connecting the two inorganic material layers to each other.

The organic material layer may include a plurality of pillar portions disposed between the two inorganic material layers to extend in a direction crossing the extending direction.

The divalent cation may coordinate with all six oxygen atoms present around the octahedral site, and may also bind with anions present in the organic layer by electrostatic attraction.

The organic material layer may form a hydrogen bond with each of the inorganic material layers.

The organic-inorganic hybrid compound may be represented by the following Chemical Formula 1:

[Formula 1]

[M ^(II) _x M ^(III) (OH) ₃ ] ^2x+ (A ^2- ) _x

wherein M ^(II) is a divalent metal cation, M ^(III) is a trivalent metal cation, A ² - is a dicarboxylic acid ion, and 0 < x < 0.2.

In Formula 1, 0.03 ≤ x ≤ 0.150.

The M ^(II) may include Zn ²⁺ , Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , or a combination thereof. .

The M ^(III) may include Al ³⁺ , Fe ³⁺ , Cr ³⁺ , B ³⁺ , Ga ³⁺ , In ³⁺ , Y ³⁺ , or a combination thereof.

A ² - is terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, unde Candiic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethyl glutaric acid, maleic acid, acetylenedicarboxylic acid, glutaconic acid, 2-disenedioic acid, traumatic acid, muconic acid, Glutinic acid, citraconic acid, mesaconic acid, itaconic acid, tartronic acid, mesosalic acid, malic acid, tartaric acid, oxaloacetic acid, aspartic acid, glutamic acid, diaminopimelic acid, saccharic acid and 2,6-naphthalene It may contain a divalent anion derived from a dicarboxylic acid or a combination thereof.

The organic-inorganic hybrid compound may have a column density of 1/(360 Å ² ) to 1/(55 Å ² ) represented by Equation 1 below:

[Equation 1]

Pillar density = total number of pillars in a single organic layer/planar surface area of a single inorganic layer.

The organic-inorganic hybrid compound may have a column density of 1/(306 Å ² ) to 1/(74 Å ² ) represented by Equation 1 above.

In the organic material layer, an average distance between adjacent pillars may be 8.0 to 20.6 Å.

An average distance between adjacent pillars in the organic material layer may be 9.2 to 18.8 Å.

The organic-inorganic hybrid compound according to an embodiment of the present invention has the following advantages.

(1) Structural stability is excellent while the column density is extremely low.

(2) A lot of empty spaces are formed between the inorganic layers, so that a pore volume and a surface area are increased.

(3) The amount of metal (e.g., Zn) doped to the octahedral site of the inorganic layer having a gibbsite structure because the column density is remarkably low and an organic material acting as a column (e.g., terephthalate ion ( The amount of terephthalate)) is much lower.

(4) The distance between the pillars is long (typically, when the nominal value of x in Formula 1 is 0.0625 or less, the distance becomes 14 Angstrom or more) 　 Even relatively large molecules (for example, benzo (a) pyrene, known as a carcinogen) It enters well between the pillars and is adsorbed.

(5) For the same volume, the weight can be reduced as the amount of constituent material is small. The intrinsic density of the material is 2.42 g/cm ³ in pure gibbsite without columnar structure, but 0.99 g when M ^(II) = Zn ²⁺ , M ^(III) = Al ³⁺ , A ^2- = terephthalate ion, x = 0.0625 /cm ³ makes it lighter. When A is terephthalic acid, if the density of the columnar compound is expressed as a function of x, it becomes (0.833 + 2.45x)g/cm ³ .

(6) The increase in empty space not only increases the amount of material adsorbed, but also makes the movement of molecules within the empty space much easier and faster, so the time required for all desired molecular reactions (adsorption, storage, equilibrium state, etc.) is greatly reduced .

(7) Compared to other porous materials such as zeolite and metal-organic frameworks (including metal organic frameworks, covalent organic frameworks), hydrothermal- or solvo-thermal synthesis, etc. It does not require a process that requires a lot of energy, and industrial mass production is possible at a low price.

(8) Carbon nanotube and graphene oxide have also been studied a lot recently for the purpose of adsorption or storage, but compared to them, they are significantly advantageous in terms of price-performance ratio and mass production possibility.

(9) Compared to all other prior technologies, it can be manufactured under low energy and low pressure conditions, so it is possible to not only reduce manufacturing costs but also secure safety.

(10) No other surfactants or catalysts are required in the manufacturing process.

(11) Al, Zn, which are representative metal components among constituent materials, and metals that can replace them (Mn, Co, Ni, Cu, Mg, Ca, Sr, Ba and Fe, Cr, B, Ga, In, Y ) does not belong to harmful heavy metals (Cd, Hg, Pb, etc.). In addition, terephthalic acid is an inexpensive and harmless organic substance that is already widely used for industrial purposes worldwide. In particular, Zn, which is the most representative metal doped for pillar formation, is also inexpensive among metals. Li, 　Co, Ni, etc., which are raw materials used in lithium ion batteries, are already expensive and the price is continuously rising as demand is expected to increase in the future. Therefore, it is possible to implement the present invention without using these materials at all.

1A to 1C are schematic views schematically illustrating an example of an organic-inorganic hybrid compound according to an embodiment of the present invention.
FIG. 2 is a diagram illustrating, in the form of pixels, an area in which molecules introduced from the outside in the organic-inorganic hybrid compound according to an embodiment of the present invention cannot be accessed due to spatial exclusion.
3 is an XRD graph of gibbsite prepared by a method other than the hydrothermal synthesis method in Example 1.
4 is an XRD graph of gibbsite prepared by hydrothermal synthesis in Comparative Example 3.
5 is an XRD graph of the gibbsite crystal (γ-Al(OH) ₃ ) disclosed in Reference 8.
6 is an XRD graph of hydrotalcite disclosed in Reference 9;
7A to 7E are XRD graphs of organic-inorganic hybrid compounds prepared by a method other than hydrothermal synthesis using gibbsite prepared by a method other than hydrothermal synthesis in Examples 1 to 5;
8A and 8B are XRD graphs of final compounds prepared by a method other than hydrothermal synthesis using gibbsite prepared by a method other than hydrothermal synthesis in Comparative Examples 1 and 2;
FIG. 8c is an XRD graph of the final compound prepared by a non-hydrothermal method using gibbsite prepared by hydrothermal synthesis in Comparative Example 3. FIG.
FIG. 8d is an XRD graph of the final compound prepared by hydrothermal synthesis using gibbsite prepared by a method other than hydrothermal synthesis in Comparative Example 4. FIG.
9 is a real photograph of an organic-inorganic hybrid compound powder prepared by a method other than hydrothermal synthesis using gibbsite prepared by a method other than hydrothermal synthesis in Example 1;
10A and 10B are SEM images of organic-inorganic hybrid compounds prepared by a method other than hydrothermal synthesis using gibbsite prepared by a method other than hydrothermal synthesis in Examples 1 and 2, respectively.
11 is a graph showing the adsorption test results of benzene on activated carbon and organic-inorganic hybrid compounds prepared in Examples 1 to 5 and Comparative Examples 1 to 2;
12A to 12D are graphs showing the adsorption test results of various volatile harmful substances on activated carbon and organic-inorganic hybrid compounds prepared in Examples 1 and 2;
13 is a schematic diagram showing the molecular structure of benzo (a) pyrene and the aspect of benzo (a) pyrene adsorbed to the organic-inorganic hybrid compound prepared in Example 1. FIG.
14 is a schematic diagram of cesium (Cs) adsorbed to the organic-inorganic hybrid compound prepared in Example 1. FIG.
15 is a schematic diagram of lead (Pb) adsorbed to the organic-inorganic hybrid compound prepared in Example 1. FIG.
16 is a graph showing the amount of hydrogen stored in the organic-inorganic hybrid compound prepared in Example 1.

Hereinafter, a method for preparing an organic-inorganic hybrid compound having a low-density columnar structure according to an embodiment of the present invention will be described in detail.

As used herein, the term “gibbsite structure” refers to all structures that are different from, but similar to, gibbsite (Al(OH) ₃ ) structure itself, or gibbsite and components (particularly, trivalent metal cations).

In addition, in the present specification, "planar surface area" means the surface area of the smooth surface (ie, PS of FIG. 1A ) observed above the organic-inorganic hybrid compound.

Also, in the present specification, "the thickness (d) of a single layer of the organic-inorganic hybrid compound" means a distance between the thickness centers of two inorganic layers adjacent to each other.

Also, in the present specification, "hydrothermal synthesis method" refers to a method of synthesizing at a temperature condition exceeding the boiling point of a solvent. Therefore, when water is used as a solvent, a method of synthesizing at a temperature exceeding 100° C., the boiling point of water, is referred to as “hydrothermal synthesis”. In the hydrothermal synthesis method, since a closed vessel (autoclave) is used to apply a temperature exceeding the boiling point of the solvent, the atmospheric pressure in the reaction vessel is generally higher than 1 atm.

Also, in the present specification, "a method other than a hydrothermal synthesis method" means a method for synthesizing at a temperature condition below the boiling point of a solvent. Therefore, when water is used as a solvent, a method of synthesizing at a temperature condition of 100° C. or less, which is the boiling point of water, is referred to as “a method other than a hydrothermal synthesis method”.

Also, in this specification, "room temperature" means 10 ~ 40 ℃ (eg, 25 ℃).

In addition, in the present specification, "nominal value" or "nominal molar ratio" means a molar ratio of components used in the preparation of the organic-inorganic hybrid compound having a low-density columnar structure.

Also, in the present specification, the term “actual molar ratio” refers to a molar ratio of components contained in the finally prepared organic-inorganic hybrid compound having a low-density columnar structure.

The method for producing an organic-inorganic hybrid compound according to an embodiment of the present invention comprises the steps of preparing a compound having a gibbsite structure by a method other than hydrothermal synthesis using a trivalent metal cation source, an alkali imparting agent, and a first solvent (S10) ) and using the compound of the gibbsite structure, a divalent metal cation source, dicarboxylic acid, and a second solvent to prepare an organic-inorganic hybrid compound by a method other than hydrothermal synthesis (S20).

The trivalent metal cation source may be a source of trivalent metal cations including Al ³⁺ , Fe ³⁺ , Cr ³⁺ , B ³⁺ , Ga ³⁺ , In ³⁺ , Y ³⁺ , or a combination thereof. .

The divalent metal cation source is 2 including Zn ²⁺ , Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ or a combination thereof It may be a source of valent metal cations.

The alkali-imparting agent is NaOH, LiOH, KOH, LiBH ₄ , NaBH ₄ , KBH ₄ , LiH, NaH, LiAlH ₄ , NaAlH ₄ , KAlH ₄ , ( i -Bu ₂ AlH) ₂ , LiHCO ₃ , NaHCO ₃ , KHCO _{3 ,} Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , NH ₄ OH, or a combination thereof.

The first solvent or the second solvent may include water.

The compound of the gibbsite structure may appear amorphous in the XRD analysis result because crystals do not grow. On the other hand, when the compound of the gibbsite structure is prepared by hydrothermal synthesis instead of the step (S10), the prepared compound of the gibbsite structure has strong crystallinity. Since the dicarboxylic acid and the divalent metal cation do not easily intercalate in the compound, the organic-inorganic hybrid compound 100 having a low-density columnar structure having the above-described configuration cannot be obtained (see Comparative Example 3 and FIG. 8c ).

The meaning of “amorphous gibbsite” in step (S10) is as follows: That is, the structure of the compound obtained in step (S10) is locally gibbsite (Al(OH) ₃ )-like structure (eg For example, if you look at Al atoms, they form a hexagonal honeycomb structure, and 6 oxygen atoms form an octahedron around the vacancy in the middle), so there is no problem in calling it a gibbsite structure. However, it is "amorphous" from the point of view of XRD, which explores the crystal structure. In other words, the leftmost main peak (about 18.2° position) representing the XRD of the gibbsite crystal disappeared because the crystal of the gibbsite particle did not grow to a sufficient size, and no other distinct peak was seen, so it was called "amorphous".

The dicarboxylic acid is terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, unde Candiic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethyl glutaric acid, maleic acid, acetylenedicarboxylic acid, glutaconic acid, 2-disenedioic acid, traumatic acid, muconic acid, Glutinic acid, citraconic acid, mesaconic acid, itaconic acid, tartronic acid, mesosalic acid, malic acid, tartaric acid, oxaloacetic acid, aspartic acid, glutamic acid, diaminopimelic acid, saccharic acid and 2,6-naphthalene dicarboxylic acids.

In the step (S10), a first metal salt solution is prepared by dissolving the trivalent metal cation source in the first solvent (S10-1), and an alkali solution is prepared by dissolving the alkali imparting agent in the first solvent (S10-2), and contacting the first metal salt solution and the alkali solution at room temperature to synthesize a compound having a gibbsite structure (S10-3).

In addition, in the step (S10), after the step (S10-3), the steps of solid-liquid separation of the prepared compound of the gibbsite structure (S10-4), washing the separated compound of the gibbsite structure ( S10-5) and drying the washed compound of the gibbsite structure (S10-6) may be further included.

The step (S20) is a step of obtaining a mixture by mixing the compound of the gibbsite structure, the divalent metal cation source, the dicarboxylic acid and the second solvent (S20-1), and 50 to 90 of the mixture It may include a step (S20-2) of synthesizing an organic-inorganic hybrid compound by heating to ℃ and maintaining it for 3 to 72 hours.

After all, the step (S20) is a step of intercalating a small amount of a divalent metal cation and dicarboxylic acid into the compound of the gibbsite structure prepared in the step (S10), and in this process, the compound of the gibbsite structure Since the basic structure of is not changed, the inorganic layer of the organic-inorganic hybrid compound synthesized in step (S20) still has a gibbsite structure. In addition, the intercalated dicarboxylic acid ion promotes crystal growth while bonding with the inorganic layer, thus clearly showing the gibbsite crystal structure with increased interlayer spacing on the XRD.

Unlike in the step (S20), when the organic-inorganic hybrid compound is prepared by a hydrothermal synthesis method using the gibbsite prepared by a method other than the hydrothermal synthesis method in the step (S10), the structure is changed due to the high temperature in the hydrothermal synthesis. The organic-inorganic hybrid compound 100 having one configuration could not be obtained (see Comparative Example 4 and FIG. 8D ).

In addition, in the step (S20), after the step (S20-2), the steps of separating the prepared compound of the gibbsite structure from solid-liquid (S20-3), and washing the separated compound of the gibbsite structure (S20) -4) and drying the washed compound of the gibbsite structure (S20-5) may be further included.

The step (S10-4) and the step (S20-3) may be performed using a centrifuge, respectively.

In addition, each of the steps (S10-5) and (S20-4) may be performed using distilled water.

In addition, the step (S10-6) and the step (S20-5) may be performed by freeze-drying, respectively.

A key feature of the organic-inorganic hybrid compound having a low-density columnar structure to be achieved in the present invention is that it has a gibbsite structure. In the first half step (S10) described above, since only a trivalent metal cation (eg, Al ³⁺ ) and a hydroxyl group (OH ^- group) were input, it is self-evident and easy to have a gibbsite (Al(OH) ₃ )-like structure. can be checked On the other hand, in the latter step (S20), a divalent metal cation (eg, Zn ²⁺ ) is added, and it is generally known that both a gibbsite structure and a hydrotalcite structure are possible when a trivalent metal cation and a divalent metal cation coexist. There is (prior art documents 1 and 2). However, the organic-inorganic hybrid compound having a low-density columnar structure of the present invention does not have a hydrotalcite structure and maintains a gibbsite structure, which is clearly demonstrated from the following description as well as examples to be described later.

Hereinafter, an organic-inorganic hybrid compound having a low-density columnar structure according to an embodiment of the present invention will be described in detail with reference to the drawings.

1A to 1C are schematic views schematically illustrating an example of an organic-inorganic hybrid compound 100 according to an embodiment of the present invention. 1A is a side view, FIG. 1B is a plan view, and FIG. 1C is a perspective view. Specifically, FIGS. 1A to 1C show the unit cells of the organic-inorganic hybrid compound 100 (thin black lines in FIGS. 1A and 1B indicate one unit cell), and the actual material is such It is a structure in which unit cells are repeated in the x, y, and z-axis (a, b, c-axis in the drawing) direction.

1A to 1C , the organic-inorganic hybrid compound 100 according to an embodiment of the present invention includes two inorganic material layers 110 and an organic material layer 120 .

Specifically, the organic-inorganic hybrid compound 100 may include at least two inorganic material layers 110 and at least one organic material layer 120 intercalated therebetween.

In addition, the organic-inorganic hybrid compound 100 may be one in which the inorganic material layer 110 and the organic material layer 120 are alternately stacked with each other.

The two inorganic material layers 110 may each extend in one direction and may be disposed to face each other.

In addition, each inorganic layer 110 may have a gibbsite structure in which a divalent cation metal is doped in an octahedral site.

The divalent cation may coordinate with all six oxygen atoms present around the octahedral site, and may also bind with anions present in the organic material layer 120 by electrostatic attraction.

The organic material layer 120 may include a plurality of pillar portions intercalated between the two inorganic material layers 110 to extend in a direction crossing the extending direction of the inorganic material layers 110 . For example, the organic material layer 120 may include a plurality of pillar portions disposed between the two inorganic material layers 110 to extend in a direction perpendicular to the direction in which they extend. As such, when the organic material layer 120 includes a plurality of pillar portions disposed between the two inorganic material layers 110 to extend in a direction perpendicular to the direction in which they extend, the space between the two inorganic material layers 110 is By being enlarged, the speed of movement of molecules into the organic-inorganic hybrid compound 100 may be increased, and the size and movement amount of movable molecules may be increased.

In addition, the organic material layer 120 may include a plurality of pillars that are chemically bonded to each inorganic material layer 110 to connect the two inorganic material layers 110 to each other. Specifically, when the two inorganic material layers 110 are formed of the first inorganic material layer 110 and the second inorganic material layer 110 disposed to face each other, the organic material layer 120 has one end of the first inorganic material layer 110 . It may include a plurality of pillars that are chemically bonded to and the other end is chemically bonded to the second inorganic material layer 110 . More specifically, in the organic material layer 120, one end and the other end form a hydrogen bond with each inorganic material layer 110, as well as anions present in the organic material layer 120 as described above of the inorganic material layer 110. It may include a plurality of pillars coupled to the divalent cation doped at the octahedral site by electrostatic attraction. Accordingly, the organic-inorganic hybrid compound 100 may have a solid structure because the organic material layer 120 is tightly coupled to each inorganic material layer 110 .

In addition, the organic molecules constituting the pillars do not need to be perfectly and periodically distributed, and the distance between the pillars actually has a certain probability distribution. Despite this probability distribution, there is no difference in performance and structural stability.

1A to 1C, the organic material layer 120 is exemplified as being composed of a divalent anion derived from terephthalic acid, but the present invention is not limited thereto.

In addition, the organic-inorganic hybrid compound 100 may be represented by the following formula (1).

[Formula 1]

[M ^(II) _x M ^(III) (OH) ₃ ] ^2x+ (A ^2- ) _x

wherein M ^(II) is a divalent metal cation, M ^(III) is a trivalent metal cation, A ² - is a dicarboxylic acid ion, and 0 < x < 0.2.

In Formula 1, [M ^(II) _x M ^(III) (OH) ₃ ] ^2x+ forms the inorganic material layer 110 having a gibbsite structure, (A ² - ) _x is the organic material layer 120 to form can

The M ^(II) may be doped at the octahedral site of the gibbsite structure (ie, M ^(III) (OH) ₃ ).

In addition, the M ^(II) may be coordinated with all six oxygen atoms present around the octahedral site, and may also bind to the anion (A ² - ) present in the organic material layer 120 by electrostatic attraction.

In addition, M ^(II) may include Zn ²⁺ , Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ or a combination thereof. can

M ^(III) may be a base metal constituting the gibbsite structure.

In addition, M ^(III) may include Al ³⁺ , Fe ³⁺ , Cr ³⁺ , B ³⁺ , Ga ³⁺ , In ³⁺ , Y ³⁺ , or a combination thereof.

The A ² - (specifically, a total of four oxygen atoms present two each at one end and the other end) has one end and the other end of each inorganic layer 110 (specifically, the upper layer and A total of 4 hydrogen atoms (two each in the lower layer) can form hydrogen bonds.

In addition, A ² - is terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethylglutaric acid, maleic acid, acetylenedicarboxylic acid, glutaconic acid, 2-disenedioic acid, traumatic acid, mu Conic, Glutinic, Citraconic, Mesaconic, Itaconic, Tartronic, Mesosalic, Malic, Tartaric, Oxalic, Aspartic, Glutamic, Diaminopimelic, Saccharic and 2,6 - May contain a divalent anion derived from naphthalenedicarboxylic acid or a combination thereof.

In Formula 1, the organic-inorganic hybrid compound 100 having a low-density columnar structure of 0 < x < 0.2 has a gibbsite structure, but cannot have a hydrotalcite structure, for the following reasons: (1) In general, a hydrotalcite structure is a form in which divalent metal cations are the main component and some of them are substituted with trivalent metal cations, and typically the molar ratio of divalent metal cations to trivalent metal cations is 3:1 (the ratio of trivalent metal cations in metals) 25 mol% of this). However, in the organic-inorganic hybrid compound 100 of the present invention, the inorganic layer 110 has a hydrotalcite structure because the trivalent metal cation is at least 80 mol% and the divalent metal cation is very small (less than 20 mol%). none. (2) If it is assumed that the inorganic material layer 110 has a hydrotalcite structure, the trivalent metal cation has a positive charge value (3+) that is one greater than that of the divalent metal cation, so the corresponding anion must be intercalated. , as in the organic-inorganic hybrid compound 100 of the present invention, when the value of x is extremely small (that is, 0 < x < 0.2) 　 80 mol% or more is a trivalent metal cation 　 To make the whole material neutral 　 The amount of anion required Even if there are too many of these, even if all spaces between floors are filled with negative ions, there is still absolutely insufficient space to fill negative ions, so this assumption is impossible to be realized in practice.

Specifically, in Formula 1, 0.03 ≤ x ≤ 0.150.

In Formula 1, when x is less than 0.03, the density of the organic material layer 120 in the organic-inorganic hybrid compound 100 is too small to maintain the columnar structure, and when x exceeds 0.150, the organic material layer in the organic-inorganic hybrid compound 100 ( 120) is too high, so that the molecular movement speed into the organic-inorganic hybrid compound 100 is slowed, and the size and movement amount of movable molecules are reduced. Specifically, in order for the organic-inorganic hybrid compound 100 of the present invention to be an excellent adsorption material, molecules must move easily and rapidly between layers (ie, diffusion), and the limiting conditions are, a-axis direction and In the b-axis direction (refer to FIG. 1b ), the pillar parts should not be attached to each other. If, as the column density increases, the case where the column parts (ie, A ² - anions arranged in a direction perpendicular to the organic material layer 120) are attached to each other increases, the diffusion is greatly hindered in the movement of molecules in the region. decreases sharply

In the organic-inorganic hybrid compound 100, if the nominal x = 1/2, the column parts in the a-axis and b-axis directions are all filled in all possible positions, and if the nominal x = 0.125, the a-axis and a case in which each of the pillars in the b-axis direction is occupied by 1/2 (there is every other empty seat). As the nominal x value increases from 0.125, molecular movement is significantly restricted, and when the nominal x = 0.2, the effect of adsorption or storage becomes very insignificant.

To find out how much the adsorption or storage capacity is reduced by the column structure, a quantitative calculation method is adopted. Using the methods of References 1 and 2 widely used in theoretical physical chemistry, M ^(II) = Zn ²⁺ , M ^(III) = Al ³⁺ , A ^2- = terephthalate (C ₈ H ₄ O ₄ ^2- ) , when nominal x = 0.125, the energy of the interaction of hydrogen molecules (H ₂ ) introduced from the outside with the organic-inorganic hybrid compound was calculated at all points in space. The region where the interaction energy has a positive value acts as an energy barrier and hydrogen molecules cannot access it. That is, a calculation was performed to find an inaccessible region where the organic-inorganic hybrid compound and the molecule were spatially excluded, and the molecule was not allowed to access. The reason for selecting H ₂ corresponding to the smallest molecule is to obtain the minimum value of the access exclusion region, and for molecules larger than this, the access exclusion region is further expanded. The space in the organic-inorganic hybrid compound 100 was subdivided into small sections, and when hydrogen molecules were present in a specific section, the interaction energy between hydrogen and the compound was calculated. presented in The dotted line indicates the layer that divides the space in the compound into 9 layers, and subdivides the cross section of each layer into small pixels. indicated. From FIG. 2 , it can be seen that an average of 28.6 Å ² of access exclusion area indicated in white is shown on each floor per column. The white area has a shape similar to an ellipse, and its average radius is about 3.0 Å. Expressing the proportion of accessible gray areas on the cross section as a function of x gives (1-2.6x). From this equation, it can be seen that the proportion of the accessible area when nominally x=0.0625 is about 84%.

In addition, the organic-inorganic hybrid compound 100 may have a column density of 1/(360 Å ² ) to 1/(55 Å ² ) represented by Equation 1 below (Å ² =square angstrom):

[Equation 1]

Pillar density = total number of pillars in a single organic layer/planar surface area of a single inorganic layer.

Specifically, the organic-inorganic hybrid compound 100 may have a column density of 1/(306 Å ² ) to 1/(74 Å ² ) represented by Equation 1 above.

If the column density is less than 1/(306 Å ² ), the density of the organic material layer 120 in the organic-inorganic hybrid compound 100 is too small, so that the synthesis of the column structure is quite difficult, and with a density of less than 1/(360 Å ² ) Column structure cannot be maintained. When the column density exceeds 1/(74 Å ² ), the density of the organic material layer 120 in the organic-inorganic hybrid compound 100 is too large, so that the movement of molecules into the organic-inorganic hybrid compound 100 is restricted as well as movement When the size and movement of possible molecules is greatly reduced and reaches 1/(55Å ² ), the effect of adsorption or storage becomes very insignificant.

The fact that structural stability can be achieved only with low column density is based on the newly formed chemical bond in the organic-inorganic hybrid compound 100 of the present invention: (1) Oxygen atoms at both ends of the dicarboxylic acid ion form a gibbsite structure Hydrogen bonding with hydrogen atoms on the surface of the inorganic layer 110 makes the greatest contribution, and 4 hydrogen bonds per one dicarboxylic acid ion (two at one end of the dicarboxylic acid ion, and the other two at the end) are present (hydrogen bonds are indicated by dashed lines in FIG. 1A ). (2) In the inorganic layer 110 of the gibbsite structure, a divalent metal ^cation (for example, Zn ²⁺ ) enters and bonds with the intercalated dicarboxylic acid anion (eg, terephthalate ion: (C ₈ H ₄ O ₄ ) ^2- ) by electrostatic attraction. (3) A weak van der Waals interaction between atoms of the inorganic layer 110 having the gibbsite structure and atoms constituting the dicarboxylic acid makes an additional small contribution to the bonding.

As a result, even if the density of the pillars made of dicarboxylic acid ions is small, it is possible to support a rigid structure.

In the organic material layer 120 , the average distance between adjacent pillars may be 8.0 to 20.6 Å (angstrom).

Specifically, the average distance between adjacent pillars in the organic material layer 120 may be 9.2 to 18.8 Å.

If the average distance between the pillars is less than 9.2 Å, the internal space in the organic-inorganic hybrid compound 100 is too narrow, and not only the movement of molecules into the organic-inorganic hybrid compound 100 is restricted, but also the size and movement amount of movable molecules It decreases greatly and when it is less than 8.0Å, the effect of adsorption or storage becomes very insignificant. When the average distance between the pillars exceeds 18.8 Å, the density of the organic material layer 120 in the organic-inorganic hybrid compound 100 is too small, so that the synthesis of the pillar structure is quite difficult, and the column structure is not maintained at a distance exceeding 20.6 Å. can not do it.

In addition, the organic-inorganic hybrid compound 100 may be usefully used to adsorb and/or store various gases and metals.

When the organic-inorganic hybrid compound 100 of the present invention is used for molecular adsorption, the hydroxyl group (OH) exposed on the surface of the inorganic material layer 110 contributes the most, and the material forming the pillar and the doped metal (dicarboxylic acid ions and divalent metal cations) also make secondary contributions. In addition, the large specific surface area and pore volume play a decisive role in improving the adsorption capacity.

For example, the organic-inorganic hybrid compound 100 is a volatile organic compound, a liquid environmentally harmful substance causing sick house syndrome, etc., polycyclic aromatic hydrocarbon, exhaust gas-based environmental pollutants, greenhouse gases, radioactive substances, hazardous heavy metals, toxic chemicals It can be usefully used to adsorb and store substances and/or hydrogen.

The volatile organic compound may include benzene, toluene, xylene, or a combination thereof.

The liquid environmentally hazardous material may include formaldehyde, chloroform, or a combination thereof.

The polycyclic aromatic hydrocarbon may include benzo (a) pyrene.

The exhaust gas-based environmental pollutants may include NO, NO ₂ , N ₂ O, SO ₂ , CO, or a combination thereof.

The greenhouse gas may include CO ₂ , CH ₄ or a combination thereof.

The radioactive material may include cesium (Cs).

The toxic chemical may include chlorine gas (Cl ₂ ), phenol (Phenol), hydrogen cyanide (HCN), acrolein, nicotine, or a combination thereof.

The harmful heavy metal may include Pb.

Hereinafter, the storage of hydrogen using the organic-inorganic hybrid compound 100 will be described in detail.

The main goal in hydrogen storage is to store large amounts of hydrogen safely at room temperature. In the case of a hydrogen molecule (H ₂ ), the absolute value of the energy at which the organic-inorganic hybrid compound 100 adsorbs hydrogen is equivalent to 27 kJ/mol or more in Tables 7 and 8 described above or in terms of per molecule of most of the harmful substances mentioned above. Therefore, it is much smaller than 280meV (millielectron volt) (2~10kJ/mol or 20~100meV per molecule), so the fact that it is extremely difficult to store hydrogen at room temperature is the case for all adsorbed materials studied previously. is already well known (see Ref. 3). At a cryogenic temperature of minus 196°C (=77K), which is the nitrogen liquefaction temperature, hydrogen can be stored even with such a small adsorption energy, but it is not economical. For this reason, the current hydrogen fuel cell vehicle compresses and stores hydrogen at a high pressure of 700 atmospheres in an empty hydrogen tank without using a separate storage material. For the stability of storage, the US Department of Energy (Dept. Of Energy) has proposed as a goal to develop a material that can be stored within 100 atmospheres. However, the organic-inorganic hybrid compound 100 of the present invention has an average value of adsorption energy greater than that of past materials, and has a relatively uniform adsorption energy value in the pores due to its layered structure, so it is a kind of potential well. works Due to this, the organic-inorganic hybrid compound 100 of the present invention increases the density of hydrogen therein, and acts synergistically with a very large pore volume, thereby remarkably improving the hydrogen storage capacity even at room temperature.

Hereinafter, the principle of the organic-inorganic hybrid compound 100 of the present invention adsorbing and storing hydrogen will be described in detail.

First, the organic-inorganic hybrid compound 100 of the present invention has many hydroxyl groups (OH) on the upper and lower surfaces of each inorganic layer 110 . In particular, since oxygen has many negative charges, a strong electric field is formed in its vicinity.

Therefore, the organic-inorganic hybrid compound 100 of the present invention uses this property to relatively well absorb hydrogen gas, which is poorly adsorbed to a material that hardly forms an electric field (eg, a material mainly composed of carbon such as activated carbon). can be adsorbed. When hydrogen is adsorbed to a substance that cannot form an electric field, it is adsorbed mainly by a very weak van der Waals interaction. However, in the presence of an electric field, the electric dipole value ( p ) of the hydrogen molecule (H ₂ ) itself is 0, but the electric polarizability value (α) is 0.804x10 ^-24 cm ³ (References 4), the electric quadrupole value (Q) is known to be 0.662x10 ^-26 esu·cm ² (see Reference 5).

)(참고문헌 6)을 써서 얻어지며, 결과적으로　수소 분자 1개 당 유도된 쌍극자와 사중극자 각각이 -10meV 및 -20meV의 추가적　흡착 에너지를 제공하는 것으로 나타났으며,　그 합(약　-30　meV)은 수소분자처럼 상온 흡착이 잘 안되는 분자의　경우 흡착에 상당히 크게 기여한다. 일반적으로　과거에　수행되어온　절대온도 77K(= -196℃)에서의 극저온 실험에서는 이러한 추가적 흡착 에너지 기여 없이도 흡착 저장이 잘 되지만,　원래 흡착 저장이 잘 안되는 상온에서는 이러한 추가적 흡착 에너지(-30meV)가 대단히 중요하고, 이로 인해 반 데르 발스 상호작용만 있을때 보다 저장량이 약 3배　증가할 수 있다. 구체적으로, 흡착 에너지가 -30meV 만큼 추가되어 그만큼의 화학 퍼텐셜(chemical potential) μ의 변화(Δμ)가 생기면 25℃에서　kT(k는 볼츠만 상수(Boltzmann constant), T(절대온도)=298.15K)값이 25.7meV이고, 평형 열역학(equilibrium thermodynamics)에 의해(참고문헌 7) 밀도 변화는　exp(-Δμ/kT)=3.2, 즉　저장하는 기체의　밀도가 약 3배 증가한다.The magnitude of the electric field (E) and electric field gradient in the vicinity of oxygen constituting the organic-inorganic hybrid compound 100 is the electronic structure in the organic-inorganic hybrid compound prepared in Example 1, the method of References 1 and 2 As a result of calculating with , it was found to be about 0.6V/Å and 0.3V/Å ² at positions where molecules adsorb inside the material. The induced dipole energies and quadrupole energies are respectively determined by the known equations (−½×α×E ² and

) (Ref. 6), and as a result, it was shown that the dipole and quadrupole induced per hydrogen molecule provide additional adsorption energies of -10 and -20 meV, respectively, and the sum (about -30 meV) ) contributes significantly to adsorption for molecules that are not well adsorbed at room temperature, such as hydrogen molecules. In general, in the cryogenic experiment at an absolute temperature of 77K (= -196℃) performed in the past, adsorption storage is good without this additional adsorption energy contribution, but at room temperature where the original adsorption storage is not well, this additional adsorption energy (-30meV) is very high. important, and this could lead to an approximately three-fold increase in storage over van der Waals interactions alone. Specifically, when the adsorption energy is added by -30 meV and a change (Δμ) of the chemical potential μ occurs, kT at 25°C (k is Boltzmann constant, T (absolute temperature)=298.15K) The value is 25.7 meV, and the density change by equilibrium thermodynamics (Ref. 7) is exp(-Δμ/kT) = 3.2, that is, the density of the gas to be stored increases by about 3 times.

The organic-inorganic hybrid compound 100 having a low-density columnar structure according to an embodiment of the present invention having the above configuration is a novel material that did not exist in the past as a material first discovered by the inventors after hard work.

In addition, the organic-inorganic hybrid compound 100 having a low-density columnar structure according to an embodiment of the present invention having the above configuration is an inorganic material having a layered structure, in particular, an organic material molecule between the layers of gibbsite (Al(OH) ₃ ). , in particular, metal-dicarboxylate series (eg, Zn-C ₈ H ₄ O ₄ , that is, zinc-terephthalate) is inserted in a vertical column to form a structure in which inorganic and organic matter are chemically combined, but the column density is extremely low. Structural stability was secured. Moreover, since the density of organic matter existing as a pillar between the inorganic layers 110 is minimized, the volume of empty pores between the layers is maximized, and a large amount of harmful substances or various gases can be captured and adsorbed or stored. ability was implemented. In addition, the interlayer spacing was also expanded from 4.86 Å of gibbsite to 14 Å or more (in the case of terephthalate), contributing to an increase in pore volume.

Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited only to the following examples.

Example

Examples 1 to 5 and Comparative Examples 1-2: Preparation of organic-inorganic hybrid compounds

(Production of gibbsite by a method other than hydrothermal synthesis)

Al(NO ₃ ) ₃ was completely dissolved in 250 ml of water through stirring to prepare an Al(NO ₃ ) ₃ aqueous solution, and NaOH was completely dissolved in 250 ml of water through stirring to prepare an aqueous NaOH solution.

Then, the Al(NO ₃ ) ₃ aqueous solution (25° C.) and the NaOH aqueous solution (25° C.) were mixed to obtain a white precipitate.

Thereafter, water was primarily removed from the precipitate through a centrifugal separator, and unreacted residues were removed by washing with distilled water three or more times to obtain white powder.

After that, the washed white powder was put in a freeze dryer and dried for about 1 week to obtain an amorphous gibbsite containing about 30% by weight of moisture.

In the production of gibbsite by a method other than the hydrothermal synthesis method, Al(NO ₃ ) ₃ Instead of AlCl ₃ or Even when Al ₂ (SO ₄ ) ₃ was used, the same amorphous gibbsite was obtained.

(Preparation of organic-inorganic hybrid compounds by methods other than hydrothermal synthesis)

Amorphous Al(OH) ₃ , ZnCl ₂ and terephthalic acid containing about 30% by weight of moisture obtained above were placed in 200 ml of distilled water, heated to 70° C., and maintained for 7 hours to obtain a precipitate.

Thereafter, water was primarily removed from the precipitate through a centrifuge, and washed once with distilled water to obtain a white powder.

Then, the obtained white powder was dried for 48 hours through a freeze dryer to obtain a Zn-doped organic-inorganic hybrid compound.

The types and contents of raw materials used in Examples 1 to 5 and Comparative Examples 1 to 2, and the nominal Zn/Al molar ratio among the raw materials used are summarized and shown in Table 1 below.

Raw material used (g) Nominal Zn/Al molar ratio in raw materials Al(OH) _3· 2H ₂ O ZnCl ₂ terephthalic acid Example 1 2.37 0.176 0.216 0.0625 Example 2 2.37 0.152 0.184 0.0534 Example 3 2.37 0.132 0.168 0.0468 Example 4 2.37 0.117 0.144 0.0417 Example 5 2.37 0.352 0.432 0.125 Comparative Example 1 2.37 0.094 0.115 0.0333 Comparative Example 2 2.37 0.563 0.691 0.2

Comparative Example 3: Preparation of organic-inorganic hybrid compound

(Production of gibbsite by hydrothermal synthesis)

Al(NO ₃ ) ₃ was completely dissolved in 250 ml of water through stirring to prepare an Al(NO ₃ ) ₃ aqueous solution, and NaOH was completely dissolved in 250 ml of water through stirring to prepare an aqueous NaOH solution.

Thereafter, the Al(NO ₃ ) ₃ aqueous solution and the NaOH aqueous solution were mixed, put into a hydrothermal synthesis reactor (autoclave), and the temperature was raised to 120° C. and maintained for 6 hours to obtain a white precipitate.

Thereafter, water was primarily removed from the precipitate through a centrifugal separator and washed once with distilled water to remove unreacted residues to obtain white powder.

Thereafter, the washed white powder was put in a freeze dryer and dried for about 48 hours to obtain gibbsite (γ-Al(OH) ₃ ) with excellent crystallinity containing about 30% by weight of moisture.

(Preparation of organic-inorganic hybrid compounds by methods other than hydrothermal synthesis)

The same method as in Example 1, except that crystalline Al(OH) ₃ prepared by hydrothermal synthesis in Comparative Example 3 was used instead of amorphous Al(OH) ₃ prepared by a method other than hydrothermal synthesis in Example 1 (that is, a method other than hydrothermal synthesis) to obtain an organic-inorganic hybrid compound.

Comparative Example 4: Preparation of organic-inorganic hybrid compound

An organic-inorganic hybrid compound was obtained in the same manner as in Example 1, except that a hydrothermal synthesis method was used instead of a non-hydrothermal synthesis method in the latter stage of preparing the organic-inorganic hybrid compound.

Specifically, in Example 1, amorphous Al(OH) ₃ , ZnCl ₂ and terephthalic acid prepared by a method other than the hydrothermal synthesis method in 200 ml of distilled water were put in 200 ml of distilled water, and the temperature was raised to 120 ° C. in the hydrothermal synthesis reactor (autoclave) for 6 hours maintained to obtain a precipitate.

Thereafter, water was primarily removed from the precipitate through a centrifuge, and washed once with distilled water to obtain a white powder.

Then, the obtained white powder was dried for 48 hours through a freeze dryer to obtain a final compound.

Evaluation Example 1: Gibbsite (Al (OH) ₃ ) XRD graph analysis of

In Example 1, the XRD of the gibbsite prepared in the gibbsite preparation step (S10), which is an intermediate process, is shown in FIG. Exactly the same as Example 1). The XRD graph of gibbsite prepared in Comparative Example 3 is shown in FIG. 4 . Rigaku's D/Max-2500VK/PC was used as the XRD device, and the analysis conditions were CuKα radiation speed 2° min ^-1 .

5 is an XRD graph of the general gibbsite crystal structure (γ-Al(OH) ₃ ) disclosed in Reference 8, and FIG. 6 is another hydrotalcite (Al and O containing hydrotalcite) disclosed in Reference 9. It is an XRD graph of a layered material).

Referring to FIGS. 3 to 6 , the XRD graph of FIG. 3 (Example 1) shows a typical form of an amorphous material in which no sharp XRD peak is present. The ratio of Al:OH input in the gibbsite manufacturing step and the Al:O ratio in EDX elemental analysis (H is generally excluded from EDX analysis) are all 1:3, forming component gibbsite (Al(OH) ₃ ) However, an amorphous form different from FIGS. 4 to 6 was obtained. The XRD graph of FIG. 4 (Comparative Example 3) showed that the pattern was similar to the XRD graph of the gibbsite crystal structure (γ-Al(OH) ₃ ) disclosed in FIG. 5, and the pattern was completely different from the XRD graph of FIG. 6 . . From these results, it was confirmed that the gibbsite putative material prepared in the first stage in Example 1 and Comparative Example 3 was not hydrotalcite. Specifically, the putative gibbsite material prepared in Example 1 has a gibbsite structure in its composition, but has an amorphous gibbsite structure rather than crystalline, and the putative gibbsite material prepared in Comparative Example 3 actually has a crystalline gibbsite structure. has been confirmed to have

Evaluation Example 2: XRD graph analysis of organic-inorganic hybrid compounds

The XRD graphs of the organic-inorganic hybrid compounds finally prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were analyzed, and the results are sequentially shown in FIGS. 7A to 7E and 8A to 8D . Rigaku's D/Max-2500VK/PC was used as the XRD device, and the analysis conditions were CuKα radiation speed 2° min ^-1 .

As described above, the finally prepared low-density columnar organic-inorganic hybrid compound has a hydrotalcite structure because the ratio of trivalent metal cations (specifically Al ³⁺ ) is overwhelmingly higher than that of divalent metal cations (specifically Zn ²⁺ ). , and may have a gibbsite structure. However, since divalent anions (specifically, terephthalate ions) are intercalated and serve as pillars, the interlayer spacing increases compared to the original pure gibbsite. The shift of the position (2θ value) of the leftmost main peak of XRD indicating the interlayer spacing to the left indicates an increase in the interlayer spacing, and the height of the peak indicates the degree to which the pillars are uniformly well formed.

5 is an XRD graph of the pure gibbsite crystal structure disclosed in Reference 8, and FIG. 6 is an XRD graph of hydrotalcite, another layered material disclosed in Reference 9.

5, 6, 7A to 7E and 8A to 8D, the XRD graphs of FIGS. 7A to 7E and 8B are similar to those of the XRD graph of FIG. 5, except that the position of the leftmost main peak is 2θ = 18.2° to 6.2°, which means that the gibbsite structure was maintained but the interlayer spacing increased from 4.86 Å to 14.1 Å, which showed a completely different pattern from the hydrotalcite XRD graph of FIG. 6 . In addition, the disappearance of the peak corresponding to 14.1 Å in FIG. 8A (Comparative Example 1) indicates that the amount of x is too small to fail in the formation of the columnar structure. The XRD graph of FIG. 8D shows that the pattern is completely different from both the XRD graph of FIG. 5 and the XRD graph of FIG. 6, and the XRD structure is changed to a third structure that is neither gibbsite nor hydrotalcite due to high temperature in hydrothermal synthesis. From these results, the organic-inorganic hybrid compounds prepared in Examples 1 to 5 and Comparative Example 2 are compounds having a gibbsite structure with increased interlayer spacing, not a hydrotalcite structure, and Comparative Examples 1 (FIG. 8a) and Comparative Example 4 (FIG. The organic-inorganic hybrid compound prepared in 8d) is a compound having neither a hydrotalcite structure nor a gibbsite structure, and the material finally prepared in Comparative Example 3 (FIG. 8c) is pure in the first step (S10) using the hydrothermal synthesis method. Since the gibbsite crystal structure was perfectly and strongly formed, it can be seen that the terephthalate ion was not inserted and the gibbsite was synthesized into a pure gibbsite structure ( FIG. 5 ) in which the interlayer spacing did not increase despite the execution of the latter step (S20).

Evaluation Example 3: Elemental Analysis of Organic-Inorganic Hybrid Compounds

EDX elemental analysis (Energy-dispersive X-ray spectroscopy) was performed on the organic-inorganic hybrid compounds prepared in Examples 1 to 5 and Comparative Examples 1 to 2, and the results (elemental composition ratio of the actually synthesized material) were shown below. It is shown in Table 2 in order. As the EDX device, Horiba's X-MaxN 50 was used.

Elemental composition (atomic %) Actual molar ratio (x) C O Al Cl Zn Zn/Al Example 1 14.85 63.38 20.38 ~0 1.35 0.0662 Example 2 12.46 63.79 22.41 ~0 1.33 0.0593 Example 3 11.31 71.65 16.36 ~0 0.67 0.041 Example 4 11.37 71.3 16.74 ~0 0.61 0.036 Example 5 23.02 62.26 12.72 ~0 1.9 0.149 Comparative Example 1 10.38 71.22 17.98 ~0 0.41 0.023 Comparative Example 2 20.73 64.2 12.42 ~0 2.49 0.200

Evaluation Example 4: Analysis of real images of organic-inorganic hybrid compounds

A photograph of the organic-inorganic hybrid compound prepared in Example 1 was taken and shown in FIG. 9 .

Referring to FIG. 9 , the sample prepared in Example 1 is in the form of white powder. The images of the organic-inorganic hybrid compounds prepared in Examples 2 to 5 are in the same white powder form as in FIG. 9 .

The two properties of the material of the present invention are: first, it forms a columnar structure firmly to support the increased interlayer spacing (XRD peak at the position of 14.1Å appears strongly), and secondly, the column density is as low as possible (the x value is as small as possible) to secure an empty space between floors. Examples 1 to 5 (especially, Examples 1 and 2) that satisfy both conditions at the same time were subjected to additional in-depth analysis and described in Evaluation Examples 5 to 7.

Evaluation Example 5: SEM analysis of organic-inorganic hybrid compound surface images

SEM photographs (Scanning Electron Microscope images) of the organic-inorganic hybrid compounds prepared in Examples 1 and 2 were taken and shown in FIGS. 10A and 10B , respectively. The SEM device used here was JEOL's JSM-6390LV.

Evaluation Example 6: Elemental Analysis of Organic-Inorganic Hybrid Compounds (XPS)

XPS elemental analysis (X-ray photoemission spectroscopy) was performed on the organic-inorganic hybrid compounds prepared in Examples 1 and 2, and the results are shown in Table 3 below. MultiLab 2000 from THERMO VG SCIENTIFIC (U.K) was used as the XPS device.

Elemental composition (atomic %) Actual molar ratio (x) C O Al Cl Zn Zn/Al Example 1 12.64 61.82 23.98 ~0 1.56 0.0655 Example 2 9.77 58.15 30.38 ~0 1.7 0.0560

Comparing the two elemental analysis methods (EDX and XPS) in Tables 2 and 3 above, it can be confirmed that the molar ratio of Zn/Al is consistent within the error range of the experiment (0.0662 compared to 0.0655 in Example 1, 0.0655 in Example 2) in 0.0593 versus 0.0560). In the present specification, if necessary for calculation, the Zn/Al molar ratio of EDX was regarded as the actual value of x.

Evaluation Example 7: Analysis of BET characteristics of gibbsite and organic-inorganic hybrid compound

The BET characteristics of the gibbsite prepared in the first step (S10) of Example 1 and the organic-inorganic hybrid compound prepared in Examples 1 and 2 were analyzed, and the results are shown in Table 4 below.

BET surface area (m ² /g) pore volume (cm ³ /g) Gibbsite (Al(OH) ₃ ) Example 1 48.327 0.3126 organic-inorganic hybrid compound Example 1 174.94 1.2487 Example 2 345.05 2.1353

Referring to Table 4, the organic-inorganic hybrid compounds prepared in Examples 1 and 2 showed significant increases in both the BET surface area and the pore volume compared to the gibbsite prepared in the first step (S10) of Example 1.

Evaluation Example 8: Structural Analysis of Organic-Inorganic Hybrid Compounds

(Confirm that Zn is doped at the octahedral site of gibbsite (Al(OH) ₃ ))

There are 6 oxygen atoms around the octahedral site of gibbsite (Al(OH) ₃ ). Specifically, 6 oxygen atoms are present at positions corresponding to the 6 vertices of the octahedron of gibbsite. This site corresponds to the central position of the octahedron of gibbsite, and when a metal atom (eg, Zn) occupies this vacant site, it forms a coordination bond with all surrounding oxygen atoms, and the coordination number is increased. 6 to complete a stable and strong bonding structure (refer to Reference 10). In other words, when a metal atom occupies this vacant site, the metal atom acts as an electron pair acceptor, and 6 surrounding oxygen atoms act as an electron pair donor to form a strong coordination bond.

(Confirmation of vertical column structure)

The most common and accurate method for measuring the monolayer thickness (d) of an organic-inorganic hybrid compound (see FIG. 1A ) is to use an XRD graph.

The value of the angle (2θ value) providing the leftmost highest peak in the XRD graphs of FIGS. 7A to 7E and FIGS. 8A to 8D was obtained from the well-known diffraction equation (d=nλ/(2sinθ)) (Reference 11 ), n = 1, λ is a single layer thickness (d = 14.1 Å) of the organic-inorganic hybrid compound prepared in Examples 1 to 5 and Comparative Example 2 by substituting 1.5406 Å, which is the wavelength when using copper Kα emissoin. got it

Thereafter, in the case of the organic-inorganic hybrid compounds prepared in Examples 1 to 5 and Comparative Example 2, it was confirmed that the terephthalate ion had vertical columnar portions by comparing the single layer thickness (d) and the length of the terephthalate ion. For example, in the case of the organic-inorganic hybrid compound prepared in Example 1, the thickness of the original gibbsite (Al(OH) ₃ ) layer is 4.86 Å and the length of the terephthalate ion is about 9.2 Å, the sum of the two numbers is Since it coincides with the single layer thickness (d) of 14.1 Å, it can be seen that terephthalate ions are vertically interposed between the two gibbsite (Al(OH) ₃ ) layers. There may be a deviation of about 0.3 Å depending on the bonding state of the tip of the terephthalate ion. Even considering this error, the conclusion that it stands vertically is the same.

However, it was found that the organic-inorganic hybrid compounds prepared in Comparative Examples 1 and 3 to 4 did not have a columnar structure.

(Calculation of column density and average distance between columns)

By analyzing the structures of the organic-inorganic hybrid compounds prepared in Examples 1 to 5 and Comparative Examples 1 to 4, the column density represented by Equation 1 and the average distance between adjacent column parts are calculated, and the results are presented in Table 5 below shown in Here, x is the actual Zn/Al molar ratio.

Pillar Density (pcs/Å ² ) Average distance between pillars (Å) Example 1 1/167 13.7 Example 2 1/186 14.7 Example 3 1/269 17.6 Example 4 1/306 18.8 Example 5 1/74 9.2 Comparative Example 1 - - Comparative Example 2 1/55 8.0 Comparative Example 3 - - Comparative Example 4 - -

Referring to Table 5, the organic-inorganic hybrid compound prepared in Examples 1 to 5 had a lower column density and a longer average distance between adjacent columnar portions compared to the organic-inorganic hybrid compound prepared in Comparative Example 2.

Since the organic-inorganic hybrid compounds prepared in Comparative Examples 1 and 3 to 4 did not have a columnar structure, the column density and the average distance between the columnar parts were not displayed.

Evaluation Example 9: Analysis of Adsorption Characteristics of Activated Carbon and Organic-Inorganic Hybrid Compound

By analyzing the adsorption characteristics of activated carbon and the organic-inorganic hybrid compound prepared in Examples 1 to 5 and Comparative Example 2, the results are shown in FIGS. 11, 12A to 12D, 13A, 13B, and 14 to 15 each is shown.

11 is a graph showing the adsorption characteristics of benzene measured at 25° C., FIG. 12a is a graph showing the adsorption characteristics of toluene measured at 25° C., and FIG. 12b is a graph showing the adsorption characteristics of xylene measured at 35° C. 12c is a graph showing the adsorption characteristics of formaldehyde measured at 50°C, and FIG. 12d is a graph showing the adsorption characteristics of chloroform measured at 25°C.

In FIG. 11, the ability of the organic-inorganic hybrid compound prepared in activated carbon or Examples 1 to 5 and Comparative Example 2 to adsorb benzene was compared and disclosed. The ability of various adsorbents to adsorb and block the outflow of continuously volatilized benzene in the experimental apparatus is shown as a function of time. Reference Example 1 (No sample) shows the case in which no adsorbent is present, and Reference Example 2 (Activated carbon) shows the case of activated carbon, which is a widely used conventional adsorbent material. A value of 0 in the Y coordinate indicates that the material is completely inhibited from leaking out. The limit of the measuring device that measures the leaked harmful gas is 10.0 mg/m ³ .

It was found that the organic-inorganic hybrid compounds having a low-density columnar structure prepared in Examples 1 to 5 adsorbed substances for a much longer period of time compared to activated carbon and Comparative Example 2 to suppress leakage to the outside.

In FIGS. 12A to 12D, Examples 1 and 2, whose excellent adsorption capacity has already been confirmed in FIG. 11, were selected, and the results of adsorption experiments as in FIG. 11 for toluene, xylene, formaldehyde and chloroform, which are representative volatile hazardous substances was started. 12a to 12d show the superior adsorption capacity of Examples 1 and 2 compared to the activated carbon.

13 is a schematic diagram showing the structure of benzo (a) pyrene, which is a representative polycyclic aromatic hydrocarbon and a carcinogen, and the aspect of benzo (a) pyrene adsorbed to the organic-inorganic hybrid compound prepared in Example 1. FIG. Like benzene, toluene, and xylene, it has a planar benzene ring and has a large size, so only the organic-inorganic hybrid compound having a low-density columnar structure with a large column spacing as shown in FIG. 13 shows that the entire molecular plane is completely adsorbed parallel to the compound plane. can see. Since the entire large area is adsorbed on the inner surface of the organic-inorganic hybrid compound, it has very strong adsorption energy. Since benzo (a) pyrene is not volatile at room temperature, the experimental data as in FIG. 12 does not exist. Instead, theoretical calculations (References 1 and 2) through computer simulation were performed, and the adsorption energy values are shown in Table 7 below. For comprehensive understanding and verification, the adsorption energy for Example 1 was calculated in the same way for all molecules in FIGS. 11 and 12A to 12D, and disclosed in Table 7 below (Example 2 has an inner surface Since it had the same atomic composition and structure as in Example 1, the adsorption energy is the same as in Example 1). For reference, since these molecules are in adsorption competition with nitrogen (N ₂ ) and oxygen (O ₂ ) in the air, the adsorption energy of N ₂ and O ₂ for Example 1 is also disclosed. Since the adsorption energy of N ₂ and O ₂ is much weaker, it can be seen that when these harmful molecules are present in the air, they are adsorbed with overwhelming preference compared to the air.

Hazardous Substances benzene toluene xylene formaldehyde chloroform Benzo (a) pyrene N ₂ O ₂ Adsorption energy (kJ/mol) -48 -54 -64 -49 -54 -114 -17 -15

Evaluation Example 10: Calculation of Hazardous Substance Adsorption Capacity of Organic-Inorganic Hybrid Compounds

Among the harmful substances, the energy adsorbed in Example 1 by automobile exhaust gas and greenhouse gases (NO, NO ₂ , N ₂ O, SO ₂ , CO, CO ₂ , CH ₄ ) related to the atmospheric environment in particular in References 1 and 2 Calculated by the method of Table 8 is disclosed. Other toxic chemicals such as chlorine gas (Cl ₂ ), phenol (C ₆ H ₆ O), hydrogen cyanide (HCN), acrolein (C ₃ H ₄ O), and nicotine (C ₁₀ N) ₂ H ₁₄ ) and the like were also calculated and shown in Table 9 to calculate the energy adsorbed in Example 1. These molecules are adsorbed on the surface of the adsorbent by weak van der Waals interactions that are universally present in all atoms. The poles make an additional significant contribution. For molecules with non-zero dipoles, dipoles make the largest contribution, and induced dipoles and electric quadrupoles by polarizability (α) make additional contributions. For molecules with zero dipole, the dipole and electric quadrupole induced by the polarizability (α) contribute to the adsorption. Methane (CH ₄ ) has both a dipole and a quadrupole, but has a similar adsorption energy as H atoms directly interact with the organic-inorganic hybrid compound.

On the other hand, the organic-inorganic hybrid compound has the ability to also adsorb radioactive substances and harmful heavy metals. 14 is a schematic diagram of cesium (Cs) adsorbed to the organic-inorganic hybrid compound prepared in Example 1, and FIG. 15 is a schematic diagram of lead (Pb) adsorbed to the organic-inorganic hybrid compound prepared in Example 1.

In particular, cesium (Cs), a representative radioactive material, and lead (Pb), a representative hazardous heavy metal, are present in a dissolved form in water to contaminate water. As shown in Fig. 8, it was confirmed that they were strongly adsorbed at -230 kJ/mol and -91 kJ/mol, respectively, so that desorption was impossible. This is due to the extremely strong polarization of cesium (59.6×10 ^-24 cm ³ ) and the relatively strong polarization of lead (6.8×10 ^-24 cm ³ ). form strong ionic bonds. As a comparative example, the adsorption energy of water (H ₂ O) is -59 kJ/mol, indicating that these radioactive substances and harmful heavy metals are adsorbed much stronger than water molecules when dissolved in water.

Chlorine gas or phenol, which can be discharged from the water purification process or chemical process, is also an important harmful substance that can be exposed in daily life and can be adsorbed with the adsorption energy as shown in Table 9. Toxic substances related to smoking (primary, secondary, or tertiary smoking) (Reference 12) can also selectively control the amount of passage by adding a low-density columnar organic-inorganic hybrid compound to the filter and adsorbing it. can

The results of the adsorption energy calculation and the absolute values of the dipole ( p ), polarization (α), and quadrupole (Q) disclosed in References 4 and 5 are disclosed in Tables 8 and 9 for these materials. Here, the dipole unit is Debye(D) (1D=3.336×10 ^-30 C·m), the polarizability unit is 10 ^-24 cm ³ , and the quadrupole unit is 10 ^-26 esu·cm ² . Their total contribution to adsorption energy varies from molecule to molecule and is mixed with hydrogen bonding energy and van der Waals energy, so it is impossible to separate them by component. make up a part

NO NO ₂ N ₂ O SO ₂ CO CO ₂ CH ₄ Cs Pb Adsorption energy (kJ/mol) -35 -27 -28 -50 -29 -31 -32 -230 -91 p 0.16 0.32 0.16 1.63 0.11 0 0 0 0 α 1.7 3.0 3.0 4.0 1.95 2.91 2.59 59.6 6.8 │Q│ 1.8 4 3.0 4.4 2.5 4.3 0 0 0

Cl ₂ Phenol HCN Acrolein Nicotine Adsorption energy (kJ/mol) -78 -38 -57 -57 -103 p 0 1.22 2.99 3.12 One α 4.61 11.1 2.5 6.38 16 │Q│ 6.14 4 4.4 2 7

Evaluation Example 11: Analysis of hydrogen storage capacity of organic-inorganic hybrid compounds

As described above, the organic-inorganic hybrid compound having a low-density columnar structure has a relatively greater H ₂ storage capacity than conventional hydrogen molecule adsorption materials due to the contribution of an internal electric field and an electric field medium.

In FIG. 16 , the hydrogen storage amount was calculated at 25° C., and specifically, it was calculated using the most representative method (GCMC: Grand Canonical Monte Carlo Method) generally used in gas storage calculations (Reference 13). The adsorption energy required for this calculation was calculated using the same method as for harmful substances (References 1 and 2), and the interaction between hydrogen and hydrogen required additionally was calculated by adopting the method of Reference 14 (the circle in Fig. 16). line marked with ). The GCMC calculation does not include the contribution of meso- and macro-pores, so the sum of the contributions of the meso- and macro-pore volumes (up to 2.1 cm ³ /g) is approximately 3 weight at 25 °C and 100 atm. % (about 30 g of hydrogen per 1 kg of storage material) is stored (line indicated by a triangle in FIG. 16). Since the energy of 30 g of hydrogen is about 1,000 Wh, 1,000 Wh is stored per 1 kg of the organic-inorganic hybrid compound prepared in Example 1. When the efficiency of the hydrogen fuel cell used in hydrogen vehicles is 50%, it is 500Wh/kg, which is about 2.5 times the general value (about 200Wh/kg) of the lithium ion battery used in electric vehicles. In terms of volume, 14 g/L of hydrogen (about 14 g of hydrogen per 1 L of storage material) is stored, which is 1.8 times the amount stored in a hydrogen tank (7.7 g/L) under the same conditions of 25 ° C and 100 atm. More than that. For reference, for an explanation of adding the contribution of the pore volume to the calculation of the total hydrogen storage (i.e., adding the contribution of the pore volume to the excess storage measured in the experiment), see Reference 15 is disclosed in Through the above analysis, it can be seen that the organic-inorganic hybrid compound is a potent hydrogen molecule storage material.

In the present application, only combinations of Al as a trivalent metal, Zn as a divalent metal, and terephthalic acid as a dicarboxylic acid have been exemplified through Examples 1 to 5 and Comparative Example 2, but those skilled in the art may use a trivalent metal, a divalent metal and a dicarboxylic acid Other combinations of carboxylic acids can be easily carried out in the same manner as in Examples 1 to 5 and Comparative Example 2, and it can be easily expected that the results will be similar to the combinations of Al, Zn, and terephthalic acid.

<List of References>

References 1. Perdew, J. P.; Burke, K,; Ernzerhof, M., Phys. Rev. Lett. 1996, 77, 3865-3868

Reference 2. Grimme, S., J. Comput. Chem. 2006, 27(15), 1787-1799

Reference 3. N. L. Rosi et al., Science 2003, 300, 1127-1129

Reference 4. Lide (ed.), CRC Handbook of Chemistry and Physics, 75th ed., 1994, pp 9-44 and 10-196

Reference 5. D.E. Stogryn et al., Mol. Phys. 11, 371 (1996)

Reference 6. J.D. Jackson, Classical Electrodynamics, 2nd ed. John Wiley and Sons, New York 1975, pp 142, 161, and 165.

References 7. C. Kittel and H. Kroemer, Thermal Physics, 2nd ed. Freeman and Company, San Francisco 1980, p265.

Reference 8. T.R. Reddy, K. Thyagarajan, O.A. Montero, S. R. L. Reddy, T. Endo, Journal of Minerals and Materials Characterization and Engineering, 2014, 2, pp 114-120.

Reference 9. A. OBADIAH, R. KANNAN, P. RAVICHANDRAN, A. RAMASUBBU, S. VASANTH KUMAR, Digest Journal of Nanomaterials and Biostructures, Vol. 7, No. 1, January - March 2012, p321 - 327

Reference 10. J.E. McMurry and R.C.Fay, General Chemistry, Pearson 2014, Chap.20.5 (translated "General Chemistry" 　Freedom Academy 2014, p838.

Reference 11. N.W. Ashcroft and N.D. Mermin, Solid State Physics, Thomson Learning, Singapore 1976, p96

Reference 12. https://en.wikipedia.org/wiki/Tar_(tobacco_residue)

Reference 13. B. K. Peterson & K. E. Gubbins, Molec. Phys. 1987, 62, 215-226

Reference 14. Silvera, I. F. & Goldman, V. V. J. Chem. Phys. 1978, 68, 4209-4213

Reference 15. M. P. Suh et al., Chemical Reviews 2012, 112, 782-835

Although the present invention has been described with reference to the drawings and embodiments, these are merely exemplary, and it will be understood by those skilled in the art that various modifications and equivalent other embodiments are possible therefrom. Accordingly, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

100: organic-inorganic hybrid compound 110: inorganic layer
120: organic layer d: layer thickness
PS: smooth surface of inorganic layer

Claims (9)

As a method for producing an organic-inorganic hybrid compound, the method for producing the organic-inorganic hybrid compound,
preparing a compound having a gibbsite structure by a method other than hydrothermal synthesis using a trivalent metal cation source, an alkali imparting agent, and a first solvent (S10); and
Using the compound of the gibbsite structure, a divalent metal cation source, dicarboxylic acid, and a second solvent to prepare an organic-inorganic hybrid compound by a method other than hydrothermal synthesis (S20),
The organic-inorganic hybrid compound is a method for producing an organic-inorganic hybrid compound having a gibbsite structure. According to claim 1,
The trivalent metal cation source is an organic-inorganic source of trivalent metal cations including Al ³⁺ , Fe ³⁺ , Cr ³⁺ , B ³⁺ , Ga ³⁺ , In ³⁺ , Y ³⁺ or a combination thereof. A method for preparing a hybrid compound. According to claim 1,
The alkali-imparting agent is NaOH, LiOH, KOH, LiBH ₄ , NaBH ₄ , KBH ₄ , LiH, NaH, LiAlH ₄ , NaAlH ₄ , KAlH ₄ , ( i -Bu ₂ AlH) ₂ , LiHCO ₃ , NaHCO ₃ , KHCO _{3 ,} Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , NH ₄ OH or a method for producing an organic-inorganic hybrid compound comprising a combination thereof. According to claim 1,
The first solvent or the second solvent is a method for producing an organic-inorganic hybrid compound comprising water. According to claim 1,
The method for producing an organic-inorganic hybrid compound, wherein the compound of the gibbsite structure is amorphous in the XRD analysis result. According to claim 1,
The divalent metal cation source is 2 including Zn ²⁺ , Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ or a combination thereof A method for producing an organic-inorganic hybrid compound that is a source of a metal cation. According to claim 1,
The dicarboxylic acid is terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, unde Candiic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethyl glutaric acid, maleic acid, acetylenedicarboxylic acid, glutaconic acid, 2-disenedioic acid, traumatic acid, muconic acid, Glutinic acid, citraconic acid, mesaconic acid, itaconic acid, tartronic acid, mesosalic acid, malic acid, tartaric acid, oxaloacetic acid, aspartic acid, glutamic acid, diaminopimelic acid, saccharic acid and 2,6-naphthalene A method for producing an organic-inorganic hybrid compound comprising a dicarboxylic acid or a combination thereof. According to claim 1,
The step (S10) comprises dissolving the trivalent metal cation source in the first solvent to prepare a first metal salt solution (S10-1), dissolving the alkali imparting agent in the first solvent to prepare an alkali solution A method for producing an organic-inorganic hybrid compound comprising the step of preparing (S10-2), and synthesizing a compound having a gibbsite structure by contacting the first metal salt solution and the alkali solution at room temperature (S10-3). According to claim 1,
The step (S20) is a step (S20-1) of obtaining a mixture by mixing the compound of the gibbsite structure, the divalent metal cation source, the dicarboxylic acid and the second solvent (S20-1), and 50~ A method of producing an organic-inorganic hybrid compound comprising the step (S20-2) of synthesizing an organic-inorganic hybrid compound by heating to 90° C. and maintaining it for 3 to 72 hours.

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