KR101094075B1 - Novel organic­inorganic hybrid nano porous material and method for preparing thereof - Google Patents

Abstract

The present invention relates to a novel organic-inorganic hybrid nanoporous body consisting of a tetravalent metal ion or a compound containing the same, and an organic ligand, and a method for producing the same.

Porous coordination polymer, organic / inorganic hybrid nanoporous body, tetravalent metal ion, titanium, adsorbent

Description

New organic-inorganic hybrid nanoporous body and its manufacturing method {NOVEL ORGANIC®INORGANIC HYBRID NANO POROUS MATERIAL AND METHOD FOR PREPARING THEREOF}

The organic-inorganic hybrid nanoporous body may be defined as a porous organic-inorganic polymer compound formed by combining a central metal with an organic ligand, and a crystalline compound containing both organic and inorganic substances in a skeletal structure and having a molecular size or a nano-sized pore structure. Means. Organic-inorganic hybrid nanoporous body is a term in a broad sense, commonly referred to as porous coordination polymers [Angew. Chem. Intl. Ed., 43, 2334, 2004], also called metal-organic framework (MOF) [Chem. Soc. Rev., 32, 276, 2003]. Research into these materials has been actively studied in recent years by combining molecular coordination and material science.

Organic-inorganic hybrid nanoporous materials have a high surface area and molecular or nano-sized pores, which are used in adsorbents, gas storage, sensors, membranes, functional thin films, catalysts and catalyst carriers, as well as trapping guest molecules smaller than pore sizes. Pores can be used to separate molecules according to their size.

Recently, many new organic-inorganic hybrid nanoporous bodies have appeared, but organic-inorganic hybrid nanoporous bodies having new inorganic structural units are difficult to ensure stability and catalytic reactivity, and thus organic-inorganic hybrid nanoporous having new inorganic structural units. Sieve is rare.

In the synthesis of organic-inorganic hybrid nanoporous bodies, the stability of the organic ligand is easily controllable, but the action of the inorganic structural unit and the interaction between the organic ligand and the inorganic structural unit are very difficult to predict. Therefore, in the synthesis of the organic-inorganic hybrid nanoporous body, there is a difficulty in selecting any metal ion in the case of the inorganic structural unit, but the discovery of the inorganic structural unit forming a stable organic-inorganic hybrid nanoporous body is successful. Once again, it is relatively easy to reproduce this structural unit or in combination with a new organic ligand. This fact is revealed by the isorecular synthesis of the same reticulated phase of IRMOF-1-16 and the fact that the following novel organic-inorganic hybrid nanoporous bodies are based on a few very few symmetric inorganic units: Cu ₂ (OH) ₂ (CO ₂ ) ₄ units of HKUST-1, Zn ₄ O (CO ₂ ) ₆ units of MOF-5 and Cr ₃ O (OH) ₃ (CO ₂ ) ₆ units of MIL-88.

Structural stability of the organic-inorganic hybrid nanoporous body is mainly determined by the strength of the individual chemical bonds between the inorganic unit and the organic ligand and the inorganic unit. It has been reported that the stability of the hybrid structure by the metal atom-nitrogen bond is excellent, but the stability is not constant according to the inorganic structural unit to be bonded, it has not been proposed the ultimate solution. As such, stable, flexible inorganic structural units are the most important part in the development of new and commercially available hybrid structures, which can never be arbitrarily chosen.

Thus, the present inventors have succeeded in the synthesis of novel organic-inorganic hybrid nanoporous body using a novel inorganic structural unit.

In one embodiment, the organic-inorganic hybrid nanopore is one comprising a tetravalent metal ion or a compound comprising the same, and an organic compound capable of acting as an organic ligand.

In one embodiment, the tetravalent metal ions may comprise Ti ⁴⁺ , Zr ⁴⁺ , or Sn ⁴⁺ metal ions.

In one embodiment, examples of compounds comprising metal ions include metal halides, metal oxy halides (eg TiOCl ₂ ), metal oxy sulfates (eg TiOSO ₄ ), metal nitrates, metal acetates (acetate) ), Metal carbonyl, metal salts such as metal alkoxides, or hydrates thereof. Halogen includes F, Cl, Br, or I.

), 아미드기 (-CONH₂), 술폰산기 (-SO₃H), 술폰산의 음이온기(-SO₃ ^-), 메탄디티오산기(-CS₂H), 메탄디티오산의 음이온기(-CS₂ ^-), 피리딘기, 피라진기 등을 포함할 수 있으나 이에 제한되는 것은 아니다.In one embodiment, an organic compound capable of acting as an organic ligand includes an organic compound having a functional group capable of coordinating, and it is also possible to have a site for coordinating so that it can be coordinated under reaction conditions. In some embodiments, examples of functional groups capable of coordinating acid group (-CO _3), of the acid anion group (-CO ₂ ^-), an anion group of a carboxyl group, a carboxylic acid (carboxylate), an amino group (-NH ₂₎ , Iminogi (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS of ₂ ^-), but it may comprise a pyridine group, a pyrazine group or the like without being limited thereto.

In one embodiment, the compound having an anionic group of carboxylic acid is benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalenetricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid It is a compound derived from a compound selected from the group consisting of acid, formic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, hexanedioic acid, heptanedioic acid, cyclohexyldicarboxylic acid and dihydroxyterephthalic acid.

In one embodiment, the organic ligands are benzenedicarboxylates such as 1,4-benzenedicarboxylate (BDC), and biphenyl-dicarboxes such as 4,4'-biphenyl-dicarboxylate. Carboxylate (BPDC), terphenyl dicarboxylate (TPDC), derivatives thereof, solvates thereof, hydrates thereof or combinations thereof.

The embodiments described in the detailed description and claims of the invention are not limiting. Other embodiments may be utilized, and changes may be made, without departing from the spirit or scope of the subject matter presented herein.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention relates to novel organic-inorganic hybrid nanoporous bodies using tetravalent metal ions or compounds containing the same, and organic compounds capable of acting as organic ligands, which have not been reported to date.

In one embodiment, the tetravalent metal ions comprise Ti ⁴⁺ , Zr ⁴⁺ , or Sn ⁴⁺ .

The present inventors act not only as a particularly stable inorganic constituent unit in the bonding of oxygen-containing organic ligands which encapsulate the metal elements with -O-, -OH, on the basis that the metal ions interact strongly with oxygen. Rather, it has been found that organic-inorganic hybrid nanoporous bodies containing such inorganic structural units can be elongated through synthesis without losing the stability of organic ligands, unlike conventional ones. In addition, when the organic-inorganic hybrid nanoporous body having the metal element as an inorganic structural unit and an organic ligand including a dicarboxylate group are used together, the edge of the polygonal structure of the organic-inorganic hybrid nanoporous body contains a dicarboxylate group. It was found that can be linked by the carboxylate group (-CO ₂ ) of the organic ligand to form a stable structure. In one embodiment, Ti is a Group 4 transition element, which has a particularly strong interaction with oxygen, so that Ti tetravalent metal ions can be used as the inorganic structural unit of the novel organic-inorganic hybrid nanoporous body.

The weakest part of the structure of the organic-inorganic hybrid nanoporous body having a tetravalent metal ion or a compound containing the same as an inorganic structural unit is an internal bond of an organic ligand, and a bond between the organic ligand and an inorganic structural unit or an organic-inorganic hybrid nanopore. It is not the sieve structure itself. This demonstrates the ultimate thermal stability of organic-inorganic hybrid structures with tetravalent metal ions as inorganic building blocks.

In the application of the organic-inorganic hybrid nanoporous material, the structural resistance and mechanical pressure of the organic-inorganic hybrid nanoporous material with respect to the solvent is very important, and in the case of the organic-inorganic hybrid nanoporous material having the above characteristics, water, DMF, benzene And after stirring for 24 hours in a solvent such as acetone, it was confirmed that it was present in a stable state without change.

One aspect of the present invention based on the above points is a novel, structurally very stable compound comprising a tetravalent metal ion or a compound comprising the inorganic structural unit, which has not been reported before, and an organic compound capable of acting as an organic ligand. It relates to an organic-inorganic hybrid nanoporous body. In one embodiment, the organic ligands are benzenedicarboxylate (BDC), biphenyl-dicarboxylate, terphenyldicarboxylate (TPDC), including -O-, -OH, -CO ₂ , Derivatives, solvates thereof, hydrates thereof or combinations thereof.

One embodiment of the present invention relates to a novel organic-inorganic hybrid nanoporous body comprising the tetravalent metal ion described above or a compound comprising the same, and an organic compound capable of acting as an organic ligand.

The novel organic-inorganic hybrid nanoporous body can be synthesized by any known method, and known manufacturing methods may include hydrothermal synthesis, solvothermal synthesis, microwave irradiation, and sono synthesis method. have.

In one embodiment, the organic-inorganic hybrid nanoporous body may be prepared by hydrothermal synthesis using solvent diffusion at room temperature or using water as a solvent to react at high temperature.

In another embodiment, the organic-inorganic hybrid nanoporous body can be prepared through solvothermal synthesis using an organic material as a solvent (Microporous Mesoporous Mater., Vol 73, p. 15 (2004)).

In another embodiment, the organic-inorganic hybrid nanoporous body uses water or a suitable organic solvent, similar to the process for preparing other inorganic porous materials such as zeolites or mesoporous compounds, and the boiling point synthesis temperature and nature of the solvent or mixed solution. It is generally prepared through a crystallization process under an autogeneous pressure state.

In some embodiments, metal ions or a compound thereof and an organic ligand are stirred or ultrasonically irradiated for a predetermined time in the presence of a solvent to allow organic substances to be coordinated with the metal to form crystal nuclei. Irradiation may be performed to carry out the crystallization reaction.

In one embodiment the organic-inorganic hybrid nanoporous body can be prepared by a manufacturing method comprising the following steps:

1) preparing a reactant mixture by mixing a tetravalent metal ion or a compound including the same, an organic compound capable of acting as an organic ligand, and a solvent; And

2) heating the reactant mixture.

The metal ions and organic ligands are as described in the relevant section.

The solvent is not limited, but a solvent capable of dissolving both metal ions or a compound containing the same and an organic compound capable of acting as an organic ligand can be used. In some embodiments, examples of solvents are water, alcohols, ketones, hydrocarbons, N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc ), Acetonitrile, dioxane, chlorobenzene, pyridine, N-methyl pyrrolidone (NMP), sulfolane, tetrahydrofuran (THF), gamma-butyrolactone, cycloaliphatic alcohols such as cyclohexanol and the like However, it is not limited thereto. In other embodiments, two or more solvents may be used in combination. In another embodiment, as the solvent, water; Mono or polyalcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, alkylene polyols such as EG (ethylene glycol), glycerol, polyalkylene polyols such as polyethylene glycol; ketones having 2 to 10 carbon atoms, such as One or two or more selected from acetone, methyl ethyl ketone, acetylacetone, and the like, and hydrocarbons having 4 to 20 carbon atoms (e.g., linear and cyclic alkanes having 4 to 10 carbon atoms, such as hexane, heptane, octane, toluene, etc.) Mixtures may be used In some exemplary embodiments, water, EG, DMF, THF may be used as the solvent.

The heating method is not limited and may be a conventional heating method. In an exemplary embodiment the heating method can be a heating method using electric heating or microwaves. The range of microwaves in the case of using a heating method using microwaves is not substantially limited. In one embodiment, microwaves of 1 to 30 GHz can be irradiated, and in an exemplary embodiment, the frequency is widely used industrially. You can irradiate microwaves at 2.54 GHz.

The heating temperature of the reactant mixture is not substantially limited. In some embodiments, the heating temperature of the reactant mixture may be at least room temperature. In other embodiments, the heating temperature of the reactant mixture may be at least 20 ° C., and in another embodiment, the heating temperature of the reactant mixture may be at least 50 ° C., at least 60 ° C., at least 80 ° C., or at least 100 ° C.

In the heating step of the reactant mixture, the reaction pressure is not substantially limited. In one embodiment, the reaction can be carried out by setting the reaction pressure to the autogeneous pressure of the reactants at the reaction temperature in the reactor. In another embodiment, the reaction can be carried out under high pressure by adding an inert gas such as nitrogen, helium. The molar ratio of tetravalent metal ions or a compound containing the same and an organic compound capable of acting as an organic ligand can be appropriately adjusted according to the kind of the metal component and the organic compound used. In one embodiment, the molar ratio of the metal ion or the compound including the same and the organic compound capable of acting as an organic ligand may be 1: 0.1 to 500, but is not limited thereto. In another embodiment, the molar ratio of the metal ion or the compound comprising the same and the organic compound capable of acting as an organic ligand may be 1: 0.1 to 100 or 1: 0.1 to 10.

In some embodiments, the organic-inorganic hybrid nanopore can be prepared by a manufacturing method comprising the following steps:

1) a pretreatment step of mixing a tetravalent metal ion or a compound comprising the same, an organic compound capable of acting as an organic ligand, and a solvent to form crystal nuclei in which the organic ligand is coordinated with the metal; And

2) performing crystallization by irradiating microwaves to the reaction solution in which the crystal nuclei are formed.

On the other hand, in the above embodiment using a microwave by stirring or ultrasonically irradiating a metal ion or a compound thereof and an organic ligand in a solvent for a predetermined time to form a crystal nucleus by coordinating the organic matter with the metal, the crystal nucleus is formed as described above The reaction solution may be irradiated with microwaves to carry out a crystallization reaction. In some embodiments, the method described above, in the case where microwave is applied as a heat source of a high temperature reaction, a predetermined pretreatment of a metal material and an organic material in the presence of a solvent in order to be able to produce an organic-inorganic hybrid nanoporous body by microwave irradiation. You may go through the steps.

The pretreatment temperature is not substantially limited, but may be maintained below 100 ° C. in an exemplary embodiment. Because microwave reactions occur at very high rates, a pretreatment step can be performed to increase the homogeneity and solubility of the reactants. In some exemplary embodiments, when irradiated with microwaves without the pretreatment step, the crystallization reaction of the organic-inorganic hybrid proceeds slowly, and impurities may be mixed during the reaction.

The above pretreatment step is carried out, for example, by stirring at 10 to 2000 rpm, or by irradiating with ultrasonic waves, and the pretreatment temperature is preferably a room temperature (approximately 20 to 25 ° C.) crystallization reaction temperature range. If the pretreatment temperature is low, the effect of the pretreatment is not sufficient, and sufficient crystal nuclei are not generated. If the pretreatment temperature is high, impurities may be easily generated, and the pretreatment facility may be complicated.

In one embodiment, a crystallization step of forming an organic-inorganic hybrid nanoporous body may be performed by irradiating microwaves to the reaction solution in which the nuclei are formed.

The production method by microwave irradiation can be carried out not only batchwise but also continuously. Batch reactors are suitable for producing small amounts of organic-inorganic hybrid nanoporous materials with low output per hour, while continuous reactors are expensive and are suitable for mass production. The reaction time is not limited, but may be 1 minute to 8 hours for batch, 1 minute to 2 hours for some embodiments, 1 minute to 2 hours for exemplary embodiments, and if the reaction time is too long, the incorporation of impurities It may happen. The residence time of the continuous reactor may be from 1 minute to 1 hour, in some embodiments from 1 minute to 20 minutes, with too long residence time resulting in low productivity and too short residence time resulting in low reaction conversion. If a batch reactor is used, the reactants may be agitated during the reaction, although the stirring speed is not limited but in one embodiment may be 10-2000 rpm. In another embodiment, the process can be performed without agitation, and agitation may be simple and easy to apply in reactor configuration or operation.

In one embodiment, the organic-inorganic hybrid nanoporous material is a powder, thin film, membrane, pellet, ball, foam, slurry, paint, paste, honeycomb, beads, mesh, fiber, corrugated sheet, It may be provided in the form of a rotor, etc., but is not limited to a specific form. For example, the organic-inorganic hybrid nanoporous body in the form of a thin film or a membrane may be prepared by immersing a predetermined substrate in a reactant mixture and then heating. In other embodiments, shaped bodies such as pellets, beads, honeycombs, meshes, membranes can be prepared using suitable organic or inorganic binders.

In some embodiments, the added organic and inorganic binder does not exceed 50% of the weight of the organic-inorganic hybrid nanoporous body and the powder. In one exemplary embodiment, examples of inorganic binders include silica, alumina, layered compounds, metal alkoxides, metal halides, and the like, and in other exemplary embodiments, examples of organic binders include one or more alcohols and cellulose, poly Vinyl alcohol, polyacrylate, and the like.

Another aspect of the present invention relates to the use of organic-inorganic hybrid nanoporous bodies, which can be used as absorbents for the storage, separation and chemical reaction of gas, liquid and solid materials. Target gases include hydrocarbons such as hydrogen, oxygen, nitrogen, methane, paraffin, and olefins, and carbon monoxide, hydrogen sulfide, ammonia, formaldehyde, amines, etc., and VOCs (volatile organic compounds, volatile organic compounds) as odorants as liquids. And disinfectants and gasoline, diesel, oil, alcohol, and the like. As a solid, it is possible to adsorb noble metal ions such as Pt and Pd and sub-nanoparticles of 1 nm or less or harmful substances such as Hg and Cr. In particular, it can be used as a useful adsorbent such as hydrogen, carbon dioxide adsorption / separation and olefin / paraffin.

In another embodiment, the organic-inorganic hybrid nanoporous body can be used as a heterogeneous catalyst, photocatalyst and moisture adsorbent. The organic-inorganic hybrid nanoporous material disclosed above is easy to desorb even at low temperatures (eg, 100 ° C. or less), has a high water adsorption amount per unit weight of the organic-inorganic hybrid nanoporous material, and has a fast adsorption rate.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1 Preparation of Organic-Inorganic Hybrid Nanoporous Ti-BDC

2.27 mmol of TiCl _{4 and} 2.27 mmol of 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, followed by addition of 680 mmol of N, N-dimethylformamide (DMF). The reaction was stirred for 20 minutes at 50 rpm at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 1 hour, and then cooled and washed to room temperature. (Distilled water) and dried to obtain an organic-inorganic hybrid nanoporous material (Ti-BDC). In addition, it was confirmed that the crystal XRD pattern of the organic-inorganic hybrid nanoporous body ^{composed of} Ti ⁴⁺ and 1,4-benzenedicarboxylate is consistent with the literature values of the hybrid nanoporous body including Zr [J. Am. CHEM. SOC. 130, 13850, 2008], but the same structure, but the surface area measurement results are 635m ² / g, the particle size distribution is also very uniform, it can be confirmed that the stability.

Example 2 Preparation of Organic-Inorganic Hybrid Nanoporous Ti-BPDC

2.27 mmol of TiCl _{4 and} 2.27 mmol of 4,4'-biphenyldicarboxylate (BPDC) were added to the Teflon reactor, followed by addition of 680 mmol of N, N-dimethylformamide (DMF). The reaction was stirred for 20 minutes at 50 rpm at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 1 hour, and then cooled and washed to room temperature. (Distilled water) and dried to obtain an organic-inorganic hybrid nanoporous material (Ti-BPDC). The crystal structure of the prepared coordination polymer confirmed that the diffraction pattern was obtained at the same position as in Example 1 as a result of XRD analysis. Analysis of the electron microscope confirmed that the particle size was about 350 nm uniform.

Example 3 Preparation of Organic-Inorganic Hybrid Nanoporous Ti-TPDC

2.27 mmol of TiCl _{4 and} 2.27 mmol of terphenyldicarboxylate (TPDC) were added to the Teflon reactor, followed by addition of 680 mmol of N, N-dimethylformamide (DMF). The reaction was stirred for 20 minutes at 50 rpm at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 1 hour, and then cooled and washed to room temperature. (Distilled water) and dried to obtain an organic-inorganic hybrid nanoporous material (Ti-TPDC). The crystal structure of the prepared coordination polymer showed that the diffraction pattern was obtained at the same position as in Example 1, although the relative intensity of the peak was different from the XRD analysis result.

Example 4 Preparation of Organic-Inorganic Hybrid Nanoporous Ti-BDC Using Metal Sulfate

2.27 mmol of TiOSO _{4 and} 2.27 mmol of 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, followed by addition of 680 mmol of N, N-dimethylformamide (DMF). The reaction was stirred for 20 minutes at 50 rpm at room temperature to prepare a mixed reaction. The reaction mixture was mounted in a hydrothermal reactor containing the reactant and held at an electric oven at 120 ° C. for 12 hours to perform a crystallization reaction, and then cooled to room temperature, washed (distilled water) and dried to obtain an organic-inorganic hybrid nanoporous material (Ti-TPDC). did. The crystal structure of the prepared coordination polymer showed that the diffraction pattern was obtained at the same position as in Example 1, although the relative intensity of the peak was different from the XRD analysis result.

Example 5 Fabrication of Organic-Inorganic Hybrid Nanoporous Zr-BDC

ZrCl ₄ and 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor followed by the addition of N, N-dimethylformamide (DMF) to give a final molar ratio of Zr: H ₂ BDC: DMF = 1: 1: 1497. The reaction was stirred for 20 minutes at 50 rpm at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone, Inc.), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 2 hours, and then cooled and washed to room temperature. (Distilled water) and dried to obtain an organic-inorganic hybrid nanoporous body (Zr-BDC). It was confirmed that the XRD pattern of the crystals obtained in this example is consistent with the literature values [J. AM. CHEM. SOC. 130, 13850, 2008]. XRD analysis showed that the crystal structure of the prepared organic-inorganic hybrid nanoporous body had a diffraction pattern obtained at the same position as that of the organic-inorganic hybrid nanoporous body containing Zr, although the relative intensity of the peak was different.

Example 6 Preparation of Organic-Inorganic Hybrid Nanoporous Zr-BDC with Various Solvents

0.227 mmol of ZrCl _{4 and} 0.227 mmol of 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, and N, N-dimethylformamide (DMF) and 2-propanol were added at a molar ratio of 5: 5. It was. The Teflon reactor containing the reactant was mounted on a microwave reactor (Milestone), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 1 hour, and then cooled and washed to room temperature. (Distilled water) and dried to obtain a porous coordination polymer (Zr-BDC). The crystal structure of the prepared coordination polymer showed that the diffraction pattern was obtained at the same position as Example 5, although the relative intensity of the peak was different from the XRD analysis result.

Example 7 Preparation of Porous Coordination Polymer Zr-BDC with Various Solvents

0.227 mmol of ZrCl _{4 and} 0.227 mmol of 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, and N, N-dimethylformamide (DMF) and ethanol were added at a molar ratio of 5: 5. The Teflon reactor containing the reactant was mounted on a microwave reactor (Milestone), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 1 hour, and then cooled and washed to room temperature. (Distilled water) and dried to obtain a porous coordination polymer (Zr-BDC). The crystal structure of the prepared coordination polymer showed that the diffraction pattern was obtained at the same position as Example 5, although the relative intensity of the peak was different from the XRD analysis result.

From the results of the above examples, it can be seen that a novel organic-inorganic hybrid nanoporous body having a compound of tetravalent metal ions as an inorganic structural unit can be stably obtained.

Claims (15)

An organic-inorganic hybrid nanoporous body comprising a tetravalent metal ion selected from the group consisting of Ti ⁴⁺ and Sn ⁴⁺ , or a compound comprising the same, and an organic compound capable of acting as an organic ligand. metal ion or compound is M ₆ O ₄ (OH) ₄ structure (M is Ti or Sn) in, nanoporous inorganic hybrid material comprising the same. The organic-inorganic hybrid nanoporous body according to claim 1, wherein the tetravalent metal ion is Ti ⁴⁺ . The organic-inorganic hybrid nanoporous body according to claim 1, wherein the tetravalent metal ion is Sn ⁴⁺ . The organic compound according to any one of claims 1 to 3, wherein the organic compound capable of acting as the organic ligand is benzenedicarboxylate, biphenyl-dicarboxylate, terphenyl dicarboxylate, derivatives thereof, these An organic-inorganic hybrid nanoporous body which is a solvate of these, a hydrate thereof, or a combination thereof. The organic-inorganic hybrid nanoporous material according to claim 1 or 2, wherein the organic-inorganic hybrid nanoporous material is powder, thin film, membrane, pellet, ball, foam, slurry, paint, paste, honeycomb, bead, mesh, fiber, corrugated cardboard. An adsorbent in the form of a corrugated sheet or a rotor. An adsorbent capable of selectively adsorbing olefins, comprising the organic-inorganic hybrid nanoporous body of claim 1. A hydrogen, hydrocarbon, hydrogen sulfide, volatile organic compound and carbon dioxide adsorbent containing the organic-inorganic hybrid nanoporous body of claim 1 or 2. A heterogeneous catalyst comprising the organic-inorganic hybrid nanoporous body of claim 1 or 2. The photocatalyst containing the organic-inorganic hybrid nanoporous body of Claim 1 or 2. A moisture adsorption agent comprising the organic-inorganic hybrid nanoporous body of claim 1 or 2. Method for producing an organic-inorganic hybrid nanoporous body comprising the following steps 1) and 2), wherein the tetravalent metal ion or a compound comprising the same is M ₆ O ₄ (OH) ₄ structure (M is Ti or Sn): 1) preparing a reactant mixture by mixing a tetravalent metal ion selected from the group consisting of Ti ⁴⁺ and Sn ⁴⁺ or a compound including the same, an organic compound capable of acting as an organic ligand, and a solvent; And 2) heating the reactant mixture. Method for producing an organic-inorganic hybrid nanoporous body comprising the following steps 1) and 2), wherein the tetravalent metal ion or a compound comprising the same is M ₆ O ₄ (OH) ₄ structure (M is Ti or Sn): 1) preparing a reactant mixture by mixing a tetravalent metal ion selected from the group consisting of Ti ⁴⁺ and Sn ⁴⁺ or a compound including the same, an organic compound capable of acting as an organic ligand, and a solvent; And 2) heating the reactant mixture with microwaves. The organic compound according to claim 11 or 12, wherein the organic compound capable of acting as the organic ligand is benzenedicarboxylate, biphenyl-dicarboxylate, terphenyldicarboxylate, derivatives thereof, solvates thereof, The organic-inorganic hybrid nanoporous body manufacturing method characterized by these hydrates or these combination. The method for producing an organic-inorganic hybrid nanoporous body according to claim 11 or 12, wherein the tetravalent metal ion is Ti ⁴⁺ . The method of claim 11 or 12, wherein the tetravalent metal ion is Sn ⁴⁺ method for producing an organic-inorganic hybrid nanoporous body.