KR20100122300A - Method for preparing organic-inorganic hybrid nano porous material, organic-inorganic hybrid nano porous materials obtained by said method and use as an absorbent - Google Patents

Abstract

PURPOSE: A manufacturing method of an organic-inorganic hybrid nanoporous material, the organic-inorganic hybrid nanoporous material manufactured therefrom, and the use thereof as an adsorber are provided to synthesize the nanoporous material using a microwave irradiation method. CONSTITUTION: A manufacturing method of an organic-inorganic hybrid nanoporous material comprises the following steps: stirring a divalent metal ion, dihydroxy-terephthalate organic ligand, and solvent, or ultrasonic wave processing the mixture to form a crystal nucleus with an organic ligand covalent-bonded with metals; and irradiating microwaves to a reaction solution including the crystal nucleus.

Description

Method for producing organic-inorganic hybrid nanoporous body, organic-inorganic hybrid nanoporous body obtained by the above method and use as adsorbent thereof AND USE AS AN ABSORBENT}

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.

The present invention relates to a method for preparing an organic-inorganic hybrid nanoporous body, which is a porous coordination polymer that reacts divalent metal ions with dihydroxyterephthalate, and more specifically, to an adsorbent application of the organic-inorganic hybrid nanoporous body. In the preparation of MOF (Metal-organic framework), which is an organic-inorganic hybrid nanoporous body by reacting divalent metal ions with dihydroxyterephthalate, the organic-inorganic hybrid nanopore is reduced by using a microwave irradiation method and uniform particle distribution. An effective method for synthesizing a sieve is provided. In particular, the organic-inorganic hybrid nanoporous body prepared by the present invention has a high surface area and molecular size or nano-sized pores, so as to adsorbents, gas storage, sensors, membranes, functional thin films, catalysts and catalyst carriers, and adsorbents of gases and moisture, etc. It can be used to capture guest molecules smaller than pore size or to separate molecules using pore size.

The organic-inorganic hybrid nanoporous body prepared according to the present invention may be defined as a porous organic-inorganic polymer compound formed by the coordination bond of divalent metal ions and dihydroxyterephthalate, and includes both organic and inorganic substances in the skeleton structure. It means a crystalline compound having a molecular size or nano-sized pore structure. 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.

In this regard, Ni-MOF, an organic-inorganic hybrid nanoporous body using Ni ²⁺ metal ions and 2,5-dihydroxyterephthalate as a hydrogen storage material, was generally synthesized by hydrothermal synthesis using an electric heating method (Chem. Commun. 959-961, 2006). In addition, porous coordination polymers made of divalent cations such as Co, Ni, Zn and Mg and 2,5-dihydroxyterephthalate (DOT), which can be applied as adsorption material of carbon dioxide by electrothermal synthesis, (J. Am. Chem. Soc., 130, 10870-10871, 2008). Recently, Ni-MOF, which can adsorb carbon dioxide even at a high temperature of 80 ° C, has been reported (Chem. Commun. 5125-5127, 2008).

Organic-inorganic hybrid nanoporous bodies are manufactured by various methods, and typically, by using a solvent diffusion or near water at room temperature using hydrothermal synthesis or an organic material as a solvent. Prepared by solvothermal synthesis [Microporous Mesoporous Mater., Vol73, p. 15 (2004)]. The organic-inorganic hybrid nanoporous body uses water or a suitable organic solvent, similar to other inorganic porous materials such as zeolites or mesoporous compounds, to synthesize boiling point of solvent or mixed solution and autogeneous pressure. It is generally prepared through a crystallization process under). However, the preparation method is very slow in the nucleation or crystallization process to obtain a complete crystalline organic-inorganic hybrid usually requires a reaction time of more than a few days, so excessive energy is consumed, and in particular, the reaction proceeds only in batch form, so the efficiency is very low. Angew. Chem. Intl. Ed. Vol. 42, p. 5314 (2003); Angew. Chem. Intl. Ed. Vol. 43, p. 6296 (2004)). That is, the existing inefficient synthesis method of the organic-inorganic hybrid nanoporous body has been pointed out as an obstacle to industrial applications because it increases the manufacturing cost. Thus, in order to solve the problems of the prior art, the present inventors are organic-inorganic hybrid formed by divalent metal ions and dihydroxy terephthalate, preferably, divalent metal ions and 2,5-dihydroxy terephthalate In the preparation of nanoporous bodies, a new manufacturing process using microwaves was developed to develop a method for preparing crystalline organic-inorganic hybrid nanoporous bodies having a relatively small and uniform particle size distribution. In addition, the inventors of the present invention have attempted to develop an adsorbent including an organic-inorganic hybrid nanoporous body obtained by the novel manufacturing method, and in particular, an adsorbent that is easy to adsorb and desorb hydrogen, olefin / paraffin and carbon dioxide.

Accordingly, the present invention, in order to solve the problems of the prior art, by stirring a divalent metal ion and dihydroxy terephthalate in the presence of a solvent such as water or an organic solvent for a certain time, the organic material coordinates with the metal to crystallize nuclei When the crystallization reaction is carried out by irradiating microwaves to the reaction solution in which the crystal nuclei are formed as described above, the rapid reaction characteristics of the microwaves are sufficiently expressed, thereby completing the present invention. According to the present invention, the organic-inorganic hybrid nanoporous body can be manufactured in a short reaction time, and thus energy consumption can be reduced, which is economically and environmentally useful, and it can be produced in batch as well as continuously in a short time reaction. The organic-inorganic hybrid nanoporous body can be manufactured in a short time, and a high surface area organic-inorganic hybrid nanoporous body which can not be obtained by conventional electric heating, which has been required for a long time, can be manufactured. Accordingly, the present invention provides a mixture of divalent metal ions (Co, Ni, Cu, Zn, Fe, Mg, Ca, Mn) and 2,5-dihydroxyterephthalate (DHT) that has not been reported to date by microwave irradiation. It is an object of the present invention to provide a method for producing an organic-inorganic hybrid nanoporous material, and to provide a use as an olefin / paraffin and carbon dioxide adsorbent of the prepared porous coordination polymer.

The present invention provides a method for preparing an organic-inorganic hybrid nanoporous body by heat-treating a divalent metal ion and a dihydroxyterephthalate organic ligand as a reaction raw material in the presence of a solvent, and in the presence of the metal ion, an organic substance, and a solvent. Pre-treatment step of stirring or irradiating with ultrasonic waves to form crystal nuclei, and organic-inorganic hybrid nanoporous body for performing crystallization reaction in the range of 60 ~ 250 ℃ by irradiating microwave of 1 ~ 30 GHz to the reaction liquid formed with the crystal nuclei Characterized in that the manufacturing method.

      Hereinafter, the present invention will be described in detail.

The present invention relates to a method for producing an organic-inorganic hybrid nanoporous material (MOF), and more particularly, hydrothermal or solvo thermal after forming a crystal nucleus by a predetermined pretreatment operation in the presence of a metal material and an organic material in a solvent. (solvothermal) As a heat source of the synthesis reaction, instead of the conventional heat treatment such as electric heating to produce an organic-inorganic hybrid nanoporous by irradiating microwave, divalent metal ions and hydroxy terephthalate is bonded, prepared by the method Organic-inorganic hybrid nanoporous body and its adsorbent application. The organic-inorganic hybrid nanoporous body has high surface area and molecular size or nano size pores, so it can be used in adsorbents, gas storage, sensors, membranes, functional thin films, catalysts and catalyst carriers, gas and moisture adsorbents, and more. It can be used to capture small guest molecules or to separate molecules using pore sizes.

That is, the present invention relates to a method for preparing an organic-inorganic hybrid nanoporous body, comprising the following steps:

1) Divalent Metal Ion and Dihydroxyterephthalate Organic Ligand and Solvent

Stirring or treating with ultrasonic waves to form crystal nuclei in which the organic ligands are coordinated with the metal; And

2) performing a crystallization reaction at 60 ~ 250 ℃ by irradiating microwave of 1 ~ 30 GHz to the reaction solution in which the crystal nucleus is formed.

Hereinafter will be described in detail for each step and the manufacturing step of the organic-inorganic hybrid nanoporous body of the present invention.

The present invention is characterized in that the technology can be applied to the microwave instead of the electric heating generally used as a heat source of high temperature reaction, in order to be able to manufacture the organic-inorganic hybrid nanoporous body by the microwave irradiation The metal material and the organic material go through a predetermined pretreatment step in the presence of a solvent.

First, a pretreatment step is performed to form crystal nuclei by irradiating with stirring or ultrasonic waves in the presence of a divalent metal ion, an organic material, and a solvent as a metal material.

As a component constituting the organic-inorganic hybrid nanoporous body of the present invention, the metal material is a divalent metal ion Ni ²⁺ , Fe ²⁺ , Mg ²⁺ , Cu ²⁺ , Ca ²⁺ , Co ²⁺ , Mn ²⁺ , Zn ²⁺ and the like can be used.

The organic material, which is another component of the organic-inorganic hybrid nanoporous body, is also called a linker, and the above-described metal material, dihydroxyterephthalate, and derivatives thereof may be used. Preferably, 2,5-dihydroxyterephthalate is used. As the dihydroxy terephthalate derivative, dihydroxy terephthalate containing Cl, Br, I, NO ₃ , NH ₂ , COOH, SO ₃ H, or the like in the benzene ring may be used.

When preparing an organic-inorganic hybrid nanoporous body, a suitable solvent is required in addition to the metal material and the organic material. The solvent may be water, mono or polyalcohol having 1 to 10 carbon atoms (for example, EG (ethylene glycol), alkylene polyol such as glycerol, polyalkylene polyol such as polyethylene glycol), DMF (dimethyl) Formamide (Dimethylformamide), DEF (Diethylformamide), DMAc (N, N-dimethylacetamide), Acetonitrile, Dioxane, Chlorobenzene, Pyridine, NMP (N -Methyl pyrrolidone), sulfolane, THF (tetrahydrofurane), gamma-butyrolactone, cycloaliphatic alcohols such as cyclohexanol, ketones having 2 to 10 carbon atoms (e.g., methyl ethyl ketone ( MEK), acetone or acetylacetone, and the like) and hydrocarbons having 4 to 20 carbon atoms (preferably, linear and cyclic alkanes having 4 to 10 carbon atoms, such as toluene, etc.), etc., may be used. Can and Desirable is supposed to water, EG, DMF, it is better to use a THF.

The metal material and the organic material may be mixed and used in a ratio (molar ratio) of 1: 0.1 to 500, and the ratio may be appropriately adjusted according to the type of each metal material and the organic material.

In addition, the present invention was found to have an amazing effect that can be completed in a few minutes when synthesized using microwave to prepare the organic-inorganic hybrid nanoporous body. In particular, compared to the synthesis using the electric heating method, despite the very short reaction time (within 10 minutes), the effect of having the same high crystallinity and yield was confirmed. Preferably, the pretreatment temperature is preferably maintained at 100 ° C. or lower, and more preferably 50 ° C. or lower. Since the reaction using microwave occurs at a very high speed, in the present invention, the uniformity and solubility of the reactants are increased, and the crystallization step is performed after the pretreatment step to generate some crystal nuclei. When microwave is irradiated without the above pretreatment step, the crystallization reaction of the organic-inorganic hybrid proceeds slowly, and impurities are easily 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. When the pretreatment temperature is low, the pretreatment effect is weak, and sufficient crystal nuclei are not generated. When the pretreatment temperature is high, impurities are easily generated, and the pretreatment facility has to be complicated.

After performing the pretreatment step as described above, the crystallization step of forming an organic-inorganic hybrid nanoporous body is performed by irradiating microwaves to the reaction solution in which the crystal nuclei are formed.

In the crystallization step, the microwave can be irradiated with a microwave of 1 ~ 30 GHz, preferably using a microwave of 2.54 GHz, which is a frequency commonly used industrially, is easy and efficient.

In the crystallization step, the reaction temperature is not actually limited, but may be performed in a range of 60 to 250 ° C., preferably, 80 to 220 ° C. At this time, if the reaction temperature is less than 60 ℃ the crystallization reaction rate is slow and ineffective, if the reaction temperature exceeds 250 ℃ is easy to obtain a material without pores and the reaction rate is too fast, it is easy to mix impurities, reactor High internal pressures make the construction of the reactor uneconomical.

The pressure in the reactor when performing the crystallization reaction is not practically limited, it is simple to synthesize at the autogeneous pressure of the reactants at the reaction temperature. In addition, an inert gas such as nitrogen or helium may be added to carry out the reaction at a high pressure.

As described above, the present invention, which includes a pretreatment reaction and a crystallization reaction, can be performed in a continuous manner as well as a batch unlike a conventional electric heating method. 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. In the case of a batch type, the reaction time is suitably 1 minute to 8 hours, preferably 1 minute to 1 hour, and when the reaction time is too long, impurities are easily mixed. The residence time of the continuous reactor is suitable for 1 minute to 1 hour, preferably 1 minute to 20 minutes. If the residence time is too long, the productivity is low, and if the residence time is too short, the reaction conversion rate is low. In the case of using a batch reactor, the reactants may be stirred during the reaction. The stirring speed may be 10 to 2000 rpm, but it may be performed without stirring, and the stirring is simple and easy to apply in the reactor configuration or operation. .

The organic-inorganic hybrid nanoporous body MOF can be used as a powder or a molded body. The shape of the shaped body is preferably in the form of pellets, beads, honeycomb, mesh or membrane. In order to produce shaped articles such as pellets, beads, honeycombs, meshes and membranes, suitable organic or inorganic binders can be used and the added oil and inorganic binders preferably do not exceed 50% of the weight of the powder. As the inorganic binder, silica, alumina, layered compounds, metal alkoxides, metal halides, and the like can be used. As the organic binder, at least one alcohol and cellulose, polyvinyl alcohol, polyacrylate, and the like are preferable.

According to the present invention configured as described above, organic-inorganic hybrid nanoporous bodies having characteristics such as high surface area, highly regular crystal structure, and relatively high thermal stability can be produced in a short time, and also drastically shorten the crystallization reaction time. Due to this, organic-inorganic hybrid nanoporous bodies having a relatively high surface area, which are not obtained when conventional electric heating is applied, can be manufactured. In addition, the organic-inorganic hybrid nanoporous body can be used as an absorbent material for the storage, separation and chemical reaction of gas, liquid and solid materials, and the gas is hydrogen, oxygen, nitrogen, methane, paraffin, olefin, etc. Hydrocarbons, carbon monoxide, hydrogen sulfide, ammonia, formaldehyde, amines, etc. are available. Liquids include odorous substances such as VOCs (volatile organic compounds, volatile organic compounds) and fungicides, gasoline, diesel, oils and alcohols. 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.

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

Comparative Example 1. Preparation of organic-inorganic hybrid nanoporous body (Ni-MOF) by electric heating method

Ni (CH ₃ COO) ₂ · 4H ₂ O, and 2,5-dihydroxyterephthalate (DHT) were added to the Teflon reactor, followed by distilled water and THF to add a final molar ratio of Ni: DOBDC: H ₂ O. : THF = 1: 0.5: 367: 140. The Teflon reactor containing the reactant was placed in an electric oven, reacted at 110 ° C. for 3 days, cooled to room temperature, washed with distilled water, and dried to obtain an organic-inorganic hybrid nanoporous material (Ni-MOF). The particle size calculated from the half-width of the FWHM of the XRD pattern was measured at ˜37 nm. It was confirmed that the XRD pattern of the crystals obtained in this comparative example was consistent with the literature values [J. AM. CHEM. SOC. 130, 10870, 2008].

Example 1 Preparation of Organic-Inorganic Hybrid Nanoporous Material (Ni-MOF) by Electromagnetic Waves

Ni (CH ₃ COO) ₂ · 4H ₂ O, and 2,5-dihydroxyterephthalate (DHT) were added to the Teflon reactor, followed by distilled water and THF to add a final molar ratio of Ni: DHT: H ₂ O. : THF = 1: 0.5: 367: 140. 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 (CEM Co., Model Mars-5) and irradiated with microwave (2.54 GHz) to raise the temperature to 110 ° C., and then maintained at 110 ° C. for 10 minutes to perform a crystallization reaction. It cooled to room temperature, wash | cleaned (distilled water), and dried, and obtained the organic-inorganic hybrid nanoporous body (Ni-MOF). 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, 10870, 2008]. The crystal structure of the prepared organic-inorganic hybrid nanoporous body was confirmed that the diffraction pattern was obtained at the same position as the electric heating method, although the relative intensity of the peak was different from the XRD analysis. In particular, it was confirmed that the particle size calculated from the half-width of the FWHM of the XRD pattern was 28 nm, which was smaller than the particle size of the comparative example 1 to 37 nm. In addition, as a result of the electron microscope analysis, the size of the secondary particles of the Ni-MOF prepared by the microwave method was 200 nm, which was 2.5 times less than that of the 500 nm electric heating method of Comparative Example 1.

Example 2 Preparation of Organic-Inorganic Hybrid Nanoporous Material (Mg-MOF) by Electromagnetic Waves

1.85 mmol of Mg (NO ₃ ) .6H ₂ O, and 0.559 mmol of 2,5-dihydroxyterephthalate (DHT) were added to the Teflon reactor, and then DMF-ethanol-water was added to 15: 50 ml was added at 1: 1 (v / v / v). 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 (CEM Co., Model Mars-5), irradiated with microwave (2.54 GHz), heated to 125 ° C., and maintained at 125 ° C. for 1 hour to carry out a crystallization reaction. It cooled to room temperature, wash | cleaned (distilled water), and dried and obtained the organic-inorganic hybrid nanoporous body (Mg-MOF). The crystal structure of the prepared organic-inorganic hybrid nanoporous body was confirmed that the diffraction pattern was obtained at the same position as Example 1, although the relative intensity of the peak was different from the XRD analysis.

Example 3 Preparation of Organic-Inorganic Hybrid Nanoporous Material (Co-MOF) by Electromagnetic Waves

8.67 mmol of Co (NO ₃ ) .6H ₂ O, and 2.43 mmol of 2,5-dihydroxyterephthalate (DHT) were added to the Teflon reactor, and then DMF-ethanol-water was 1: 1. 50 ml was added at 1: 1 (v / v / v). 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 (CEM Co., Model Mars-5), irradiated with microwave (2.54 GHz), heated to 100 ° C., and maintained at 100 ° C. for 1 hour to perform a crystallization reaction. It cooled to room temperature, wash | cleaned (distilled water), and dried, and obtained the organic-inorganic hybrid nanoporous body (Co-MOF). The crystal structure of the prepared organic-inorganic hybrid nanoporous body was confirmed that the diffraction pattern is obtained at the same position as Example 1, although the relative intensity of the peak is different from the XRD analysis.

Example 4 (Ni-CPO) Organic-Inorganic Hybrid Nanoporous Carbon Dioxide Adsorbent Prepared by Microwave Irradiation

In order to analyze the gas adsorption characteristics of the organic-inorganic hybrid nanoporous body Ni-MOF obtained in Example 1, gas adsorption experiments were performed in a glass vacuum manifold equipped with a diffusion pump at low temperature and room temperature. Adsorption data of small gas molecules in the pressure range of 5 to 760 Torr was obtained using standard volumetric techniques. Prior to the gas adsorption experiment, Ni-MOF was maintained at room temperature under vacuum for 1 hour and then slowly activated by heating to a specified temperature between 298K and 523K. The exhaust temperature was 523 K. Highly pure gas was used for the adsorption measurement. Desorption isotherms were obtained by reducing the pressure after adsorption at approximately 760 Torr. 0.2 g was vacuum dried at 250 ° C. for 5 hours and then subjected to CO ₂ adsorption experiment. In addition, 3% graphite and 3% activated carbon were added to the catalyst together in a Teflon barrel, mixed with a ball mill, and pressed using a lab press to form. The coating of the adsorbent was mixed with the catalyst using 10% alumina sol, or mixed with the catalyst using 1-5% carbon and then coated at a speed of 5 mm / min using a dip coater. Compared to the Ni-MOF prepared by the electric heating method, the Ni-MOF produced by the microwave irradiation method showed high carbon dioxide adsorption at room temperature and 75 ° C.

Example 5. Propane / propylene adsorption of organic-inorganic hybrid nanocomposites prepared by (Ni-MOF) microwave irradiation

Adsorption data of small gas molecules in the pressure range of 5 to 760 Torr was obtained using standard volumetric techniques. Prior to the gas adsorption experiment, 0.2 g of Ni-CPO was maintained at room temperature under vacuum (<10 to 5 Torr), then heated to a temperature of 250 ° C. to activate slowly (1 K / min). Highly pure gas was used for the adsorption measurement. Desorption isotherm was obtained at 760 Torr with decreasing pressure after adsorption. Propane / propylene adsorption-desorption isotherms obtained at 40 ° C. were compared to FIG. 4. At 100 Torr the amount of propylene adsorbed to Ni-MOF (137 ml / g) was 1.3 times higher than the amount adsorbed (105 ml / g) of adsorbed propane.

From the results of the above examples and comparative examples, when preparing the organic-inorganic hybrid nanoporous body by microwave from divalent metal ions and dihydroxy terephthalate as in the present application, the organic-inorganic hybrid nanopore than the case of the conventional heating method The sieve confirmed that the particle size was 2.5 times smaller. It was also confirmed that the particle size distribution was very uniform.

In addition, in the case of the organic-inorganic hybrid nanoporous body produced by the production method of the present invention, it can be used as an adsorbent having excellent adsorption and desorption capacity, in particular, as an adsorbent of olefins and an adsorbent of carbon dioxide.

      1 is an X-ray diffraction pattern and optical microscope image of a nickel hydroxy terephthalate organic-inorganic hybrid nanoporous body.

2 is an X-ray diffraction pattern according to the synthesis time of the nickel hydroxy terephthalate organic-inorganic hybrid nanoporous body.

FIG. 3 is a result of CO ₂ adsorption isotherm in nickel hydroxy terephthalate which is an organic-inorganic hybrid nanoporous body obtained in Example 1 (a) and Comparative Example 1 (b) of the present invention.

4 is a propylene-propane adsorption-desorption isotherm using the organic-inorganic hybrid nanoporous body obtained in Example 1. FIG.

Claims (11)

Method for producing an organic-inorganic hybrid nanoporous body, comprising the following steps: 1) a pretreatment step of stirring or ultrasonically treating a divalent metal ion with a dihydroxyterephthalate organic ligand and a solvent to form crystal nuclei in which the organic ligand is coordinated with the metal; And 2) performing a crystallization reaction at 60 ~ 250 ℃ by irradiating a microwave of 1 ~ 30 GHz to the reaction solution in which the crystal nucleus is formed. The metal ion of claim 1, wherein the metal ion is selected from the group consisting of Ni ²⁺ , Fe ²⁺ , Mg ²⁺ , Cu ²⁺ , Ca ²⁺ , Co ²⁺ , Mn ²⁺ and Zn ²⁺ . Method for producing an organic-inorganic hybrid nanoporous body, characterized in that the ion. The method of claim 1, wherein the dihydroxyterephthalate organic ligand is a 2,5-dihydroxyterephthalate organic ligand. The organic-inorganic hybrid nanopore according to claim 1, wherein the dihydroxyterephthalate organic ligand is a dihydroxyterephthalate derivative organic ligand substituted with Cl, Br, I, NO ₃ , NH ₂ , COOH, or SO ₃ H. Method of making sieves. The method of claim 1, wherein the solvent is water, mono or polyalcohol having 1 to 10 carbon atoms, DMF (dimethylformamide), DEF (diethylformamide), DMAc (N, N-dimethylformamide), acetonitrile, Dioxane, chlorobenzene, pyridine, NMP (N-methyl pyrrolidone), sulfolane, THF (tetrahydrofuran), gamma-butyrolactone, cycloaliphatic alcohol, 2-10 ketones and 4-20 carbon atoms A method for producing an organic-inorganic hybrid nanoporous body, characterized in that one or a mixture of two or more selected from the group consisting of hydrocarbons. The method of claim 1, wherein the organic-inorganic hybrid nanoporous body is synthesized by using the microwave irradiation method in step 2). The method for producing an organic-inorganic hybrid nanoporous body according to claim 1, wherein a batch reactor or a continuous reactor is used. An organic-inorganic hybrid nanoporous body prepared by the method of any one of claims 1 to 7. An adsorbent in the form of a powder, pellet, bead, honeycomb, mesh or membrane containing the organic-inorganic hybrid nanoporous body of claim 8. An adsorbent capable of selectively adsorbing olefins containing the organic-inorganic hybrid nanoporous material of claim 8. Carbon dioxide adsorbent containing the organic-inorganic hybrid nanoporous body of claim 8.

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