KR20110019804A - Method for preparing organic-inorganic hybrid nanoporous material, organic-inorganic hybrid nanoporous materials obtained by said method and use thereof - Google Patents

Abstract

PURPOSE: A method for preparing organic-inorganic hybrid nanoporous materials is provided to ensure high crystallinity with aluminum and high thermal stability using tri(C1-C7)alkyl-1,3,5-benzenetricarboxylate. CONSTITUTION: A method for preparing organic-inorganic hybrid nanoporous materials comprises the steps of: mixing aluminum salts as an aluminum precursor with tri(C1-C7)alkyl-1,3,5-benzenetricarboxylate as an organic ligand, acids and solvents to prepare a reactant mixed solution; and heating the reactant mixed solution to perform a crystallization reaction. The heating temperature of the reactant mixed solution is 25~250°C.

Description

Method for producing organic-inorganic hybrid nanoporous body, organic-inorganic hybrid nanoporous body obtained by the above method and use 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 molecular or 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 provides a method for producing an organic-inorganic hybrid nanoporous body in which an aluminum salt is reacted as an aluminum precursor and tri (C 1 -C 7) alkyl-1,3,5-benzenetricarboxylate as an organic ligand and the organic-inorganic hybrid nanoporous body More specifically, it relates to an adsorbent application of, in more detail, an aluminum-inorganic nanoporous body by reacting an aluminum salt as an aluminum precursor with tri (C1-C7) alkyl-1,3,5-benzentricarboxylate as an organic ligand, Unlike organic ligand 1,3,5-benzenetricarboxylate (BTC), which is conventionally used to prepare a metal-organic framework (MOF), tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate It is used to increase the solubility to improve the crystallinity provides an efficient method for synthesizing pure organic-inorganic hybrid nanoporous body. In particular, the organic-inorganic hybrid nanoporous body prepared by the present invention has a high surface area and molecular or nano-sized pores, so that the adsorbent, gas storage, sensor, membrane, functional thin film, catalyst and catalyst carrier, separation of gas and moisture It can be used in materials and the like and can be used to capture guest molecules smaller than the pore size or to separate the molecules using the pore size.

The organic-inorganic hybrid nanoporous body prepared according to the present invention is a porous organic-inorganic polymer formed by the coordination bond of aluminum salt as aluminum precursor and tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate as organic ligand. It can be defined as a compound, it refers to a crystalline compound containing both organic and inorganic in the skeleton structure and having a molecular size or nano-sized pore structure. Organic-inorganic hybrid nanoporous material has high surface area and molecular size or nano sized pores, so it is not only used for adsorbent, gas storage, sensor, membrane, functional thin film, catalyst and catalyst carrier, gas and water separation material, but also pore size It can be used to capture smaller guest molecules or to separate molecules according to their size using pores.

In this regard, Cr-MOF, an organic-inorganic hybrid nanoporous body, has been reported. However, in the case of the organic-inorganic hybrid nanoporous body made of Cr, its application is inevitably limited due to Cr components harmful to the human body. When preparing an organic-inorganic hybrid nanoporous body by reacting with an aluminum precursor using 1,3,5-benzenetricarboxylate (BTC), which had been used as a solvent, the solubility of BTC was low and crystallization was difficult. . Therefore, there is a need for the development of organic-inorganic hybrid nanoporous material for aluminum.

Thus, in order to solve the problems of the prior art, the present inventors have organic-inorganic hybrid nanopore formed by aluminum salt as aluminum precursor and tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate as organic ligand. Through the new manufacturing process for manufacturing the sieve, the solubility is increased compared to the organic ligand benzene tricarboxylate (BTC) used in the prior art to improve the crystallinity with Al, high crystallinity and pure MIL-100, MIL-110 or their The purpose of this study was to develop a method for preparing an organic-inorganic hybrid nanoporous body having a mixed structure. In addition, the inventors of the present invention attempted to produce an organic-inorganic hybrid nanoporous body having a thermal stability of 100 ° C. or more compared to Cr-MIL-100 by the above-described method. 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 particularly, an adsorbent that is easily adsorbable and desorbable of water, hydrogen, olefin / paraffin and carbon dioxide. In addition to Al (NO ₃ ) .9H ₂ O, precursors such as AlCl ₃ , Al ₂ (SO ₄ ) ₃ , Al (iPr) ₃ , and hydrates thereof may be used as the precursor of aluminum.

Accordingly, the present invention, in order to solve the problems of the prior art, the aluminum salt as an aluminum precursor and tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate as an organic ligand, nitric acid and water or an organic solvent. In the case of preparing a reactant mixture by mixing a solvent such as crystallization by hydrothermal synthesis method, the solubility is increased compared to the organic ligand benzenetricarboxylate (BTC) used in the prior art to improve the crystallinity with Al, high crystallinity and pure MIL It was found that organic-inorganic hybrid nanoporous bodies of -100, MIL-110 or a mixed structure thereof were obtained and completed the present invention. In addition, it was found that the obtained organic-inorganic hybrid nanoporous body has a thermal stability of 100 ° C. or more higher than Cr-MIL-100 and Fe-MIL-100.

Therefore, the present invention is a method for producing an organic-inorganic hybrid nanoporous body by hydrothermally synthesizing a mixture of tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate as an organic ligand and an aluminum salt as an aluminum precursor, which has not been reported to date. The present invention aims to provide the use as hydrogen, methane, carbon monoxide, olefins / paraffins, carbon dioxide and moisture adsorbents of the prepared porous coordination polymers.

The present invention is an organic-inorganic hybrid nanopore by using aluminum salt as an aluminum precursor and tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate as an organic ligand as a raw material and heat treatment in the presence of nitric acid and a solvent. It relates to a method for producing a sieve.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for preparing an organic-inorganic hybrid nanoporous material (MOF), and more particularly, tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate as an aluminum salt and an organic ligand as an aluminum precursor. The present invention relates to a method for preparing an organic-inorganic hybrid nanoporous body prepared by mixing a reaction mixture prepared by mixing nitric acid and a solvent and crystallizing the organic-inorganic hybrid nanoporous body prepared by the manufacturing method and an adsorbent thereof. 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, 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) preparing a reactant mixture by mixing an aluminum salt as an aluminum precursor and tri (C 1 -C 7) alkyl-1,3,5-benzenetricarboxylate, nitric acid and a solvent as an organic ligand; And

2) performing a crystallization reaction by heating the reactant mixture.

In addition, the organic-inorganic hybrid nanoporous body prepared by the manufacturing method according to the present invention may be in the form of a powder or a thin film or a membrane.

In the case of using tri (C1-C7) alkyl-1,3,5-benzenetricarboxylate as an organic ligand as in the present invention, the solubility is increased compared to the organic ligand benzenetricarboxylate (BTC), which has been used in the past, The crystallinity was improved to prepare an aluminum organic-inorganic hybrid nanoporous body having a high crystallinity and a pure zeolite MTN structure. In addition, the aluminum organic-inorganic hybrid nanoporous body prepared according to the present invention was confirmed that the thermal stability is higher than 100 ℃ higher than MIL-100 (Cr). These organic-inorganic hybrid nanoporous bodies have pores of surface area and molecular size or nano size, which can be used in adsorbents, gas storage, sensors, membranes, functional thin films, catalysts and catalyst carriers, gas and moisture separation materials, and more. It can be used to capture small guest molecules or to separate molecules using pore sizes. In particular, it can be used as an adsorbent of olefins, an adsorbent of carbon dioxide, and a moisture adsorbent.

Hereinafter, the manufacturing steps and constituents of the organic-inorganic hybrid nanoporous material of the present invention will be described in detail.

First, a reactant mixture is prepared by mixing only an aluminum salt as an aluminum precursor and tri (C 1 -C 7) alkyl-1,3,5-benzenetricarboxylate as an organic ligand, an acid, and a solvent or a solvent.

Preferably, Al (NO ₃ ) ₃ .H ₂ O, AlCl ₃ , Al ₂ (SO ₄ ) ₃ , Al (iPr) ₃ and hydrates thereof are used as aluminum precursors and trimethyl-1,3,5- as organic ligands. Benzenetricarboxylate (Me ₃ BTC) is used and nitric acid is used as the acid;

In order to prepare the organic-inorganic hybrid nanoporous body, a suitable solvent is required in addition to the Al (NO ₃ ) ₃ .H ₂ O and trimethyl-1,3,5-benzenetricarboxylate (Me ₃ BTC). The solvent may be water, mono or polyalcohol having 1 to 10 carbon atoms (e.g., ethylene glycol (EG), 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 bar It is preferable to use water, EG, DMF, and THF.

In order to control the crystal growth rate of the organic-inorganic hybrid nanoporous body containing Al, it was conventionally used a complex acid containing hydrofluoric acid, but in the process using hydrofluoric acid it is limited to using a reactor other than Teflon reactor There was this. To date, crystal growth rates of organic-inorganic hybrid nanoporous bodies are slow in nucleation, while crystal growth rates are relatively fast. Therefore, in the reaction product containing hydrofluoric acid, due to the strong binding property between the metal ion and the fluorine ion, the rate of nucleation was relatively low, and thus the nanoporous body having a small crystal size could not be obtained.

In the crystallization step, the reaction temperature is not actually limited, but 25 ° C. or more is appropriate, a temperature of 50-250 ° C. is preferable, and a temperature of 100-230 ° C. is more preferable. If the reaction temperature is too low, the reaction rate is slow and ineffective. If the reaction temperature is too high, a material free of pores is easily obtained, and the reaction rate is too fast, and impurities are easily mixed. In addition, the internal pressure of the reactor is high, making the construction of the reactor uneconomical. The reactor pressure is practically unlimited, but 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.

The reaction may be carried out by a batch or continuous method by microwave irradiation in addition to hydrothermal synthesis and solvent thermal synthesis. In addition, the organic-inorganic hybrid nanoporous membrane or the thin film may be prepared by hydrothermal and solvent thermal synthesis after immersing the substrate in the reactant mixture in step 1).

In addition, the organic-inorganic hybrid nanoporous body obtained by the production method of the present invention can be used as a powder or a molded body. The shape of the molded 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, an organic-inorganic hybrid nanoporous body having high surface area, highly regular crystal structure, relatively high thermal stability, and the like can be produced in a short time, and also a remarkable shortening of the crystallization reaction time. Due to this, it is possible to prepare a relatively high surface area organic-inorganic hybrid nanoporous body, which is not obtained when conventional electric heating is applied. In addition, the organic-inorganic hybrid nanoporous material 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. In addition, the organic-inorganic hybrid nanoporous body according to the present invention can be easily used as a moisture adsorbent since the adsorption and desorption of moisture at 100 ° C. or less is easy. In addition, the aluminum organic-inorganic hybrid prepared by the present invention can be used as a catalyst for heterogeneous reactions.

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] Aluminum by hydrothermal synthesis Organic / Inorganic Hybrid Nanoporous  Manufacture I

After the addition of Al (NO ₃ ) ₃ H ₂ O and trimethyl-1,3,5-benzenetricarboxylate (Me ₃ BTC) to the Teflon reactor, distilled water and 4M HNO ₃ were added to give a final molar ratio of Al: Me ₃ BTC: H ₂ O: HNO ₃ = 1: 0.667: 300: 2. Put the Teflon reactor containing the above reactant into an electric oven, perform a crystallization reaction at 160 ° C. for 1 day, and then cool, wash (ethanol), and dry it to room temperature. _{3 OH (H 2 O) 2} O [C 6 H 4 (CO 2) 2] 3 hydrate) was obtained. The XRD pattern of the crystals obtained in this example was confirmed to have the same crystal structure as Cr-MOF reported in the literature [ Bull . Kor . Chem . Soc. , 27 (10) , 1523-1524 (2006).

[ Comparative example  1] by hydrothermal synthesis Organic-inorganic hybrid  Produce

After the addition of Al (NO ₃ ) ₃ H ₂ O and 1,3,5-benzenetricarboxylate (BTC) to the Teflon reactor, distilled water and 4M HNO ₃ were added to give a final molar ratio of Al: BTC: H. ₂ O: was adjusted to _{2: HNO 3 = 1: 0.667} : 300. The Teflon reactor containing the reactants was placed in an electric oven and subjected to crystallization reaction at 160 ° C. for 1 day, and then cooled to room temperature, filtered, and dried to form an aluminum inorganic mixture (Al ₃ OH (H ₂ O) ₂ O [C ₆ H _4). (CO ₂ ) ₂ ] ₃ ). As a result of XRD crystal structure analysis of the obtained product, it was confirmed that pure aluminum organic-inorganic hybrid crystals were not produced well and some undissolved BTC ligands existed due to low dissolution of BTC ligand at a reaction temperature of 160 ° C. [FIG. 3] .

From the results of Example 1 and Comparative Example 1, when using trimethylbenzene dicarboxylate (Me ₃ BTC) as the organic ligand as in the present invention, the solubility is increased compared to the organic ligand benzene tricarboxylate (BTC) conventionally used By improving the crystallinity with Al was able to produce a high crystallinity pure aluminum organic-inorganic nanoporous body of MTN structure. In addition, the organic-inorganic hybrid nanoporous material (M100-AL) prepared according to the present invention was confirmed that the thermal stability is higher than 100 ℃ higher than MIL-100 (Cr).

In addition, as shown in FIG. 2, by the thermogravimetric analysis, the water is reduced by 40% at 100 ° C. or less, and when it is converted into the amount of moisture deposition, about 67% can be adsorbed. Can be applied.

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

[ Example  2] aluminum by hydrothermal synthesis Organic / Inorganic Hybrid Nanoporous  Produce II

After the addition of Al (NO ₃ ) ₃ H ₂ O and trimethyl-1,3,5-benzenetricarboxylate (Me ₃ BTC) to the Teflon reactor, distilled water and 4M HNO ₃ were added to give a final molar ratio of Al: Me ₃ BTC: H ₂ O: HNO ₃ = 1: 0.667: 300: 2. The Teflon reactor containing the reactant was placed in an electric oven, and then subjected to crystallization reaction at 180 ° C. for 1 day, followed by cooling to room temperature, washing (ethanol) and drying to mix organic-inorganic hybrid nanoporous material (Al ₃ OH (H ₂ O)). 8: 2 mixture of ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ and Al ₈ (OH) ₁₂ {(OH) ₃ (H ₂ O) ₃ } [btc] ₃ ). The XRD pattern of the crystal obtained in this Example are described in the MIL-100 (Cr) reported in (Bull. Kor. Chem. Soc ., 27 (10), 1523 ~ 1524 (2006) and Nature Materials 2007, 6, 760) And Al ₈ (OH) ₁₂ {(OH) _3. (H ₂ O) ₃ } [btc] ₃ (MIL-110 (Al)).

The MIL-110 / 100-Al mixed organic-inorganic hybrid nanoporous body obtained in Example 2 showed higher thermal stability than MIL-110-Al, and showed the same thermal characteristics as MIL-100 [FIG. 4]. In particular, Al ₃ OH (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ and Al ₈ (OH) ₁₂ {(OH) ₃ (H ₂ O) ₃ } [btc] ₃ mixed or not In the case of the mixed nanoporous body, it was confirmed that the synthesis yield was increased by 30% or more than when Al ₃ OH (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ was synthesized alone.

1 is an X-ray crystal structure analysis result of the organic-inorganic hybrid nanoporous material (Al ₃ OH (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ ) obtained in Example 1.

2 is a thermogravimetric analysis result of the organic-inorganic hybrid nanoporous material (Al ₃ OH (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ ) obtained in Example 1. FIG.

Figure 3 is the result of X-ray crystal structure analysis of the product after the reaction when 1,3,5-benzenetricarboxylate (BTC) of Comparative Example 1 is used.

FIG. 4 is a mixed organic-inorganic hybrid nanoporous body (Al ₃ OH (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ and Al ₈ (OH) ₁₂ {(OH) ₃ obtained in Example 2). (H ₂ O) ₃ } [btc] ₃ · nH ₂ O) Thermogravimetric analysis.

Claims (16)

Method for producing an organic-inorganic hybrid nanoporous body comprising the following steps: 1) preparing a reactant mixture by mixing an aluminum salt as an aluminum precursor and tri (C 1 -C 7) alkyl-1,3,5-benzenetricarboxylate, an acid and a solvent or a solvent as an organic ligand; And 2) performing a crystallization reaction by heating the reactant mixture. The method of claim 1, The temperature for heating the reactant mixture is a manufacturing method, characterized in that 25 ~ 250 ℃. The method of claim 1, The solvent is water, mono or polyalcohol having 1 to 10 carbon atoms, DMF (dimethylformamide), DEF (diethylformamide), DMAc (N, N-dimethylformamide), acetonitrile, dioxane, chlorobenzene, In the group consisting of pyridine, NMP (N-methyl pyrrolidone), sulfolane, THF (tetrahydrofuran), gamma-butyrolactone, cycloaliphatic alcohols, ketones of 2 to 10 carbon atoms and hydrocarbons of 4 to 20 carbon atoms Production method characterized in that the selected one or a mixture of two or more. The method of claim 1, Process for producing a batch reactor or a continuous reactor. The method of claim 1, The aluminum precursor is Al (NO ₃ ) ₃ H ₂ O, AlCl ₃ , Al ₂ (SO ₄ ) ₃ , Al (iPr) ₃ And a manufacturing method characterized in that it comprises a hydrate thereof. The method of claim 1, The organic-inorganic hybrid nanoporous body is represented by Al ₃ OH (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ or a hydrate thereof, it is characterized in that it does not contain fluorine. The method of claim 5, The organic-inorganic hybrid nanoporous material is Al ₃ OH (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ and Al ₈ (OH) ₁₂ {(OH) ₃ (H ₂ O) ₃ } [btc ] ₃ · nH ₂ O A manufacturing method characterized by having a mixed structure. The method of claim 1, An organic ligand, trimethyl-1,3,5-benzenetricarboxylate (Me ₃ BTC) and benzenetricarboxylate (BTC) are mixed and used. The method of claim 1, The organic-inorganic hybrid nanoporous body is prepared in the form of nanoparticles of 500 nm or less. The method of claim 1, The organic-inorganic hybrid nanoporous body is characterized in that the manufacturing method in the form of a thin film or membrane. An organic-inorganic hybrid nanoporous body prepared by the method of any one of claims 1 to 10. An adsorbent in the form of a powder, pellet, bead, honeycomb, mesh or membrane containing the organic-inorganic hybrid nanoporous body of claim 11. An adsorbent capable of selectively adsorbing olefins containing the organic-inorganic hybrid nanoporous material of claim 11. Carbon dioxide adsorbent containing the organic-inorganic hybrid nanoporous body of claim 11. A moisture adsorbent containing the organic-inorganic hybrid nanoporous body of claim 11. Heterogeneous catalyst containing the organic-inorganic hybrid nanoporous body of claim 11.

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