CN104370820B - Preparation method and applications of porous metal organic skeleton material - Google Patents

Abstract

A method for preparing a porous metal organic framework material, the porous metal organic framework material contains at least one metal ion and at least one organic compound that can coordinate with the metal ion, and the synthesis method adopts a metal compound, an organic The ligand and the slow-release base are mixed in a solvent, and the porous metal organic framework material is synthesized directly in water (solvent) under a certain temperature and pressure. The operation method of the invention is simple, suitable for large-scale industrial production, suitable for the synthesis of porous metal organic framework membranes, and the involved porous metal organic framework materials are suitable for adsorption, separation and storage of gases.

Description

Preparation method and application of a porous metal organic framework material

technical field

The invention belongs to the technical field of chemical material synthesis and application engineering, and in particular relates to a preparation method and application of a porous metal organic framework material.

Background technique

Porous metal-organic frameworks (Metal-organic Frameworks, MOFs), with specific pore structures, ultra-high specific surface areas, and finely adjustable surface structures, have been a research hotspot in the field of porous materials in the past decade.

The research team represented by Professor Yaghi from the United States has successively published methods for the synthesis, pore size adjustment, and surface performance adjustment of novel structure MOFs in Science in recent years [Science, 2002, 295, 469; 2010, 330, 650; 2012, 336, 1018;]. At the same time, large international chemical companies represented by BASF SE in Germany have also disclosed a large number of preparation technologies for porous metal organic framework materials, including metal organic framework materials of Al, Mg, Cu, Zn and other metals and their preparation methods. The preparation methods of current MOFs mainly include: electrochemical synthesis [CN1886536A, WO2005049892], water or solvothermal synthesis [CN101384537A, Cu-BTC US5648502, US20030078311, US20030148165, US20030222023, US2004600816412, US5607 ball milling method [ng. .Ed.2006,45,142,2010,49,712], microwave method [WO2008057140], and diffusion method [US6965026], etc. From the perspective of the preparation technologies of these MOFs materials, hydrothermal and solvothermal synthesis technologies are still one of the best technologies for mass synthesis of MOFs materials.

Generally speaking, the preparation of metal-organic complexes mostly adopts the direct synthesis method, that is, the metal salt solution and the ligand are mixed in an aqueous solution or an organic solvent (such as DMF, methanol, ethanol, ethylene glycol, etc.), by hydrothermal method or solvothermal method. reaction to obtain a bridged complex. From the perspective of chemical composition, porous metal-organic framework materials are composed of metal ions and anionic ligands, similar to metal salts, so theoretically they can be directly prepared by replacement or acid-base reaction. However, there are many factors affecting the synthesis of MOFs with porous metal-organic frameworks, such as pH, concentration, temperature, anion type, hydrogen bonding, π-π stacking interactions, osmosis, inclusions, and guest molecules. Among them, temperature is the key factor, however, the influence of these factors on the synthesis of MOFs is interrelated.

The structure of metal-organic complexes is mainly influenced by the degree of ligand deprotonation and the nature of auxiliary ligands coordinated to the metal center. Because the expected network structure can be obtained by deprotonation with the help of solvent and organic ligand, and the thermal stability and rigidity of the resulting structure can be enhanced at the same time. In the synthesis process of porous metal organic framework materials, sodium hydroxide, potassium hydroxide, pyrimidine, triethylamine, sodium acetate, acetic acid or dilute hydrochloric acid are usually used to adjust the pH. At different pH, the organic coordinating groups can be completely or partially deprotonated, so that the ligands show a variety of coordination modes, and the structure of the generated complexes also changes significantly.

According to the current patented technology, the MOFs synthesis technology in a weak alkaline environment has disadvantages such as low yield and harsh synthesis conditions; the MOFs synthesis technology in a strong alkaline environment usually uses a large amount of highly corrosive alkali (such as NaOH, US2012 /0082864) for deprotonation of organic ligands. The use of strong corrosive alkali can realize the synthesis of MOFs materials at low temperature, but it will also cause corrosion of equipment and danger of operation, and will cause difficulties in the subsequent purification of materials, and may also affect some of the porous MOFs materials due to the presence of alkali metal ions. performance.

In view of the shortcomings existing in the existing MOFs material hydrothermal or solvothermal synthesis techniques, the purpose of the present invention is to provide a simple, practical and easy mass-produced porous MOFs material synthesis method.

Contents of the invention

The object of the present invention is to provide a preparation method and application of a porous metal organic framework material.

The invention provides a method for preparing a porous metal-organic framework material. A metal compound containing metal ions, an organic ligand coordinating with the metal ions, and a slow-release base are fully mixed in a solvent. , self-assemble through coordination and complexation to form a compound with a supramolecular network structure, and then filter, wash, dry, and activate to form a porous metal-organic framework material;

The metal ion is one or more of Cu ^II , Al ^III , Mg ^II , Mn ^II , Fe ^III , Ni ^II , Co ^II , Zn ^II ;

The organic ligand has at least one atom independently selected from oxygen, sulfur, and nitrogen, and the organic ligand can coordinate and complex with the metal ion through them.

The porous metal framework material involved in the present invention does not necessarily contain two or more kinds of metal ions, nor does it need to contain more than two kinds of organic ligands, but there must be at least one pair of metal ions and organic ligands that can interact with each other. Coordinated to form a porous metal-organic framework structure.

In the preparation method of porous metal organic framework material provided by the present invention, the organic ligand includes any one of organic carboxylic acid compounds, organic sulfonic acid compounds, imidazole compounds, pyridine compounds, amine compounds and their derivatives species or any combination of species.

The preparation method of the porous metal organic framework material provided by the present invention, the organic ligand is selected from succinic acid, fumaric acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1 ,3,5-Benzenetricarboxylic acid, 1,4-benzenedicarboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, isonicotinic acid, 3-pyridine carboxylic acid, 3,4-pyridine dicarboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-sodium naphthalene disulfonate, 3-pyridine sulfonic acid, 4,5 -Dihydroxy-1,3-dibenzenesulfonic acid, imidazole, 2-methylimidazole, 4-methylimidazole, 2-nitroimidazole, benzimidazole, 4,4'-bipyridine, ethylenediamine, tri Ethylenediamine. Particularly preferred organic ligands are selected from fumaric acid, 1,3,5-benzenetricarboxylic acid, 1,4-benzenedicarboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, 1,3- Phthalic acid, isonicotinic acid, imidazole, 2-methylimidazole, 4,4'-bipyridine, triethylenediamine. Especially particularly preferred organic ligands are fumaric acid, 1,3,5-benzenetricarboxylic acid, 1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, isonicotinic acid, imidazole, 2-methylimidazole, Triethylenediamine.

In the preparation method of the porous metal organic framework material provided by the present invention, the metal ions are preferably selected from Cu ^II , Al ^III , Fe ^III , Ni ^II , Co ^II , Zn ^II . Particularly preferred metal ions are selected from Cu ^II , Al ^III , Co ^II , Zn ^II .

In the preparation method of the porous metal organic framework material provided by the present invention, the metal compound is nitrate, sulfate, chloride, acetate, oxalate, hydroxide, carbonate, basic carbon corresponding to the metal ion One or more combinations of acid salts.

In the preparation method of the porous metal organic framework material provided by the present invention, the solvent is one or a mixture of water, methanol, ethanol, ethylene glycol, and DMF. A particularly preferred solvent is selected from one or more of water, methanol, and ethanol. An especially particularly preferred solvent is water.

In the preparation method of the porous metal-organic framework material provided by the present invention, the slow-release base is one of urea and hexamethylenetetramine or a mixture thereof, preferably urea.

The design basis for the proportion of metal ions and organic ligands involved in the present invention is that the ratio of the total number of metal charges to the total number of teeth of the organic ligands is 1. Considering the actual water (solvent) thermal process, one of the metal compounds or organic ligands Excessive use. In the synthesis of the porous metal-organic framework material involved in the present invention, the use ratio of the metal compound and the organic ligand is such that the ratio of the total charge of the metal to the total number of teeth of the organic ligand is between 0.5 and 2; the metal compound and the organic ligand The use ratio of the ligand is preferably between 0.8 and 1.2 in the ratio of the total charge number of the metal to the total tooth number of the organic ligand.

In the synthesis of the porous metal-organic framework material involved in the present invention, the ratio of the slow-release base to the organic ligand is that the ratio of the molar number of the slow-release base to the total number of teeth of the organic ligand is between 0.1 and 10; the slow-release The ratio of the number of moles of base to the total number of teeth of the organic ligands is preferably between 0.2 and 2. One of the characteristics of the present invention is that the use of slow-release base is necessary. If the production cost is not considered, the ratio of the amount (moles) of slow-release base to the total number of teeth of the organic ligand can be greater than 10. However, considering the actual production cost and subsequent washing problems, the amount of slow-release alkali used should be reduced as much as possible.

In the preparation method of the porous metal organic framework material provided by the present invention, the temperature is 40-180°C, preferably 80-150°C.

In some embodiments of the method for preparing a porous metal-organic framework material involved in the present invention, the reaction temperature used is between 90°C and 150°C.

In the preparation method of the porous metal organic framework material provided by the present invention, the synthesis pressure is the saturated vapor pressure (preferably normal pressure) of the corresponding solution at the reaction temperature.

Atmospheric pressure reactions are carried out in normal pressure reaction vessels, such as glass round bottom flasks, normal pressure reaction kettles; high pressure reactions are carried out in high pressure reactors, such as autoclaves with Teflon liners.

In some embodiments of the preparation method of the porous metal organic framework material involved in the present invention, the reaction vessel used is a 150ml autoclave lined with polytetrafluoroethylene.

The reaction temperature is the most critical influencing parameter in the synthesis of metal-organic frameworks. The greatest feature of the present invention is to use the adjustability of the deprotonation performance of the slow-release base with the change of reaction temperature to meet the growth environment required by different ligands and metals to form metal-organic frameworks.

The second major feature of the present invention is that the slow-release base can be used as a deprotonated base in the synthesis of porous metal-organic framework materials with water as a solvent, or in the synthesis of porous metal-organic framework materials with organic solvents as a solvent Used as a proton base.

The present invention provides a method for preparing porous metal organic framework materials. In some embodiments of the preparation of porous metal organic framework materials involved in the present invention, the reaction time used is between 30 minutes and 48 hours.

In the preparation method of the porous metal organic framework material provided by the present invention, the filtration process may adopt natural sedimentation separation, vacuum filtration, pressure filtration, or centrifugal separation to obtain the porous metal organic framework material.

In some embodiments of the preparation method of the porous metal organic framework material involved in the present invention, the method of separating the precipitated solid is vacuum filtration or centrifugation.

In the preparation method of the porous metal organic framework material provided by the invention, the solid is washed with a solvent in the filtration process. On the one hand, solid washing needs to use a solvent to remove unreacted organic ligands and metal salts, and on the other hand, it needs to use a solvent to replace the organic ligands retained in the pores and the solvent required for the reaction by "extraction". Especially when the organic ligand and the solvent required for the reaction are high boiling point compounds, such as DMF, DEF, NMP, the solvent required for the reaction can be replaced by a low boiling point solvent. Preferred extraction solvents are water, methanol, ether, acetone.

In the preparation method of the porous metal organic framework material provided by the invention, the porous metal organic framework material after washing is usually dried and activated to form the porous metal organic framework material.

The porous metal-organic framework material synthesized according to the method provided by the present invention has a high specific surface area, and often absorbs water, air, organic matter, etc., and requires further activation before it can be used for the separation of mixed gases. Generally, supercritical _CO2 replacement or long-term high-temperature and high-vacuum treatment are used to activate MOFs.

In the preparation method of the porous metal-organic framework material provided by the present invention, in some embodiments of the activation of the metal-organic framework material involved, vacuum is used for activation treatment. However, vacuum conditions are not necessary to activate the MOF involved in the present invention. Due to the different physical properties of solvents and ligands used in the synthesis of different porous MOFs materials, the activation temperature used in the present invention is also different. During the activation process of the porous metal organic framework material provided by the present invention, the activation temperature used is between 60-200° C., the activation pressure is between 0-1 bar, and the activation time is usually between 2-72 hours. In some embodiments of the present invention, the activation temperature used is selected to be 100-160° C., and the activation time is recommended to be 2-8 hours. In order to improve the efficiency, the activation is usually performed under a vacuum condition of 0.1-0.2 bar. In addition, if the washing of metal-organic framework materials is insufficient or incomplete due to washing difficulties or cost factors, the performance of the adsorbent can be improved by increasing the activation temperature, and the highest activation temperature can reach above 300 °C.

The preparation method of the porous metal organic framework material provided by the present invention is particularly suitable for growing porous metal organic framework membranes on any solid substrate such as glass, ceramics, carbon materials, organic polymers, silicon oxide, and silicon.

The present invention also provides a porous metal organic framework material prepared by the method. The porous metal organic framework material contains at least one metal ion and at least one organic ligand capable of coordinating with the metal ion.

The preparation method of the porous metal organic framework material provided by the present invention, the porous metal organic framework material has a specific surface area determined by the Langmuir method greater than 10m ² /g. A preferred specific surface area is greater than 100 m ² /g. A more preferred specific surface area is greater than 500m ² /g, and a more preferred specific surface area is greater than 1000m ² /g.

The invention provides a method for preparing a porous metal organic framework material, wherein the porous metal organic framework material contains pores, especially micropores and (or) mesopores. According to the classification of pores by the International Union of Pure and Applied Chemistry (IUPAC), micropores are pores less than or equal to 2 nm, and mesopores are pores greater than 2 nm and less than or equal to 50 nm.

According to the porous metal organic framework material prepared by a method for preparing porous metal organic framework material provided by the present invention, the porous metal organic framework material is used for gas storage, gas separation, as a catalyst, sensor or ion conductor, for Optical or magnetic applications, as a porous material, it is especially suitable for the adsorption separation and storage of natural gas, air, and inert gases.

The porous metal-organic frameworks produced according to the invention and/or shaped bodies produced according to the invention and comprising at least one porous metal-organic framework produced according to the invention can be used in various ways, such as sensors or ion conductors, for light or magnetic applications.

Particular preference is given to applications in which the high specific surface area of the framework can be utilized. Examples include purification or separation of gases or liquids, catalysts or catalyst supports, and storage and release of liquids or gases.

The metal-organic framework materials prepared by the method of the invention are particularly suitable for gas separation. Especially as a new and efficient adsorbent, it has a good application effect in the field of natural gas purification. It can decarbonize natural gas through the separation of CO ₂ /CH ₄ , CH ₄ /N ₂ and CO ₂ /N ₂ /CH ₄ and denitrification.

The organic framework material prepared by the method of the invention is suitable for use as a catalyst or a catalyst support.

The beneficial effects of the present invention are: the preparation method of the porous metal organic framework material provided by the present invention uses a slow-release base as the deprotonating base, and its deprotonating properties can be adjusted according to the reaction temperature, so the operation method of the present invention is simple and the conditions are relatively mild. It is suitable for large-scale industrial production, and the involved porous metal organic framework material is suitable for adsorption, separation and storage of gases.

detailed description

The following examples will further illustrate the present invention, but do not limit the present invention thereby.

Unless otherwise indicated, all numbers appearing in the description and claims of the present invention should not be understood as absolute precise values, and the numerical values are understood by those skilled in the art and within the range of error allowed by known techniques Inside. The precise numerical values appearing in the specification and claims of the present invention should be construed as forming part of the embodiments of the present invention.

The term "A, B, C, ... and combinations thereof" refers to a combination of the following elements: A, B, C, ..., and a combination of any two or more of them in any proportion.

Embodiment 1: Synthesis of Zn-dimethylimidazole framework

Dissolve 26g of ZnSO ₄ ·7H ₂ O in 150g of water; dissolve 16g of urea and 15g of 2-methylimidazole in a mixture of 50g of water and 100g of methanol; then mix the zinc sulfate solution with the 2-methylimidazole solution and stir After 20 minutes until the mixture is uniform, transfer to a 500ml autoclave and react at 110°C for 5 hours. Cool down naturally, filter the white precipitate, and then wash twice with 100ml of water. The filter cake was dried at 100°C for 6 hours, then activated by drying at 130°C under vacuum (0.2 bar) for 8 hours to obtain 21 g of product;

N ₂ specific surface area is 1476m ² /g (determined by Langmuir method).

Embodiment 2: Synthesis of Zn-dimethylimidazole framework

Dissolve 26g of ZnSO ₄ ·7H ₂ O, 20g of urea and 15g of 2-methylimidazole in 300g of water, and reflux at 100°C for 7 hours while stirring. A white precipitate formed and was washed once with 100 ml of water and three times with 50 ml of water. The filter cake was dried at 100°C for 6 hours and then activated for 12 hours at 130°C under vacuum (0.2 bar) to obtain 20.2 g of product;

N ₂ specific surface area is 876m ² /g (determined by Langmuir method).

Embodiment 3: Synthesis of Zn-dimethylimidazole framework

Dissolve 27g ZnNO ₃ 6H ₂ O in 150g water; dissolve 12g hexamethylenetetramine and 15g 2-methylimidazole in a mixture of 50g water and 100g methanol; then dissolve zinc nitrate solution with 2-methyl The imidazole solution was mixed, stirred for 20 minutes until the mixture was uniform, then transferred to a 500ml autoclave, and reacted at 120°C for 6 hours. Cool down naturally, filter the white precipitate, and then wash twice with 100ml of water. The filter cake was dried at 100°C for 6 hours, then activated by drying at 130°C under vacuum (0.2 bar) for 8 hours to obtain 22 g of product;

N ₂ specific surface area is 1346m ² /g (determined by Langmuir method).

Embodiment 4: Atmospheric pressure synthesis Al-aluminum fumarate frame

35g of Al ₂ (SO ₄ ) ₃ ·18H ₂ O, 20g of urea and 12g of fumaric acid were dissolved in 300g of water, heated to 100°C, and refluxed for 6 hours to form a white precipitate. Filter and wash 5 times with 50 ml of water. The filter cake was dried at 100°C for 2 hours and then activated for 12 hours at 130°C under vacuum (0.2 bar) to obtain 15 g of product.

N ₂ specific surface area is 1176m ² /g (determined by Langmuir method).

Example 5: High-pressure synthesis of Al-aluminum fumarate framework

Dissolve 35g of Al ₂ (SO ₄ ) ₃ ·18H ₂ O, 12g of hexamethylenetetramine and 12g of fumaric acid in 300g of water, stir for 30min until evenly mixed, then transfer to a 500ml autoclave, at 130°C The reaction was carried out without stirring for 5 hours under the conditions, and a white precipitate was formed. Cool down naturally, filter, and then wash 5 times with 50ml of water. The filter cake was dried at 100°C for 2 hours and then activated for 12 hours at 130°C under vacuum (0.2 bar) to obtain 15 g of product.

N ₂ specific surface area is 931m ² /g (determined by Langmuir method).

Example 6: Synthesis of Cu-2-methylimidazole framework

Weigh 9g of copper acetate (Cu(CH ₃ COO) ₂ ·H ₂ O), 8g of 2-methylimidazole and 10g of urea, dissolve in a mixed solution of 100ml of methanol and 200ml of water, stir for 30min until uniform, and obtain a mixed solution; The solution was transferred to a 500ml autoclave with a polytetrafluoroethylene liner, sealed tightly, placed in an oven at 140°C for 48 hours, and then cooled naturally. The resulting solid was separated by centrifugation; the solid was washed successively with methanol (100 ml) and water (100 ml); the solid was dried overnight at 110°C and then activated by drying at 160°C under vacuum (0.2 bar) for 12 hours to yield 11 g.

N ₂ specific surface area is 183.2m ² /g (determined by Langmuir method).

Example 7: Synthesis of Cu-BTC framework

Weigh 11g of copper nitrate trihydrate and 12g of trimesic acid (H ₃ BTC) and dissolve in 240ml of water-ethanol (water:ethanol=1:1 weight ratio), add 3.5g of urea, stir for 30min until uniform; transfer to 500ml Heat the autoclave to 110°C, react for 18 hours, cool down naturally, and centrifuge the obtained solid; wash the solid once with 150ml of ethanol. The solid was dried at 80°C and then activated by drying at 130°C under vacuum (0.2 bar) for 4 hours, yielding 12 g of solid.

N ₂ specific surface area is 2435m ² /g (determined by Langmuir method).

Example 8: Synthesis of Co-2-methylimidazole framework

Dissolve 26g of Co(NO ₃ ) ₂ ·6H ₂ O in 150g of water; dissolve 16g of urea and 15g of 2-methylimidazole in 150g of methanol; then mix the cobalt nitrate solution with the 2-methylimidazole solution and stir for 20min until After mixing evenly, transfer to a 500ml autoclave and react at 120°C for 24 hours. Cool down naturally, filter the precipitate, and then wash twice with 100ml of water. The filter cake was dried at 100°C for 6 hours and then activated by drying at 160°C under vacuum (0.2 bar) for 8 hours, yielding 18.6 g of product.

N ₂ specific surface area is 1986m ² /g (determined by Langmuir method).

Example 9: Synthesis of Co-imidazole framework

Dissolve 26g of Co(NO ₃ ) ₂ ·6H ₂ O in 150g of water; dissolve 16g of urea and 13g of imidazole in a mixture of 100g of methanol and 50g of butanol; then mix the cobalt nitrate solution with the imidazole solution and stir for 20min until After mixing evenly, transfer to a 500ml autoclave and react at 140°C for 36 hours. Cool down naturally, filter the precipitate, and then wash twice with 100ml of water. The filter cake was dried at 100°C for 6 hours and then activated by drying at 130°C under vacuum (0.2 bar) for 8 hours, yielding 17 g of product.

N ₂ specific surface area is 113m ² /g (determined by Langmuir method).

Comparative Example 10: Synthesis of Zn-2-methylimidazole framework—CN101830918A

Add 40.7g of ZnO and 82.1g of dimethylimidazole to a mixture of 200ml of methanol and 50ml of 25% ammonia water, and vigorously stir in a 500ml flask at room temperature for 24 hours. After filtering, the filter cake was washed three times with 100ml of methanol, and dried at 120°C to obtain 110g of the product. It was then activated at 120 °C under vacuum (0.2 bar) for 6 h.

N ₂ specific surface area is 1076m ² /g (determined by Langmuir method).

Comparative example 11: Synthesis of aluminum fumarate - BASF patent US2012/0082864Al

Dissolve 70g of Al ₂ (SO ₄ ) ₃ ·18H ₂ O in 300g of water and heat to 60°C; dissolve 25.32g of NaOH and 24.47g of fumaric acid in 362g of water and heat to 60°C; The solution was pumped into the aluminum sulfate solution under stirring for 30 minutes to form a white precipitate, which was then washed once with 100 ml of water and three times with 50 ml of water. The filter cake was dried at 100°C for 12 hours, then activated by drying at 130°C under vacuum (0.2 bar) for 12 hours to obtain 30 g of product;

N ₂ specific surface area is 1076m ² /g (determined by Langmuir method).

Claims (7)

1. A method for preparing a porous metal-organic framework, characterized in that: the metal compound containing metal ions, the organic ligand coordinated with the metal ions, and the slow-release alkali are fully mixed in a solvent, and the mixture is mixed at a certain temperature and Under pressure, self-assemble through coordination and complexation to form a compound with a supramolecular network structure, and then filter, wash, dry, and activate to form a porous metal-organic framework material; the temperature is 40-180 ° C; the pressure is The saturated vapor pressure of the corresponding solution at the reaction temperature; The metal ion is one or more of Cu ^II , Al ^III , Mg ^II , Mn ^II , Fe ^III , Ni ^II , Co ^II , Zn ^II ; The organic ligand has at least one independently selected from fumaric acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, imidazole, 2 - Methylimidazole; and said organic ligands can coordinate complex to said metal ion through them; The slow-release base is one of urea, hexamethylenetetramine or a mixture thereof. 2. according to the preparation method of the described porous metal organic framework material of claim 1, it is characterized in that: described metal ion is Cu ^II , Al ^III , Fe ^III , Ni ^II , Co ^II , Zn ^II in one or more . 3. according to the preparation method of the described porous metal organic framework material of claim 1, it is characterized in that: described metal compound is the corresponding nitrate, sulfate, chloride, acetate, oxalate, hydroxide of metal ion , one or more combinations of carbonates and basic carbonates. 4. The preparation method of the porous metal-organic framework material according to claim 1, wherein the solvent is one or more of water, methanol, ethanol, ethylene glycol, and DMF. 5. According to the preparation method of the porous metal organic framework material according to claim 1, it is characterized in that: the use ratio of the slow-release base and the organic ligand is that the ratio of the molar number of the slow-release base to the total number of teeth of the organic ligand is between 0.1 and 10. between. 6. A porous metal organic framework material prepared by the method of claim 1, characterized in that the porous metal organic framework material contains at least one metal ion and at least one organic ligand capable of coordinating with the metal ion. 7. The application of the porous metal organic framework material according to claim 6, characterized in that: the porous metal organic framework material is used as a catalyst, sensor or ion conductor for optical or magnetic applications; as a porous material, it is suitable for air, inert gas Adsorption separation and storage.