CN113797973B - Method for rapidly preparing alkaline framework material catalyst and application thereof - Google Patents

Method for rapidly preparing alkaline framework material catalyst and application thereof Download PDF

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CN113797973B
CN113797973B CN202110985216.8A CN202110985216A CN113797973B CN 113797973 B CN113797973 B CN 113797973B CN 202110985216 A CN202110985216 A CN 202110985216A CN 113797973 B CN113797973 B CN 113797973B
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dbu
alkaline
polyazole
framework material
methanol
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CN113797973A (en
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齐兆洋
邱挺
李淮芳
叶长燊
陈杰
杨臣
黄智贤
李玲
王红星
王清莲
葛雪惠
王晓达
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Qingyuan Innovation Laboratory
Fuzhou University
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Fuzhou University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract

The invention provides a method for preparing an alkaline framework material catalyst and application thereof, which utilizes strong alkaline 1, 8-diazabicyclo [5.4.0] undec-7-ene DBU and polyazole to combine to generate an ionic liquid with anions of polyazole, takes the DBU-polyazole ionic liquid as a ligand and a structure directing agent to carry out coordination assembly with Co and Zn ions of a first transition system, and rapidly generates the framework material at normal temperature. The composite catalytic material prepared by the method has the characteristics of large specific surface area, stable active site immobilization and adjustable immobilization capacity, and the preparation process is extremely simple, can be rapidly synthesized in methanol and water in a large scale, and is a method for producing the alkaline catalyst in a large scale.

Description

Method for rapidly preparing alkaline framework material catalyst and application thereof
Technical Field
The invention belongs to the technical field of composite material synthesis, and particularly relates to a synthesis method and application of an alkaline framework material catalyst.
Background
The metal organic framework material is a compound formed by assembling metal ions or metal clusters and inorganic/organic ligands through coordination bonds. In recent 30 years, metal-organic framework materials have attracted extensive interest and intensive research by various national chemistry, chemical industry and material scientists, and have become important research hotspots and begin to exhibit end-use of commercial applications because of excellent performance in catalysis, separation, sensing and the like. Particularly in terms of catalysis, current research has found that metal-organic framework materials can participate in a variety of catalytic reactions, including: acid-catalyzed reactions, base-catalyzed reactions, condensation reactions, redox reactions, and the like.
Despite the great advances made in the catalytic field in metal-organic framework materials, there are still many challenges that need to be overcome. (1) Although there are a variety of methods for producing metal organic framework materials, including: hydrothermal method, diffusion method, mechanical grinding method, etc., but the above methods have the problems of complicated preparation process, high preparation cost, low yield, etc., and are not suitable for large-scale industrial production. (2) Although materials with different properties can be obtained by modifying the ligands of the metal-organic framework material with functional groups, modification of the functional groups often implies a decrease in stability and a substantial increase in ligand costs. Therefore, a preparation method of the alkaline framework material, which has good economy and simple operation and is suitable for large-scale synthesis, needs to be explored.
Disclosure of Invention
The invention aims to solve the problems that the existing metal organic frame material is high in preparation cost, complex in preparation process and incapable of being produced in a large scale, and the main purpose of the invention is to provide a method for rapidly synthesizing an alkaline metal organic frame material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for rapidly preparing an alkaline framework material catalyst: the ionic liquid with anions of polyazole is generated by combining strongly alkaline 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and polyazole, and the framework material can be quickly (less than 1 min) generated at normal temperature by coordination and assembly of the DBU-polyazole ionic liquid serving as a ligand and a structure directing agent with Co and Zn ions of a first transition system. The framework material contains DBU in the cavity, so that further alkali anion substitution can be performed, and the framework material with different alkali strength can be prepared.
A method for rapidly preparing a framework material catalyst: dissolving zinc nitrate hexahydrate or cobalt nitrate hexahydrate in methanol or deionized water to generate a solution A, dissolving DBU and polyazole in methanol or deionized water according to a certain proportion to generate a solution B, then dropwise adding the solution A into the solution B at room temperature under stirring, and carrying out centrifugal separation after the dropwise adding is finished to obtain the framework material containing DBU in the cavity.
A method for rapidly preparing an alkaline framework material catalyst, which comprises the following specific steps:
(1) Dissolving zinc nitrate hexahydrate or cobalt nitrate hexahydrate in methanol or deionized water to generate a solution A, dissolving DBU and polyazole in methanol or deionized water according to a certain proportion to generate a solution B, then dropwise adding the solution A into the solution B at room temperature under stirring, and performing centrifugal separation after the dropwise adding is finished to obtain a framework material containing DBU in a cavity;
(2) Dispersing the obtained frame material in methanol, adding a certain amount of organic matters containing alkaline groups, stirring at room temperature for a certain time, and centrifuging to obtain the alkaline frame material.
The polyazole in the step (1) is one of imidazole, 2-methylimidazole, benzimidazole, mercaptoimidazole, 2, 5-dicarboxyimidazole, 2-ethylimidazole, 1,2, 4-triazole, tetrazole and histidine.
The ratio of the amounts of DBU and polyazole in the step (1) is 0.1-2.
The ratio of the amount of the zinc nitrate hexahydrate or cobalt nitrate hexahydrate to the amount of the polyazole in the step (1) is 0.1-1.
The dropping time of the solution A to the solution B in the step (1) is 10-50 s.
The organic matter containing the alkaline group in the step (2) is one of phenol, triethanolamine, 4-hydroxypyridine, 2-picolinic acid, glycine, aspartic acid, glutamic acid, histidine, imidazole, 2-methylimidazole, benzimidazole, mercaptoimidazole, 2, 5-dicarboxyimidazole, 2-ethylimidazole, 1,2, 4-triazole and tetrazole.
The adding amount of the organic matters containing the alkaline groups in the step (2) is 2% -20% of the mass of the framework material containing DBU.
The stirring time in the step (2) is 20-80 min.
The alkaline framework material obtained by the method is prepared.
Application 1: the application of the basic framework material catalyst in the reaction of preparing methyl ethyl carbonate by transesterification of dimethyl carbonate and ethanol.
Application 2: the application of the alkaline framework material catalyst in the reaction of propylene oxide and methanol to generate propylene glycol methyl ether.
The invention discovers that DBU is an amidine compound with steric hindrance, has stronger alkalinity, can be combined with polyazole to generate ionic liquid with anions of polyazole, and polyazole can form anionic multiport ligand after losing one proton, and the stronger alkalinity can form stronger coordination with metal ions, so that the coordination rate and coordination stability of polyazole and metal ions are greatly increased. In addition, DBU cations can be combined with nitrate anions to form new ionic liquid which exists in the metal organic framework hole cage, and composite material catalysts containing different alkaline groups and different alkali strengths can be prepared through further anion exchange. Therefore, the invention greatly increases the synthesis speed of the metal organic framework material and provides the binding site of the basic functional group by adding DBU in a system of coordination and binding of the polyazole and the metal.
The invention has the beneficial effects that:
the invention utilizes the characteristic that the strong alkaline DBU and the polyazole are combined to generate the ionic liquid with anions of polyazole, and the DBU-polyazole ionic liquid is used as a ligand and a structure directing agent to carry out coordination assembly with Co and Zn ions of a first transition system, so that a framework material can be generated rapidly (less than 1 min) at normal temperature. The framework material contains DBU in the cavity, so that further alkali anion substitution can be performed, and the framework material with different alkali strength can be prepared. The composite material catalyst prepared by the method has the characteristics of large specific surface area, stable active site immobilization and adjustable immobilization capacity, and the preparation process is extremely simple, can be rapidly synthesized in methanol and water in a large scale, and is a method for producing the alkaline catalyst in a large scale. The alkaline framework material catalyst prepared by the invention is used in the reaction of preparing methyl ethyl carbonate by transesterification of dimethyl carbonate and ethanol, and has good activity, selectivity and stability.
Drawings
FIG. 1 is a schematic diagram showing the mechanism and structure of the composite material according to example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of the composites prepared in examples 1-5;
FIG. 3 is a scanning electron microscope image of the composites of examples 1 and 5;
FIG. 4 is N of the composites prepared in examples 1 and 5 2 Adsorption-desorption isotherms and pore size distribution plots.
Detailed description of the preferred embodiments
The invention is further illustrated by the following specific examples. The scope of the invention is not limited to the following examples.
Example 1
(1) Synthesis of DBU-ZIF-8 in methanol
Zinc nitrate hexahydrate (5 mmol) of 0.95 and g is dissolved in 25 mL of methanol to generate solution A, 0.929 g of DBU (6.1 mmol) and 2 g of 2-methylimidazole (24.4 mmol) are dissolved in 25 of mL of methanol to generate solution B, then the solution A is dripped into the solution B in a short time under the condition of room temperature and stirring, the dripping time is 30s, a large amount of white floccules are separated out during the dripping process, centrifugal separation is carried out after the dripping is finished, and the obtained powder is DBU-ZIF-8 framework material containing DBU in a cavity.
1 g of DBU-ZIF-8 obtained in the above way is dispersed in 10 mL of methanol, then 0.2 g of 1,2, 4-triazole (Tri) is added, and after stirring for 1 h at room temperature, the DBU-Tri@ZIF-8 framework material containing DBU-Tri ionic liquid is obtained through centrifugal separation.
(2) Synthesis of DBU-ZIF-8 in water
0.95 g zinc nitrate hexahydrate (5 mmol) is dissolved in 25 mL water to generate solution A, 0.929 g DBU (6.1 mmol) and 2 g 2-methylimidazole (24.4 mmol) are dissolved in 25 mL water to generate solution B, then the solution A is dripped into the solution B in a short time under the condition of room temperature and stirring, the dripping time is 30s, a large amount of white floccules are separated out during the dripping process, centrifugal separation is carried out after the dripping is finished, and the obtained powder is DBU-ZIF-8 framework material containing DBU in a cavity.
1 g of DBU-ZIF-8 obtained in the above way is dispersed in 10 mL of methanol, then 0.2 g of 1,2, 4-triazole (Tri) is added, and after stirring for 1 h at room temperature, the DBU-Tri@ZIF-8 framework material containing DBU-Tri ionic liquid is obtained through centrifugal separation.
Example 2
Preparation of DBU-ZIF-4
0.95 g zinc nitrate hexahydrate (5 mmol) is dissolved in 25 mL methanol to generate solution A, 7.6 g DBU (5 mmol) and 0.68 g imidazole (10 mmol) are dissolved in 25 mL methanol to generate solution B, then solution A is dropwise added into solution B at room temperature under stirring for 30s in a short time, a large amount of white floccules are separated out during the dropwise adding process, centrifugal separation is carried out after the dropwise adding is finished, and the obtained powder is DBU-ZIF-4 framework material containing DBU in a cavity.
1 g of DBU-ZIF-4 obtained above is dispersed in 10 mL of methanol, then 0.2 g of 1,2, 4-triazole (Tri) is added, and after stirring for 1 h at room temperature, the DBU-Tri@ZIF-4 framework material containing DBU-Tri ionic liquid is obtained through centrifugal separation.
Example 3
Preparation of DBU-ZIF-7
0.95 g zinc nitrate hexahydrate (5 mmol) is dissolved in 25 mL methanol to generate solution A, 7.6 g DBU (5 mmol) and 1.18 g benzimidazole (10 mmol) are dissolved in 25 mL methanol to generate solution B, then solution A is dropwise added into solution B at room temperature under stirring for 30s in a short time, a large amount of white floccules are separated out during the dropwise adding process, centrifugal separation is carried out after the dropwise adding is completed, and the obtained powder is DBU-ZIF-7 framework material containing DBU in the cavity.
1 g of DBU-ZIF-7 obtained in the above way is dispersed in 10 mL of methanol, then 0.2 g of 1,2, 4-triazole (Tri) is added, and after stirring for 1 h at room temperature, the DBU-Tri@ZIF-7 framework material containing DBU-Tri ionic liquid is obtained through centrifugal separation.
Example 4
Preparation of DBU-hdp@ZIF-8-SH
0.95 g zinc nitrate hexahydrate (5 mmol) is dissolved in 25 mL methanol to generate solution A, 7.6 g DBU (5 mmol) and 1.0 g 2-mercaptoimidazole (10 mmol) are dissolved in 25 mL methanol to generate solution B, then the solution A is dripped into the solution B in a short time under the condition of stirring at room temperature for 30s, a large amount of white floccules are separated out during the dripping process, and centrifugal separation is carried out after the dripping is finished, so that the obtained powder is DBU-ZIF-8-SH framework material containing DBU in a cavity.
1 g of DBU-ZIF-8-SH obtained in the above way is taken to be dispersed in 10 mL of methanol, then 0.2 g of 4-hydroxypyridine (Hdp) is added, after stirring is carried out at room temperature for 1 h, the DBU-hdp@ZIF-8-SH framework material containing DBU-Hdp ionic liquid is obtained through centrifugal separation.
Example 5
Preparation of DBU-Tri-Zn complex
Zinc nitrate hexahydrate (5 mmol) 0.95 and g is dissolved in 25 and mL methanol to generate solution A, 7.6 g DBU (5 mmol) and 1.04 g 1,2, 4-triazole (15 mmol) are dissolved in 25 and mL methanol to generate solution B, then the solution A is dripped into the solution B at room temperature under stirring for a short time, the dripping time is 30s, a large amount of white floccules are separated out during the dripping process, centrifugal separation is performed after the dripping is finished, and the obtained powder is DBU-Tri-Zn coordination polymer containing DBU-Tri in cavities.
FIG. 1 is a schematic diagram showing the mechanism and structure of the composite material produced in the examples.
FIG. 2 is an X-ray diffraction pattern (XRD) of the composites prepared in examples 1-5. Wherein a is 1 And a 2 The XRD pattern of the DBU-Tri@ZIF-8 composite material synthesized by taking methanol and water as solvents respectively, c is the XRD pattern of the DBU-Tri@ZIF-4 composite material, d is the XRD pattern of the DBU-Tri@ZIF-7 composite material, e is the XRD pattern of the DBU-hdp@ZIF-8-SH composite material, and f is the XRD pattern of the DBU-Tri-Zn complex. As can be seen from fig. 2, the framework material rapidly synthesized after DBU addition has a better crystal structure, demonstrating successful preparation of the target framework material.
FIG. 3 is a scanning electron microscope image of the composites of examples 1 and 5. Wherein a is 1 And a 2 The micro-morphology diagram of the DBU-Tri@ZIF-8 composite material synthesized by taking methanol and water as solvents is shown, and b is the micro-morphology diagram of the DBU-Tri-Zn complex, and the micro-morphology diagram shows that the particle diameters of the framework material after DBU is added are smaller, which is related to the rapid nucleation of the framework material, and indirectly illustrates the feasibility of the rapid synthesis of the framework material.
FIG. 4 is an N of DBU-Tri@ZIF-8 prepared by using methanol as a solvent in example 1 and DBU-Tri-Zn prepared in example 5 2 Adsorption-desorption isotherms and pore size distribution plots. As shown in the figure, the DBU-Tri@ZIF-8 composite material has a larger specific surface area (988.17 m 2 And/g), the pore size distribution is relatively uniform (average pore size of 0.94. 0.94 nm). The DBU-Tri-Zn complex has smaller specific surface area (43.06 m) 2 /g), but with a larger pore size (average pore size of 9.2, nm), further demonstrating the feasibility of adding DBU to rapidly synthesize framework materials.
Application example 1
0.45 g of DBU-Tri@ZIF-8 catalyst prepared by taking methanol as a solvent in example 1, 4.5 g of dimethyl carbonate and 2.3 g of ethanol are added into a pressure-resistant bottle, and are magnetically stirred for 5 h at a reaction temperature of 85 ℃, and after the reaction is finished, sampling analysis is carried out, wherein the conversion rate of the dimethyl carbonate is 55.3%, and the yield of the ethyl methyl carbonate is 46.2%.
Under the aforementioned reaction conditions, the reusability of the DBU-Tri@ZIF-8 catalyst prepared by taking methanol as a solvent was examined, and the catalyst was reused for 5 times, and the conversion rate of dimethyl carbonate and the yield of methyl ethyl carbonate were as shown in Table 1:
table 1 reusable properties of DBU-Tri@ZIF-8 in the reaction of catalyzing transesterification of dimethyl carbonate with ethanol to prepare ethyl methyl carbonate.
The results in table 1 show that: the DBU-Tri@ZIF-8 catalyst has slightly reduced activity after five times of repeated use, and shows good catalytic stability.
Application example 2
The DBU-Tri@ZIF-4 catalyst prepared in example 2 of 0.45. 0.45 g, 4.5 g dimethyl carbonate and 2.3 g ethanol are added into a pressure-resistant bottle, and the mixture is magnetically stirred for 5 h at a reaction temperature of 85 ℃, and after the reaction is finished, sampling analysis is carried out, wherein the conversion rate of the dimethyl carbonate is 50.9%, and the yield of the ethyl methyl carbonate is 42.5%.
Under the aforementioned reaction conditions, the reusability of the DBU-Tri@ZIF-4 catalyst was examined, and the catalyst was reused 5 times, and the conversion of dimethyl carbonate and the yield of ethyl methyl carbonate were as shown in Table 2:
table 2 reusable properties of DBU-Tri@ZIF-4 in the reaction of catalyzing transesterification of dimethyl carbonate with ethanol to prepare ethyl methyl carbonate.
The results in table 2 show that: the DBU-Tri@ZIF-4 catalyst has slightly reduced catalytic activity after five times of repeated use, and shows excellent catalytic stability.
Application example 3
The DBU-Tri@ZIF-7 catalyst prepared in example 3 of 0.45. 0.45 g, 4.5 g dimethyl carbonate and 2.3 g ethanol are added into a pressure-resistant bottle, and the mixture is magnetically stirred for 5 h at a reaction temperature of 85 ℃, and after the reaction is finished, sampling analysis is carried out, wherein the conversion rate of the dimethyl carbonate is 52.4%, and the yield of the ethyl methyl carbonate is 41.3%.
Under the aforementioned reaction conditions, the reusability of the DBU-Tri@ZIF-7 catalyst was examined, and the catalyst was reused 5 times, and the conversion of dimethyl carbonate and the yield of ethyl methyl carbonate were as shown in Table 3:
table 3 reusable properties of DBU-Tri@ZIF-7 in the reaction of catalyzing transesterification of dimethyl carbonate with ethanol to prepare ethyl methyl carbonate.
The results in table 3 show that: the DBU-Tri@ZIF-7 has no obvious reduction of catalytic activity after five times of repeated use, and shows good catalytic stability.
Application example 4
The DBU-Tri-Zn complex catalyst prepared in example 5 of 0.45. 0.45 g, 4.5. 4.5 g dimethyl carbonate and 2.3. 2.3 g ethanol were added into a pressure-resistant bottle, magnetically stirred at a reaction temperature of 85 ℃ for 5. 5 h, and after the reaction, the sample analysis was performed, the conversion of dimethyl carbonate was 60.6%, and the yield of ethyl methyl carbonate was 48.3%.
Under the aforementioned reaction conditions, the reusability of the DBU-Tri-Zn complex catalyst was examined, and the catalyst was reused 5 times, and the conversion of dimethyl carbonate and the yield of ethyl methyl carbonate were as shown in Table 4:
table 4 the reusability of DBU-Tri-Zn complex in the reaction of catalyzing transesterification of dimethyl carbonate with ethanol to prepare ethyl methyl carbonate.
The results in table 4 show that: the DBU-Tri-Zn complex catalyst has only slight reduction of activity after five repeated use, and shows excellent catalytic stability.
Application example 5
0.23 g of DBU-Tri@ZIF-8 catalyst prepared by taking methanol as a solvent in example 1, 5.81 g of propylene oxide and 9.61 g of methanol are added into a pressure-resistant bottle, and the mixture is magnetically stirred at the reaction temperature of 80 ℃ for 5 h, and after the reaction is finished, sampling analysis is carried out, so that the yield of propylene glycol methyl ether is 84.1%.
Under the reaction conditions, the reusability of the DBU-Tri@ZIF-8 catalyst in the reaction of propylene oxide and methanol to generate propylene glycol methyl ether is examined, the propylene glycol methyl ether is reused for 5 times, and the yield of the propylene glycol methyl ether is shown in Table 5:
table 5 the reusability of DBU-Tri@ZIF-8 in catalyzing the reaction of propylene oxide with methanol to propylene glycol methyl ether.
Table 5 the results show that: after the DBU-Tri@ZIF-8 is repeatedly used for five times, the activity is slightly reduced, which proves that the DBU-Tri@ZIF-8 has good repeated use performance in catalyzing the reaction of propylene oxide and methanol to generate propylene glycol monomethyl ether.
Application example 6
0.23 g of DBU-hdp@ZIF-8-SH catalyst prepared in example 4, 5.81 g of propylene oxide and 9.61 g of methanol are added into a pressure-resistant bottle, and the mixture is magnetically stirred at the reaction temperature of 80 ℃ for 5 h, and after the reaction is finished, sampling analysis is carried out, so that the yield of propylene glycol methyl ether is 82.7%.
Under the reaction conditions, the repeated use performance of the DBU-hdp@ZIF-8-SH catalyst in the reaction of generating propylene glycol methyl ether from propylene oxide and methanol is examined, and the propylene glycol methyl ether is repeatedly used for 5 times, and the yield of the propylene glycol methyl ether is shown in Table 6:
table 6 reusable properties of DBU-hdp@ZIF-8-SH in catalyzing the reaction of propylene oxide with methanol to propylene glycol methyl ether.
The results in table 6 show that: after the DBU-hdp@ZIF-8-SH is repeatedly used for five times, the activity is slightly reduced, which proves that the DBU-hdp@ZIF-8-SH has good stability in catalyzing the reaction of propylene oxide and methanol to generate propylene glycol methyl ether.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (5)

1. A method for rapidly preparing an alkaline framework material catalyst, which is characterized by comprising the following specific steps:
(1) Dissolving zinc nitrate hexahydrate or cobalt nitrate hexahydrate in methanol or deionized water to generate a solution A, dissolving DBU and polyazole in methanol or deionized water according to a certain proportion to generate a solution B, then dropwise adding the solution A into the solution B at room temperature under stirring, and performing centrifugal separation after the dropwise adding is finished to obtain a framework material containing DBU in a cavity;
(2) Dispersing the obtained frame material in methanol, adding a certain amount of organic matters containing alkaline groups, stirring at room temperature for a certain time, and centrifuging to obtain an alkaline frame material;
the polyazole is one of imidazole, 2-methylimidazole, benzimidazole, mercaptoimidazole, 2, 5-dicarboxyimidazole, 2-ethylimidazole, 1,2, 4-triazole, tetrazole and histidine;
the organic matter containing the alkaline group in the step (2) is one of phenol, triethanolamine, 4-hydroxypyridine, 2-picolinic acid, glycine, aspartic acid, glutamic acid, histidine, imidazole, 2-methylimidazole, benzimidazole, mercaptoimidazole, 2, 5-dicarboxyimidazole, 2-ethylimidazole, 1,2, 4-triazole and tetrazole, and the organic matter containing the alkaline group and the polyazole are not the same substance at the same time;
the alkaline framework material catalyst is applied to the reaction of propylene oxide and methanol to generate propylene glycol methyl ether.
2. The method according to claim 1, characterized in that: the ratio of the amounts of DBU and polyazole is between 0.1 and 2; the ratio of the amount of zinc nitrate hexahydrate or cobalt nitrate hexahydrate to the amount of polyazole is 0.1 to 1.
3. The method according to claim 1, characterized in that: the dropping time of the solution A to the solution B is 10-50 s.
4. The method according to claim 1, characterized in that: the addition amount of the organic matters containing the alkaline groups in the step (2) is 2% -20% of the mass of the frame material.
5. An alkaline framework material prepared by the method of claim 1.
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