CN110698687A - Synthesis method of cadmium-metal-organic framework material - Google Patents
Synthesis method of cadmium-metal-organic framework material Download PDFInfo
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- CN110698687A CN110698687A CN201911057966.8A CN201911057966A CN110698687A CN 110698687 A CN110698687 A CN 110698687A CN 201911057966 A CN201911057966 A CN 201911057966A CN 110698687 A CN110698687 A CN 110698687A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G83/008—Supramolecular polymers
Abstract
A method for synthesizing a cadmium-metal-organic framework material belongs to the technical field of crystalline material preparation. Mixing cadmium nitrate tetrahydrate, 3 ', 5, 5' -biphenyltetracarboxylic acid, N-dimethylacetamide and acetic acid, and carrying out ultrasonic treatment to completely dissolve solids; after ultrasonic treatment, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven with the temperature of 80-100 ℃ for constant-temperature reaction for 12-24 h. The method greatly shortens the synthesis time, reduces the reaction temperature, reduces the cost and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the technical field of crystalline material preparation, and particularly relates to a preparation method of a cadmium-based metal-organic framework material.
Background
Metal-Organic Frameworks (MOFs) are crystalline porous materials with periodic infinite topological structures formed by bonding Metal ions or Metal clusters and Organic ligands through coordination bonds. Since the advent of metal-organic framework materials, researchers have conducted a great deal of research on the synthesis and performance of metal-organic framework materials, and it has been found that metal-organic framework materials exhibit excellent performance in the aspects of sensing, gas storage and separation, ion exchange, heavy metal ion adsorption, and the like. The synthesis conditions of the metal-organic framework material are continuously optimized, so that the synthesis process can be simplified, the synthesis time is shortened, the preparation cost is reduced, and the method is applied to large-scale industrial production.
[Cd4(bptc)2(DMA)4(H2O)2·4DMA]The material is a cadmium-metal-organic framework material, shows good performance in the sensing field, and can be used as a fluorescence sensor for nitroaromatic explosives; in the application of photocatalysis, the photocatalyst can degrade various organic pollutants to achieve the effect of purifying sewage.
2016 scientific research workers proposed to synthesize [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]The method of (patent application No. 201710179182.7). Taking a mixed solution of N, N-dimethylacetamide, ethanol and deionized water in a volume ratio of 5-8: 1-3: 1 as a solvent, allowing cadmium nitrate tetrahydrate and 3,3 ', 5, 5' -biphenyltetracarboxylic acid to stand and react for 4-6 days at a constant temperature of 110-130 ℃ under a sealed condition at a molar ratio of 1: 2-4, cooling to room temperature, filtering, washing and drying to prepare the cadmium metal organic framework material based on the 3,3 ', 5, 5' -biphenyltetracarboxylic acid.
The method has long reaction time, causes higher cost and is not suitable for industrial production, so that the improvement of a synthetic method is needed to shorten the time required for synthesizing the compound for industrial mass production. The subject group is continuously searched and finally [ Cd ] is not changed4(bptc)2(DMA)4(H2O)2·4DMA]On the premise of crystal structure, the synthesis process is simplified, and the reaction time is shortened.
Disclosure of Invention
The invention provides a method for synthesizing a cadmium-metal-organic framework material by a solvothermal method, which has short synthesis time and is suitable for industrial application.
The technical scheme of the invention is as follows:
a method for synthesizing a cadmium-metal-organic framework material by a solvothermal method is characterized by comprising the following steps:
(1) mixing cadmium nitrate tetrahydrate, 3 ', 5, 5' -biphenyltetracarboxylic acid, N-dimethylacetamide and acetic acid, and performing ultrasonic treatment to completely dissolve solids;
the molar ratio of the acetic acid to the cadmium nitrate tetrahydrate is 1 (3-6);
the molar ratio of the acetic acid to the 3,3 ', 5, 5' -biphenyltetracarboxylic acid is 1 (3-6);
the molar ratio of the acetic acid to the N, N-dimethylacetamide is 1 (80-100).
(2) After ultrasonic treatment, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven with the temperature of 80-100 ℃ for constant-temperature reaction for 12-24 hours.
When the reaction kettle is kept at the constant temperature for 12 hours, crystals can be generated. In the reaction process of the invention, crystals can be generated within 12 hours, and compared with the prior art, the reaction time is shortened by dozens of hours, thereby being the shortest path of the reaction time at present.
The invention has the advantages of successfully searching out a synthetic [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]In the presence of a new method of not changing [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]On the premise of crystal structure, the synthesis steps are simplified, and the reaction time is shortened.
Drawings
FIG. 1 crystal powder diffraction pattern and simulated diffraction pattern of cadmium metal organic framework material based on 3,3 ', 5, 5' -biphenyltetracarboxylic acid of the present invention, the crystal powder diffraction pattern having a preferred orientation.
Detailed Description
The reagents used in the present invention:
cadmium nitrate tetrahydrate, 3,3 ', 5, 5' -biphenyltetracarboxylic acid, N, N-dimethylacetamide, acetic acid, formic acid and concentrated hydrochloric acid solution.
The purity of the tetrahydrate cadmium nitrate is 99% (mass fraction);
the purity of the 3,3 ', 5, 5' -biphenyltetracarboxylic acid is 98% (mass fraction);
the concentration of the N, N-dimethylacetamide is 99.5 percent (mass fraction);
the concentration of acetic acid was 99.5% (mass fraction);
the concentration of formic acid is 98% (mass fraction);
the concentration of the concentrated hydrochloric acid is as follows: 36-38% (mass fraction).
Example 1:
1.1. 5mg of cadmium nitrate tetrahydrate, 5mg of 3,3 ', 5, 5' -biphenyltetracarboxylic acid, 3mL of N, N-dimethylacetamide and 200. mu.L of acetic acid were mixed together, and the mixture was sonicated until the solid was completely dissolved and was colorless and transparent.
1.2. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an environment with the temperature of 100 ℃ for constant temperature for 16 hours, removing the upper-layer liquid by using a suction pipe after the reaction is finished, and drying in the environment with the temperature of 100 ℃ to obtain [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]And (4) crystals.
Example 2:
2.1. 5mg of cadmium nitrate tetrahydrate, 5mg of 3,3 ', 5, 5' -biphenyltetracarboxylic acid, 3mL of N, N-dimethylacetamide and 200. mu.L of acetic acid were mixed together, and the mixture was subjected to ultrasonic treatment until the solid was completely dissolved and was colorless and transparent.
2.2. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an environment with the temperature of 80 ℃ for constant temperature for 12 hours, sucking out the upper-layer liquid by a suction pipe after the reaction is finished, and drying in an environment with the temperature of 100 ℃ to obtain [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]Crystals, but in less yield than in example 1.
Comparative example 3:
3.1. 5mg of cadmium nitrate tetrahydrate, 5mg of 3,3 ', 5, 5' -biphenyltetracarboxylic acid, 3mL of N, N-dimethylacetamide and 200. mu.L of formic acid were mixed together and sonicated until the solid was completely dissolved and was colorless and transparent.
3.2. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an environment with the temperature of 100 ℃ for constant temperature for 16 hours to obtain the [ Cd4(bptc)2(DMA)4(H2O)2·4DMA]The crystals, but XRD testing showed that the crystals crystallized less well than example 1.
Comparative example 4:
4.1. 5mg of cadmium nitrate tetrahydrate, 5mg of 3,3 ', 5, 5' -biphenyltetracarboxylic acid and 3mL of N, N-dimethylacetamide were mixed together, and the mixture was subjected to ultrasonic treatment until the solid was completely dissolved and was colorless and transparent.
4.2. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an environment with the temperature of 100 ℃ and keeping the temperature for 16 hours to obtain the [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]And (4) crystals.
Comparative example 5:
5.1. 30mg of cadmium nitrate tetrahydrate, 30mg of 3,3 ', 5, 5' -biphenyltetracarboxylic acid, 18mL of N, N-dimethylacetamide and 1200. mu.L of acetic acid were mixed together, and the mixture was sonicated until the solid was completely dissolved and was colorless and transparent.
5.2. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an environment with the temperature of 100 ℃ for constant temperature for 16 hours, removing the upper-layer liquid by using a suction pipe after the reaction is finished, and drying in the environment with the temperature of 100 ℃ to obtain [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]And (4) crystals.
Claims (2)
1. A method for synthesizing a cadmium-metal-organic framework material is characterized by comprising the following steps:
1.1 mixing cadmium nitrate tetrahydrate, 3 ', 5, 5' -biphenyltetracarboxylic acid, N-dimethylacetamide and acetic acid, and carrying out ultrasonic treatment to completely dissolve solids; the molar ratio of the acetic acid to the cadmium nitrate tetrahydrate is 1 (3-6); the molar ratio of the acetic acid to the 3,3 ', 5, 5' -biphenyltetracarboxylic acid is 1 (3-6); the molar ratio of the acetic acid to the N, N-dimethylacetamide is 1 (80-100);
1.2 after ultrasonic treatment, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven with the temperature of 80-100 ℃ for constant-temperature reaction for 12-24 hours,filtering and drying to obtain [ Cd ]4(bptc)2(DMA)4(H2O)2·4DMA]And (4) crystals.
2. The method for synthesizing a cadmium-metal-organic framework material according to claim 1, wherein the reaction is carried out in an oven at 100 ℃ for 16 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113354828A (en) * | 2021-05-08 | 2021-09-07 | 沈阳大学 | Preparation and application of novel stable metal organic framework material |
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Application publication date: 20200117 |