CN108129670B - Preparation method of gradient porous metal organic framework ZIF-8 - Google Patents
Preparation method of gradient porous metal organic framework ZIF-8 Download PDFInfo
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Abstract
The invention relates to a preparation method of a gradient porous metal organic framework ZIF-8, which comprises the steps of dissolving an organic ligand 2-methylimidazole in deionized water, adding a poly (diallyldimethylammonium chloride) solution after the 2-methylimidazole is completely dissolved, and uniformly stirring; dissolving divalent zinc salt in deionized water, mixing with the organic ligand solution after completely dissolving, and stirring to react to obtain a suspension; and filtering or centrifugally separating the suspension to obtain a solid product, washing the solid product with deionized water, and drying to obtain the ZIF-8 series material. Due to the control of the poly diallyl dimethyl quaternary ammonium cation on the deprotonation balance and the crystal growth process, the prepared ZIF-8 material has a micropore and mesopore structure, and the mesopore volume is adjustable, the performance is stable, and the application prospect is wide. The preparation method disclosed by the invention is simple, convenient and feasible, green and pollution-free, and is convenient for industrial operation.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to a preparation method of a gradient porous metal organic framework ZIF-8.
Background
Metal organic framework Materials (MOFs) have the characteristics of high specific surface area, adjustable structure, permanent pore space and the like, have obvious advantages compared with the traditional porous materials, and are widely applied to the fields of adsorption and separation, energy storage, catalysis, sensing, medicine carrying and the like. However, most MOFs materials including zeotype imidazolate framework materials (ZIFs) have only micropore (<2nm) characteristics, and hinder the diffusion of adsorbates, reactants, precursors or drug molecules with larger volume in the pore channels, thereby limiting the expanded application of the materials in the corresponding fields.
The most direct solution to solve the above problems is to prepare MOFs materials having mesoporous structures. At present, methods for preparing MOFs materials with mesoporous structures mainly include methods for increasing the length of organic ligands, surfactant template methods and the like. However, the method for increasing the length of the ligand has the defects of high difficulty in ligand synthesis, low yield, interpenetrating material structures, unstable properties and the like; the surfactant template method requires template removal at the later stage, is complicated to operate and is not easy to industrialize. Therefore, it is urgently needed to develop a reliable, simple and convenient method with good repeatability to prepare a stable mesoporous MOFs material with adjustable structure and performance so as to meet the future application requirements.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of a gradient porous metal organic framework ZIF-8, and provides the preparation method of the gradient porous metal organic framework ZIF-8, which is simple, convenient, feasible, green, pollution-free and convenient for industrial operation. In particular, the preparation method adopts green nontoxic poly diallyl dimethyl ammonium chloride as a regulator for deprotonation balance and crystal growth of a ligand, and realizes the preparation of the gradient porous ZIF-8 material with a mesoporous structure at normal temperature and normal pressure by one step. The prepared material has stable structure and performance, and the method has simple process, is green and pollution-free and is easy for industrialization.
Technical scheme
A preparation method of a gradient porous metal organic framework ZIF-8 is characterized by comprising the following steps:
step 1: dissolving organic ligand 2-methylimidazole in deionized water, adding polydiallyl dimethyl ammonium chloride solution after the 2-methylimidazole is dissolved, and stirring and mixing;
step 2: dissolving divalent zinc salt in deionized water, mixing with the solution in the step (1), and stirring for reaction to obtain a suspension; the molar ratio of the organic ligand 2-methylimidazole to the divalent zinc salt is 15: 1-2: 1; the dosage of the poly diallyl dimethyl ammonium chloride solution is as follows: when the mass fraction is 20%, 0.5-4.5 ml of divalent zinc salt is added in each 10mmol of divalent zinc salt
And step 3: and filtering or centrifugally separating the suspension to obtain a solid product, washing the solid product with deionized water for multiple times, and drying to obtain the gradient porous metal organic framework ZIF-8 material.
The divalent zinc salt is zinc sulfate heptahydrate ZnSO4·7H2O, zinc chloride ZnCl2Zinc nitrate hexahydrate Zn (NO)3)2·6H2O, Zinc acetate dihydrate Zn (CH)3COO)2·2H2And any one or more of O.
When polydiallyl dimethyl ammonium chloride solutions with different concentrations are used, the dosage is converted into pure polydiallyl dimethyl ammonium chloride: 0.109-0.981 g of divalent zinc salt is added in every 10mmol of divalent zinc salt.
The stirring and mixing reaction time of the step 1 and the step 2 is 0.5-3 hours.
Advantageous effects
The invention provides a preparation method of a gradient porous metal organic framework ZIF-8, which comprises the steps of dissolving an organic ligand 2-methylimidazole in deionized water, adding a poly (diallyldimethylammonium chloride) solution after the 2-methylimidazole is completely dissolved, and uniformly stirring; dissolving divalent zinc salt in deionized water, mixing with the organic ligand solution after completely dissolving, and stirring to react to obtain a suspension; and filtering or centrifugally separating the suspension to obtain a solid product, washing the solid product with deionized water, and drying to obtain the ZIF-8 series material.
The invention adopts polydiallyl dimethyl ammonium chloride as a regulator, can control the deprotonation balance of a ligand at the initial stage, simultaneously compete with metal ions for coordination, control the later curing and growth forming process of a crystal, and finally form an assembled mesoporous and a defect mesoporous in a crystal grain. Due to the control of the poly diallyl dimethyl quaternary ammonium cation on the deprotonation balance and the crystal growth process, the prepared ZIF-8 material has a micropore and mesopore structure, and the mesopore volume is adjustable, the performance is stable, and the application prospect is wide. The preparation method disclosed by the invention is simple, convenient and feasible, green and pollution-free, and is convenient for industrial operation.
The regulator used in the invention is green and nontoxic, has stable property and good system controllability, and has the following obvious advantages compared with the prior art:
(1) the invention provides a preparation method of the gradient porous metal organic framework ZIF-8, which is simple, convenient, feasible, green and pollution-free and is convenient for industrial operation, and the method does not need an organic solvent, has mild reaction conditions, and is efficient in production and pollution-free.
(2) The gradient porous metal organic framework ZIF-8 prepared by the method has a mesoporous structure, and has the advantages of adjustable mesoporous volume, high material specific surface area, stable performance and wide application prospect.
Drawings
FIG. 1: SEM photograph of the prepared material when the feed ratio is 7.5:1 and the addition amount of the regulator is 1.0 ml;
FIG. 2: SEM photograph of the prepared material when the feeding ratio is 10:1 and the addition amount of the regulator is 2.0 ml;
FIG. 3: XRD patterns of gradient porous ZIF-8 prepared by different addition amounts of regulators;
FIG. 4: preparing nitrogen absorption-desorption curves of the gradient porous ZIF-8 with different addition amounts of the regulator;
FIG. 5: the pore size distribution curves of the gradient porous ZIF-8 prepared by different addition amounts of the regulator.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
Weighing 4.10g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, measuring 0.5mL of poly (diallyldimethylammonium chloride) solution (20 wt.%) by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 1.0h under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 2
Weighing 4.10g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, weighing 1.5mL of poly (diallyldimethylammonium chloride) solution (20 wt.%) by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 1.5 hours under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 3
Weighing 6.15g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, measuring 0.5mL of poly (diallyldimethylammonium chloride) solution (20 wt.%) by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 2.0h under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 4
Weighing 6.15g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, weighing 1.5mL of poly (diallyldimethylammonium chloride) solution (20 wt.%) by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.97g of zinc nitrate hexahydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 1.5 hours under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 5
Weighing 8.20g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, weighing 1.0mL of poly (diallyldimethylammonium chloride) solution (20 wt.%) by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 1.5 hours under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 6
Weighing 8.20g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, weighing 1.5mL of poly (diallyldimethylammonium chloride) solution (20 wt.%) by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 2.0h under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 7
Weighing 8.20g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, weighing 2.0mL of poly (diallyldimethylammonium chloride) (20 wt.%) solution by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 2.5 hours under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 8
Weighing 8.20g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, weighing 3.0mL of poly (diallyldimethylammonium chloride) (20 wt.%) solution by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 3.0 hours under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 9
Weighing 10.25g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, weighing 3.0mL of poly (diallyldimethylammonium chloride) (20 wt.%) solution by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; weighing 1.36g of zinc chloride, adding the zinc chloride into a 100ml beaker, and adding 30ml of deionized water to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 2.5 hours under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Example 10
Weighing 10.25g of 2-methylimidazole, adding into a 250mL beaker, adding 50mL of deionized water, dissolving completely under magnetic stirring, measuring 5.0mL of poly (diallyldimethylammonium chloride) (20 wt.%) solution by using a liquid transfer gun, adding into the beaker, and stirring and mixing uniformly; 2.20g of zinc acetate dihydrate is weighed and added into a 100ml beaker, and 30ml of deionized water is added to dissolve the divalent zinc salt; under the condition of stirring continuously, mixing the obtained divalent zinc salt solution with the 2-methylimidazole solution, and stirring and reacting for 3.0 hours under the conditions of normal temperature and normal pressure to obtain milky white suspension; and separating by adopting a filtering or centrifuging mode to obtain a white solid product, washing the product in deionized water for multiple times to remove unreacted monomers or regulators, and drying the obtained product in a vacuum drying oven to obtain the gradient porous metal organic framework ZIF-8.
Claims (3)
1. A preparation method of a gradient porous metal organic framework ZIF-8 is characterized by comprising the following steps:
step 1: dissolving organic ligand 2-methylimidazole in deionized water, adding polydiallyl dimethyl ammonium chloride solution after the 2-methylimidazole is dissolved, and stirring and mixing;
step 2: dissolving divalent zinc salt in deionized water, mixing with the solution in the step (1), and stirring for reaction to obtain a suspension; the molar ratio of the organic ligand 2-methylimidazole to the divalent zinc salt is 15: 1-2: 1; the mass fraction of the poly (diallyldimethylammonium chloride) solution is 20%, and 0.5-4.5 ml of divalent zinc salt is added into each 10mmol of the poly (diallyldimethylammonium chloride) solution;
and step 3: and filtering or centrifugally separating the suspension to obtain a solid product, washing the solid product with deionized water for multiple times, and drying to obtain the gradient porous metal organic framework ZIF-8 material.
2. The method for preparing the gradient porous metal organic framework ZIF-8 according to claim 1, wherein the method comprises the following steps: the divalent zinc salt is zinc sulfate heptahydrate ZnSO4·7H2O, zinc chloride ZnCl2Zinc nitrate hexahydrate Zn (NO)3)2·6H2O, Zinc acetate dihydrate Zn (CH)3COO)2·2H2And any one or more of O.
3. The method for preparing the gradient porous metal organic framework ZIF-8 according to claim 1, wherein the method comprises the following steps: the stirring and mixing reaction time of the step 1 and the step 2 is 0.5-3 hours.
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