CN111408358A - Double-ligand constructed water-stable microporous dye adsorbent and preparation method thereof - Google Patents

Double-ligand constructed water-stable microporous dye adsorbent and preparation method thereof Download PDF

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CN111408358A
CN111408358A CN202010054242.4A CN202010054242A CN111408358A CN 111408358 A CN111408358 A CN 111408358A CN 202010054242 A CN202010054242 A CN 202010054242A CN 111408358 A CN111408358 A CN 111408358A
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夏昌坤
朱光辉
宋慧玲
魏君梅
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Abstract

The invention belongs to the technical field of adsorption material preparation, and particularly relates to a microporous water-stable dye adsorbent taking a mixed ligand of 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridyl as a substrate and a preparation method thereof. The adsorbent takes 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridine double ligands as substrates, and the water-stable MOFs dye adsorbent with good pore size and selective adsorption is generated by utilizing the synergistic regulation and control of the double ligands. The adsorbent is synthesized by a hydrothermal method, can keep good stability in water, does not use an organic solvent in the synthesis process, and does not pollute the environment. The adsorption performance test shows that the adsorbent has good adsorption performance on methylene blue and crystal violet, has poor adsorption performance on methyl orange and rhodamine B, and shows certain selective adsorption performance.

Description

Double-ligand constructed water-stable microporous dye adsorbent and preparation method thereof
Technical Field
The invention belongs to the technical field of adsorption material preparation, and particularly relates to a microporous water-stable dye adsorbent taking a mixed ligand of 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridyl as a substrate and a preparation method thereof.
Background
With the rapid development of the dye industry, a great deal of various dyes are used, so that the components of the dye wastewater are more complicated, the chroma is higher, the dye wastewater is difficult to degrade, and the treatment difficulty is increased. The dyes enter into the water environment and cause serious pollution to the environment. Most dye molecules and intermediates thereof have carcinogenic effect, can induce the gene mutation of organisms in water environment to cause deformity and even kill the organisms, and meanwhile, the dye molecules cannot be metabolized and degraded in organisms and can be finally accumulated in animals and human bodies through food chains to induce various diseases. In addition, the organic dye is easy to enrich the water body, breaks the self-regulation capability of the environment and aggravates the pollution to the environment. Therefore, the treatment before the discharge of various dye waste water is important.
At present, common treatment methods of dye wastewater mainly comprise a flocculation method, an adsorption method, an electrochemical method, an oxidation method, a biological method, a biofilm method and the like. Wherein, the physical adsorption method in the adsorption method has the advantages of simple operation process, high efficiency and the like, and is one of the most effective methods for treating the dye wastewater. Common physical adsorbents include activated carbon, zeolites, silicates, and Metal Organic Frameworks (MOFs). Among them, MOFs is a novel material, and has attracted much attention because of its advantages such as regular pore structure, large specific surface area, high porosity, and adjustable pore size according to the precursor ligand. On the other hand, if the generated MOFs contains unsaturated metal coordination sites or the ligand contains uncoordinated active groups, the adsorption performance is enhanced to a certain degree, and even the effect of selective adsorption separation is achieved.
The preparation methods of the MOFs materials are various, and mainly comprise hydrothermal methods, solvothermal methods, ionic thermal methods, microwave synthesis methods and the like. Although the synthesis method of MOFs materials is various, the solvothermal method is used more frequently. The solvothermal method involves the use of high boiling organic solvents such as DMF, DMA, DME, etc., which are inherently difficult to degrade and cause unnecessary environmental pollution. On the other hand, as a dye adsorbing material, the stability in water is important. For example, MOF-5 has been objectively limited in its application to wastewater treatment due to its poor stability in water.
Disclosure of Invention
The invention provides a preparation method of a microporous water-stable dye adsorbent. The invention aims to provide a water-stable MOFs dye adsorbent which is simple and convenient in process, small in pollution in the preparation process and good in pore size and selective adsorption and is generated through cooperative regulation and control of two ligands.
The invention purposefully utilizes 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC) and 4,4 '-bipyridine (bpy), under the condition of hydrothermal method by controlling reaction conditions, a microporous water-stable complex [ Cu ] taking a mixed ligand of 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridine as a substrate is synthesized3(BTEC)(OH)2(bpy)0.5(H2O)2]·4H2O, the complex utilizes H4Two bridging ligands BTEC and bpy, which can synergistically regulate the pore size, are different from the method of only using H4BTEC is a ligand-produced microporous material. Moreover, the unsaturated metal coordination sites of the complex can easily react with anions, so that the adsorption performance of the complex on cationic dyes methylene blue and crystal violet is enhanced. Meanwhile, the complex is prepared under the hydrothermal condition by using water as a solvent, is a microporous material with stable water, does not use an organic solvent in the preparation process, does not cause secondary pollution to the environment, and is a novel dye adsorbent material with application prospect. The application discloses a preparation method of the novel dual-ligand constructed water-stable microporous dye adsorbent.
The invention relates to a water-stable dye adsorbent constructed on the basis of 1,2,3, 5-benzenetetracarboxylic acid and 4,4 '-bipyridyl double ligands, which is characterized in that two ligands, namely Cu ions, 1,2,3, 5-benzenetetracarboxylic acid serving as an organic ligand and 4,4' -bipyridyl are controlled under alkaline conditionsPrepared by hydrothermal reaction. The chemical structural formula of the compound can be expressed as [ Cu3(BTEC)(OH)2(bpy)0.5(H2O)2]·4H2O。
From the connection construction point of view, each crystallographically asymmetric structural unit comprises three crystallographically independent Cu (II) atoms, and one completely deprotonated BTEC4-The ligand, two bridging hydroxyls, one-half of 4,4' -bipyridine ligand, two coordinated water molecules and four crystal water molecules. In three crystallographically independent Cu (II) atoms, Cu (1) is penta-coordinated to form a distorted tetragonal pyramid configuration coordination environment, Cu (2) is tetracoordinated to form a parallelogram coordination environment, in addition, the Cu (2) atom is also weakly coordinated with two adjacent oxygen atoms to form a hexa-coordinated octahedral coordination environment configuration on the whole, and Cu (3) is directly hexa-coordinated to form an octahedral coordination environment. Two different Cu (II) atoms of Cu (2) and Cu (3) both contain coordinated water molecules, and the coordinated water molecules are activated and removed on the premise of keeping the metal framework structure, so that unsaturated metal coordination sites are formed. In the complex, the Cu-N bond length is
Figure BDA0002372263040000021
Cu-O bond length in the range of
Figure BDA0002372263040000024
Two weak Cu-O bonds of the Cu (2) atom are of length
Figure BDA0002372263040000022
Three different Cu (II) atoms passing through BTEC4-The bridging oxygen atom of carboxylic acid and the hydroxyl bridging oxygen atom in the ligand are connected into a six-core copper cluster secondary structure unit. The secondary structural unit is formed by 4,4' -bipyridyl and BTEC4-The ligand is connected into a compound with a three-dimensional pore structure, and one ligand is arranged along the direction of the b axis
Figure BDA0002372263040000023
The one-dimensional holes. From a topological perspective, BTEC4-The ligand is connected with three different six-nuclear copper secondary structure units, and is a 3-connection node, each of which isSix-core copper secondary structure unit except for six BTEC4-In addition, the ligand is connected with two adjacent 4,4 '-bipyridine molecules as an 8-connection node, and the bridged 4,4' -bipyridine is used as a 2-connection node, so that a novel (3,8) -connected topological structure compound is formed
Figure BDA0002372263040000031
The symbol is (4.5)2)2(42·510·612·7·83)。
From the perspective of framework connection construction, complex [ Cu ]3(BTEC)(OH)2(bpy)0.5(H2O)2]·4H2O belongs to monoclinic system and has space group P21Unit cell parameters a is 10.986(2), b is 17.248(3), c is 11.009(2), α is 90 °, β is 90.00(3), γ is 90 ° (3) °
The invention relates to a synthesis method of a metal-organic framework complex, which comprises the following steps:
step 1: accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC) and 4,4' -bipyridine (bpy) are dissolved in deionized water, and a mixed solution 1 is obtained after ultrasonic mixing is carried out uniformly for standby; precursor ligand H in the mixed solution4The molar ratio of BTEC, bpy and deionized water is 1: 0.5: 1700;
step 2: accurately weighing sodium hydroxide, adding the sodium hydroxide into the mixed solution 1 in the step 1, uniformly mixing by using ultrasonic waves, and recording the mixture as a mixed solution 2, wherein the molar ratio of the sodium hydroxide to the precursors 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridine is 4-6: 2: 1;
and step 3: accurately weighing Cu (NO)3)2·3H2Adding O into the mixed solution 2 obtained in the step 2 to obtain a mixed solution 3, and ultrasonically mixing the mixed solution 3 uniformly for later use, wherein the Cu (NO) is3)2·3H2O is according to the formula4The BTEC is added in a molar ratio of 2: 1;
and 4, step 4: firstly, putting the mixed solution 3 in the step 3 into a stainless steel kettle with a polytetrafluoroethylene lining, then putting the reaction kettle into an oven with the temperature of 90-110 ℃, keeping for 4 days, cooling to room temperature after 1 day, taking out, washing with deionized water, filtering, and naturally drying to obtain blue crystals.
In step 2, the molar ratio of sodium hydroxide to the precursors 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridine is preferably 6: 2: 1.
in step 4, the oven temperature is preferably 90 ℃ to 100 ℃, and the optimal temperature of the oven is 90 ℃.
The invention has the advantages that:
1. the metal-organic framework material prepared by the hydrothermal method has good water stability, and no organic solvent is used in the synthesis process, so that secondary pollution is avoided.
2. The metal-organic framework material prepared by the invention contains abundant coordinated water molecules and can be used as potential unsaturated active sites, and the exposed unsaturated active sites can interact with ionic dye molecules to enhance the adsorption performance of the dye.
3. The invention selects 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridine as double ligands, and uses H as a ligand4The BTEC and bpy two ligands are bridged to construct, and the water-stable MOFs dye adsorbent with good pore size and selective adsorption can be generated through synergistic regulation.
Drawings
FIG. 1 is a diagram of coordination environment of a sample prepared by the present invention. Three crystallographically independent Cu (II) exist, wherein Cu (1) is penta-coordination to form a coordination environment with a distorted tetragonal pyramid configuration, Cu (2) is tetracoordination to form a slightly deformed parallelogram coordination environment, and Cu (3) is hexa-coordination to form a distorted octahedral coordination environment.
FIG. 2 is a diagram of a six-core copper secondary structure unit of a sample prepared by the present invention. Three different Cu (ii) atoms are connected by a carboxyloxy atom and a hydroxyl bridging oxygen atom to form a hexanuclear copper cluster secondary structural unit, wherein the dotted line indicates that Cu (2) is weakly coordinated to two adjacent oxygen atoms from tetracoordinate to hexacoordinate.
FIG. 3 is a three-dimensional frame structure of a sample prepared according to the present invention, which can be observed from the b-axis direction
Figure BDA0002372263040000042
Figure BDA0002372263040000041
The one-dimensional hole structure of (1).
FIG. 4 is a view showing a topology of a sample prepared according to the present invention. The topological structure of the complex is a (3,8) -connected three-dimensional framework. It is composed of
Figure BDA0002372263040000043
The symbol is (4.5)2)2(42·510·612·7·83)。
Fig. 5, fig. 6, fig. 7 and fig. 8 are ultraviolet absorption curves of samples prepared according to the present invention adsorbing four harmful dyes, namely Methylene Blue (MB), Crystal Violet (CV), Methyl Orange (MO) and rhodamine b (rhb), respectively. Under the condition of normal temperature, the material has good adsorption performance on methylene blue and crystal violet in an aqueous solution, has poor adsorption performance on methyl orange and rhodamine B, and shows certain selective adsorption performance.
FIG. 9 is a graph showing the relationship between the adsorption amount of the sample of the present invention to four dyes and time. Under the condition of normal temperature, the adsorption capacity of the material to methylene blue, crystal violet, methyl orange and rhodamine B reaches 381.5mg/g, 361.5mg/g, 75mg/g and 87.5mg/g within 8h, and further shows that the material adsorbent has better adsorption capacity to methylene blue and crystal violet, has poorer adsorption performance to methyl orange and rhodamine B and shows certain selectivity.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to the following examples.
Example 1
Accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC 0.127g (0.5mmol), 4' -bipyridine (bpy)0.078g (0.25mmol) and deionized water 15m L are mixed in a sample bottle, mixed solution 1 is obtained after uniform ultrasonic mixing, sodium hydroxide 0.06g (1.5mmol), sodium hydroxide 0.05g (1.25mmol) and sodium hydroxide 0.04g 1.0mmol are accurately weighed and respectively added into the three different mixed solution 1 samples, uniform ultrasonic mixing is recorded as mixed solution 2, Cu (NO) is accurately weighed3)2·3H2And respectively adding O0.248g (1.0mmol) into each mixed solution 2, sealing and ultrasonically treating for 10min, then placing a sample bottle into a stainless steel reaction kettle with a tetrafluoroethylene lining, keeping the sample bottle in an oven at 90 ℃ for 4 days, cooling for 1 day, finding that all crystals are generated, taking out the sample bottle, washing the sample bottle with deionized water, and naturally drying the sample bottle to obtain blue crystals. Wherein sodium hydroxide and H4The optimum condition is that the BTEC has a 3:1 molar ratio, regular crystals, good permeability and a yield of about 60%.
Example 2: sodium hydroxide with H in comparison with example 14The molar ratio of BTEC is more than 3:1
Accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC 0.127g (0.5mmol), 4' -bipyridine (bpy)0.078g (0.25mmol) and deionized water 15m L are mixed in a sample bottle, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 1 for later use, sodium hydroxide 0.08g (2.0mmol) and sodium hydroxide 1.75mmol (0.07g) are accurately weighed and respectively added into the mixed solution 1, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 2, Cu (NO) is accurately weighed3)2·3H20.248g (1.0mmol) of O is respectively added into each mixed solution 2, the ultrasonic treatment is carried out again for 10min, then the sample bottle is put into a stainless steel reaction kettle with a tetrafluoroethylene lining, the stainless steel reaction kettle is kept in an oven at 90 ℃ for 4 days, the temperature is reduced for 1 day, and both reactions are found to generate a large amount of precipitates and no crystal is generated.
Example 3: sodium hydroxide with H in comparison with example 14The molar ratio of BTEC is less than 2:1
Accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC 0.127g (0.5mmol), 4' -bipyridine (bpy)0.078g (0.25mmol) and deionized water 15m L are mixed in a sample bottle, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 1 for later use, sodium hydroxide 0.03g (0.75mmol) and sodium hydroxide 0.02g (0.5mmol) are accurately weighed and respectively added into the mixed solution 1, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 2, and Cu (NO) is accurately weighed3)2·3H2Adding 0.248g (1.0mmol) of O into each mixed solution 2, sealing and ultrasonically treating for 10min, placing a sample bottle into a stainless steel reaction kettle with a tetrafluoroethylene lining, keeping the sample bottle in an oven at 90 ℃ for 4 days, cooling for 1 day, and allowing neither reaction to occurAnd (4) generating a target product.
Example 4: the temperature was 100 ℃ as compared with example 1.
Accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC 0.127g (0.5mmol), 4' -bipyridine (bpy)0.078g (0.25mmol) and deionized water 15m L are mixed in a sample bottle, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 1 for standby, sodium hydroxide 0.06g (1.5mmol) is accurately weighed and added into the mixed solution 1, the mixed solution is recorded as a mixed solution 2 by ultrasonic mixing evenly, Cu (NO) is accurately weighed3)2·3H2Adding 0.248g (1.0mmol) of O into the mixed solution 2, sealing and ultrasonically treating for 10min again, then placing the sample bottle into a stainless steel reaction kettle with a tetrafluoroethylene lining, keeping the sample bottle in an oven at 100 ℃ for 4 days, cooling for 1 day, finding that crystals are generated, taking out the sample bottle, washing the sample bottle by using deionized water, and naturally drying the sample bottle to obtain blue crystals, wherein the yield is similar to that of the sample bottle in example 1.
Example 5: the temperature was 110 ℃ as compared with example 1.
Accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC 0.127g (0.5mmol), 4' -bipyridine (bpy)0.078g (0.25mmol) and deionized water 15m L are mixed in a sample bottle, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 1 for standby, sodium hydroxide 0.06g (1.5mmol) is accurately weighed and added into the mixed solution 1, the mixed solution is recorded as a mixed solution 2 by ultrasonic mixing evenly, Cu (NO) is accurately weighed3)2·3H2Respectively adding 0.248g (1.0mmol) of O into each mixed solution 2, sealing and ultrasonically treating for 10min, then placing a sample bottle into a stainless steel reaction kettle with a tetrafluoroethylene lining, keeping the sample bottle in an oven at 110 ℃ for 4 days, cooling for 1 day to generate crystals, taking out the sample bottle, washing the sample bottle with deionized water, and naturally drying to obtain blue crystals, wherein the yield is low.
Example 6: the temperature was 120 ℃ compared to example 1.
Accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC)0.127g (0.5mmol), 4' -bipyridine (bpy)0.078g (0.25mmol) and deionized water 15m L are mixed in a sample bottle, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 1 for standby, sodium hydroxide 0.06g (1.5mmol) is accurately weighed and added into the mixed solution 1, the mixture is mixed evenly by ultrasonic and recorded as mixedSolution 2; accurately weighing Cu (NO)3)2·3H20.248g (1.0mmol) of O is added into the mixed solution 2, the ultrasonic treatment is carried out again for 10min, and then the sample bottle is put into a stainless steel reaction kettle with a tetrafluoroethylene lining, is kept in an oven at 120 ℃ for 4 days, is cooled for 1 day, and only a large amount of precipitate is found without crystal generation.
Example 7: the temperature was 80 ℃ compared to example 1.
Accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC 0.127g (0.5mmol), 4' -bipyridine (bpy)0.078g (0.25mmol) and deionized water 15m L are mixed in a sample bottle, the mixture is mixed evenly by ultrasonic to obtain a mixed solution 1 for standby, sodium hydroxide 0.06g (1.5mmol) is accurately weighed and added into the mixed solution 1, the mixed solution is recorded as a mixed solution 2 by ultrasonic mixing evenly, Cu (NO) is accurately weighed3)2·3H2O0.248g (1.0mmol) was added to each mixed solution 2, the mixture was again subjected to ultrasonic sealing for 10min, and then the sample bottle was put into a stainless steel reaction vessel with a tetrafluoroethylene liner, and held in an oven at 80 ℃ for 4 days, cooled for 1 day, and found to be substantially unreacted, and the resulting mixture was not greatly different from the mixture before the initial reaction.
Example 8: adsorption Performance test
The method comprises the following specific steps of soaking a complex in a methanol solvent for three days, replacing the methanol solvent once every 6 hours on average, and finally placing the complex in a vacuum drying oven at 60 ℃ for drying for 12 hours to activate the adsorbent material, wherein the mass of the sample adsorbent used in the test is 30mg, and the mass of the sample adsorbent corresponds to 100m L Methylene Blue (MB), Crystal Violet (CV), Methyl Orange (MO) and rhodamine B (RhB) dye solutions (the mass concentration is 50 mg/L), the absorbance of each dye aqueous solution at different moments within 0h-8h is measured, and the absorbance of the MB solution (the maximum absorption wavelength of 664nm) and the absorbance of the CV solution (the maximum absorption wavelength of 590nm) are obviously reduced along with the increase of time, while the absorbance of the MO solution (the maximum absorption wavelength of 664nm) and the RhB solution (the maximum absorption wavelength of 552nm) are reduced less.
The target products were obtained in examples 1, 4 and 5, wherein the best results were obtained in example 1 when the molar ratio of sodium hydroxide to 1,2,3, 5-benzenetetracarboxylic acid was 3:1, and the samples obtained in this ratio were subjected to single crystal testing, and the crystal data and refinement parameters are shown in table 1.
TABLE 1 Crystal data and refinement parameters for samples prepared according to the invention
Figure BDA0002372263040000071

Claims (6)

1. A dual-ligand constructed water-stable microporous dye adsorbent is characterized in that: the water-stable dye adsorbent is based on a Cu metal-organic framework, and structurally comprises Cu ions and organic ligands 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC) and 4,4' -bipyridine (bpy) under the hydrothermal condition with water as solvent to construct a water-stable microporous adsorbing material with a chemical formula of [ Cu3(BTEC)(OH)2(bpy)0.5(H2O)2]·4H2And O, the microporous adsorption material can selectively adsorb methylene blue and crystal violet organic dyes in an aqueous solution.
2. The microporous water stable dye adsorbent of claim 1, wherein: from the connection construction point of view, each crystallographically asymmetric structural unit comprises three crystallographically independent Cu (II) atoms, and one completely deprotonated BTEC4-The ligand consists of two bridging hydroxyls, one half of a 4,4' -bipyridine bridging ligand, two coordinated water molecules and four crystal water molecules; three crystallographically independent Cu (II) atoms show three different coordination environments, wherein Cu (1) is penta-coordinated to form a distorted tetragonal pyramid configuration coordination environment, Cu (2) is tetradentate to form a parallelogram coordination environment, and Cu (2) is also weakly coordinated with two adjacent oxygen atoms to form a slightly deformed hexagonal octahedron structure as a wholeType, Cu (3) is a strong six-coordination octahedral coordination environment; cu (2) and Cu (3) atoms which are different and are Cu (II) atoms both contain coordinated water molecules, and the water molecules are removed on the premise of keeping the metal organic framework structure to form unsaturated metal coordination sites; three different Cu (II) atoms passing through BTEC4-Bridging oxygen atoms of carboxylic acid and hydroxyl bridging oxygen atoms in the ligand are connected to form a six-core copper cluster secondary structure unit; the secondary structural unit is formed by 4,4' -bipyridyl and BTEC4-The ligand is connected into a compound with a three-dimensional pore structure, and one ligand is arranged along the direction of the b axis
Figure RE-FDA0002517991080000011
The one-dimensional holes.
3. The method of claim 1, wherein the method comprises the steps of:
step 1: accurate weighing of the precursor ligand 1,2,3, 5-benzenetetracarboxylic acid (H)4BTEC) and 4,4' -bipyridine (bpy) are dissolved in deionized water, and a mixed solution 1 is obtained after ultrasonic mixing is carried out uniformly for standby; precursor ligand H in the mixed solution4The molar ratio of BTEC, bpy and deionized water is 1: 0.5: 1700;
step 2: accurately weighing sodium hydroxide, adding the sodium hydroxide into the mixed solution 1 in the step 1, uniformly mixing by using ultrasonic waves, and recording the mixture as a mixed solution 2, wherein the molar ratio of the sodium hydroxide to the precursors 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridine is 4-6: 2: 1;
and step 3: accurately weighing Cu (NO)3)2·3H2Adding O into the mixed solution 2 obtained in the step 2 to obtain a mixed solution 3, and ultrasonically mixing the mixed solution 3 uniformly for later use, wherein the Cu (NO) is3)2·3H2O is according to the formula4The BTEC is added in a molar ratio of 2: 1;
and 4, step 4: firstly, putting the mixed solution 3 in the step 3 into a stainless steel kettle with a polytetrafluoroethylene lining, then putting the reaction kettle into an oven with the temperature of 90-110 ℃, keeping for 4 days, cooling to room temperature after 1 day, taking out, washing with deionized water, filtering, and naturally drying to obtain blue crystals.
4. The method for preparing a dual-ligand-constructed water-stable microporous dye adsorbent according to claim 3, wherein in the step 2, the molar ratio of sodium hydroxide to the precursors 1,2,3, 5-benzenetetracarboxylic acid and 4,4' -bipyridine is 6: 2: 1.
5. the method for preparing the dual-ligand constructed water-stable microporous dye adsorbent according to claim 3, wherein in the step 4, the oven temperature is 90 ℃ to 100 ℃.
6. The method for preparing the dual-ligand constructed water-stable microporous dye adsorbent according to claim 5, wherein in the step 4, the oven temperature is 90 ℃.
CN202010054242.4A 2020-01-17 2020-01-17 Double-ligand constructed water-stable microporous dye adsorbent and preparation method thereof Withdrawn CN111408358A (en)

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