CN113234235A - Preparation method of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead - Google Patents
Preparation method of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead Download PDFInfo
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Abstract
The invention provides a preparation method of a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead. The invention takes zinc acetate and meso-tetra (4-carboxyphenyl) porphyrin as raw materials to prepare meso-tetra (4-carboxyphenyl) zinc porphyrin in a flask containing N, N-dimethylformamide; then, reacting with TPE-2COOH micromolecules with aggregation induction phenomenon to prepare meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF; dissolving the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in deionized water to prepare an MOF solution; then respectively dissolving metal chloride in deionized water to obtain metal ion solution 1.0X 10‑4mol/L; and adding a certain amount of metal ion solution into the MOF solution, performing fluorescence detection and determining the detection limit of the MOF solution on lead ions.
Description
Technical Field
The invention relates to the field of porphyrin-MOF fluorescent film materials, in particular to a preparation method of a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead.
Background
The science and technology is a double-edged sword, the science and technology are rapidly developed after 20 th century, the development of economy is promoted, and the living standard of people is improved. At the same time, however, human beings also pay disastrous costs. Due to the emission of the exhaust gas of the industrial three wastes (waste gas, waste water and industrial residue), the irrigation of sewage, the use of pesticides, herbicides, fertilizers and the like and the development of mining industry, the soil, the water quality and the atmosphere are seriously polluted.
Lead is a toxic metal that can accumulate in human and animal tissues. Mainly comes from various paints, coatings, storage batteries, smelting, hardware, machinery, electroplating, cosmetics, hair dyes, glazed bowls and dishes, tableware, fire coal, puffed food, tap water pipes and the like. It enters the body through skin, digestive tract and respiratory tract to act with various organs, the main toxic effect is anemia, nerve dysfunction and kidney injury, and the easily damaged people include children, the old and people with low immunity. In this case, it is necessary to find a method for better detecting Pb in water2+。
Metal Organic Frameworks (MOFs) are a class of compounds consisting of metal ions or clusters of metal ions, which are coordinated with organic ligands to form one-, two-or three-dimensional structures, which are achieved by the reaction of different organic ligands with metal ions. Many MOFs have a regular controllable structure, adjustable size, high active center and excellent optical properties, and the arrangement of organic ligands and metal ions or clusters has a significant directionality, and can form different framework pore structures, thereby exhibiting different adsorption properties, optical properties, electromagnetic properties, etc. MOFs present great development potential and attractive development prospects in modern materials science. Due to its good performance, it can be tried to detect Pb2+。
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead. The invention takes zinc acetate and meso-tetra (4-carboxyphenyl) porphyrin as raw materials to prepare meso-tetra (4-carboxyphenyl) zinc porphyrin in a flask containing N, N-dimethylformamide; then theReacting with TPE-2COOH micromolecules which have aggregation induction phenomenon to prepare meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF; dissolving the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in deionized water to prepare an MOF solution; then respectively dissolving metal chloride in deionized water to obtain metal ion solution 1.0X 10-4mol/L; and adding a certain amount of metal ion solution into the MOF solution, performing fluorescence detection and determining the detection limit of the MOF solution on lead ions.
The specific technical scheme of the invention is as follows: a method of preparing a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for the detection of lead, comprising the steps of:
step 1: preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin: dissolving zinc acetate and meso-tetra (4-carboxyphenyl) porphyrin in N, N-dimethylformamide, and carrying out ultrasonic treatment on the obtained solution; then carrying out condensation reflux reaction on the solution after the ultrasonic treatment at the temperature of 120-150 ℃; stirring for reaction for 1-3 h, cooling the reaction solution to room temperature, and adding deionized water; refrigerating the reaction solution, standing, taking out the reaction solution, and centrifuging; vacuum drying to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin, and storing for later use.
Taking zinc acetate and meso-tetra (4-carboxyphenyl) porphyrin as raw materials, and leading Zn to be subjected to hydrothermal reaction in N, N-dimethylformamide solution2+Forming a coordination bond with N on the pyridyl of the meso-tetra (4-carboxyphenyl) porphyrin, further connecting to form a two-dimensional plane structure, and finally forming the meso-tetra (4-carboxyphenyl) zinc porphyrin.
Step 2: preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material: dissolving benzoic acid, 1, 2-di (4-carboxyphenyl) -1, 2-stilbene and meso-tetra (4-carboxyphenyl) zinc porphyrin in a mixed solution of DMF and ethanol, carrying out ultrasonic treatment on the obtained solution until the solution is fully dissolved, transferring the ultrasonic solution to a polytetrafluoroethylene reaction kettle, and reacting for 1-3 days at 80-120 ℃; and then cooling the reaction liquid to room temperature, washing with N, N-dimethylformamide, centrifuging until supernatant is clear to obtain purple precipitate, drying to obtain the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material, and storing for later use.
By adopting a solvothermal method, 1, 2-bis (4-carboxyphenyl) -1, 2-stilbene and meso-tetra (4-carboxyphenyl) zinc porphyrin can better form meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF with a three-dimensional structure in the presence of a surfactant benzoic acid.
The invention takes zinc acetate and meso-tetra (4-carboxyphenyl) porphyrin as raw materials to prepare meso-tetra (4-carboxyphenyl) zinc porphyrin in a flask containing N, N-dimethylformamide; then, reacting with TPE-2COOH micromolecules with aggregation induction phenomenon to prepare meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF; dissolving the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in deionized water to prepare an MOF solution; then respectively dissolving metal chloride in deionized water to obtain metal ion solution 1.0X 10-4mol/L; and adding a certain amount of metal ion solution into the MOF solution, performing fluorescence detection and determining the detection limit of the MOF solution on lead ions. Due to Pb2+And their strong interaction with electron donors of the elements N and O, Pb2+Rapidly coordinates with O element in 1, 2-di (4-carboxyl benzene) -1, 2-stilbene and in mid-tetra (4-carboxyl phenyl) zinc porphyrin, changes the structure of ZnTCPP-MOF, and further causes fluorescence quenching phenomenon.
Preferably, in step 1: the dosage of the zinc acetate is 60-80 mg, the dosage of the meso-tetra (4-carboxyphenyl) porphyrin is 110-120 mg, and the dosage of the N, N-dimethylformamide is 40-50 mL.
Preferably, in step 1: the dosage of the deionized water is 100-120 mL; then the reaction solution is put into the environment with the temperature of 1-5 ℃ and is kept stand for 10-15 h, and then the reaction solution is taken out.
Preferably, in step 1: centrifuging at 10000-.
Preferably, in step 1: vacuum drying at 60-80 deg.C for 4-6h to obtain meso-tetra (4-carboxyphenyl) porphyrin, and storing.
Preferably, in step 2: the dosage of the benzoic acid is 150 mg of benzoic acid, 30-50 mg of 1, 2-di (4-carboxyphenyl) -1, 2-stilbene and 50-70 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin.
Preferably, in step 2: the dosage of N, N-dimethylformyl is 6-8 mL, the dosage of ethanol is 2-4 mL, and the obtained solution is subjected to ultrasonic treatment for 20-40 min until the solution is fully dissolved.
Preferably, in step 2: centrifuging for 8-10 min at 11000-13000 rpm until supernatant is clear to obtain purple precipitate, and washing with N, N-dimethylformamide for 3-5 times.
Preferably, in step 2: and precipitating the precipitate for 6-10h at 60-80 ℃ in vacuum to obtain a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material, and storing for later use.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention compounds the organic micromolecules with aggregation induction phenomenon and the metalloporphyrin based on the excellent properties of the organic micromolecules and the metalloporphyrin to form a stable three-dimensional structure, thereby improving the sensitivity of the material to light, increasing the mobility of electrons due to the huge specific surface area of the material and further leading the reaction of the material to light to be more obvious.
2. The invention synthesizes a two-dimensional plane structure by the reaction of metal ions or clusters and porphyrin, and then the metalloporphyrin reacts with an organic ligand to form a three-dimensional porous three-dimensional structure which has sensitive reaction to light and can emit corresponding color under the illumination of light, thereby realizing the fluorescence phenomenon.
3. Due to Pb2+And their strong interaction with electron donors of the elements N and O, Pb2+Rapidly coordinates with O element in 1, 2-di (4-carboxyl benzene) -1, 2-stilbene and in mid-tetra (4-carboxyl phenyl) zinc porphyrin, changes the structure of ZnTCPP-MOF, and further causes fluorescence quenching phenomenon.
Drawings
FIG. 1 is a photograph of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF obtained in example 1 under UV light.
FIG. 2 is SEM and TEM pictures of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF obtained in example 1.
FIG. 3 shows fluorescence intensity of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF obtained in example 1 in different solvents.
FIG. 4 is a picture of aqueous meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF solutions obtained in example 2 in different metal ion solutions under UV and natural light conditions, respectively.
FIG. 5 is the mid-tetrakis (4-carboxyphenyl) zinc porphyrin-MOF versus Pb obtained in example 22+Titration curves of (c).
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin:
dissolving 60 mg of zinc acetate and 110 mg of meso-tetra (4-carboxyphenyl) porphyrin in a beaker containing 40 mL of N, N-dimethylformamide, and carrying out ultrasonic treatment on the solution for 30 min; and transferring the solution after ultrasonic treatment into a 250 mL single-neck flask, carrying out condensation reflux reaction at 120 ℃, and stirring for reaction for 1.5 h. Closing the oil bath, and adding 100 mL of deionized water when the reaction liquid is cooled to room temperature; then placing the reaction solution into a refrigerator at 4 ℃, standing for 12 h, taking out the reaction solution, and centrifuging for 10 min at 12000 rpm; drying in a vacuum drying oven to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin, and storing for later use.
2) Preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF:
dissolving 150 mg of benzoic acid, 30 mg of 1, 2-bis (4-carboxyphenyl) -1, 2-stilbene and 50 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin in 10 mL of mixed solution (DMF: ethanol = 4: 1), carrying out ultrasonic treatment on the solution for 30 min to fully dissolve the solution, transferring the ultrasonic solution to a 25 mL polytetrafluoroethylene reaction kettle, and reacting for 1-3 days at the temperature of 80 ℃; and then cooling the reaction solution to room temperature, washing with N, N-dimethylformamide, centrifuging at 13000 rpm for 10 min until supernatant is clear to obtain purple precipitate, drying the precipitate to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF, and storing for later use.
3) Preparation of metal ion solution:
are respectively provided withWeighing corresponding mass of metal chloride salt (LiCl, KCl, NaCl, AgCl, NiCl)2, CaCl2, MgCl2, CuCl2, ZnCl2, CoCl2, MnCl2And PbCl2) Dissolving in deionized water to obtain a solution of 1.0 × 10-2Refrigerating the metal ion solution of mol/L; then diluted to 5 mL with a concentration of 1.0X 10-4mol/L solution.
4) Fluorescence detection of meso-tetrakis (4-carboxyphenyl) zinc porphyrin-MOF:
3 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF is respectively dissolved in 5 mL of solvents such as deionized water, methanol, ethanol, butanol, dichloromethane, N-Dimethylacetamide (DMA), carbon tetrachloride, acetonitrile and the like, the solvents are subjected to ultrasonic treatment for 20 min to obtain uniformly mixed purple suspension, the solution is subjected to fluorescence test under the same excitation wavelength and test range, and the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF with better fluorescence performance in water is obtained.
5) Detecting different metal ions by using a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF fluorescent material:
dissolving 5 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 50 mL of deionized water, carrying out ultrasonic treatment for 20 min, subpackaging the solutions in identical 5 mL vials, respectively adding a certain amount of different metal ion solutions into the vials, irradiating the vials with ultraviolet light with a wavelength of 365nm in an ultraviolet dark box to observe the red fluorescence phenomenon of the MOF, and adding Pb2+This results in fluorescence quenching of the MOF.
6) Titration of lead ions by meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF fluorescent material:
dissolving 5 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 50 mL of deionized water, carrying out ultrasonic treatment for 20 min, placing 2 mL of MOF mixed solution in a cuvette, and testing the excitation wavelength of the mixed solution to be 440 nm in a fluorescence photometer. Under the condition of excitation wavelength, gradually increasing Pb2+The fluorescence intensity of the added amount (0-550 μ L) was measured and recorded respectively to calculate the detection limit of the metal ions. Under the same test condition, fluorescence detection is carried out on different metal ions, and the quenching effects of the metal ions on the MOF are compared, so that the MOF can realize Pb on the metal ions2+Detected and calculated, and the detection line is 4.99 multiplied by 10-8 M。
FIG. 1 is a photograph of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF obtained in example 1 under UV light. FIG. 2 is SEM and TEM pictures of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF obtained in example 1. FIG. 3 shows fluorescence intensity of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF obtained in example 1 in different solvents.
Example 2
1) Preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin:
dissolving 70 mg of zinc acetate and 118 mg of meso-tetra (4-carboxyphenyl) porphyrin in a beaker containing 45 mL of N, N-dimethylformamide, and carrying out ultrasonic treatment on the solution for 30 min; and transferring the solution after ultrasonic treatment into a 250 mL single-neck flask, carrying out condensation reflux reaction at 130 ℃, and stirring for reaction for 2 h. Closing the oil bath, and adding 110 mL of deionized water when the reaction liquid is cooled to room temperature; then placing the reaction solution into a refrigerator at 4 ℃, standing for 12 h, taking out the reaction solution, and centrifuging for 10 min at 12000 rpm; drying in a vacuum drying oven to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin, and storing for later use.
2) Preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF:
dissolving 150 mg of benzoic acid, 40 mg of 1, 2-bis (4-carboxyphenyl) -1, 2-stilbene and 60 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin in 12 mL of mixed solution (DMF: ethanol = 4: 1), carrying out ultrasonic treatment on the solution for 30 min to fully dissolve the solution, transferring the ultrasonic solution to a 25 mL polytetrafluoroethylene reaction kettle, and reacting for 1 day at the temperature of 100 ℃; and then cooling the reaction solution to room temperature, washing with N, N-dimethylformamide, centrifuging at 13000 rpm for 10 min until supernatant is clear to obtain purple precipitate, drying the precipitate to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF, and storing for later use.
3) Preparation of metal ion solution:
respectively weighing corresponding mass of metal chloride salt (LiCl, KCl, NaCl, AgCl, NiCl)2, CaCl2, MgCl2, CuCl2, ZnCl2, CoCl2, MnCl2And PbCl2) Dissolving in deionized water to obtain a solution of 1.0 × 10-2Refrigerating the metal ion solution of mol/L; then diluted to 5 mL with a concentration of 1.0X 10-4mol/L solution.
4) Fluorescence detection of meso-tetrakis (4-carboxyphenyl) zinc porphyrin-MOF:
dissolving 2 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 5 mL of solvents such as deionized water, methanol, ethanol, butanol, dichloromethane, N-Dimethylacetamide (DMA), carbon tetrachloride, acetonitrile and the like respectively, performing ultrasonic treatment for 20 min to obtain uniformly mixed purple suspension, performing fluorescence test on the solution under the same excitation wavelength and test range, and obtaining the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF with better fluorescence performance in water.
5) Detecting different metal ions by using a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF fluorescent material:
dissolving 3 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 50 mL of deionized water, carrying out ultrasonic treatment for 20 min, subpackaging the solutions in identical 5 mL vials, respectively adding a certain amount of different metal ion solutions into the vials, irradiating the vials with ultraviolet light with a wavelength of 365nm in an ultraviolet dark box to observe the red fluorescence phenomenon of the MOF, and adding Pb2+This results in fluorescence quenching of the MOF.
6) Titration of lead ions by meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF fluorescent material:
dissolving 3 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 50 mL of deionized water, carrying out ultrasonic treatment for 20 min, placing 2 mL of MOF mixed solution in a cuvette, and testing the excitation wavelength of the mixed solution to be 440 nm in a fluorescence photometer. Under the condition of excitation wavelength, gradually increasing Pb2+The fluorescence intensity of the added amount (0-550 μ L) was measured and recorded respectively to calculate the detection limit of the metal ions. Under the same test condition, fluorescence detection is carried out on different metal ions, and the quenching effects of the metal ions on the MOF are compared, so that the MOF can realize Pb on the metal ions2+Detected and calculated, and the detection line is 4.99 multiplied by 10-8 M。
FIG. 4 shows the aqueous solution of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF obtained in example 2, withoutAnd pictures in the same metal ion solution under ultraviolet light and natural light conditions respectively. FIG. 5 is the mid-tetrakis (4-carboxyphenyl) zinc porphyrin-MOF versus Pb obtained in example 22+Titration curves of (c).
Example 3
1) Preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin:
dissolving 80 mg of zinc acetate and 120 mg of meso-tetra (4-carboxyphenyl) porphyrin in a beaker containing 50 mL of N, N-dimethylformamide, and carrying out ultrasonic treatment on the solution for 30 min; and transferring the solution after ultrasonic treatment into a 250 mL single-neck flask, carrying out condensation reflux reaction at 125 ℃, and stirring for reaction for 1.5 h. Closing the oil bath, and adding 120 mL of deionized water when the reaction liquid is cooled to room temperature; then placing the reaction solution into a refrigerator at 4 ℃, standing for 12 h, taking out the reaction solution, and centrifuging for 10 min at 12000 rpm; drying in a vacuum drying oven to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin, and storing for later use.
2) Preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF:
dissolving 150 mg of benzoic acid, 50 mg of 1, 2-bis (4-carboxyphenyl) -1, 2-stilbene and 70 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin in 15 mL of mixed solution (DMF: ethanol = 4: 1), carrying out ultrasonic treatment on the solution for 30 min to fully dissolve the solution, transferring the ultrasonic solution to a 25 mL polytetrafluoroethylene reaction kettle, and reacting for 1 day at the temperature controlled within the range of 80 ℃; and then cooling the reaction solution to room temperature, washing with N, N-dimethylformamide, centrifuging at 13000 rpm for 10 min until supernatant is clear to obtain purple precipitate, drying the precipitate to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF, and storing for later use.
3) Preparation of metal ion solution:
respectively weighing corresponding mass of metal chloride salt (LiCl, KCl, NaCl, AgCl, NiCl)2, CaCl2, MgCl2, CuCl2, ZnCl2, CoCl2, MnCl2And PbCl2) Dissolving in deionized water to obtain a solution of 1.0 × 10-2Refrigerating the metal ion solution of mol/L; then diluted to 5 mL with a concentration of 1.0X 10-4mol/L solution.
4) Fluorescence detection of meso-tetrakis (4-carboxyphenyl) zinc porphyrin-MOF:
dissolving 1 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 5 mL of solvents such as deionized water, methanol, ethanol, butanol, dichloromethane, N-Dimethylacetamide (DMA), carbon tetrachloride, acetonitrile and the like respectively, performing ultrasonic treatment for 20 min to obtain uniformly mixed purple suspension, performing fluorescence test on the solution under the same excitation wavelength and test range, and obtaining the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF with better fluorescence performance in water.
5) Detecting different metal ions by using a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF fluorescent material:
dissolving 2 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 50 mL of deionized water, carrying out ultrasonic treatment for 20 min, subpackaging the solutions in identical 5 mL vials, respectively adding a certain amount of different metal ion solutions into the vials, irradiating the vials with ultraviolet light with a wavelength of 365nm in an ultraviolet dark box to observe the red fluorescence phenomenon of the MOF, and adding Pb2+This results in fluorescence quenching of the MOF.
6) Titration of lead ions by meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF fluorescent material:
dissolving 2 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF in 50 mL of deionized water, carrying out ultrasonic treatment for 20 min, placing 2 mL of MOF mixed solution in a cuvette, and testing the excitation wavelength of the mixed solution to be 440 nm in a fluorescence photometer. Under the condition of excitation wavelength, gradually increasing Pb2+The fluorescence intensity of the added amount (0-550 μ L) was measured and recorded respectively to calculate the detection limit of the metal ions. Under the same test condition, fluorescence detection is carried out on different metal ions, and the quenching effects of the metal ions on the MOF are compared, so that the MOF can realize Pb on the metal ions2+Detected and calculated, and the detection line is 4.99 multiplied by 10-8 M。
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead, characterized by comprising the following steps:
step 1: preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin: dissolving zinc acetate and meso-tetra (4-carboxyphenyl) porphyrin in N, N-dimethylformamide, and carrying out ultrasonic treatment on the obtained solution; then carrying out condensation reflux reaction on the solution after the ultrasonic treatment at the temperature of 120-150 ℃; stirring for reaction for 1-3 h, cooling the reaction solution to room temperature, and adding deionized water; refrigerating the reaction solution, standing, taking out the reaction solution, and centrifuging; vacuum drying to obtain meso-tetra (4-carboxyphenyl) zinc porphyrin, and storing for later use;
step 2: preparation of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material: dissolving benzoic acid, 1, 2-di (4-carboxyphenyl) -1, 2-stilbene and meso-tetra (4-carboxyphenyl) zinc porphyrin in a mixed solution of DMF and ethanol, carrying out ultrasonic treatment on the obtained solution until the solution is fully dissolved, transferring the ultrasonic solution to a polytetrafluoroethylene reaction kettle, and reacting for 1-3 days at 80-120 ℃; and then cooling the reaction liquid to room temperature, washing with N, N-dimethylformamide, centrifuging until supernatant is clear to obtain purple precipitate, drying to obtain the meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material, and storing for later use.
2. The method of claim 1, wherein in step 1: the dosage of the zinc acetate is 60-80 mg, the dosage of the meso-tetra (4-carboxyphenyl) porphyrin is 110-120 mg, and the dosage of the N, N-dimethylformamide is 40-50 mL.
3. The method of claim 2, wherein in step 1: the dosage of the deionized water is 100-120 mL; then the reaction solution is put into the environment with the temperature of 1-5 ℃ and is kept stand for 10-15 h, and then the reaction solution is taken out.
4. The method of claim 3, wherein in step 1: centrifuging at 10000-.
5. The method of claim 4, wherein in step 1: vacuum drying at 60-80 deg.C for 4-6h to obtain meso-tetra (4-carboxyphenyl) porphyrin, and storing.
6. The method of claim 1, wherein in step 2: the dosage of the benzoic acid is 150 mg of benzoic acid, 30-50 mg of 1, 2-di (4-carboxyphenyl) -1, 2-stilbene and 50-70 mg of meso-tetra (4-carboxyphenyl) zinc porphyrin.
7. The method of claim 6, wherein in step 2: the dosage of N, N-dimethylformyl is 6-8 mL, the dosage of ethanol is 2-4 mL, and the obtained solution is subjected to ultrasonic treatment for 20-40 min until the solution is fully dissolved.
8. The method of claim 7, wherein in step 2: centrifuging for 8-10 min at 11000-13000 rpm until supernatant is clear to obtain purple precipitate, and washing with N, N-dimethylformamide for 3-5 times.
9. The method of claim 8, wherein in step 2: and precipitating the precipitate for 6-10h at 60-80 ℃ in vacuum to obtain a meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material, and storing for later use.
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| CN113881062A (en) * | 2021-10-28 | 2022-01-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Cubic three-dimensional porphyrin metal-organic framework nano-structure material and preparation method thereof |
| CN115400798A (en) * | 2022-08-30 | 2022-11-29 | 合肥工业大学 | Preparation method and application of bimetallic modified porphyrin-based MOF catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113881062A (en) * | 2021-10-28 | 2022-01-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Cubic three-dimensional porphyrin metal-organic framework nano-structure material and preparation method thereof |
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| GB2619448A (en) * | 2022-03-23 | 2023-12-06 | Univ Jiangsu | Porphyrin zinc europium phosphorus cluster material, preparation method therefor and application thereof |
| GB2619448B (en) * | 2022-03-23 | 2024-05-08 | Univ Jiangsu | Zinc-europium-phosphorus porphyrin cluster material and preparation method and use thereof |
| CN115400798A (en) * | 2022-08-30 | 2022-11-29 | 合肥工业大学 | Preparation method and application of bimetallic modified porphyrin-based MOF catalyst |
| CN115400798B (en) * | 2022-08-30 | 2023-09-26 | 合肥工业大学 | Preparation method and application of bimetallic modified porphyrin-based MOF catalyst |
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