CN115521470B - N-chloro zirconium-porphyrin MOF, N-chloro zirconium-porphyrin MOF/polymer composite material and preparation method - Google Patents
N-chloro zirconium-porphyrin MOF, N-chloro zirconium-porphyrin MOF/polymer composite material and preparation method Download PDFInfo
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- CN115521470B CN115521470B CN202211047612.7A CN202211047612A CN115521470B CN 115521470 B CN115521470 B CN 115521470B CN 202211047612 A CN202211047612 A CN 202211047612A CN 115521470 B CN115521470 B CN 115521470B
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000013097 PCN-222 Substances 0.000 description 1
- BAFQDKPJKOLXFZ-UHFFFAOYSA-N Paraoxon-methyl Chemical compound COP(=O)(OC)OC1=CC=C([N+]([O-])=O)C=C1 BAFQDKPJKOLXFZ-UHFFFAOYSA-N 0.000 description 1
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- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical group N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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Abstract
The invention discloses an N-chloro zirconium-porphyrin MOF, an N-chloro zirconium-porphyrin MOF/polymer composite material and a preparation method thereof. The preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material is that an organic polymer fiber film is added into the reaction liquid in the preparation process. The N-chloro zirconium-porphyrin MOF and the N-chloro zirconium-porphyrin MOF/polymer composite material can have excellent detoxification performance of nerve agents and erosive agents and excellent biological protection performance.
Description
Technical Field
The invention belongs to the field of chemical biological protective materials, and relates to a metal organic framework nano material with the detoxification and sterilization performances of nerve agents and erosive agents, a preparation method of the metal organic framework nano material, a composite material loaded with the metal organic framework nano material and a preparation method of the composite material, in particular to an N-chloro zirconium-porphyrin MOF, an N-chloro zirconium-porphyrin MOF/polymer composite material and a preparation method of the composite material.
Background
In the face of unpredictable biochemical threats, the development of a functional material with both chemical and biological protection has been a continuing effort. For chemical protection, the nerve agent and the blister agent are the most deadly of the two types, and there are many protective materials for each type, but materials with the characteristics of the two types are relatively few. To date, zr (OH) has been reported 4 NiO NPs/Ag-clinoptilolite, HKUST-1, uiO-66@LiOtBu, MOF-808 and H 5 PV 2 Mo 10 O 4 @MOF-808, etc. It is noted that the detoxification experiments of the above materials for two classes of chemical warfare agents were performed separately under different conditions. In addition, some materials, such as NU-1000, have also reported in various literature hydrolysis of nerve agents (and mimics thereof) and catalytic oxidative detoxification of blister agents (and mimics thereof), respectively. Liu et al report that nano PCN-222 metal organic frameworks can hydrolyze nerve agent mimetic DMNP simultaneously in one system and oxidize mustard gas mimetic CEES to non-toxic products with half-lives of 8 minutes and 12 minutes, respectively, but performance needs to be further improved. More importantly, materials with both detoxification and biological protection properties of these two types of deadly chemical agents have been reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and particularly aims to solve the problems of the detoxification performance and biological protection performance of two types of deadly chemical agents, namely nerve agent and erosive agent, and the like.
In order to solve the technical problems, the invention adopts the following technical scheme.
The N-chloro zirconium-porphyrin MOF is formed by coaxially growing and radially stretching a plurality of two-dimensional metal-organic framework nano-sheets, and the two-dimensional metal-organic framework nano-sheets are circumferentially distributed at intervals (around the axis). Wherein, the coaxial growth is also called co-edge growth, namely, the two-dimensional metal organic framework nano sheets share one edge, are separated by a certain distance and extend along the radial direction.
Preferably, the microstructure of the N-chloro zirconium-porphyrin MOF is a carambola-shaped nanostructure.
As a general technical concept, the invention also provides a preparation method of the N-chloro zirconium-porphyrin MOF, which comprises the following steps:
mixing zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent for dissolution, carrying out solvothermal reaction at the temperature of 60-90 ℃, centrifugally separating and washing the obtained precipitate after the reaction, adding the precipitate into an aqueous solution containing a chlorinated reagent, carrying out chlorination reaction at room temperature, centrifugally separating the obtained product again, washing and drying the obtained product again, and obtaining the N-chloro zirconium-porphyrin MOF.
In the preparation method of the N-chloro zirconium-porphyrin MOF, preferably, the chloro reagent is sodium dichloroisocyanurate, the chloro reaction time is 3-12 h, and the ratio of the chloro reagent to the substance of the tetracarboxylic porphyrin ligand is 3-12:1.
In the above preparation method of the N-chloro zirconium-porphyrin MOF, preferably, the acid regulator is monocarboxylic acid, the monocarboxylic acid is formic acid, the porphyrin ligand of the tetracarboxylic acid is one or more of meso-tetra (4-carboxyphenyl) porphine and derivatives thereof, and the organic solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide and N, N-dimethylacetamide.
In the above preparation method of the N-chloro zirconium-porphyrin MOF, preferably, the ratio of the amount of the substances of zirconium chloride and the amount of the substances of the tetracarboxylic porphyrin ligand is 3-8:1, the amount of the acid regulator is 16mL/mmol of the tetracarboxylic porphyrin ligand to 64mL/mmol of the tetracarboxylic porphyrin ligand, the amount of the organic solvent is 120mL/mmol of the tetracarboxylic porphyrin ligand to 240mL/mmol of the tetracarboxylic porphyrin ligand, and the amount of the water is 20mL/mmol of the tetracarboxylic porphyrin ligand to 100mL/mmol of the tetracarboxylic porphyrin ligand.
In the preparation method of the N-chloro zirconium-porphyrin MOF, preferably, the reaction time is 24-96 hours; the ultrasonic vibration is assisted during the dissolution, so that the dissolution is fully carried out; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, wherein the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; the concentration of the washed precipitate product dispersed into the aqueous solution containing the chlorinated reagent is calculated according to the reaction feeding amount of the porphyrin tetracarboxylic acid ligand, 2 mmol-5 mmol of porphyrin tetracarboxylic acid ligand/L of water, and the concentration of the chlorinated reagent in the water is 6 mmol/L-50 mmol/L so as to ensure that the mass ratio of the chlorinated reagent to the porphyrin tetracarboxylic acid ligand is 3-12:1; the re-washing is carried out by adopting water, and the washing times are 2-4 times; the drying is vacuum drying, the temperature of the vacuum drying is 30-120 ℃, and the time of the vacuum drying is 2-24 hours.
As a general technical concept, the invention also provides a preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material, which comprises the following steps:
mixing zirconium chloride, porphyrin tetracarboxylic ligand, acid regulator, water and organic solvent, dissolving, adding organic polymer fiber membrane, performing solvothermal reaction at 60-80 ℃, washing the modified organic polymer fiber membrane after the reaction, adding the modified organic polymer fiber membrane into aqueous solution containing chlorinated reagent, performing chlorination reaction at room temperature, washing and drying the obtained product again, and obtaining the N-chloro zirconium-porphyrin MOF/polymer composite material.
In the above preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material, preferably, the organic polymer fiber film includes one or more of a polyethylene fiber film, a polypropylene fiber film and cotton cloth, and when the organic polymer fiber film is a polyethylene fiber film and/or a polypropylene fiber film, the polyethylene fiber film and/or the polypropylene fiber film is modified with an oxygen-containing functional group, and the oxygen-containing functional group includes a carboxyl group and/or a hydroxyl group.
In the preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material, preferably, the chloro reagent is sodium dichloroisocyanurate, the chloro reaction time is 3-12 h, and the ratio of the chloro reagent to the substance of the tetracarboxylic porphyrin ligand is 3-12:1.
In the preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material, preferably, the acid regulator is monocarboxylic acid, and the monocarboxylic acid is formic acid; the porphyrin tetracarboxylic ligand is one or more of meso-tetra (4-carboxyphenyl) porphin and derivatives thereof; the organic solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide and N, N-dimethylacetamide.
In the preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material, preferably, the ratio of the zirconium chloride to the substance of the tetracarboxylic porphyrin ligand is 3-8:1, the amount of the acid regulator is 16-64 mL/mmol of the tetracarboxylic porphyrin ligand, the amount of the organic solvent is 120-240 mL/mmol of the tetracarboxylic porphyrin ligand, and the amount of the water is 20-100 mL/mmol of the tetracarboxylic porphyrin ligand.
In the preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material, preferably, the reaction time is 24-96 h, and the chlorination reaction time is 3-10 h; the ultrasonic vibration is assisted during the dissolution, so that the dissolution is fully carried out; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, wherein the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; the modified organic polymer fiber membrane is placed into an aqueous solution containing a chlorinated reagent, wherein the amount of the modified organic polymer fiber membrane is calculated by the reaction feeding amount of the porphyrin tetracarboxylic acid ligand, the concentration of the chlorinated reagent in water is 6-50 mmol/L, and the ratio of the chlorinated reagent to the substance of the porphyrin tetracarboxylic acid ligand is 3-12:1; the re-washing is carried out by adopting water, and the washing times are 2-4 times; the drying is vacuum drying, the temperature of the vacuum drying is 30-120 ℃, and the time of the vacuum drying is 2-24 hours.
As a general technical concept, the invention also provides the N-chloro zirconium-porphyrin MOF/polymer composite material prepared by the preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material. The N-chloro zirconium-porphyrin MOF/polymer composite material comprises N-chloro zirconium-porphyrin MOF and an organic polymer fiber film, wherein the zirconium-porphyrin MOF is firstly grown on the organic polymer fiber film in an in-situ growth mode, and then the N-chloro zirconium-porphyrin MOF/polymer composite material is obtained through a chloro method.
As a general technical concept, the invention also provides an application of the N-chloro zirconium-porphyrin MOF or the N-chloro zirconium-porphyrin MOF prepared by the preparation method of the N-chloro zirconium-porphyrin MOF or the N-chloro zirconium-porphyrin MOF/polymer composite material in degrading nerve agents, degrading erosive agents or sterilizing.
Compared with the prior art, the invention has the advantages that:
(1) According to the N-chloro zirconium-porphyrin MOF disclosed by the invention, the N atoms in the porphyrin ring are modified, so that the metal nodes of zirconium are not changed, the catalytic performance of the zirconium based on the nodes is not influenced, and the efficient catalytic hydrolysis performance of the nerve agent is still maintained.
According to the N-chloro zirconium-porphyrin MOF, the quantum efficiency of singlet oxygen generation of the porphin ring is regulated and controlled by modifying the N atom in the porphyrin ring, so that the catalytic oxidation performance of the N-chloro zirconium-porphyrin MOF on the erosive agent is improved. The regulation and control method is simple and repeatable, and can be expanded to F, br, I, CN, SCN and other halogen and halogen-like atoms.
The N-chloro zirconium-porphyrin MOF modifies N atoms in porphyrin rings to form active N-Cl bonds, and can slowly release active chlorine atoms, so that the N-chloro zirconium-porphyrin MOF has long-acting sterilization performance.
(2) Compared with the traditional three-dimensional metal organic framework material, the N-chloro zirconium-porphyrin MOF consists of two-dimensional MOF nano-sheets, so that the transmission distance of substrate molecules in the MOF is greatly reduced, the transmission resistance in the three-dimensional metal organic framework material is overcome, the substrate transmission and the product diffusion are facilitated, and the MOF has better catalytic performance.
(3) According to the preparation method of the N-chloro zirconium-porphyrin MOF, the carambola-shaped structure can be obtained by a simple solvothermal method through optimizing the metal/ligand ratio, the reaction temperature, the types and the amounts of water, a regulator and a solvent; the chlorination method is simple and can be completed through simple soaking.
(4) The N-chloro zirconium-porphyrin MOF/polymer composite material can maintain the performance of the N-chloro zirconium-porphyrin MOF and has the detoxification performance and biological protection performance of two deadly chemical agents, namely nerve agent and erosive agent.
Drawings
FIG. 1 is an SEM image of the N-chlorozirconium porphyrin MOF of example 1 of the present invention.
FIG. 2 is an AFM image and thickness of a monolithic two-dimensional MOF nanolayer in an N-chlorozirconium-porphyrin MOF according to example 1 of the present invention.
FIG. 3 is a graph showing the UV absorption spectrum of N-chlorozirconium-porphyrin MOF at various reaction times in the degradation of the nerve agent mimetic DMNP in example 2 of the present invention.
FIG. 4 is a graph showing the conversion of the nerve agent mimetic DMNP over time with N-chlorozirconium-porphyrin MOF as the catalyst in example 2 of the present invention.
FIG. 5 is a graph showing the conversion of the blister agent mimetic CEES over time with the use of the N-chlorozirconium-porphyrin MOF as the catalyst in example 3 of the present invention.
FIG. 6 is a schematic diagram of Zr-TCPP-Cl according to example 4 of the invention 2 Conversion of the blister agent mimetic CEES upon repeated use.
FIG. 7 is a schematic illustration of Zr-TCPP-Cl according to example 5 of the invention 2 Is an optical photograph of the bacteriostatic effect of (a).
FIG. 8 is a schematic representation of hollow white starch and non-chlorinated Zr-TCPP-H according to the invention in example 5 2 Is an optical photograph of the bacteriostatic effect of (a).
FIG. 9 shows the Zr-TCPP-Cl content in example 5 according to the invention 2 Is a graph of the bacteriostatic effect over time.
FIG. 10 is a schematic illustration of an N-chlorozirconium porphyrin MOF/polymer composite (CT/Zr-TCPP-Cl) in example 6 of the invention 2 Composite material).
FIG. 11 is a graph of CT/Zr-TCPP-Cl according to example 6 of the invention 2 SEM image of the composite.
FIG. 12 is a graph showing the UV absorption spectrum of the nerve agent mimetic DMNP at various times when the N-chlorozirconium-porphyrin MOF/polymer composite material in example 7 of the present invention is a catalyst.
FIG. 13 is a graph showing the conversion of the nerve agent mimetic DMNP over time with the N-chlorozirconium-porphyrin MOF/polymer composite as a catalyst in example 7 of the present invention.
FIG. 14 is a graph showing the conversion of the blister agent mimetic CEES over time with the use of the N-chlorozirconium-porphyrin MOF as the catalyst in example 8 of the present invention.
FIG. 15 is a graph of CT/Zr-TCPP-Cl according to example 9 of the invention 2 An optical photograph of the bacteriostatic effect of the composite material.
FIG. 16 is a schematic illustration of hollow white starch and non-chlorinated Zr-TCPP-H according to the invention as in example 9 2 Optical photograph of bacteriostatic effect of cotton composite.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby. The materials and instruments used in the examples below are all commercially available.
The room temperature is usually 20℃to 32 ℃.
Example 1:
the N-chloro zirconium-porphyrin MOF is formed by coaxially growing and radially stretching a plurality of two-dimensional metal organic framework nano-sheets, and the two-dimensional metal organic framework nano-sheets are distributed at intervals in the circumferential direction. In this example, the microstructure of the N-chlorozirconium-porphyrin MOF is specifically a starfruit-shaped nanostructure.
The preparation method of the N-chloro zirconium-porphyrin MOF comprises the following steps:
176mg of zirconium chloride ZrCl is taken 4 (0.75 mmol) and 100mg of meso-tetra (4-carboxyphenyl) porphine (TCPP-H) 2 ) (0.125 mmol) was added 5mL formic acid, 12.5mL deionized water and 15mL N, N-Dimethylformamide (DMF), and after sufficient dissolution by sonication, transferred to a 100mL sealed reaction flask, placed in an oven at 65℃and held for 72h to effect a reaction. After the reaction, the product was centrifuged, washed three times with DMF, water and absolute ethanol, respectively, and dispersed again into 30mL of 1wt% sodium dichloroisocyanurate solution (containing 1.36mmol of sodium dichloroisocyanurate) and reacted at room temperature for 6 hours. After the reaction is finished, centrifugal separation is carried out, water is used for cleaning for three times, and vacuum drying is carried out for 12 hours at the temperature of 85 ℃ to obtain N-chloro zirconium-porphyrin MOF which is marked as Zr-TCPP-Cl 2 。
The N-chloro zirconium-porphyrin MOF nanomaterial prepared in the embodiment is characterized by adopting a scanning electron microscope, as shown in fig. 1, the metal-organic framework nanomaterial can be clearly seen under a 5000X scanning electron microscope to form a carambola-shaped nanostructure, the whole length of the carambola is about 3.6 mu m, and the radial width of each two-dimensional thin layer is 0.8 mu m. As shown in FIG. 2, the thickness of a two-dimensional thin layer was measured by atomic force microscopy to be about 0.9nm. The content of chlorine element in the TCPP molecule is 5.4wt% by ion chromatography, and it can be calculated that 2 chlorine atoms in each TCPP molecule, namely 2N-H atoms on the porphine ring are replaced by N-Cl.
Example 2:
the use of the N-chloro zirconium-porphyrin MOF of the present invention for degrading neurotoxic agents, using the N-chloro zirconium-porphyrin MOF prepared in example 1, comprises the steps of:
putting 14mg of N-chloro zirconium-porphyrin MOF sample into a centrifuge tube, adding 4mL of N-ethylmorpholine water solution (the concentration is 0.45 mol/L), carrying out ultrasonic treatment for 5 minutes, stirring at the speed of 1100r/min for 5 minutes, taking 20 mu L of reaction solution, diluting in 10mL of N-ethylmorpholine water solution, and testing the absorbance change between 250nm and 500nm after shaking uniformly for deducting the interference of porphin p-nitrophenol ultraviolet absorption peak in the starfruit zirconium MOFs in the solution. mu.L of the nerve agent simulator agent methyl paraoxon (DMNP, 0.09 mmol) was added while stirring was continued at 1100r/min, and 20. Mu.L of the reaction solution was diluted in 10mL of an aqueous solution of N-ethylmorpholine at several time points of 1, 3,5, 10, 20, 30, 40, 60, 100min, and after shaking, the absorbance change between 250nm and 500nm was measured against the UV-vis spectrum of the aqueous solution of N-ethylmorpholine as background before the measurement. The product concentration was determined by the maximum absorption peak intensity of the product para-nitrophenol at 402nm and the conversion calculated. Each group of degradation was repeated 3 times to obtain a degradation half-life.
Characterization data are shown in fig. 3 and 4. FIG. 3 shows that as the reaction proceeds, the characteristic absorption of DMNP at 275nm of the reaction system decreases significantly over time and the characteristic absorption of 4-nitrophenol, a hydrolysis product at 407nm, increases significantly, indicating that the prepared N-chlorozirconium-porphyrin MOF is effective in catalyzing the hydrolysis of the simulator DMNP. FIG. 4 shows that the reaction speed of catalytic decomposition is very fast, and the decomposition rate can reach 100% within 10 minutes. Half-life (time at 50% degradation) is less than 1min.
Example 3:
the application of the N-chloro zirconium-porphyrin MOF in degrading the erosive agent disclosed by the invention adopts the N-chloro zirconium-porphyrin MOF prepared in the embodiment 1, and comprises the following steps of:
to a 10mL quartz gas chromatography headspace bottle was added 5mg of N-chlorozirconium-porphyrin MOF as catalyst, 1mL of methanol, and after 5 minutes of sonication, the solution was bubbled with oxygen for 5 minutes, and the bottle was sealed. 10. Mu.L of the internal standard 1-bromo-3, 5-difluorobenzene and 23. Mu.L of the blister agent simulator chloroethyl sulfide (CEES) were added, and the mixture was stirred with a small magnet, and after stirring uniformly, 25. Mu.L of the mixture was taken out and diluted into 0.3mL of methanol, which was used as a reference (0-time sample). The reaction was carried out under 405nm light, 25. Mu.L of each sample (gas chromatograph injection needle with long needle) was taken out at 2, 4, 6, 8, 10, 15, 20, 25, 30min, diluted into 0.3mL of methanol, filtered and monitored by GC-MS. Quantitative analysis was performed by comparison with the retention time of the 0-time sample.
The characterization data are shown in fig. 5, and fig. 5 shows that the reaction speed of catalytic oxidation is very fast, and 100% decomposition can be realized within 8 minutes. As can be seen from FIG. 5, the half-life of the reaction was about 4min.
Example 4:
the repeated application of the N-chloro zirconium-porphyrin MOF in degrading the erosive agent adopts the N-chloro zirconium-porphyrin MOF prepared in the example 1, and comprises the following steps:
after the completion of the reaction in example 3, 23. Mu.L of CEES was added again, and after 10 minutes of the reaction, the amount of CEES was monitored. Repeated 5 times.
The characterization data are shown in fig. 6, and fig. 6 shows that 100% of complete catalytic oxidation can be obtained in the first 4 times at 10min after repeated use, and 95% of complete catalytic oxidation can still be degraded in the 5 th time, so that the N-chloro zirconium-porphyrin MOF has excellent repeated use performance.
Example 5:
the application of the N-chloro zirconium-porphyrin MOF in sterilization adopts the N-chloro zirconium-porphyrin MOF prepared in the example 1, and comprises the following steps:
uniformly mixing the powder of the N-chloro zirconium-porphyrin MOF with soluble starch according to a certain mass fraction, putting the mixture into a manual tablet press for tabletting, controlling the mass of the antibacterial tablet to be 0.2g, controlling the diameter of the antibacterial tablet to be 9mm, and respectively controlling the mass fractions of the powder of the N-chloro zirconium-porphyrin MOF to be 5%,10% and 15% respectively for standby after tabletting. The control group is blank starch tablet, starch tablet of non-chlorinated zirconium-porphyrin MOF with mass fraction of 15%.
On a super clean bench, the slant E.coli (ATCC 25922) was scraped with an inoculating loop into 5mL of liquid medium, activated at 220rpm and 37℃for 20 hours, and the OD600 of the activated E.coli was 2.3267Abs. Taking 100 mu L of activated bacterial liquid, uniformly coating the bacterial liquid on the surface of a solid culture medium, putting a prepared tablet in the center of the culture medium, placing the culture medium in a baking oven at 37 ℃ for culturing, and observing the size of a bacteriostasis ring.
Characterization data are shown in fig. 7, 8, and 9. The apparent inhibition ring appears in FIG. 7, indicating that the N-chlorozirconium-porphyrin MOF has bactericidal properties. FIG. 8 is a blank amyloid and non-chlorinated zirconium-porphyrin MOF (Zr-TCPP-H) 2 ) Indicating that neither of these had bacteriostatic effects. FIG. 9 shows the sizes of the antibacterial rings of the N-chloro zirconium-porphyrin MOF with different contents, which shows that the antibacterial effect can last for more than 24 hours.
Example 6:
the preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material comprises the following steps:
176mg of zirconium chloride ZrCl is taken 4 (0.75 mmol) and 100mg of meso-tetra (4-carboxyphenyl) porphine (TCPP-H) 2 ) (0.125 mmol), 5mL of formic acid, 12.5mL of deionized water and 15mL of N, N-Dimethylformamide (DMF) were added, and after sufficient dissolution by sonication, the mixture was transferred to a 100mL sealed reaction flask, a cotton cloth film (length and width dimensions: 2 cm. Times.2 cm) was placed in the reaction solution, and the solution was placed in an oven at 65℃and kept for 72 hours to carry out the reaction. After the reaction was completed, the cotton cloth was taken out with tweezers, washed three times with DMF, water and absolute ethanol, and put into 30mL of 1wt% sodium dichloroisocyanurate solution (containing 1.36 mmol) again, and reacted at room temperature for 6 hours. After the reaction, taking out cotton cloth with tweezers, washing with water for three times, and vacuum drying at 85 ℃ for 12 hours to obtain the N-chloro zirconium-porphyrin MOF/polymer composite material, which is marked as CT/Zr-TCPP-Cl 2 。
FIG. 10 is an optical photograph of a blank cotton cloth and an N-chlorozirconium-porphyrin MOF/polymer composite material, showing that the N-chlorozirconium-porphyrin MOF is successfully loaded on the cotton cloth after the reaction, and the N-chlorozirconium-porphyrin MOF/polymer composite material prepared in the embodiment is characterized by adopting a scanning electron microscope, as shown in FIG. 11, a large amount of N-chlorozirconium-porphyrin MOF is loaded on cotton cloth fibers.
Example 7:
the application of the N-chloro zirconium-porphyrin MOF/cotton cloth composite material in degrading organophosphorus toxin agent is carried out in the same steps as in the example 2, and the N-chloro zirconium-porphyrin MOF is replaced by the N-chloro zirconium-porphyrin MOF/polymer composite material prepared in the example 6.
Characterization data are shown in fig. 12 and 13. FIG. 12 shows that as the reaction proceeds, the characteristic absorption of DMNP at 275nm of the reaction system is significantly reduced over time, and the characteristic absorption of 4-nitrophenol as a hydrolysate at 407nm is significantly increased, which indicates that the prepared N-chlorozirconium-porphyrin MOF/polymer composite material can effectively catalyze the hydrolysis of the simulator DMNP. FIG. 13 shows that the reaction rate of catalytic decomposition is very fast and the decomposition rate can be completely converted within 15 minutes (in the figure, the conversion rate is not 100% because the hydrolysis product is absorbed by cotton cloth and cannot be monitored by ultraviolet-visible spectrum). Half-life (time at 50% degradation) is less than 3min.
Example 8:
use of the N-chloro zirconium-porphyrin MOF/polymer composite film of the present invention for degrading an blister agent, substantially the same procedure as in example 2, substituting the N-chloro zirconium-porphyrin MOF with the N-chloro zirconium-porphyrin MOF/polymer composite material prepared in example 6:
a piece of chlorinated zirconium-porphyrin MOF/cotton cloth composite material with the size of 1cm multiplied by 1cm is added into a 10mL quartz gas chromatography headspace bottle to be used as a catalyst, 1mL of methanol is used as a catalyst, the solution is bubbled with oxygen for 5 minutes, and the bottle is sealed. After adding 5. Mu.L of the internal standard 1-bromo-3, 5-difluorobenzene and 5. Mu.L of the blister agent simulator chloroethyl sulfide (CEES) and shaking uniformly, 25. Mu.L was taken out and diluted into 50. Mu.L of methanol to be used as a reference (0-time sample). The reaction was carried out under 405nm light, 25. Mu.L of each sample (gas chromatograph needle with long needle) was taken out at 5, 10, 15, 20, 30min, diluted into 50. Mu.L of methanol, and monitored by GC-MS. Quantitative analysis was performed by comparison with the retention time of the 0-time sample.
Characterization data are shown in fig. 14. FIG. 14 shows that the reaction rate of the catalytic oxidation is very fast for the first 10min, and 50% decomposition can be achieved within 5 min. As can be seen from the figure, the material can be thoroughly decomposed for about 20 minutes.
Example 9:
the application of the N-chloro zirconium-porphyrin MOF/polymer composite material in sterilization comprises the following steps:
on an ultra-clean bench, 100 mu L of activated escherichia coli bacterial liquid is uniformly coated on the surface of a solid culture medium, two pieces of N-chloro zirconium-porphyrin MOF/polymer composite material with the size of 1cm multiplied by 1cm are placed on the center of the culture medium in an overlapping manner, and the culture medium is placed in a baking oven at 37 ℃ for culturing, so that the size of a bacteriostasis ring is observed. The control group was blank cotton swatch and non-chlorinated zirconium-porphyrin MOF (Zr-TCPP-H) 2 ) Cotton cloth composite material.
Characterization data are shown in fig. 15 and 16, and a clear inhibition ring appears in fig. 15, which shows that the N-chloro zirconium-porphyrin MOF/polymer composite material has bactericidal performance. Fig. 16 is a blank cotton swatch and an unclaimed zirconium-porphyrin MOF/cotton composite, indicating that neither had a bacteriostatic effect.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The N-chloro zirconium-porphyrin MOF is characterized by comprising a plurality of two-dimensional metal organic framework nano-sheets which coaxially grow and radially stretch, wherein the two-dimensional metal organic framework nano-sheets are distributed at intervals in the circumferential direction;
the preparation method of the N-chloro zirconium-porphyrin MOF comprises the following steps:
mixing zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent for dissolution, carrying out solvothermal reaction at the temperature of 60-90 ℃, centrifugally separating and washing the obtained precipitate after the reaction, adding the precipitate into an aqueous solution containing a chlorinated reagent, carrying out chlorination reaction at room temperature, centrifugally separating the obtained product again, washing and drying the obtained product again, and obtaining the N-chloro zirconium-porphyrin MOF.
2. The N-chloro-zirconium-porphyrin MOF according to claim 1, wherein the microstructure of the N-chloro-zirconium-porphyrin MOF is a starfruit-shaped nanostructure.
3. A method for preparing an N-chlorozirconium-porphyrin MOF according to claim 1 or 2, comprising the steps of:
mixing zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent for dissolution, carrying out solvothermal reaction at the temperature of 60-90 ℃, centrifugally separating and washing the obtained precipitate after the reaction, adding the precipitate into an aqueous solution containing a chlorinated reagent, carrying out chlorination reaction at room temperature, centrifugally separating the obtained product again, washing and drying the obtained product again, and obtaining the N-chloro zirconium-porphyrin MOF.
4. The method for producing an N-chlorozirconium-porphyrin MOF according to claim 3, wherein the chlorinating agent is sodium dichloroisocyanurate, the time of the chlorinating reaction is 3-12 hours, and the ratio of the amount of the chlorinating agent to the amount of the substance of the porphyrin tetracarboxylic acid ligand is 3-12:1.
5. The method for producing an N-chlorozirconium-porphyrin MOF according to claim 3, wherein the acidity regulator is a monocarboxylic acid, the monocarboxylic acid is formic acid, the porphyrin ligand is one or more of meso-tetra (4-carboxyphenyl) porphin and derivatives thereof, and the organic solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide and N, N-dimethylacetamide;
and/or the ratio of the amount of the substances of the zirconium chloride and the porphyrin tetracarboxylic acid ligand is 3-8:1, the amount of the acid regulator is 16-64 mL/mmol of porphyrin tetracarboxylic acid ligand, the amount of the organic solvent is 120-240 mL/mmol of porphyrin tetracarboxylic acid ligand, and the amount of the water is 20-100 mL/mmol of porphyrin tetracarboxylic acid ligand.
6. The method for producing an N-chlorozirconium-porphyrin MOF according to any one of claims 3-5, wherein the reaction time is 24-96 hours; the ultrasonic vibration is assisted during the dissolution, so that the dissolution is fully carried out; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, wherein the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; the concentration of the washed precipitate product dispersed into the aqueous solution containing the chlorinated reagent is 2 mmol-5 mmol of the porphyrin tetracarboxylic ligand/L water according to the reaction feeding amount of the porphyrin tetracarboxylic ligand, and the concentration of the chlorinated reagent in the water is 6 mmol/L-50 mmol/L; the re-washing is carried out by adopting water, and the washing times are 2-4 times; the drying is vacuum drying, the temperature of the vacuum drying is 30-120 ℃, and the time of the vacuum drying is 2-24 hours.
7. The preparation method of the N-chloro zirconium-porphyrin MOF/polymer composite material is characterized by comprising the following steps:
mixing zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent, dissolving, adding an organic polymer fiber film, carrying out solvothermal reaction at the temperature of 60-80 ℃, washing the modified organic polymer fiber film after the reaction, adding the modified organic polymer fiber film into an aqueous solution containing a chlorinated reagent, carrying out chlorination reaction at room temperature, and washing and drying the obtained product again to obtain the N-chloro zirconium-porphyrin MOF/polymer composite material, wherein the N-chloro zirconium-porphyrin MOF is the N-chloro zirconium-porphyrin MOF as claimed in claim 1 or 2.
8. The method for producing an N-chloro zirconium-porphyrin MOF/polymer composite material according to claim 7, wherein the organic polymer fiber film comprises one or more of a polyethylene fiber film, a polypropylene fiber film and cotton cloth, and when the organic polymer fiber film is a polyethylene fiber film and/or a polypropylene fiber film, the polyethylene fiber film and/or the polypropylene fiber film is modified with an oxygen-containing functional group, the oxygen-containing functional group comprises a carboxyl group and/or a hydroxyl group;
and/or the chlorinating agent is sodium dichloroisocyanurate, the chlorinating reaction time is 3-12 h, and the ratio of the chlorinating agent to the substance of the porphyrin tetracarboxylic acid ligand is 3-12:1;
and/or, the acidity regulator is a monocarboxylic acid, which is formic acid; the porphyrin tetracarboxylic ligand is one or more of meso-tetra (4-carboxyphenyl) porphin and derivatives thereof; the organic solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide and N, N-dimethylacetamide;
and/or the ratio of the amount of the substances of the zirconium chloride and the porphyrin tetracarboxylic acid ligand is 3-8:1, the amount of the acid regulator is 16-64 mL/mmol of porphyrin tetracarboxylic acid ligand, the amount of the organic solvent is 120-240 mL/mmol of porphyrin tetracarboxylic acid ligand, and the amount of the water is 20-100 mL/mmol of porphyrin tetracarboxylic acid ligand;
and/or the reaction time is 24-96 h, and the chlorination reaction time is 3-10 h; the ultrasonic vibration is assisted during the dissolution, so that the dissolution is fully carried out; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, wherein the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; the modified organic polymer fiber membrane is placed into an aqueous solution containing a chlorinated reagent, wherein the concentration of the chlorinated reagent in the water is 6-50 mmol/L based on the reaction feeding amount of the porphyrin tetracarboxylic acid ligand and 2-5 mmol of water; the re-washing is carried out by adopting water, and the washing times are 2-4 times; the drying is vacuum drying, the temperature of the vacuum drying is 30-120 ℃, and the time of the vacuum drying is 2-24 hours.
9. An N-chloro zirconium-porphyrin MOF/polymer composite material produced by the method for producing an N-chloro zirconium-porphyrin MOF/polymer composite material according to claim 7 or 8.
10. Use of an N-chloro zirconium-porphyrin MOF according to claim 1 or 2 or an N-chloro zirconium-porphyrin MOF prepared according to the method of any one of claims 3-6 or an N-chloro zirconium-porphyrin MOF/polymer composite according to claim 9 for degrading nerve agents, for degrading blister agents or for sterilizing.
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