CN115521470A - N-zirconium chloride-porphyrin MOF, N-zirconium chloride-porphyrin MOF/polymer composite material and preparation method - Google Patents
N-zirconium chloride-porphyrin MOF, N-zirconium chloride-porphyrin MOF/polymer composite material and preparation method Download PDFInfo
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- porphyrin
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- zirconium chloride
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- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 73
- UBQIJJVYMFNLOE-UHFFFAOYSA-N C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1.Cl Chemical compound C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1.Cl UBQIJJVYMFNLOE-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 210000005036 nerve Anatomy 0.000 claims abstract description 16
- 229920000620 organic polymer Polymers 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 claims description 121
- -1 tetracarboxylic porphyrin Chemical class 0.000 claims description 61
- 239000003446 ligand Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
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- 239000004744 fabric Substances 0.000 claims description 11
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- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 239000012320 chlorinating reagent Substances 0.000 claims description 8
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical group ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 239000002135 nanosheet Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
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- 238000002156 mixing Methods 0.000 claims description 5
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- SMOZAZLNDSFWAB-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,24-dihydroporphyrin-5-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C=1C=CC(N=1)=C(C=1C=CC(=CC=1)C(O)=O)C1=CC=C(N1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)C(O)=O)=C2N=C1C=C2 SMOZAZLNDSFWAB-UHFFFAOYSA-N 0.000 claims description 3
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 2
- 239000003899 bactericide agent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
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- 238000001784 detoxification Methods 0.000 abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 230000003628 erosive effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000003385 bacteriostatic effect Effects 0.000 description 11
- 125000001309 chloro group Chemical group Cl* 0.000 description 11
- 239000000463 material Substances 0.000 description 11
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- 239000003054 catalyst Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- TUUPIFDTVOTCJS-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Zr] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Zr] TUUPIFDTVOTCJS-UHFFFAOYSA-N 0.000 description 6
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- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 4
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- 150000004032 porphyrins Chemical group 0.000 description 4
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- 241000588724 Escherichia coli Species 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
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- 231100000518 lethal Toxicity 0.000 description 3
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- 230000002829 reductive effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JHLKSIOJYMGSMB-UHFFFAOYSA-N 1-bromo-3,5-difluorobenzene Chemical compound FC1=CC(F)=CC(Br)=C1 JHLKSIOJYMGSMB-UHFFFAOYSA-N 0.000 description 2
- GBNVXYXIRHSYEG-UHFFFAOYSA-N 1-chloro-2-ethylsulfanylethane Chemical compound CCSCCCl GBNVXYXIRHSYEG-UHFFFAOYSA-N 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- 235000010082 Averrhoa carambola Nutrition 0.000 description 2
- 240000006063 Averrhoa carambola Species 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
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- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000002575 chemical warfare agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
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- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 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
- 229910052698 phosphorus Inorganic materials 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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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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Abstract
The invention discloses an N-zirconium chloride-porphyrin MOF, an N-zirconium chloride-porphyrin MOF/polymer composite material and a preparation method thereof. The preparation method of the N-zirconium chloride-porphyrin MOF/polymer composite material is characterized in that an organic polymer fiber membrane is added into the reaction liquid in the preparation process. The N-zirconium chloride-porphyrin MOF and N-zirconium chloride-porphyrin MOF/polymer composite material disclosed by the invention can have the detoxification performance and the excellent biological protection performance of both nerve agents and erosive agents.
Description
Technical Field
The invention belongs to the field of chemical biological protective materials, and relates to a metal organic framework nano material with nerve agent and blister agent detoxification and sterilization performance, a preparation method thereof, a composite material loaded with the metal organic framework nano material and a preparation method thereof, in particular to an N-zirconium chloride-porphyrin MOF and N-zirconium chloride-porphyrin MOF/polymer composite material and a preparation method thereof.
Background
In the face of unpredictable biochemical threats, people have been striving to develop a functional material with both chemical protection and biological protection. For chemical protection, nerve agents and blister agents are the most deadly of the two, and there are many types of protective materials for each, but relatively few materials that combine these two properties. 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, and the like. It is noted that the detoxification experiments of the above materials for both classes of chemical warfare agents were performed separately under different conditions. In addition, some materials, such as NU-1000, have also been reported in different literature for hydrolysis of nerve agents (and their mimetics) and catalytic oxidative detoxification of blister agents (and their mimetics), respectively. Liu et al reported that a nano-PCN-222 metal organic framework can simultaneously hydrolyze nerve agent mimic DMNP in one system, andthe mustard gas simulant CEES was oxidized to a non-toxic product with half-lives of 8 minutes and 12 minutes, respectively, but further performance improvements were needed. More importantly, materials with both the detoxification performance and the biological protection performance of the two types of lethal chemical toxicants are rarely reported.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art, in particular to the problems of requirements on detoxification performance and biological protection performance of two types of lethal chemical agents, namely nerve agents and blister agents, and the like, and provides N-zirconium chloride-porphyrin MOF and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme.
The N-zirconium chloride-porphyrin MOF is formed by coaxially growing and radially extending a plurality of two-dimensional metal organic framework nano-sheet layers, wherein the two-dimensional metal organic framework nano-sheet layers are circumferentially distributed at intervals (distributed at intervals around an axis). The two-dimensional metal organic framework nanosheets share one edge, are separated at a certain distance and extend along the radial direction.
Preferably, the microstructure of the N-chlorozirconium-porphyrin MOF is a carambola-shaped nano structure.
As a general technical concept, the present invention also provides a method for preparing N-chlorozirconium-porphyrin MOF, comprising the steps of:
mixing and dissolving zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent, carrying out a solvothermal reaction at the temperature of 60-90 ℃, carrying out centrifugal separation and washing on the obtained precipitation product after the reaction, then adding the obtained precipitation product into an aqueous solution containing a chlorinated reagent, carrying out a chlorination reaction at room temperature, carrying out centrifugal separation again on the obtained product, washing again and drying again, and thus obtaining the N-zirconium chloride-porphyrin MOF.
In the preparation method of the N-chlorozirconium-porphyrin MOF, preferably, the chlorinating reagent is sodium dichloroisocyanurate, the time of chlorination reaction is 3-12 h, and the mass ratio of the chlorinating reagent to the tetracarboxylic porphyrin ligand is 3-12: 1.
In the above method for preparing the N-chlorozirconium-porphyrin MOF, preferably, the acidic regulator is a monocarboxylic acid, the monocarboxylic acid is formic acid, the tetracarboxylic acid 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.
In the above preparation method of the N-chlorozirconium-porphyrin MOF, preferably, the ratio of the amounts of the zirconium chloride and 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-chlorozirconium-porphyrin MOF, the reaction time is preferably 24-96 hours; ultrasonic oscillation is assisted during the dissolution so as to fully dissolve; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, and the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; dispersing the washed precipitation product into an aqueous solution containing a chlorinated reagent, wherein the concentration of the dispersed precipitation product is 2-5 mmol of the tetracarboxylic porphyrin ligand/L of water based on the reaction charging amount of the tetracarboxylic porphyrin ligand, and the concentration of the chlorinated reagent in the water is 6-50 mmol/L so as to ensure that the mass ratio of the chlorinated reagent to the tetracarboxylic porphyrin ligand is 3-12: 1; the secondary washing is washing 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 present invention also provides a method for preparing an N-chlorozirconium-porphyrin MOF/polymer composite, comprising the steps of:
mixing and dissolving zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent, adding an organic polymer fiber membrane, carrying out a solvothermal reaction at the temperature of 60-80 ℃, washing the modified organic polymer fiber membrane after the reaction, then adding the organic polymer fiber membrane into an aqueous solution containing a chlorinated reagent, carrying out a chlorination reaction at room temperature, washing and drying the obtained product again, and thus obtaining the N-zirconium chloride-porphyrin MOF/polymer composite material.
In the above method for preparing the N-zirconium chloride-porphyrin MOF/polymer composite material, preferably, the organic polymer fiber film comprises one or more of polyethylene fiber film, polypropylene fiber film and cotton cloth, and when the organic polymer fiber film is polyethylene fiber film and/or polypropylene fiber film, the polyethylene fiber film and/or polypropylene fiber film is first modified with oxygen-containing functional groups, and the oxygen-containing functional groups comprise carboxyl groups and/or hydroxyl groups.
In the preparation method of the N-chlorozirconium-porphyrin MOF/polymer composite material, preferably, the chlorinating reagent is sodium dichloroisocyanurate, the time of chlorination reaction is 3-12 h, and the mass ratio of the chlorinating reagent to the tetracarboxylic porphyrin ligand is 3-12: 1.
In the above method for preparing the N-zirconium chloride-porphyrin MOF/polymer composite material, preferably, the acidity regulator is a monocarboxylic acid, and the monocarboxylic acid is formic acid; the tetracarboxylic porphyrin 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.
Preferably, the ratio of the zirconium chloride to the amount of the tetracarboxylic porphyrin ligand is 3-8: 1, the dosage of the acid regulator is 16mL/mmol to 64mL/mmol of the tetracarboxylic porphyrin ligand, the dosage of the organic solvent is 120mL/mmol to 240mL/mmol of the tetracarboxylic porphyrin ligand, and the dosage of the water is 20mL/mmol to 100mL/mmol of the tetracarboxylic porphyrin ligand.
In the preparation method of the N-zirconium chloride-porphyrin MOF/polymer composite material, preferably, the reaction time is 24-96 h, and the chlorination reaction time is 3-10 h; ultrasonic vibration is assisted during the dissolution, so that the solution is fully dissolved; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, and the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; the amount of the modified organic polymer fiber membrane put into the water solution containing the chlorinated reagent is 2-5 mmol of tetracarboxylic porphyrin ligand/L of water in terms of the reaction charging amount of the tetracarboxylic porphyrin ligand, the concentration of the chlorinated reagent in the water is 6-50 mmol/L, and the mass ratio of the chlorinated reagent to the tetracarboxylic porphyrin ligand is ensured to be 3-12: 1; the secondary washing is washing by adopting water, and the washing frequency is 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-zirconium chloride-porphyrin MOF/polymer composite material prepared by the preparation method of the N-zirconium chloride-porphyrin MOF/polymer composite material. The N-zirconium chloride-porphyrin MOF/polymer composite material comprises N-zirconium chloride-porphyrin MOF and an organic polymer fiber membrane, wherein the zirconium-porphyrin MOF is grown on the organic polymer fiber membrane in an in-situ growth mode, and then the N-zirconium chloride-porphyrin MOF/polymer composite material is obtained by a chlorination method.
As a general technical concept, the invention also provides application of the N-zirconium chloride-porphyrin MOF or the N-zirconium chloride-porphyrin MOF prepared by the preparation method of the N-zirconium chloride-porphyrin MOF or the N-zirconium chloride-porphyrin MOF/polymer composite material in nerve agent degradation, blister agent degradation or sterilization.
Compared with the prior art, the invention has the advantages that:
(1) The N-chlorozirconium-porphyrin MOF of the invention modifies the N atom in the porphyrin ring, does not change the metal node of zirconium and does not influence the catalytic performance based on the node, thereby still maintaining the high-efficiency catalytic hydrolysis performance to nerve toxicants.
The N-chlorozirconium-porphyrin MOF modifies N atoms in porphyrin rings, regulates and controls the quantum efficiency of the generation of singlet oxygen of the porphyrin rings, and thus improves the catalytic oxidation performance of the N-chlorozirconium-porphyrin MOF on erosive agents. The regulation and control method is simple and repeatable, and can be expanded to halogen and halogen-like atoms such as F, br, I, CN, SCN and the like.
The N-chlorozirconium-porphyrin MOF forms an active N-Cl bond by modifying the N atom in the porphyrin ring, and can slowly release active chlorine atoms, thereby having long-acting bactericidal performance.
(2) Compared with the traditional three-dimensional metal organic framework material, the N-zirconium chloride-porphyrin MOF is composed of two-dimensional MOF nano-sheet layers, so that the transmission distance of substrate molecules in the material 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 N-zirconium chloride-porphyrin MOF has better catalytic performance.
(3) According to the preparation method of the N-zirconium chloride-porphyrin MOF, the Yang Taoxing structure can be obtained through a simple solvothermal method by optimizing the metal/ligand ratio, the reaction temperature, the types and the amounts of water, a regulator and a solvent; the chlorination process is simple and can be completed by simple soaking.
(4) The N-zirconium chloride-porphyrin MOF/polymer composite material can keep the performance of the N-zirconium chloride-porphyrin MOF, and has the detoxification performance and the biological protection performance of two lethal chemical agents, namely nerve agents and blister agents.
Drawings
FIG. 1 is an SEM image of N-chlorozirconium-porphyrin MOF in example 1 of the present invention.
FIG. 2 is an AFM map and thickness of monolithic two-dimensional MOF nanolayers in N-chlorozirconium-porphyrin MOF in example 1 of the present invention.
FIG. 3 is a graph of the UV absorption spectra of N-chlorozirconium-porphyrin MOF of example 2 of the present invention at different reaction times during the degradation of the nerve agent mimic DMNP.
FIG. 4 is a graph showing the conversion of DMNP, a nerve agent mimic, as a function of time, when N-chlorozirconium-porphyrin MOF is used as a catalyst in example 2 of the present invention.
Fig. 5 is a graph showing the conversion of the blister agent simulant CEES over time with N-chlorozirconium-porphyrin MOF as the catalyst in example 3 of the present invention.
FIG. 6 shows Zr-TCPP-Cl in example 4 of the present invention 2 The conversion rate of CEES (vesicant elimination reagent) of the blister agent simulator when the blister agent is repeatedly used.
FIG. 7 shows Zr-TCPP-Cl in example 5 of the present invention 2 The optical photograph of the bacteriostatic effect of (1).
FIG. 8 shows a white starch and a non-chlorinated Zr-TCPP-H in example 5 of the present invention 2 The optical photograph of the bacteriostatic effect of (1).
FIG. 9 shows Zr-TCPP-Cl contents in different amounts in example 5 of the present invention 2 The bacteriostatic effect of the composition is shown as a time-dependent change graph.
FIG. 10 shows the N-chlorozirconium-porphyrin MOF/polymer composite material (CT/Zr-TCPP-Cl) in example 6 of the present invention 2 Composite) optical photographs.
FIG. 11 shows CT/Zr-TCPP-Cl in example 6 of the present invention 2 SEM image of the composite material.
FIG. 12 is a graph of the UV absorption spectra of DMNP as a nerve agent mimic at different times, when N-chlorozirconium-porphyrin MOF/polymer composite is used as a catalyst in example 7 of the present invention.
FIG. 13 is a graph showing the time-dependent change of the conversion rate of DMNP as a nerve agent mimic in example 7 of the present invention when N-chlorozirconium-porphyrin MOF/polymer composite is used as a catalyst.
Fig. 14 is a graph showing the conversion of the blister agent simulant CEES over time with N-chlorozirconium-porphyrin MOF as the catalyst in example 8 of the present invention.
FIG. 15 shows CT/Zr-TCPP-Cl in example 9 of the present invention 2 Optical photograph of the bacteriostatic effect of the composite material.
FIG. 16 shows a combination of hollow white starch and non-chlorinated Zr-TCPP-H according to example 9 of the present invention 2 An optical photo of the bacteriostatic effect of the cotton cloth composite material.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
The room temperature is usually 20 ℃ to 32 ℃.
Example 1:
the invention relates to N-zirconium chloride-porphyrin MOF, which is formed by coaxially growing and radially extending a plurality of two-dimensional metal organic framework nano-sheet layers, wherein the two-dimensional metal organic framework nano-sheet layers are distributed at intervals in the circumferential direction. In this example, the microstructure of the N-zirconium chloride-porphyrin MOF is specifically a carambola-shaped nanostructure.
The invention discloses a preparation method of N-zirconium chloride-porphyrin MOF, which comprises the following steps:
176mg of zirconium chloride ZrCl was 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 and placed in an oven at 65 ℃ for 72 hours to effect a reaction. After the reaction is finished, the product is centrifugally separated, washed by DMF, water and absolute ethyl alcohol respectively for three times, and dispersed into 30mL of 1wt% sodium dichloroisocyanurate solution (containing 1.36mmol of sodium dichloroisocyanurate) again for reaction for 6h at room temperature. After the reaction is finished, centrifugally separating, washing with water for three times, and vacuum drying at 85 ℃ for 12h to obtain the N-zirconium chloride-porphyrin MOF which is recorded as Zr-TCPP-Cl 2 。
The N-chlorozirconium-porphyrin MOF nanomaterial prepared in this example is characterized by using a scanning electron microscope, and as shown in fig. 1, under a 5000X scanning electron microscope, it can be clearly seen that the metal organic framework nanomaterial is in a carambola-like nanostructure morphology composed of two-dimensional thin layers, the overall length of carambola is about 3.6 μm, and the radial width of each two-dimensional thin layer is 0.8 μm. As shown in FIG. 2, the thickness of a two-dimensional thin layer was about 0.9nm as measured by atomic force microscopy. The chlorine content was 5.4wt% as determined by ion chromatography, and 2 chlorines per TCPP molecule were calculated, i.e. 2N-H groups on the porphine ring were all replaced by N-Cl.
Example 2:
an application of the N-zirconium chloride-porphyrin MOF of the invention in the degradation of nerve agents, the N-zirconium chloride-porphyrin MOF prepared in example 1 is adopted, and the method comprises the following steps:
putting a 14mg N-chlorozirconium-porphyrin MOF sample into a centrifuge tube, adding 4mL of N-ethylmorpholine aqueous solution (the concentration is 0.45 mol/L), carrying out ultrasonic treatment for 5 minutes, stirring for 5 minutes at the speed of 1100r/min, taking 20 mu L of reaction liquid, diluting the reaction liquid in 10mL of N-ethylmorpholine aqueous solution, deducting the interference of porphin-p-nitrophenol ultraviolet absorption peaks in carambola zirconium MOFs in the solution, shaking uniformly, and testing the absorbance change between 250nm and 500 nm. Adding 16 mu L of nerve agent stimulant methyl paraoxon (DMNP, 0.09 mmol) while continuously stirring at the speed of 1100r/min, taking 20 mu L of reaction solution from the reaction solution at several time points of 1, 3,5, 10, 20, 30, 40, 60 and 100min to dilute the reaction solution in 10mL of N-ethyl morpholine water solution, testing the absorbance change between 250nm and 500nm after shaking, and using the UV-vis spectrum of the N-ethyl morpholine water solution as a background before testing. The concentration of the product is determined by the maximum absorption peak intensity of the product at 402nm to nitrophenol, and the conversion rate is calculated. Each group of degradation was repeated 3 times to obtain the degradation half-life.
The characterization data are shown in fig. 3 and 4. FIG. 3 shows that the characteristic absorption of DMNP at 275nm of the reaction system is obviously reduced along with the time along with the progress of the reaction, and the characteristic absorption of 4-nitrophenol of a hydrolysis product at 407nm is obviously increased, which shows that the prepared N-zirconium chloride-porphyrin MOF can effectively catalyze the hydrolysis of the analogue DMNP. FIG. 4 shows that the reaction rate of catalytic decomposition is very fast, and the decomposition rate can reach 100% in 10 minutes. The half-life (time to 50% degradation) was less than 1min.
Example 3:
the invention relates to an application of N-zirconium chloride-porphyrin MOF in degrading blister agents, wherein the N-zirconium chloride-porphyrin MOF prepared in example 1 comprises the following steps:
5mg of N-zirconium chloride-porphyrin MOF as a catalyst and 1mL of methanol are added into a 10mL quartz gas chromatography headspace bottle, ultrasonic treatment is carried out for 5 minutes, then the solution is bubbled with oxygen for 5 minutes, and the bottle is sealed. 10 μ L of internal standard 1-bromo-3,5-difluorobenzene and 23 μ L of blister agent simulant chloroethyl ethyl sulfide (CEES) are added, small magnetons are added and stirred, after stirring uniformly, 25 μ L of internal standard is taken out and diluted into 0.3mL of methanol to be used as a reference (0 time sample). The reaction was carried out under light of 405nm, and 25. Mu.L of each sample was taken out (using a long-tipped gas chromatography needle) for 2, 4, 6, 8, 10, 15, 20, 25, and 30min, diluted into 0.3mL of methanol, filtered, and then monitored by GC-MS. Quantitative analysis was performed by comparing the retention time of the samples with time 0.
The characterization data is shown in fig. 5, and fig. 5 shows that the reaction rate of catalytic oxidation is very fast, and 100% decomposition can be achieved within 8 minutes. As can be seen from FIG. 5, the half-life of the reaction was about 4min.
Example 4:
a repeated use of the N-zirconium chloride-porphyrin MOF of the present invention in the degradation of blister agents, using the N-zirconium chloride-porphyrin MOF prepared in example 1, comprising the following steps:
after the reaction in example 3 was completed, 23. Mu.L of CEES was added again, and after 10min of the reaction, the amount of CEES was monitored. Repeat 5 times.
The characterization data are shown in fig. 6, and fig. 6 shows that after repeated use, 100% of complete catalytic oxidation can be obtained in the first 4 times within 10min, and 95% of complete catalytic oxidation can be degraded to the 5 th time, which shows that the N-zirconium chloride-porphyrin MOF has excellent repeated use performance.
Example 5:
an application of the N-zirconium chloride-porphyrin MOF in sterilization, which is prepared in example 1, comprises the following steps:
uniformly mixing the powder of the N-zirconium chloride-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 bacteriostatic tablet to be 0.2g, controlling the diameter to be 9mm, controlling the mass fractions of the powder of the N-zirconium chloride-porphyrin MOF to be 5%,10% and 15%, and tabletting for later use. The control group was a blank starch tablet, a starch tablet of non-chlorinated zirconium-porphyrin MOF with a mass fraction of 15%.
On a clean bench, slant Escherichia coli (ATCC 25922) was scraped to 5mL of a liquid medium by an inoculating loop, and activated at 220rpm at 37 ℃ for 20 hours, and the OD600 of the activated Escherichia coli was 2.3267Abs. And (3) uniformly coating 100 mu L of activated bacteria liquid on the surface of a solid culture medium, putting a prepared tablet in the center of the culture medium, putting the culture medium in a 37 ℃ oven for culture, and observing the size of a bacteriostatic ring.
The characterization data are shown in fig. 7, 8, and 9. A significant antibacterial ring appears in figure 7, indicating that N-zirconium chloride-porphyrin MOF has bactericidal properties. FIG. 8 is a graph of blank amyloid and non-chlorinated zirconium-porphyrin MOF (Zr-TCPP-H) 2 ) Both of which show no bacteriostatic effect. Fig. 9 shows the size of the inhibition ring of N-zirconium chloride-porphyrin MOF with different contents, which indicates that the inhibition effect can last for more than 24h.
Example 6:
the invention relates to a preparation method of an N-zirconium chloride-porphyrin MOF/polymer composite material, which comprises the following steps:
176mg of zirconium chloride ZrCl was 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, the mixture was transferred to a 100mL sealed reaction flask after being sufficiently dissolved by sonication, a cotton film (2 cm. Times.2 cm in length and width) was placed in the reaction solution, and the reaction solution was placed in an oven at 65 ℃ for 72 hours to effect a reaction. After the reaction, the cotton cloth was taken out with tweezers, washed with DMF, water, and absolute ethanol, respectively, three times, and then put into 30mL of 1wt% sodium dichloroisocyanurate solution (containing 1.36mmol of sodium dichloroisocyanurate) again, and reacted at room temperature for 6h. After the reaction is finished, the cotton cloth is taken out by tweezers, washed by water for three times and dried in vacuum at 85 ℃ for 12 hours to obtainTo N-chlorozirconium-porphyrin MOF/polymer composite material, noted as CT/Zr-TCPP-Cl 2 。
Fig. 10 is an optical photograph of blank cotton cloth and N-chlorozirconium-porphyrin MOF/polymer composite, which shows that after the reaction, N-chlorozirconium-porphyrin MOF is successfully loaded on the cotton cloth, and the N-chlorozirconium-porphyrin MOF/polymer composite prepared in this example is characterized by using a scanning electron microscope, as shown in fig. 11, a large amount of N-chlorozirconium-porphyrin MOF is loaded on the cotton cloth fiber.
Example 7:
an application of the N-zirconium chloride-porphyrin MOF/cotton cloth composite material of the invention in degrading organic phosphorus toxicants is carried out by replacing the N-zirconium chloride-porphyrin MOF with the N-zirconium chloride-porphyrin MOF/polymer composite material prepared in example 6 in the same manner as in example 2.
The characterization data are shown in fig. 12 and 13. FIG. 12 shows that the characteristic absorption of DMNP at 275nm of the reaction system is obviously reduced along with the time, and the characteristic absorption of 4-nitrophenol as a hydrolysis product at 407nm is obviously increased, which shows that the prepared N-zirconium chloride-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 that the decomposition rate is completely converted within 15 minutes (in the figure, the conversion rate is not 100% because the hydrolysate is absorbed by cotton cloth and cannot be detected by UV-visible spectroscopy) to 100%. The half-life (time to 50% degradation) was less than 3min.
Example 8:
an application of the N-zirconium chloride-porphyrin MOF/polymer composite film of the present invention in degrading blister agents, the procedure was substantially the same as in example 2, replacing N-zirconium chloride-porphyrin MOF with N-zirconium chloride-porphyrin MOF/polymer composite prepared in example 6:
a10 mL quartz gas chromatography headspace bottle was charged with a 1cm by 1cm pad of chlorinated zirconium-porphyrin MOF/cotton composite as catalyst, 1mL methanol, and the solution was bubbled with oxygen for 5 minutes, sealing the bottle. 5 μ L of internal standard 1-bromo-3,5-difluorobenzene and 5uL of blister agent simulant chloroethyl ethyl sulfide (CEES) were added, and after shaking uniformly, 25 μ L was taken out and diluted into 50 μ L of methanol for use as a reference (0 time sample). The reaction was carried out under light of 405nm, and 25. Mu.L of each sample (gas chromatography needle with long needle) was taken out at 5, 10, 15, 20, and 30min, diluted into 50. Mu.L of methanol, and monitored by GC-MS. Quantitative analysis was performed by comparing the retention time of the samples with time 0.
The 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, about 20min can be completely decomposed.
Example 9:
the invention discloses an application of an N-zirconium chloride-porphyrin MOF/polymer composite material in sterilization, which comprises the following steps:
on a super clean bench, 100 mu L of activated escherichia coli liquid is uniformly coated on the surface of a solid culture medium, two pieces of N-chlorozirconium-porphyrin MOF/polymer composite materials with the size of 1cm multiplied by 1cm are vertically overlapped and placed in the center of the culture medium, the culture medium is placed in a 37 ℃ oven for culture, and the size of a bacteriostatic ring is observed. The control group was a blank cotton cloth-like and a non-chlorinated zirconium-porphyrin MOF (Zr-TCPP-H) 2 ) A cotton cloth composite material.
The characterization data are shown in fig. 15 and 16, and a bacteriostatic ring appears in fig. 15, which indicates that the N-zirconium chloride-porphyrin MOF/polymer composite material has bactericidal performance. FIG. 16 is a blank cotton cloth-like and non-chlorinated zirconium-porphyrin MOF/cotton composite, showing that neither has bacteriostatic effects.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many variations and modifications to the disclosed embodiments, or equivalent variations, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. The N-zirconium chloride-porphyrin MOF is characterized in that the N-zirconium chloride-porphyrin MOF is formed by coaxially growing and radially extending a plurality of two-dimensional metal organic framework nanosheet layers, and the two-dimensional metal organic framework nanosheet layers are circumferentially distributed at intervals.
2. The N-chlorozirconium-porphyrin MOF of claim 1, wherein the microstructure of said N-chlorozirconium-porphyrin MOF is a carambola-shaped nanostructure.
3. A preparation method of N-zirconium chloride-porphyrin MOF is characterized by comprising the following steps:
mixing and dissolving zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent, carrying out a solvothermal reaction at the temperature of 60-90 ℃, carrying out centrifugal separation and washing on the obtained precipitation product after the reaction, then adding the obtained precipitation product into an aqueous solution containing a chlorinated reagent, carrying out a chlorination reaction at room temperature, carrying out centrifugal separation again on the obtained product, washing again and drying again, and thus obtaining the N-zirconium chloride-porphyrin MOF.
4. The method for preparing N-chlorozirconium-porphyrin MOF according to claim 3, wherein the chlorinating agent is sodium dichloroisocyanurate, the chlorinating reaction time is 3-12 h, and the mass ratio of the chlorinating agent to the tetracarboxylic porphyrin ligand is 3-12: 1.
5. The method of preparing an N-chlorozirconium-porphyrin MOF according to claim 3, wherein said acidic modifier is a monocarboxylic acid, said monocarboxylic acid is formic acid, said tetracarboxylic acid porphyrin ligand is one or more of meso-tetra (4-carboxyphenyl) porphine and derivatives thereof, said organic solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide and N, N-dimethylacetamide;
and/or the mass ratio of the zirconium chloride to the tetracarboxylic porphyrin ligand is 3-8: 1, the dosage of the acid regulator is 16mL/mmol of the tetracarboxylic porphyrin ligand to 64mL/mmol of the tetracarboxylic porphyrin ligand, the dosage of the organic solvent is 120mL/mmol of the tetracarboxylic porphyrin ligand to 240mL/mmol of the tetracarboxylic porphyrin ligand, and the dosage of the water is 20mL/mmol of the tetracarboxylic porphyrin ligand to 100mL/mmol of the tetracarboxylic porphyrin ligand.
6. A process for the preparation of an N-chlorozirconium-porphyrin MOF according to any of the claims 3 to 5, characterized in that said reaction time is comprised between 24h and 96h; ultrasonic vibration is assisted during the dissolution, so that the solution is fully dissolved; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, and the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; dispersing the washed precipitate into an aqueous solution containing a chlorinated reagent, wherein the concentration of the dispersed precipitate is 2-5 mmol of tetracarboxylic porphyrin ligand per liter of water, and the concentration of the chlorinated reagent in the water is 6-50 mmol/L, based on the reaction dosage of the tetracarboxylic porphyrin ligand; the secondary washing is washing by adopting water, and the washing frequency is 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. A preparation method of an N-zirconium chloride-porphyrin MOF/polymer composite material is characterized by comprising the following steps:
mixing and dissolving zirconium chloride, a tetracarboxylic porphyrin ligand, an acid regulator, water and an organic solvent, adding an organic polymer fiber membrane, carrying out a solvothermal reaction at the temperature of 60-80 ℃, washing the modified organic polymer fiber membrane after the reaction, then adding the organic polymer fiber membrane into an aqueous solution containing a chlorinated reagent, carrying out a chlorination reaction at room temperature, washing and drying the obtained product again, and thus obtaining the N-zirconium chloride-porphyrin MOF/polymer composite material.
8. The method of making an N-chlorozirconium-porphyrin MOF/polymer composite material according to claim 7, wherein said organic polymer fiber film comprises one or more of polyethylene fiber film, polypropylene fiber film and cotton cloth, when said organic polymer fiber film is polyethylene fiber film and/or polypropylene fiber film, said polyethylene fiber film and/or polypropylene fiber film is first modified with oxygen-containing functional groups, said oxygen-containing functional groups comprise carboxyl groups and/or hydroxyl groups;
and/or the chlorinating reagent is sodium dichloroisocyanurate, the time of chlorination reaction is 3-12 h, and the mass ratio of the chlorinating reagent to the tetracarboxylic porphyrin ligand is 3-12: 1;
and/or, the acidity regulator is a monocarboxylic acid, and the monocarboxylic acid is formic acid; the tetracarboxylic acid porphyrin 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 mass ratio of the zirconium chloride to the tetracarboxylic porphyrin ligand is 3-8: 1, the dosage of the acid regulator is 16mL/mmol of the tetracarboxylic porphyrin ligand to 64mL/mmol of the tetracarboxylic porphyrin ligand, the dosage of the organic solvent is 120mL/mmol of the tetracarboxylic porphyrin ligand to 240mL/mmol of the tetracarboxylic porphyrin ligand, and the dosage of the water is 20mL/mmol of the tetracarboxylic porphyrin ligand to 100mL/mmol of the tetracarboxylic porphyrin ligand;
and/or the reaction time is 24-96 h, and the chlorination reaction time is 3-10 h; ultrasonic vibration is assisted during the dissolution, so that the solution is fully dissolved; the washing is carried out by adopting a reaction solvent, water and absolute ethyl alcohol, and the washing times of the reaction solvent, the water and the absolute ethyl alcohol are respectively 2-4 times; the amount of the modified organic polymer fiber membrane put into the aqueous solution containing the chlorinated reagent is 2-5 mmol of the tetracarboxylic porphyrin ligand per liter of water according to the reaction charging amount of the tetracarboxylic porphyrin ligand, and the concentration of the chlorinated reagent in the water is 6-50 mmol/L; the secondary washing is washing by adopting water, and the washing frequency is 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. A N-zirconium chloride-porphyrin MOF/polymer composite produced by the method of preparing the N-zirconium chloride-porphyrin MOF/polymer composite of claim 7 or 8.
10. Use of N-zirconium chloride-porphyrin MOF according to claim 1 or 2 or of N-zirconium chloride-porphyrin MOF prepared by the process according to any one of claims 3 to 6 or of N-zirconium chloride-porphyrin MOF/polymer composite according to claim 9 for the degradation of nerve agents, blister agents or bactericides.
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