CN116832791A - Novel magnetic covalent organic framework material, preparation method and application thereof - Google Patents
Novel magnetic covalent organic framework material, preparation method and application thereof Download PDFInfo
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- CN116832791A CN116832791A CN202311002429.XA CN202311002429A CN116832791A CN 116832791 A CN116832791 A CN 116832791A CN 202311002429 A CN202311002429 A CN 202311002429A CN 116832791 A CN116832791 A CN 116832791A
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 78
- 239000000696 magnetic material Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229940123317 Sulfonamide antibiotic Drugs 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 17
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 239000002105 nanoparticle Substances 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
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- 238000004885 tandem mass spectrometry Methods 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 description 18
- 229940088710 antibiotic agent Drugs 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 5
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical group NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
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- 241001465754 Metazoa Species 0.000 description 2
- PJSFRIWCGOHTNF-UHFFFAOYSA-N Sulphormetoxin Chemical compound COC1=NC=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=C1OC PJSFRIWCGOHTNF-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- ASDNEBPDUGBTRQ-UHFFFAOYSA-N benzene;sulfane Chemical compound S.C1=CC=CC=C1 ASDNEBPDUGBTRQ-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PLQIOFZPHAZJAM-UHFFFAOYSA-N oxo(phenyl)methanesulfonamide Chemical compound NS(=O)(=O)C(=O)C1=CC=CC=C1 PLQIOFZPHAZJAM-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- GQLNDUDWXKHBND-UHFFFAOYSA-N quinoxaline-2-sulfonic acid Chemical compound C1=CC=CC2=NC(S(=O)(=O)O)=CN=C21 GQLNDUDWXKHBND-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229960004673 sulfadoxine Drugs 0.000 description 2
- 229960005404 sulfamethoxazole Drugs 0.000 description 2
- GPTONYMQFTZPKC-UHFFFAOYSA-N sulfamethoxydiazine Chemical compound N1=CC(OC)=CN=C1NS(=O)(=O)C1=CC=C(N)C=C1 GPTONYMQFTZPKC-UHFFFAOYSA-N 0.000 description 2
- 229960002229 sulfametoxydiazine Drugs 0.000 description 2
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- 238000009360 aquaculture Methods 0.000 description 1
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- 239000011258 core-shell material Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 239000003651 drinking water Substances 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960000304 folic acid Drugs 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002607 hemopoietic effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 244000144972 livestock Species 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 239000013384 organic framework Substances 0.000 description 1
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- 238000002203 pretreatment Methods 0.000 description 1
- 239000006041 probiotic Substances 0.000 description 1
- 235000018291 probiotics Nutrition 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a novel magnetic covalent organic framework material, a preparation method and application thereof. The novel magnetic covalent organic framework material adopts Fe 3 O 4 The nanometer particle is used as the inner core, and tetraethyl orthosilicate is utilized on the surface of the nanometer particleCoating silicon dioxide formed by hydrolysis to obtain Fe 3 O 4 @SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the And then the PDE-TATP-COF formed by combining 2, 6-pyridine dicarboxaldehyde and 1,3, 5-tri (4-aminophenyl) benzene is used as the shell of the magnetic adsorption material to obtain the magnetic material Fe with rich benzene rings and nitrogen atoms 3 O 4 @SiO 2 PDE-TATP-COF. The novel magnetic covalent organic framework material synthesized by the invention has the advantages of simple preparation process, larger specific surface area, larger porosity and strong stability, can be used for simultaneously detecting various sulfonamide antibiotics in an environmental water sample, and meets the requirement of rapid separation analysis.
Description
Technical Field
The invention relates to the field of adsorption material synthesis, in particular to a novel magnetic covalent organic framework material, a preparation method and application thereof.
Background
Antibiotics are a class of drugs with antibacterial or antiparasitic activity, one part of which is produced by microorganisms such as bacteria and the other part of which is obtained by artificial synthesis. The antibiotics have good sterilization effect and are widely applied to medical treatment, livestock and poultry and aquaculture. Humans and animals can only absorb a small fraction and most antibiotics are discharged into the environment, so that the ecosystem is destroyed. The abuse of antibiotics can cause environmental pollution, and residues in water environments are of increasing concern. At present, the sulfonamide antibiotics are one of the antibiotics with the widest application range in China, and have the characteristics of wide antibacterial spectrum, high stability, strong hydrophilicity and the like. The sulfonamide antibiotics are artificially synthesized antibiotics with a p-aminobenzenesulfonamide structure, inhibit bacterial activity by destroying bacteria to synthesize folic acid, inhibit most gram-positive bacteria and partial gram-negative bacteria, and have remarkable antibacterial effect. Because of the good stability of the sulfonamide antibiotics, most of the antibiotics are not metabolized in animals and are discharged into the environment in the form of raw medicines, and the antibiotics can remain in the environmental water for a long time. The residual sulfonamide antibiotics in the water body environment have a certain toxic effect on aquatic organisms, and can inhibit the activity of probiotics and even block the circulation of an ecological system; in addition, it may be enriched in human body through drinking water or food chain, and may cause allergic reaction, hemopoietic function abnormality and other diseases, even cause certain harm to urinary system and thyroid gland of human body, and serious thyroid cancer may be induced. In order to protect the environmental safety and the human health, it is important to detect the sulfonamide antibiotic residues in the water body environment.
Gas Chromatography (GC), high Performance Liquid Chromatography (HPLC), liquid chromatography tandem mass spectrometry (LC-MS/MS) and the like are main methods for detecting the residue of the sulfonamide antibiotics, wherein the LC-MS/MS has the characteristics of good selectivity, high accuracy, low detection limit and the like, and is suitable for detecting various sulfonamide antibiotics in a water sample.
Because the residual concentration of antibiotics in a water sample is low and the interference in a matrix is more, the sulfonamide antibiotics in the water are usually required to be separated and enriched before detection. The accurate and efficient sample pretreatment technology is a key for ensuring the accuracy of detection results, and the pretreatment method of the quinolone antibiotics in the sample comprises a liquid-liquid extraction method, a solid-phase extraction method and the like. However, liquid-liquid extraction consumes a large amount of organic reagents, the solid-phase extraction method is complex in operation and long in time consumption, and the solid-phase extraction column is easy to block and has high economic cost. The magnetic solid phase extraction technology solves the problem, and has high efficiency and simple operation, and is widely focused in the technical field of sample pretreatment. The development of novel magnetic materials is the core of magnetic solid-phase extraction technology, and currently common functional materials include molecularly imprinted polymers, metal organic framework materials, covalent organic framework materials (COFs) and the like, wherein the COFs materials with large specific surface area and good thermal stability have great development potential in the field of sample pretreatment. The magnetic material developed based on the COFs not only has the characteristic of the COFs, but also has strong magnetism, and can realize the effects of rapidly separating and enriching target compounds. At present, the report of using magnetic COFs material to extract sulfonamide antibiotics is less, and the detection types are not more. Therefore, the development of a novel magnetic COFs material capable of rapidly and efficiently extracting various sulfa antibiotics in water has important significance for improving the detection technology level.
Disclosure of Invention
The invention aims to provide a novel magnetic covalent organic framework material, a preparation method and application thereof, wherein the novel magnetic covalent organic framework material can rapidly and efficiently extract various sulfanilamide antibiotics in water, and the material can be reused.
The invention is realized in the following way:
novel magnetism is covalent hasAn organic framework material which can be used for adsorbing sulfonamide antibiotics in water and is prepared from Fe 3 O 4 The nanoparticle is formed by taking PDE-TATP-COF covalent organic framework generated by the reaction of 2, 6-pyridine dicarboxaldehyde and 1,3, 5-tri (4-aminophenyl) benzene as a core and taking the shell.
The novel magnetic covalent organic framework material is synthesized through the following steps:
(1) Spherical magnetic Fe prepared by solvothermal method 3 O 4 Nanoparticle, prepared magnetic Fe 3 O 4 Washing and vacuum drying the nano particles for later use;
(2) Hydrolysis of tetraethyl orthosilicate in Fe 3 O 4 Surface-coated SiO 2 Obtaining magnetic nano particle Fe 3 O 4 @SiO 2 ；
(3) Magnetic nanoparticle Fe 3 O 4 @SiO 2 Placing 2, 6-pyridine dicarboxaldehyde, 1,3, 5-tri (4-aminophenyl) benzene and acetic acid aqueous solution (12 mol/L) in a 1, 4-dioxane solvent, carrying out ultrasonic mixing, and heating the reaction mixed solution at 70 ℃ for reaction for 20-28 h; washing and drying the obtained product after magnetic separation to obtain the magnetic covalent organic framework material Fe 3 O 4 @SiO 2 PDE-TATP-COF; the magnetic nanoparticle Fe 3 O 4 @SiO 2 The ratio of 2, 6-pyridine dicarboxaldehyde, 1,3, 5-tris (4-aminophenyl) benzene and acetic acid aqueous solution (12 mol/L) is 130-180 mg/0.75 mmol/0.5 mmol/5-6 mL.
The specific method of the step (1) comprises the following steps: PEG-4000 and CH 3 COONa·3H 2 O adding FeCl 3 ·6H 2 Fully stirring in glycol of O; feCl 3 ·6H 2 O, PEG-4000 and CH 3 COONa·3H 2 The mass ratio of O is 1.62:1.8-2.4:7.0-7.4; transferring the reaction mixture into a reaction kettle, reacting for 7-9 h at 200 ℃, washing the product by absolute ethyl alcohol, and vacuum drying for 2-4 h at 70 ℃.
The specific method of the step (2) is as follows: fe is added to 3 O 4 Dispersing the nano particles in a mixed solution of absolute ethyl alcohol and water by ultrasonic wave, adding ammonia water and tetraethyl orthosilicate, and reactingFe should be obtained 3 O 4 @SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The Fe is 3 O 4 The ratio of ammonia water to tetraethyl orthosilicate is 0.1 g:1.2-1.7 mL:0.8-1.2 mL, the volume ratio of absolute ethyl alcohol to water is 3-6:1, the reaction temperature is 25-32 ℃, and the reaction time is 20-26 h.
In the step (3), after magnetic separation, washing the product with absolute ethyl alcohol and ultrapure water in turn, and vacuum drying for 2-4 hours at 70 ℃ to obtain the magnetic covalent organic framework material Fe 3 O 4 @SiO 2 @PDE-TATP-COF。
The novel magnetic material Fe provided by the invention 3 O 4 @SiO 2 the@PDE-TATP-COF can be used as an adsorbent for enriching and extracting various sulfonamide antibiotics in a water sample, and is a novel magnetic material Fe 3 O 4 @SiO 2 The @ PDE-TATP-COF is obtained by the preparation method, and the enrichment extraction process comprises the following specific steps:
adding magnetic material Fe into water sample containing various sulfonamide antibiotics 3 O 4 @SiO 2 PDE-TATP-COF, pH is 3-5, vortex oscillation extraction is carried out; to-be-magnetic material Fe 3 O 4 @SiO 2 After sedimentation under the action of an externally applied magnetic field, the supernatant was removed under the protection of the magnetic field. Then to magnetic material Fe 3 O 4 @SiO 2 The sulfonamide antibiotics were recovered by addition of an eluent to PDE-TATP-COF and were determined by liquid chromatography tandem mass spectrometry (LC-MS/MS).
Preferably, the adsorption time of the adsorbent is 10 to 25 minutes.
Preferably, the elution time is 3 to 9 minutes.
Preferably, the eluent is acetonitrile.
The invention has the beneficial effects that:
(1) The invention successfully designs and synthesizes a novel magnetic material Fe 3 O 4 @SiO 2 The novel magnetic material has the advantages of simple preparation method, high adsorption efficiency and repeated use, and realizes the purpose of simultaneously extracting and enriching various sulfanilamide antibiotics from a water sample.
(2) The invention usesFe 3 O 4 The nano particles are used as cores of magnetic adsorption materials, PDE-TATP-COF covalent organic frameworks generated by the reaction of 2, 6-pyridine dicarboxaldehyde and 1,3, 5-tri (4-aminophenyl) benzene are used as shells of the magnetic adsorption materials, and the novel magnetic COFs adsorption materials are constructed. The compound has benzene ring with conjugated structure and rich nitrogen atoms, can form various acting forces with target compounds, such as intermolecular hydrogen bond, pi-pi conjugation, and the like, and can extract 11 sulfonamide antibiotics simultaneously. The magnetic material Fe synthesized by the invention 3 O 4 @SiO 2 the@PDE-TATP-COF has the advantages of simple preparation process, large specific surface area, strong magnetism, stable structure, reusability and the like, and can meet the requirements of rapid separation and analysis of various sulfonamide antibiotics.
Drawings
FIG. 1 shows a magnetic material Fe 3 O 4 @SiO 2 The synthesis scheme of @ PDE-TATP-COF.
FIG. 2 shows magnetic Fe 3 O 4 Nanoparticles (A) and Fe 3 O 4 @SiO 2 Scanning electron microscope image of @ PDE-TATP-COF (B) and Fe 3 O 4 Nanoparticles (C) and Fe 3 O 4 @SiO 2 Transmission electron microscopy of PDE-TATP-COF (D).
FIG. 3 shows a magnetic material Fe 3 O 4 @SiO 2 N of PDE-TATP-COF 2 Adsorption-desorption characterization map.
FIG. 4 is Fe 3 O 4 Nanoparticle and magnetic material Fe 3 O 4 @SiO 2 Magnetic properties characterization of PDE-TATP-COF.
FIG. 5 is a magnetic material Fe 3 O 4 @SiO 2 Adsorption efficacy profile of @ PDE-TATP-COF on 5 recovery-recycle cycles of 11 sulfonamide antibiotics in water samples.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, wherein the raw materials or reagents used in the examples are commercially available unless otherwise specified.
Example 1
Fe 3 O 4 @SiO 2 Preparation of PDE-TATP-COFThe preparation process is shown in fig. 1.
(1) Magnetic Fe 3 O 4 Preparation of nanoparticles: accurately weigh 1.62g FeCl 3 ·6H 2 O was dissolved in 60mL of ethylene glycol, and after dissolution by stirring with a magnetic stirrer (1000 r/min), 2.0g of PEG-4000 and 7.2g of CH were added thereto, respectively 3 COONa·3H 2 O, stirring for 30min at 1000r/min to obtain brown turbid solution, transferring to a reaction kettle, reacting at 200 ℃ for 8h, and cleaning the product with absolute ethyl alcohol to obtain Fe 3 O 4 The magnetic nanoparticles were dried in vacuo at 70℃for 4h.
(2) Preparation of Fe 3 O 4 @SiO 2 : to 100mL of a mixed solution of absolute ethanol and water was added 0.1g of Fe in step (1) 3 O 4 Dispersing the nano particles by ultrasonic for 30min, adding 1.5mL of ammonia water and 1.0mL of tetraethyl orthosilicate, and reacting to obtain the magnetic nano particles Fe 3 O 4 @SiO 2 The volume ratio of the absolute ethyl alcohol to the water is 4:1, and the reaction condition is that the mixture is heated and stirred for 24 hours at 30 ℃.
(3) Preparation of magnetic Material Fe 3 O 4 @SiO 2 PDE-TATP-COF: 150mg of Fe is first added 3 O 4 @SiO 2 Magnetic nanoparticles were added to a round-bottomed flask containing 30mL of 1, 4-dioxane, after 5min of sonication, 101mg of 2, 6-pyridinedicarboxaldehyde (0.75 mmol), 176mg of 1,3, 5-tris (4-aminophenyl) benzene (0.5 mmol) and 5mL of aqueous acetic acid (12 mol/L) were sequentially added to the round-bottomed flask, and the reaction mixture was heated to 70℃to react for 24h; the obtained product is washed by absolute ethyl alcohol and ultrapure water respectively after magnetic separation until the supernatant becomes clear, and is dried in vacuum at 70 ℃ for 3 hours to obtain Fe 3 O 4 @SiO 2 PDE-TATP-COF. The resulting material was characterized and the results are shown in figures 2-4.
The prepared magnetic Fe is observed by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) 3 O 4 Nanoparticle and magnetic material Fe 3 O 4 @SiO 2 PDE-TATP-COF. In FIG. 2 (A) and (B) are Fe respectively 3 O 4 And Fe (Fe) 3 O 4 @SiO 2 SEM image of PDE-TATP-COF, magnetic Fe can be seen 3 O 4 Nanoparticle presentationSpherical structure due to Fe 3 O 4 The magnetic property of the material is easy to cause agglomeration, so that the surface layer is coated with SiO in advance 2 To increase Fe 3 O 4 And uniformity of coating COF, fe after coating 3 O 4 @SiO 2 The particle-particle aggregation phenomenon can be obviously observed for the PDE-TATP-COF material. In FIG. 2 (C) and (D) are Fe, respectively 3 O 4 And Fe (Fe) 3 O 4 @SiO 2 TEM image of PDE-TATP-COF, it can be seen that PDE-TATP-COF was successfully coated with Fe 3 O 4 On the nanoparticle, this is consistent with the SEM image results, and it can be seen that the PDE-TATP-COF coated magnetic material has a typical core-shell structure morphology.
Fe at 77K using nitrogen adsorption-desorption curve 3 O 4 @SiO 2 The @ PDE-TATP-COF was characterized as shown in FIG. 3. Through analysis and calculation, the specific surface area of the material is 349m 2 And/g, the pore diameter is between 31 and 40nm, and the porous ceramic material has a larger specific surface area and a unique pore structure, so that the excellent adsorption performance of the porous ceramic material is ensured.
Magnetic Fe prepared by adopting hysteresis curve 3 O 4 Nanoparticle and magnetic material Fe 3 O 4 @SiO 2 The @ PDE-TATP-COF was characterized and the results are shown in FIG. 4. The results show Fe 3 O 4 And Fe (Fe) 3 O 4 @SiO 2 The saturation magnetization at room temperature of PDE-TATP-COF was 86.5emu/g and 24.2emu/g, respectively. With Fe 3 O 4 In comparison with Fe 3 O 4 @SiO 2 The saturation magnetization of PDE-TATP-COF is reduced due to the non-magnetic coverage of PDE-TATP-COF, but it still shows good superparamagnetism, and rapid separation can be achieved under the action of an externally applied magnetic field.
Fe synthesized by the method of this example 3 O 4 @SiO 2 PDE-TATP-COF is used as an adsorbent for extracting sulfonamide antibiotics in water samples. 10mg of magnetic material Fe is weighed 3 O 4 @SiO 2 PDE-TATP-COF, added to 10mL of water sample having pH 4 and containing 11 sulfonamide antibiotics (see Table 1 below, each at 20 ng/mL), vortexedSpin oscillating for 20min to obtain magnetic material Fe 3 O 4 @SiO 2 After sedimentation under the action of an externally applied magnetic field, the supernatant was removed under the protection of the magnetic field. To magnetic material Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into the @ PDE-TATP-COF, vortex oscillation is carried out for 5min, and 4mL of acetonitrile is completely moved into another centrifuge tube under the action of an external magnetic field; to Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into PDE-TATP-COF, vortex oscillation is carried out for 5min, acetonitrile is removed under the action of an external magnetic field, after vortex mixing of the eluent is carried out twice, 4mL of eluent nitrogen is taken to be blown to dryness, 1mL of acetonitrile-0.1% (the volume ratio of formic acid and the same below) of formic acid water (1:4, v:v) are used for redissolution, and after filtration through a 0.2 mu m filter membrane, the solution is injected into LC-MS/MS for analysis. Evaluation of Fe by calculation of recovery 3 O 4 @SiO 2 The effect of the @ PDE-TATP-COF on the enrichment of 11 sulfonamide antibiotics was 78.81-98.40% recovery and the results are shown in Table 1.
Table 1 enrichment extraction efficiency of the magnetic Material of the invention for 11 Sulfan antibiotics in example 1
| Compounds of formula (I) | Recovery (%) |
| Sulfomethorphan | 84.39 |
| Sulfamoxypyrimidine | 84.73 |
| Sulfamethoxypyrimidine | 81.90 |
| Sulfochloridazine | 89.84 |
| Sulfadoxine medicine | 90.53 |
| Sulfamethoxazole | 78.81 |
| Sulfadiazole | 84.37 |
| Benzoyl sulfonamide | 83.10 |
| Sulfadixoxin | 95.48 |
| Sulfoquinoxaline | 98.40 |
| Sulfanide benzene | 97.72 |
Example 2
(1) Magnetic Fe 3 O 4 Preparation of nanoparticles: accurately weigh 1.62g FeCl 3 ·6H 2 O was dissolved in 60mL of ethylene glycol, and after dissolution by stirring with a magnetic stirrer (1000 r/min), 1.8g of PEG-4000 and 7.0g of CH were added thereto, respectively 3 COONa·3H 2 O, stirring for 30min at 1000r/min to obtain brown turbid solution, transferring to a reaction kettle, reacting at 200 ℃ for 7h, and cleaning the product with absolute ethyl alcohol to obtain Fe 3 O 4 The magnetic nanoparticles were dried in vacuo at 70℃for 3h.
(2) Preparation of Fe 3 O 4 @SiO 2 : to 100mL of a mixed solution of absolute ethanol and water was added 0.1g of Fe in step (1) 3 O 4 Dispersing the nano particles by ultrasonic for 30min, adding 1.2mL of ammonia water and 0.8mL of tetraethyl orthosilicate, and reacting to obtain the magnetic nano particles Fe 3 O 4 @SiO 2 The volume ratio of the absolute ethyl alcohol to the water is 3:1, and the reaction condition is that the mixture is heated and stirred for 26 hours at 25 ℃.
(3) Preparation of magnetic Material Fe 3 O 4 @SiO 2 PDE-TATP-COF: 130mg of Fe is first added 3 O 4 @SiO 2 Magnetic nanoparticles were added into a round-bottomed flask containing 30mL of 1, 4-dioxane, after 5min of sonication, 101mg of 2, 6-pyridinedicarboxaldehyde (0.75 mmol), 176mg of 1,3, 5-tris (4-aminophenyl) benzene (0.5 mmol) and 5mL of aqueous acetic acid (12 mol/L) were sequentially added into the round-bottomed flask, and the reaction mixture was heated to 70℃for reaction for 20h; the obtained product is washed by absolute ethyl alcohol and ultrapure water respectively after magnetic separation until the supernatant becomes clear, and is dried in vacuum at 70 ℃ for 2 hours to obtain Fe 3 O 4 @SiO 2 PDE-TATP-COF. Characterization results showed that it was similar to the material obtained in example 1.
Fe synthesized by the method of this example 3 O 4 @SiO 2 PDE-TATP-COF is used as an adsorbent for extracting sulfonamide antibiotics in water samples. 10mg of magnetic material Fe is weighed 3 O 4 @SiO 2 PDE-TATP-COF, added to 10mL of water sample containing 11 sulfonamide antibiotics (see Table 2 below, each concentration 20 ng/mL) at pH 5, vortexed for 25min, and subjected to magnetic material Fe 3 O 4 @SiO 2 After sedimentation under the action of an externally applied magnetic field, the supernatant was removed under the protection of the magnetic field. To magnetic material Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into the @ PDE-TATP-COF, vortex is carried out for 9min, and the acetonitrile is completely moved into another centrifuge tube under the action of an external magnetic field; to Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into the @ PDE-TATP-COF, vortex oscillation is carried out for 9min, acetonitrile is removed under the action of an external magnetic field, after the two eluents are uniformly mixed by vortex, 4mL of eluent nitrogen is taken to be blown to dryness, 1mL of acetonitrile-0.1% formic acid water (1:4, v:v) is used for redissolution, and after filtration through a 0.2 mu m filter membrane, the solution is injected into LC-MS/MS for analysis. Evaluation of Fe by calculation of recovery 3 O 4 @SiO 2 PDE-TATP-COF pair of 11 sulfonamidesThe enrichment effect of the antibiotics, recovery rate was 74.57-90.10%, and the results are shown in Table 2.
Table 2 enrichment extraction efficiency of the magnetic Material of the invention for 11 Sulfan antibiotics in example 2
Example 3
(1) Magnetic Fe 3 O 4 Preparation of nanoparticles: accurately weigh 1.62g FeCl 3 ·6H 2 O was dissolved in 60mL of ethylene glycol, and after dissolution by stirring with a magnetic stirrer (1000 r/min), 2.4g of PEG-4000 and 7.4g of CH were added thereto, respectively 3 COONa·3H 2 O, stirring for 30min at 1000r/min to obtain brown turbid solution, transferring to a reaction kettle, reacting at 200 ℃ for 9h, and cleaning the product with absolute ethyl alcohol to obtain Fe 3 O 4 The magnetic nanoparticles were dried in vacuo at 70℃for 2h.
(2) Preparation of Fe 3 O 4 @SiO 2 : to 100mL of a mixed solution of absolute ethanol and water was added 0.1g of Fe in step (1) 3 O 4 Dispersing the nano particles by ultrasonic for 30min, adding 1.7mL of ammonia water and 1.2mL of tetraethyl orthosilicate, and reacting to obtain the magnetic nano particles Fe 3 O 4 @SiO 2 The volume ratio of the absolute ethyl alcohol to the water is 6:1, and the reaction condition is that the mixture is heated and stirred for 20 hours at the temperature of 32 ℃.
(3) Preparation of magnetic Material Fe 3 O 4 @SiO 2 PDE-TATP-COF: 180mg of Fe is firstly added 3 O 4 @SiO 2 Magnetic nanoparticles were added to a round-bottomed flask containing 30mL of 1, 4-dioxane, after 5min of sonication, 101mg of 2, 6-pyridinedicarboxaldehyde (0.75 mmol), 176mg of 1,3, 5-tris (4-aminophenyl) benzene (0.5 mmol) and 6mL of aqueous acetic acid (12 mol/L) were sequentially added to the round-bottomed flask, and the reaction mixture was heated to 70℃to react for 28h; the obtained product is washed by absolute ethyl alcohol and ultrapure water after magnetic separation,until the supernatant became clear, and was dried under vacuum at 70℃for 4 hours to give Fe 3 O 4 @SiO 2 PDE-TATP-COF. Characterization results showed that it was similar to the material obtained in example 1.
Fe synthesized by the method of this example 3 O 4 @SiO 2 PDE-TATP-COF is used as an adsorbent for extracting sulfonamide antibiotics in water samples. 10mg of magnetic material Fe is weighed 3 O 4 @SiO 2 PDE-TATP-COF, added into 10mL of water sample with pH of 3 and containing 11 sulfonamide antibiotics (see Table 3 below, each concentration of 20 ng/mL), vortexed for 10min, and subjected to magnetic material Fe 3 O 4 @SiO 2 After sedimentation under the action of an externally applied magnetic field, the supernatant was removed under the protection of the magnetic field. To magnetic material Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into the @ PDE-TATP-COF, vortex oscillation is carried out for 3min, and 4mL of acetonitrile is completely moved into another centrifuge tube under the action of an external magnetic field; to Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into the @ PDE-TATP-COF, vortex oscillation is carried out for 3min, acetonitrile is removed under the action of an external magnetic field, after the two eluents are uniformly mixed by vortex, 4mL of eluent nitrogen is taken to be blown to dryness, 1mL of acetonitrile-0.1% formic acid water (1:4, v:v) is used for redissolution, and after filtration through a 0.2 mu m filter membrane, the solution is injected into LC-MS/MS for analysis. Evaluation of Fe by calculation of recovery 3 O 4 @SiO 2 The effect of the @ PDE-TATP-COF on the enrichment of 11 sulfonamide antibiotics was 73.83-92.26% recovery and the results are shown in Table 3.
TABLE 3 enrichment extraction efficiency of the magnetic Material of the invention on 11 sulfonamide antibiotics in example 3
| Compounds of formula (I) | Recovery (%) |
| Sulfomethorphan | 87.22 |
| Sulfamoxypyrimidine | 79.64 |
| Sulfamethoxypyrimidine | 73.83 |
| Sulfochloridazine | 84.93 |
| Sulfadoxine medicine | 80.01 |
| Sulfamethoxazole | 80.68 |
| Sulfadiazole | 79.34 |
| Benzoyl sulfonamide | 87.77 |
| Sulfadixoxin | 81.30 |
| Sulfoquinoxaline | 91.17 |
| Sulfanide benzene | 92.26 |
Example 4
The magnetic material Fe obtained in example 1 3 O 4 @SiO 2 Recovery-reuse of 11 sulfonamide antibiotics in water samples by PDE-TATP-COFThe specific application method comprises the following steps:
the magnetic material Fe prepared in example 1 was weighed 3 O 4 @SiO 2 10mg of PDE-TATP-COF is added into 10mL of water sample which has pH of 4 and contains 11 sulfanilamide antibiotics (each concentration of 20 ng/mL), vortex oscillation is carried out for 20min, and the magnetic material Fe is prepared 3 O 4 @SiO 2 After sedimentation under the action of an externally applied magnetic field, the supernatant was removed under the protection of the magnetic field. To magnetic material Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into the @ PDE-TATP-COF, vortex oscillation is carried out for 5min, and the acetonitrile is completely moved into another centrifuge tube under the action of an external magnetic field; to magnetic material Fe 3 O 4 @SiO 2 4mL of acetonitrile is added into the @ PDE-TATP-COF, the mixture is vortexed for 5min, acetonitrile is removed under the action of an external magnetic field, after the two eluents are vortexed and uniformly mixed, 4mL of eluent nitrogen is taken to be blown to dryness, 1mL of acetonitrile-0.1% formic acid water (1:4, v:v) is used for redissolution, and after the mixture is filtered by a 0.2 mu m filter membrane, 11 sulfanilamide antibiotics are analyzed by sample injection. After the magnetic COFs material used above was recovered, the above adsorption experiment was repeated after washing and drying with 4mL of acetonitrile, and the recovery rate was calculated. As shown in figure 5, after 5 recycling cycles, the material still maintains good enrichment efficiency for 11 sulfonamide antibiotics, and the recovery rate is still maintained above 70%, which indicates that the material has good stability and repeatability.
It should be noted that the scope of the present invention is not limited to the above. Modifications and variations based on the embodiments of the present invention may be made by those skilled in the art, and any equivalent or similar variations to the present invention are within the scope of the present invention.
Claims (10)
1. A novel magnetic covalent organic framework material is characterized in that the novel magnetic covalent organic framework material is prepared from Fe 3 O 4 The nanoparticle is formed by taking PDE-TATP-COF covalent organic framework compound generated by the reaction of 2, 6-pyridine dicarboxaldehyde and 1,3, 5-tri (4-aminophenyl) benzene as a core and taking the core as a shell.
2. The preparation method of the novel magnetic covalent organic framework material is characterized by comprising the following steps:
a. spherical magnetic Fe prepared by solvothermal method 3 O 4 Nanoparticle, prepared magnetic Fe 3 O 4 Washing and vacuum drying the nano particles for later use;
b. hydrolysis of tetraethyl orthosilicate in magnetic Fe 3 O 4 Coating SiO on the surface of nano particles 2 Obtaining magnetic nano particle Fe 3 O 4 @SiO 2 ；
c. Magnetic nanoparticle Fe 3 O 4 @SiO 2 Placing 2, 6-pyridine dicarboxaldehyde, 1,3, 5-tri (4-aminophenyl) benzene and acetic acid aqueous solution in a 1, 4-dioxane solvent, carrying out ultrasonic mixing, and heating the reaction mixed solution at 70 ℃ for reaction for 20-28 h; the obtained product is washed and dried after magnetic separation, and the novel magnetic covalent organic framework material Fe is obtained 3 O 4 @SiO 2 @PDE-TATP-COF。
3. The method for preparing a novel magnetic covalent organic framework material according to claim 2, wherein in step c, the magnetic nanoparticles Fe 3 O 4 @SiO 2 The proportion of the 2, 6-pyridine dicarboxaldehyde, 1,3, 5-tri (4-aminophenyl) benzene and acetic acid aqueous solution is 130-180 mg, 0.75mmol, 0.5mmol, and 5-6 mL.
4. The method for preparing a novel magnetic covalent organic framework material according to claim 2, wherein in the step c, after magnetic separation, products are washed by absolute ethyl alcohol and ultrapure water respectively in turn, and vacuum drying is carried out for 2-4 hours at 70 ℃ to obtain the novel magnetic covalent organic framework material Fe 3 O 4 @SiO 2 @PDE-TATP-COF。
5. The method for preparing a novel magnetic covalent organic framework material according to claim 2, wherein the step a is specifically: PEG-4000 and CH 3 COONa·3H 2 O adding FeCl 3 ·6H 2 Fully stirring in glycol of O; feCl 3 ·6H 2 O、PEG-4000 and CH 3 COONa·3H 2 The mass ratio of O is 1.62:1.8-2.4:7.0-7.4; transferring the reaction mixture into a reaction kettle, reacting for 7-9 h at 200 ℃, washing the product by absolute ethyl alcohol, and vacuum drying for 2-4 h at 70 ℃.
6. The method for preparing a novel magnetic covalent organic framework material according to claim 2, wherein the step b is specifically: magnetic Fe 3 O 4 The nano particles are dispersed in a mixed solution of absolute ethyl alcohol and water by ultrasonic, ammonia water and tetraethyl orthosilicate are added, and magnetic nano particle Fe is obtained by reaction 3 O 4 @SiO 2 。
7. The method for preparing a novel magnetic covalent organic framework material according to claim 6, wherein the magnetic Fe 3 O 4 The ratio of the nano particles to the ammonia water to the tetraethyl orthosilicate is 0.1 g:1.2-1.7 mL:0.8-1.2 mL, the volume ratio of the absolute ethyl alcohol to the water is 3-6:1, the reaction temperature is 25-32 ℃, and the reaction time is 20-26 h.
8. The novel magnetic covalent organic framework material prepared by the preparation method of claim 1 and the novel magnetic covalent organic framework material prepared by the preparation method of claims 2-7 are used as adsorbents for enrichment and extraction of sulfonamide antibiotics in water samples.
9. The use according to claim 8, characterized in that the novel magnetic covalent organic framework material is applied as an adsorbent for enrichment extraction of sulfonamide antibiotics in water samples, and specifically comprises the following steps: adding magnetic material Fe into water sample containing sulfonamide antibiotics and having pH of 3-5 3 O 4 @SiO 2 PDE-TATP-COF, vortex oscillation extraction; to-be-magnetic material Fe 3 O 4 @SiO 2 After sedimentation of the @ PDE-TATP-COF is completed under the action of an external magnetic field, removing supernatant under the protection of the magnetic field; then to magnetic material Fe 3 O 4 @SiO 2 Recovering sulfonamide antibiotics by adding eluent into PDE-TATP-COF, and performing liquid phaseAnd (5) measuring by chromatography tandem mass spectrometry.
10. The use according to claim 9, wherein the adsorbent has an adsorption time of 10 to 25min, an elution time of 3 to 9min and the eluent is acetonitrile.
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