CN111777730B - Reticular covalent organic framework material and preparation method and application thereof - Google Patents
Reticular covalent organic framework material and preparation method and application thereof Download PDFInfo
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- CN111777730B CN111777730B CN202010669693.9A CN202010669693A CN111777730B CN 111777730 B CN111777730 B CN 111777730B CN 202010669693 A CN202010669693 A CN 202010669693A CN 111777730 B CN111777730 B CN 111777730B
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 49
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 42
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 28
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- UPNBETHEXPIWQX-UHFFFAOYSA-N 4-bromophenyl 2,4-dibromophenyl ether Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1Br UPNBETHEXPIWQX-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
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- VHNPZYZQKWIWOD-UHFFFAOYSA-N 2,2',4,4',5,6'-Hexabromodiphenyl ether Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=CC(Br)=C(Br)C=C1Br VHNPZYZQKWIWOD-UHFFFAOYSA-N 0.000 description 1
- XYBSIYMGXVUVGY-UHFFFAOYSA-N 2,2',4,4'-Tetrabromodiphenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1Br XYBSIYMGXVUVGY-UHFFFAOYSA-N 0.000 description 1
- WHPVYXDFIXRKLN-UHFFFAOYSA-N 2,4-dibromophenyl 2,4,5-tribromophenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC(Br)=C(Br)C=C1Br WHPVYXDFIXRKLN-UHFFFAOYSA-N 0.000 description 1
- NSKIRYMHNFTRLR-UHFFFAOYSA-N 2,4-dibromophenyl 2,4,6-tribromophenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=C(Br)C=C(Br)C=C1Br NSKIRYMHNFTRLR-UHFFFAOYSA-N 0.000 description 1
- -1 3.40) Chemical compound 0.000 description 1
- 229910015395 B-O-Si Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- XEKVBIXIBCYLRT-RSAXXLAASA-N [4-[(2e)-2-[3-[(2s)-2-amino-2-carboxyethyl]-6-oxocyclohexa-2,4-dien-1-ylidene]hydrazinyl]phenyl]-trimethylazanium;chloride Chemical compound [Cl-].C1=CC([N+](C)(C)C)=CC=C1N\N=C/1C(=O)C=CC(C[C@H](N)C(O)=O)=C\1 XEKVBIXIBCYLRT-RSAXXLAASA-N 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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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
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- B01J20/28054—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 surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a reticular covalent organic framework material and a preparation method and application thereof, and the reticular covalent organic framework material is obtained by carrying out Schiff base reaction on 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and 2, 5-dimethoxyterephthalaldehyde, wherein the Schiff base reaction system comprises 1, 2-dichlorobenzene, n-butanol and a catalyst aqueous solution, the volume ratio of the 1, 2-dichlorobenzene, the n-butanol and the catalyst aqueous solution is 4.5-5.5: 1, the concentration of the catalyst aqueous solution is 5.5-6.5M, and the temperature is 115-125 ℃. The imine bond, triazine and methoxyl in the pore wall of the reticular covalent organic framework material enable strong electrostatic interaction to occur between N/O atoms of the reticular covalent organic framework material and the electropositive bromine atoms on the polybrominated diphenyl ether. Meanwhile, the material has large specific surface area, and has high enrichment capacity and rapid adsorption rate on polybrominated diphenyl ethers.
Description
Technical Field
The invention relates to a reticular covalent organic framework material and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polybrominated diphenyl ethers (PBDEs) are a class of endocrine disrupting compounds, and serious diseases in humans (e.g., neurobehavioral defects and cancer, etc.) have been shown to be closely related to their biological accumulation in human tissues and organs. Residues of polybrominated diphenyl ethers are found in environmental samples (e.g., air, sediment, water and biota lines) and food samples (e.g., fish, dairy products, poultry eggs and shellfish in weiskan river, sweden in 1981). In 1972, their residues were also found in breast milk, as well as in human adipose tissue and blood. Against this background, food and environmental safety issues with polybrominated diphenyl ethers have become one of the core problems in the past few decades. At present, due to trace and ultra-trace levels of polybrominated diphenyl ethers and complex matrix effects of real samples in real life, various sample pretreatment methods including solid phase micro-extraction, magnetic solid phase extraction and dispersed solid phase extraction are widely established and used for analyzing polybrominated diphenyl ethers in real samples. In the above devices, the adsorbents play a decisive role in their adsorption capacity, rate, sensitivity and reproducibility.
Covalent organic framework materials, as "organic zeolites," build and expand two-or three-dimensionally ordered structures by utilizing a variety of reversible covalent bonds, such as B-O, C ═ N, B-N, C-N and B-O-Si, among others. The partial covalent organic framework material can be used for preparing a sample pretreatment device and has high adsorption rate and high stability. According to the research of the inventor, the morphology of the material of the covalent organic framework is also one of important factors in influencing the adsorption efficiency in the sample pretreatment. The morphology of the material includes spherical, flower-like, net-like, etc. Different shapes of the materials lead to different adsorption sites exposed on the surface, and more adsorption sites can adsorb more target molecules. The inventor researches and discovers that no report is provided for a reticular covalent organic framework material with high stability.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a reticular covalent organic framework material, a preparation method and application thereof, which have higher specific surface area and pore volume, can better enrich polybrominated diphenyl ethers in environment and food, and improve the detection effect of the polybrominated diphenyl ethers.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the reticular covalent organic framework material contains a hexagonal chemical structural unit, wherein the hexagonal chemical structural unit is formed by forming a C ═ N bond by taking 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as a knot and 2, 5-dimethoxyterephthalaldehyde as a connecting group; the specific surface area is 1500-2000 m2g-1The pore volume is 1-5 cm3g-1。
The reticular covalent organic framework material provided by the invention has higher specific surface area and pore volume, so that the adsorption rate of the reticular covalent organic framework material can be increased.
On the other hand, the preparation method of the reticular covalent organic framework material is obtained by carrying out Schiff base reaction on 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and 2, 5-dimethoxyterephthalaldehyde serving as raw materials, wherein the reaction system of the Schiff base reaction comprises an organic solvent and a catalyst aqueous solution, the organic solvent is 1, 2-dichlorobenzene, n-butanol, 1, 2-dichlorobenzene, n-butanol and the catalyst aqueous solution are in a volume ratio of 4.5-5.5: 1, the concentration of the catalyst aqueous solution is 5.5-6.5M, and the temperature is 115-125 ℃.
According to the invention, through experiments, the solvent, the catalyst concentration and the reaction temperature of the Schiff base reaction system have influence on the specific surface area and the pore volume of the reticular covalent organic framework material, and when the solvent containing the catalyst with a specific concentration is adopted, the prepared reticular covalent organic framework material has higher specific surface area and pore volume.
In a third aspect, the reticular covalent organic framework material is applied to detection of polybrominated diphenyl ethers by dispersive solid-phase extraction.
In a fourth aspect, a dispersed solid phase extraction adsorbent comprises the above-described reticulated covalent organic framework material.
In a fifth aspect, a method for detecting polybrominated diphenyl ethers includes uniformly mixing a sample to be detected with the solid phase extraction adsorbent, performing dispersed solid phase extraction adsorption, eluting the adsorbed dispersed solid phase extraction adsorbent with an eluent to obtain an eluent, removing the eluent from the eluent to obtain a sample to be detected, and performing GC-MS/MS detection on the sample to be detected.
In a sixth aspect, the method for detecting polybrominated diphenyl ethers is applied to monitoring environmental pollution or monitoring food safety.
The imine bond, triazine and methoxyl in the pore wall of the reticular covalent organic framework material provided by the invention not only enable the reticular covalent organic framework material to become a firm adsorbent for dispersed solid-phase extraction, but also enable the reticular covalent organic framework material to have abundant N and O atoms with strong electronegativity, thereby enabling the strong electrostatic interaction to occur between the N/O atoms of the reticular covalent organic framework material and the bromine atoms with positive electronegativity on polybrominated diphenyl ethers. Meanwhile, the reticular covalent organic framework material provided by the invention has large specific surface area, can provide abundant exposed geometric centers and short diffusion paths, and thus has high enrichment capacity and rapid adsorption rate on polybrominated diphenyl ethers.
The invention has the beneficial effects that:
1. the experimental conditions for preparing the reticular covalent organic framework material are optimized, and the experimental conditions show that the influence of the selection of the solvent and the concentration of the catalyst on the performance of the reticular covalent organic framework material is large, and the reticular covalent organic framework material prepared by the solvent provided by the invention has high specific surface area and pore volume. Meanwhile, the reaction temperature also influences the performance of the reticular covalent organic framework material, and the performance is better when the reaction temperature is 115-125 ℃.
2. The reticular covalent organic framework material provided by the invention is used as an adsorbent to perform solid phase extraction, and has the advantages of low extraction efficiency, low consumption, short extraction time and the like; meanwhile, the content of polybrominated diphenyl ethers in the actual environment and food samples can be detected more stably and more reliably by combining GC-MS/MS detection.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a diagram showing the overall preparation and adsorption process of TAPT-DMTA-COF material according to an embodiment of the present invention.
FIG. 2 is a scanning electron microscope image of TAPT-DMTA-COF material synthesized under different synthesis conditions in the embodiment of the invention; the synthesis conditions of A are as follows: 1, 2-dichlorobenzene/n-butanol/6M acetic acid aqueous solution (5:5:1 by volume), 120 ℃,72 h; the synthesis conditions of B are as follows: mesitylene/1, 4-dioxane/3M acetic acid (3:3:1 by volume) at 25 ℃ for 72 h; the synthesis conditions of C are as follows: 1, 2-dichlorobenzene/tetrahydrofuran/6M acetic acid (5:5:1 by volume), 120 ℃ for 72 h.
FIG. 3 is a structural composition representation of TAPT-DMTA-COF material prepared by the embodiment of the invention; a is an infrared spectrum, B is a polycrystalline powder X-ray diffraction spectrum, C is an XPS N1s spectrum, and D is XPS.
FIG. 4 is a structural morphology representation diagram of a TAPT-DMTA-COF material prepared according to an embodiment of the present invention; a is a scanning electron microscope image, B is a high-resolution transmission electron microscope image, and C is a high-resolution transmission electron microscope imageIn a radio-electron microscope picture, D is N2Adsorption-desorption diagram, E is aperture distribution diagram, F is TG and DSC curve.
FIG. 5 is a chemical stability characterization diagram of TAPT-DMTA-COF material prepared by the embodiment of the invention; a is an infrared spectrogram, and B is a polycrystalline powder X-ray diffraction spectrogram.
FIG. 6 is a diagram showing the extraction conditions of TAPT-DMTA-COF material prepared by the embodiment of the present invention; a is the extraction temperature vs. pH; b is the extraction temperature vs. ionic strength; c is ion time vs. pH; d is the ionic strength vs. ph.
FIG. 7 is a bar graph showing the elution rate of the resolution solvent of TAPT-DMTA-COF material prepared in the example of the present invention.
FIG. 8 is a chromatogram of TAPT-DMTA-COF material prepared in the example of the invention for detecting polybrominated diphenyl ethers in milk; a is blank; b is labeled 5ng L-1(ii) a c is labeled 50ng L-1。
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention provides a reticular covalent organic framework material and a preparation method and application thereof.
In one exemplary embodiment of the present invention, a network covalent organic framework material is provided, which comprises hexagonal chemical structural units, wherein the hexagonal chemical structural units comprise 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine as kink and 2, 5-dimethoxyterephthalaldehyde as linker, and the linker comprisesC ═ N bond formation; the specific surface area is 1500-2000 m2g-1The pore volume is 1-5 cm3g-1。
The reticular covalent organic framework material provided by the invention has higher specific surface area and pore volume, so that the adsorption rate of the reticular covalent organic framework material can be increased.
In the C ═ N bond, groups with multiple functionalized N atoms (triazines, imines) can provide enough electronegative N atoms for the covalent organic framework material, thus, strong electrostatic interaction is generated between the material and the positively charged Br on the PBDEs, and the adsorption efficiency is improved; and the functional groups can also lead the material to have prolonged rich pi electron conjugation property, thereby improving the stability of the material.
In some embodiments of this embodiment, the stacking is an overlapping stack.
In some examples of this embodiment, the polycrystalline powder has an X-ray diffraction spectrum in which 2.80. + -. 0.02 ℃ corresponds to the (100) plane, 4.87. + -. 0.02 ℃ corresponds to the (110) plane, 5.80. + -. 0.02 ℃ corresponds to the (200) plane, 7.42. + -. 0.02 ℃ corresponds to the (220) plane, 9.36. + -. 0.02 ℃ corresponds to the (220) plane, and 24.86. + -. 0.02 ℃ corresponds to the (001) plane.
In some embodiments of this embodiment, the pore size is 2 to 3 nm.
In some examples of this embodiment, the specific surface area is 1700 to 1750m2g-1The pore volume is 1.3-1.4 cm3g-1。
The invention also provides a preparation method of the reticular covalent organic framework material, which is obtained by carrying out Schiff base reaction on 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and 2, 5-dimethoxyterephthalaldehyde serving as raw materials, wherein the reaction system of the Schiff base reaction comprises an organic solvent and a catalyst aqueous solution, the organic solvent is 1, 2-dichlorobenzene, n-butanol, 1, 2-dichlorobenzene, n-butanol and the catalyst aqueous solution are in a volume ratio of 4.5-5.5: 1, the concentration of the catalyst aqueous solution is 5.5-6.5M, and the temperature is 115-125 ℃.
According to the invention, through experiments, the concentration of the solvent and the catalyst of the Schiff base reaction system has an influence on the specific surface area and the pore volume of the reticular covalent organic framework material, and when the solvent containing the catalyst with a specific concentration is adopted, the prepared reticular covalent organic framework material has higher specific surface area and pore volume.
The catalyst used in the present invention is a catalyst used in general Schiff base reaction, such as acetic acid.
In some examples of this embodiment, the Schiff base is reacted for 60 to 80 hours.
In some embodiments of this embodiment, the process is: uniformly mixing 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, 2, 5-dimethoxyterephthalaldehyde, 1, 2-dichlorobenzene, n-butanol and a catalyst water solution, freezing by adopting liquid nitrogen, vacuumizing, freezing and vacuumizing at least once, and heating to 115-125 ℃ for reaction.
In some examples of this embodiment, the purification process to remove unreacted impurities and catalyst adhering to the material is: and (3) centrifugally separating the material after the Schiff base reaction, washing the separated precipitate with methanol, and drying.
In a third embodiment of the invention, the application of the reticular covalent organic framework material in detection of polybrominated diphenyl ethers by dispersive solid-phase extraction is provided.
In a fourth embodiment of the invention, a dispersed solid phase extraction adsorbent is provided, comprising the above-described reticulated covalent organic framework material.
The fifth embodiment of the invention provides a method for detecting polybrominated diphenyl ethers, which comprises the steps of uniformly mixing a sample to be detected with the dispersed solid phase extraction adsorbent, then carrying out dispersed solid phase extraction adsorption, eluting the adsorbed dispersed solid phase extraction adsorbent by using an eluent to obtain an eluent, removing the eluent in the eluent to obtain a solid to be detected, and carrying out GC-MS/MS detection on the solid to be detected.
In some examples of this embodiment, the conditions for the dispersed solid phase extraction adsorption are: the time is 9-11 min, the temperature is 43-46 ℃, the pH is 5.5-6.5, and the ionic strength is 0%. The adsorption effect under the condition is better.
The detection of polybrominated diphenyl ethers is influenced by the elution effect of the eluent, and acetone, dichloromethane, normal hexane, methanol and the like can be selected as the eluent. In some embodiments of this embodiment, the eluent is n-hexane. The elution rate for most of the polybrominated diphenyl ethers using n-hexane as eluent was found to be close to 90% by optimization of the choice of eluent.
In some examples of this embodiment, the gas chromatography column is an HP-5MS column having a length of 30m, an internal diameter of 0.25mm, and a stationary phase coating thickness of 0.25 μm.
In some examples of this embodiment, the gas chromatography conditions are: a pulse no-shunt mode; the sample injection volume is 0.9-1.1 mu L; sample inlet temperature; 275-285 ℃; ion source temperature; 145-155 ℃; the temperature raising procedure is that the initial temperature is 70 ℃ and the temperature is 15 ℃ for min-1Raise to 300 ℃ and keep for 1 min.
In a sixth embodiment of the invention, the application of the method for detecting polybrominated diphenyl ethers in monitoring environmental pollution or monitoring food safety is provided.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
In the embodiment of the invention, a novel reticular covalent organic framework material which takes imine as a connecting group and triazine as a core and is called TAPT-DMTA-COF is designed and prepared by Schiff base reaction between nitrogen-enriched 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and 2, 5-dimethoxyphthaldialdehyde. And as a new adsorbent for dispersed solid phase extraction for analyzing the content of trace polybrominated diphenyl ethers in water, fish and milk samples. The overall preparation and adsorption process of TAPT-DMTA-COF material is shown in FIG. 1.
Synthesis of TAPT-DMTA-COF:
by screening the reaction conditions (such as solvent, catalyst concentration and reaction temperature), the TAPT-DMTA-COF material with high ordered structure is successfully synthesized. The optimal synthesis conditions are as follows: to a 48mL, 46X 70mm (diameter. times. length) pressure tube were added 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TAPT,113mg,0.32mmol) and 2, 5-dimethoxyterephthalaldehyde (DMTA,93mg,0.48mmol), 2.0mL of 1, 2-dichlorobenzene, 2.0mL of n-butanol, 0.4mL of 6M aqueous acetic acid in that order. Then, the reaction tube was frozen in liquid nitrogen and then evacuated. After three times of freezing-vacuum circulation, the reaction tube is put into an oil bath kettle at 120 ℃ for reaction for 72 hours, and yellow precipitate is obtained at the bottom. The yellow precipitate was centrifuged and washed three times with methanol to remove excess impurities. Finally the solid was dried in an oven at 80 ℃ for 24h to give 150mg of a yellow powder.
Weather chromatography-tandem mass spectrometry conditions:
the gas chromatography-triple quadrupole mass spectrometer is used for measuring gas experiments, and an SIM mode is adopted. A chromatographic column: HP-5MS column (30m × 0.25mm,0.25 μm); the gas phase conditions were as follows: a pulse no-shunt mode; the sample injection volume is 1.0 mu L; sample inlet temperature; 280 ℃; ion source temperature; 150 ℃; temperature rising procedure: initial temperature 70 deg.C, 15 deg.C min-1Raise to 300 ℃ and keep for 1 min. Mass spectrometry uses a negative ion chemistry ion source mode and collects two bromide isotope peaks 79 and 81.
A dispersed solid phase extraction flow:
the synthesized adsorbent (TAPT-DMTA-COF, 10mg) was weighed and then charged into a 50mL centrifuge tube containing 20mL of the sample solution. The sample was shaken at 45 ℃ for 10 minutes in an air bath constant temperature shaker at 400 rpm. The water sample and material were then separated by centrifugation. Polybrominated diphenyl ethers were eluted with 6mL of n-hexane (2 mL. times.3). Sonication was required for 5 minutes for each elution. The collected eluate was evaporated with a gentle stream of nitrogen until dry, and the obtained extract was redissolved in 500 μ L of methanol. Finally, the resulting solution was filtered with a 0.45 μm filter and analyzed for polybrominated diphenyl ethers therein by GC-MS/MS.
Collection and pretreatment of environmental and food samples:
well water and river water are respectively obtained from upstream well (Zhangqiu in south of Shandong province, China) and Roshan village (Ningyang in Tai' an in Shandong province, China). All water samples were filtered through a 0.45 μm microporous membrane, stored in a clean brown glass bottle, and stored in a refrigerator at 4 ℃ for subsequent dispersion-solid phase extraction experiments.
Pure milk and fish are from local supermarkets (china south china). The specific pretreatment steps are as follows: 1g of milk or minced fish was weighed into a 50mL centrifuge tube, then a stock solution of spiked PBDEs (10. mu.L) was added and the mixture was sonicated for 5 minutes. Finally, 5mL of acetonitrile was added to the spiked samples. The mixture was shaken for 15 minutes and then centrifuged at 10000rpm for 10 minutes. The supernatant was collected and evaporated under a gentle stream of nitrogen. The residue was diluted to 10mL with water for subsequent dispersion-solid phase extraction experiments.
Characterization of the synthesis of TAPT-DMTA-COF:
in the preparation of TAPT-DMTA-COF, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine is selected as a kink, and 2, 5-dimethoxyterephthalaldehyde is selected as a linking group, so as to prepare the hexagonal covalent organic framework material based on the principle of C3+ C2. To obtain the best performance material, the most suitable synthesis conditions are selected by varying experimental conditions, such as solvent, catalyst concentration and reaction temperature. The results of the screening experiments are shown in figure 2 and table 1, and the results show that two monomers can obtain netlike yellow crystal TAPT-DMTA-COF with high specific surface area and pore volume in a solvent of 1, 2-dichlorobenzene/n-butanol/6M acetic acid aqueous solution (5/5/1 by volume) at the temperature of 120 ℃ and under the condition of reaction time of 72 hours. Under the reaction condition, the high reversibility of C-N bond is facilitated, so that the self-repairing capability of the structure is enhanced, and the TAPT-DMTA-COF material with high quality is finally obtained. The highly crystalline ordered material was then characterized and tested by analytical instrumentation.
TABLE 1 specific surface area and pore volume of TAPT-DMTA-COF under different synthesis conditions
Structural analysis of TAPT-DMTA-COF:
infrared and XPS characterization of TAPT-DMTA-COF was performed to characterize if imine bonds were formed, as shown in FIG. 3. As expected, 2, 5-dimethoxyp-benzene2956cm in dimethylaldehyde monomer-1The aldehyde group in (A) has a C ═ O signal and 3460, 3321 and 3210cm in the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine monomer-1The amine signal was substantially absent, confirming that the two starting materials were highly copolymerized, as shown in FIG. 3A. Meanwhile, in TAPT-DMTA-COF, a new characteristic C ═ N peak was observed, indicating that schiff base reaction between the two monomers forms an imine bond. Furthermore, in the N1s XPS spectrum, the characteristic energy peak at 398.39eV was attributed to C ═ N, from which the successful formation of imine bonds in the material can be further inferred, as shown in fig. 3C and 3D. Next, the optimal geometry was optimized using DFT method, and the theoretical PXRD pattern of possible predicted structures (i.e. overlap and staggered-layer stacking) for TAPT-DMTA-COF was simulated using powder diffraction method, as shown in fig. 3B. In the overlap-and-pile (AA) mode, the lattice parameters are:
α ═ β ═ 90 ° and γ ═ 120 °, see table 2; in the staggered layer stacking (AB) mode, the lattice parameters are:
α ═ β ═ 90 ° and γ ═ 120 °, see table 3. By comparing the experimental values and the simulated values in FIG. 3B, it was found that the experimental values substantially match the simulated values of the overlapping stacks, and thus the structure can be inferred to be overlapping stacks. From the experimental data, it can be found that the lattice spacing of the peaks of TAPT-DMTA-COF is 2.80 °, 4.87 °, 5.80 °, 7.42 °, 9.36 °, 24.86 ° respectively correspond to the crystal planes of (100), (110), (200), (210), (220) and (001), thereby indicating that the novel material has a high crystal form.
Table 2 atomic coordinates of TAPT-DMTP-COF unit cell optimized using DFT method.
TABLE 3 atomic coordinates of TAPT-DMTP-COF unit cell optimized using DFT method
High power scanning electron micrographs and transmission electron micrographs of TAPT-DMTA-COF are shown in FIGS. 4A-C. The TAPT-DMTA-COF material can be found to be a net-shaped structure and consists of a large number of rods with the average diameter of 40-70 nm. Theoretically, the network structure can provide abundant adsorption sites and short adsorption paths during adsorption, so that the nano material can be used as an ideal adsorbent. FIG. 4C clearly shows the layer-by-layer structure of TAPT-DMTA-COF, which restricts the access of PBDEs between layers of the material. As a pore material, the pore and specific surface area properties of the material are important, especially for adsorption applications of the material. Thus, the nitrogen desorption and pore size distribution as well as the specific surface area of TAPT-DMTA-COF were characterized. The adsorption-desorption curve of TAPT-DMTA-COF in FIG. 4 shows that the isotherm is a typical type IV isotherm, thereby indicating that the synthesized material has mesoporous characteristics. And the pore size distribution was mainly 2.82nm based on DFT calculation, as shown in FIG. 4E, the specific surface area and pore volume were as high as 1734m, respectively2g-1And 1.346cm3g-1。
Thermal stability of TAPT-DMTA-COF As shown in FIG. 4F, there was only a 10% mass loss of TAPT-DMTA-COF when the temperature reached 409 ℃. Furthermore, both curves imply that between 30 and 700 ℃ there are two points of mass loss of TAPT-DMTA-COF powder. At 100 ℃ an initial weight loss of TAPT-DMTA-COF occurred, possibly due to the removal of residual water in the wells, and at 409 ℃ a second loss of mass occurred, possibly a collapse and decomposition of the TAPT-DMTA-COF framework.
The chemical stability of the material was examined by dispersing it in different conditions (e.g., methanol, acetone, dichloromethane, hexane, HCl (0.01M) and NaOH (1.0M)) for 3 days, as shown in fig. 5. Unexpectedly, the locations of all characteristic peaks and PXRD curve peaks in the FT-IR spectrum were consistent with the results for the starting material, even under harsh acid and base solutions, indicating that the material had no change in chemistry and skeletal structure. Such high chemical stability may be due to enhanced 2D interlayer interactions by introducing methoxy groups to weaken charge repulsion in TAPT-DMTA-COF. The results demonstrate the potential of the tough TAPT-DMTA-COF as an adsorption material, which can adsorb polybrominated diphenyl ethers in complex environments.
Optimization and verification of a method for detecting polybrominated diphenyl ethers by dispersive solid-phase extraction:
the response surface method optimizes the extraction conditions of the dispersed solid phase extraction and the single-factor method optimizes the analysis conditions:
the 3D response surface analysis model is characterized in that reasonable test design is utilized, certain data are obtained through experiments, and a mathematical statistic tool is utilized to analyze the experimental data to obtain a visual graph, so that the relation between the extraction efficiency of the polybrominated diphenyl ethers and any two independent parameters is visually analyzed. The design of the response surface experiment was performed with a 4-factor 3 level. The four factors are: the extraction temperature is X1The extraction time is X2pH of X3NaCl is X4. The response surface test is designed with 29 groups of tests shown in tables 4 and 5, and the test is carried out according to the test conditions designed by the software, so as to obtain the response values of each factor and each level, and the result is shown in figure 6. Analysis of variance (ANOVA) was an indicator to evaluate the suitability and significance of this fitted model, and the results are listed in table 6. Fitting the experimental result with the simulation of a multivariate quadratic equation, and adjusting R294.94%, predicted R2＝89.87％。X1，X2，X3，X4，X12，X32，X42All of these factors are significant, suggesting that the established response surface analysis model is reliable. According to the above studies, the best experimental extraction parameters are: the extraction time and temperature were 10 minutes, 45 ℃; pH: 6; ionic strength: 0 percent.
TABLE 4 encoding and non-encoding of parameters based on Box-Behnken design
TABLE 6 analysis of variance squares in the experimental parameters
In the analysis process, the polarity of the analysis solvent has an important influence on the analysis efficiency of the target small molecule on the material. In the experiment, the research system selects four solvents with different polarities [ i.e. n-hexane (0.06), acetone (ACE, 5.10), dichloromethane (DCM, 3.40), methanol (MA, 6.60) ], and the results are shown in fig. 7. The experimental result shows that when n-hexane is used as an analytic solvent, the elution rate of most polybrominated diphenyl ethers is close to 90%. This is probably due to the fact that the nonpolar solvent n-hexane (0.06) is suitable for resolving nonpolar polybrominated diphenyl ethers, following the "similar phase solubility" principle. Therefore, n-hexane was chosen as the eluent for the experiment.
The methodological parameters are as follows:
the established analysis method is evaluated by investigating the linear range and relevant parameters such as relevant coefficient, lowest detection limit, lowest quantitative limit, precision and the like. The corresponding quantification results are shown in table 7. The linear range of the method is 0.1-5000ngL-1Linear correlation coefficient of R2>0.9911. The detection limit was calculated based on the S/N-3 signal-to-noise ratio and found to be 0.03-0.13ng L-1Significantly lower than the methods reported in other literatures. The limit of quantitation was calculated from S/N-10 in the range of 0.10-0.43ng L-1. For five polybrominated diphenyl ethers, 2,4,4 '-tribromodiphenyl ether (BDE-28), 2',4,4 '-tetrabromobiphenyl ether (BDE-47), 2',4,4', 6-pentabrominated diphenyl ether (BDE-100), 2',4,4', 5-pentabrominated diphenyl ether (BDE-99) and 2,2',4,4',5,6' -hexabrominated diphenyl ether (BDE-154), the intra-day deviation (n ═ 5) and the inter-day deviation (n ═ 5) were 0.39-4.99% and 1.57-5.21%, respectively. These data demonstrate the ultrasensitiveness and reliability of the established assays and promise for the extraction and analysis of measured/overdimensioned levels of polybrominated diphenyl ethers in complex real samples.
TABLE 7 analytical parameters for the dispersed solid phase extraction
Detection of polybrominated diphenyl ethers in real water, fish and milk samples by dispersive solid phase extraction in combination with GC/MS/MS:
after a quantitative method for detecting polybrominated diphenyl ethers based on newly prepared TAPT-DMTA-COF was successfully constructed, it was used to measure polybrominated diphenyl ethers in environmental samples (e.g., well water and river water) and food samples (e.g., milk and fish), thereby verifying the utility of the method. The corresponding milk chromatograms and quantitative results are shown in fig. 8 and table 8. As shown in table 8, no residue of the objective polybrominated diphenyl ether was found in the selected real samples. Then, two different concentration levels (i.e., 5 and 50ng L) were added to the water, milk and fish samples-1) The spiking recovery experiment was performed. The experimental results are as follows: the recovery rates of the well water, river water, fish and milk samples are 71.8-114.4%, 73.5-119.6%, 73.0-106.1% and 75.5-118.5% respectively. The data clearly demonstrate that the extraction efficiency of the novel dispersed solid phase extraction material TAPT-DMTA-COF on the poly-modified diphenyl ether is not influenced by the complex matrix effect in the real sampleThus proving that the analysis method is used for detecting the reliability and the accuracy of measuring/over-measuring the polybrominated diphenyl ethers in actual samples.
TABLE 8 analysis results of actual water, fish, milk samples
aAdding 5 ng. L-1；bAdding 50 ng. L-1；cBlank.
Conclusion
The invention successfully prepares a novel imine bond-based triazine-core-based reticular TAPT-DMTA-COF material. Imine bonds, triazine and methoxy groups in the pore walls of the material not only enable the material to be a firm adsorbent for dispersed solid phase extraction, but also enable the material to possess abundant N and O atoms with strong electronegativity, so that strong electrostatic interaction (namely halogen bonds) occurs between N/O atoms on TAPT-DMTA-COF and bromine atoms with electronegativity on polybrominated diphenyl ethers. In addition, the possessed large-surface-area TAPT-DMTA-COF nano structure can provide abundant exposed geometric centers and short diffusion paths, so that the material has high enrichment capacity and rapid adsorption rate on polybrominated diphenyl ethers. Therefore, compared with other food sample pretreatment methods based on the adsorption principle, the method has the remarkable advantages of low extraction efficiency, less adsorbent consumption and obviously shortened extraction time. The effectiveness and reliability of the established method are proved by analyzing the content of polybrominated diphenyl ethers in actual environment and food samples. These excellent data suggest that: the covalent organic framework material with imine bond as a connecting bond, triazine as a core and a net structure can provide an important strategy for accurately designing an effective covalent organic framework material, and the covalent organic framework material is used as a novel adsorbent to capture pollutants with electropositive atoms, thereby realizing high adsorption efficiency.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a reticular covalent organic framework material for detecting polybrominated diphenyl ethers is characterized by comprising the step of carrying out Schiff base reaction on 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 2, 5-dimethoxyterephthalaldehyde serving as raw materials, wherein the Schiff base reaction system comprises an organic solvent and a catalyst aqueous solution, the organic solvent is 1, 2-dichlorobenzene, n-butyl alcohol, 1, 2-dichlorobenzene, n-butyl alcohol and the catalyst aqueous solution are in a volume ratio of 4.5-5.5: 1, the concentration of the catalyst aqueous solution is 5.5-6.5M, and the temperature is 115-125 ℃;
the reticular covalent organic framework material is characterized by comprising a hexagonal chemical structural unit, wherein the hexagonal chemical structural unit is formed by forming a C-N bond by taking 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as a kink and 2, 5-dimethoxyterephthalaldehyde as a connecting group; the specific surface area is 1500-2000 m2 g-1The pore volume is 1-5 cm3 g-1。
2. The method according to claim 1, wherein the network covalent organic framework material is stacked in an overlapping manner;
or in the X-ray diffraction spectrum of the polycrystalline powder, 2.80 +/-0.02 degrees corresponds to a (100) crystal face, 4.87 +/-0.02 degrees corresponds to a (110) crystal face, 5.80 +/-0.02 degrees corresponds to a (200) crystal face, 7.42 +/-0.02 degrees corresponds to a (220) crystal face, 9.36 +/-0.02 degrees corresponds to a (220) crystal face, and 24.86 +/-0.02 degrees corresponds to a (001) crystal face.
3. The method of claim 1, comprising the steps of: uniformly mixing 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, 2, 5-dimethoxyterephthalaldehyde, 1, 2-dichlorobenzene, n-butanol and a catalyst water solution, freezing by adopting liquid nitrogen, vacuumizing, freezing and vacuumizing at least once, and heating to 115-125 ℃ for reaction.
4. Use of a reticular covalent organic framework material obtained by the preparation method according to any one of claims 1 to 3 in detection of polybrominated diphenyl ethers by dispersive solid-phase extraction.
5. A dispersed solid phase extraction adsorbent comprising a network-like covalent organic framework material obtained by the production method according to claims 1 to 3.
6. A method for detecting polybrominated diphenyl ethers is characterized in that a sample to be detected is uniformly mixed with the dispersed solid phase extraction adsorbent disclosed by claim 5 and then subjected to dispersed solid phase extraction adsorption, an eluent is adopted to elute the adsorbed dispersed solid phase extraction adsorbent to obtain an eluent, the eluent in the eluent is removed to obtain a sample to be detected, and the sample to be detected is subjected to GC-MS/MS detection.
7. The method for detecting polybrominated diphenyl ethers according to claim 6, characterized in that the conditions of solid phase extraction adsorption are as follows: the time is 9-11 min, the temperature is 43-46 ℃, the pH is 5.5-6.5, and the ionic strength is 0%.
8. The method for detecting polybrominated diphenyl ethers according to claim 6, characterized in that the eluent is n-hexane.
9. Use of the method for detecting polybrominated diphenyl ethers according to any one of claims 6 to 8 in monitoring environmental pollution or monitoring food safety.
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