CN111111618A - Magnetic covalent organic framework material, preparation method and application thereof in detecting perfluorinated compounds - Google Patents
Magnetic covalent organic framework material, preparation method and application thereof in detecting perfluorinated compounds Download PDFInfo
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Abstract
The invention discloses a magnetic covalent organic framework material, a preparation method and application thereof in detecting perfluorinated compounds, wherein the preparation method comprises the following steps: carrying out covalent connection on the surfaces of ferroferric oxide nanoparticles by taking 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde intermediates as raw materials under the catalytic action of acetic acid to obtain a covalent organic framework material precursor layer containing azido; then reducing the azide groups of the covalent organic framework material precursor layer into primary amine groups to generate a magnetic covalent organic framework material containing the primary amine groups; the terephthalaldehyde intermediate is terephthalaldehyde with benzene rings connected with azido groups through chemical bonds. The magnetic covalent organic framework material provided by the invention can be rapidly synthesized at room temperature, and the efficient separation and enrichment of PFCs are realized by a magnetic solid-phase extraction mode.
Description
Technical Field
The invention relates to a magnetic covalent organic framework material, a preparation method and application thereof in detecting perfluorinated compounds, belonging to the technical field of environmental inspection.
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.
Perfluorinated compounds (PFCs) are a class of fluorochemicals formed by replacing all of the hydrogen atoms attached to all or more of the carbon atoms in an aliphatic hydrocarbon carbon chain with fluorine atoms. Has better thermal stability and chemical stability, can resist photolysis, hydrolysis, OH free radical oxidation and biodegradation, has obvious environmental persistence and also has stronger biological enrichment effect. Causing serious environmental hazards to the environment, soil, plants and even organisms. Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) were listed as Persistent Organic Pollutants (POPs) as two representative PFCs as early as 2009.
Currently, the common methods of detecting PFCs are Gas Chromatography (GC), gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-mass spectrometry (HPLC-MS). Among them, there are few reports of measurement by GC method, because PFCs are not volatile and are subjected to derivatization treatment during detection. With the rapid development and continuous improvement of mass spectrometry technology, especially the development of liquid chromatography tandem mass spectrometry technology (HPLC-MS/MS), compared with the HPLC-MS method, the HPLC-MS/MS method further improves the selectivity and accuracy, and simultaneously reduces the detection limit, so that the method is favored by researchers.
For a complex matrix sample, pretreatment is required, impurity interference is removed, and PFCs are enriched. Currently, the main pretreatment techniques for PFCs detection include the following: liquid-liquid extraction, solid-phase micro-extraction, ultrasonic extraction, a QuEChERS method and the like. In recent years, magnetic solid phase extraction technology has attracted much attention in the field of sample pretreatment because, on the one hand, magnetic adsorption materials can be rapidly separated under the action of an external magnetic field. On the other hand, the magnetic adsorption materials all have a core-shell structure and comprise iron ore cores and shell carbon materials. The core-shell structure can prevent the aggregation of the magnetic iron core and prevent the magnetic loss, and simultaneously, the aim of separating and enriching PFCs can be fulfilled by selecting different types of porous carbon materials as shells. However, the inventors of the present invention have found that the existing magnetic adsorbent has the defects of long preparation time, harsh reaction conditions, low separation efficiency for PFCs, and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a magnetic covalent organic framework material, a preparation method and application thereof in detecting perfluorinated compounds, wherein the material can be rapidly synthesized at room temperature, and the PFCs can be efficiently separated and enriched by a magnetic solid-phase extraction mode.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect, the magnetic covalent organic framework material is a core-shell structure, the core-shell structure takes ferroferric oxide nano particles as a core and a covalent organic framework as a shell, the covalent organic framework is formed by connecting 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde derivatives through carbon-nitrogen double bonds, and the terephthalaldehyde derivatives are terephthalaldehyde of which benzene rings are connected with primary amine groups through chemical bonds.
The magnetic covalent organic framework material provided by the invention can realize high-efficiency separation and enrichment of PFCs by a magnetic solid-phase extraction mode.
On the other hand, the preparation method of the magnetic covalent organic framework material comprises the steps of taking 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde intermediates as raw materials, and carrying out covalent connection on the surfaces of ferroferric oxide nanoparticles under the catalytic action of acetic acid to obtain a covalent organic framework material precursor layer containing azido; then reducing the azide groups of the covalent organic framework material precursor layer into primary amine groups to generate a magnetic covalent organic framework material containing the primary amine groups; the terephthalaldehyde intermediate is terephthalaldehyde with benzene rings connected with azido groups through chemical bonds.
Experiments show that the covalent organic framework material precursor layer can be obtained on the surface of the ferroferric oxide nanoparticles only within 3 hours at room temperature by the method provided by the invention, and then the magnetic covalent organic framework material capable of efficiently separating and enriching PFCs is obtained by azido reduction.
In a third aspect, the application of the magnetic covalent organic framework material in detecting perfluorinated compounds is provided.
In the fourth aspect, the method for enriching the perfluorinated compounds in the wastewater comprises the steps of adding the magnetic covalent organic framework material into the wastewater containing the perfluorinated compounds, oscillating for a period of time, performing magnetic hysteresis separation, and eluting the separated magnetic covalent organic framework material.
In a fifth aspect, a method for detecting perfluorinated compounds in wastewater is provided, wherein mixed liquor eluted by the enrichment method is dissolved after being dried by nitrogen, and a dissolved sample is analyzed by adopting liquid chromatography tandem mass spectrometry.
The invention has the beneficial effects that:
1. the surface of the magnetic covalent organic framework material provided by the invention is covered with a large number of benzene ring structures and a large number of primary amine groups, and PFCs in an environmental water sample can be efficiently and quickly enriched and separated through hydrophobic effect and electrostatic adsorption effect.
2. The invention provides a preparation method of a magnetic covalent organic framework material containing primary amino, which has the advantages of simple synthesis steps and mild reaction conditions, and combines the advantages of porosity, stable structure, large specific surface area and the like of a covalent organic framework material with the advantages of good magnetic nanoparticle dispersibility, good magnetic field inductivity, easy separation (separation can be realized by adopting simple magnetic action) and the like.
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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 transmission electron microscope image of example 1 of the present invention, wherein A is a ferroferric oxide nanoparticle, B is an azido magnetic covalent organic framework material, and C is a primary amino magnetic covalent organic framework material;
FIG. 2 is a picture of the magnetic covalent organic framework material of example 1 in an aqueous solution, where A is before the application of a magnetic field and B is after the application of a magnetic field;
FIG. 3 is an IR spectrum of example 1 of the present invention, wherein A is ferroferric oxide nanoparticles, B is azido magnetic covalent organic framework material, and C is primary amino magnetic covalent organic framework material;
FIG. 4 is a graph of the recovery rates of the magnetic covalent organic framework materials with different mass of primary amine groups for nine kinds of perfluorocarboxylic acids and perfluorosulfonic acids in example 1 of the present invention.
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 magnetic covalent organic framework material, a preparation method and application thereof in detecting perfluorinated compounds, wherein the magnetic adsorption material has the defects of long preparation time, harsh reaction conditions, low PFCs separation efficiency and the like.
The invention provides a magnetic covalent organic framework material which is a core-shell structure, wherein the core-shell structure takes ferroferric oxide nano particles as a core and a covalent organic framework as a shell, the covalent organic framework is formed by connecting 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde derivatives by carbon-nitrogen double bonds, and the terephthalaldehyde derivatives are terephthalaldehyde of which benzene rings are connected with primary amine groups through chemical bonds.
The magnetic covalent organic framework material provided by the invention can realize high-efficiency separation and enrichment of PFCs by a magnetic solid-phase extraction mode.
In one or more embodiments of the embodiment, the ratio of the ferroferric oxide nanoparticles, 1,3, 5-tris (4-aminophenyl) benzene, and total terephthalaldehyde is 100-300 mg: 0.2-0.6 mmol: 0.3 to 0.9 mmol.
In one or more embodiments of this embodiment, the terephthalaldehyde derivative is 1 to 100% of the total molar amount of the total terephthalaldehyde. The total terephthalaldehyde in the present invention means terephthalaldehyde and terephthalaldehyde derivatives.
In one or more embodiments of this embodiment, the primary amine groups are attached through
Is linked to the benzene ring of terephthalaldehyde.
Representing the attachment location.
In one or more embodiments of this embodiment, the benzene ring of the phthalaldehyde is linked to two primary amine groups.
In this series of examples, two primary amine groups of one phthalaldehyde are located at the 2-and 5-positions of the benzene ring, respectively.
In another embodiment of the invention, 1,3, 5-tris (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde intermediates are used as raw materials, and covalent connection is carried out on the surfaces of ferroferric oxide nanoparticles under the catalytic action of acetic acid to obtain a precursor layer of the covalent organic framework material containing azido groups; then reducing the azide groups of the covalent organic framework material precursor layer into primary amine groups to generate a magnetic covalent organic framework material containing the primary amine groups; the terephthalaldehyde intermediate is terephthalaldehyde with benzene rings connected with azido groups through chemical bonds.
The structural formula of the terephthalaldehyde intermediate is as follows:
Experiments show that the covalent organic framework material precursor layer can be obtained on the surface of the ferroferric oxide nanoparticles only within 3 hours at room temperature by the method provided by the invention, and then the magnetic covalent organic framework material capable of efficiently separating and enriching PFCs is obtained by azido reduction.
In one or more embodiments of this embodiment, the terephthalaldehyde intermediate is 2, 5-bis (2- (2-azidoethoxy) ethoxy) -1, 4-benzenedicarboxaldehyde.
The structural formula of the 2, 5-bis (2- (2-azidoethoxy) ethoxy) -1, 4-benzenedicarboxaldehyde is as follows:
in one or more embodiments of this embodiment, the process of covalently attaching is: adding 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde intermediate into the ferroferric oxide nano particle dispersion liquid, adding acetic acid after uniform dispersion, mixing uniformly, and reacting at room temperature. For more uniform dispersion and mixing, ultrasonic treatment is adopted in the dispersion and/or mixing process. The time for the dispersion ultrasonic treatment is 1-15 min. The mixed ultrasonic treatment time is 3-15 min. The room temperature refers to the indoor environment temperature, and is generally 15-30 ℃. The reaction time at room temperature is 30-180 min. And in the reaction process at room temperature, standing for reaction.
Covalent attachment involves schiff base reactions.
In one or more embodiments of this embodiment, the ratio of the ferroferric oxide nanoparticles, 1,3, 5-tris (4-aminophenyl) benzene, and total terephthalaldehyde (terephthalaldehyde and terephthalaldehyde intermediate) is 100-300 mg: 0.2-0.6 mmol: 0.3 to 0.9 mmol.
In one or more embodiments of this embodiment, the intermediate terephthalaldehyde is 1 to 100% of the total molar amount of the total terephthalaldehyde.
In one or more embodiments of this embodiment, the amount of acetic acid used is 1-5 mL (17.5M).
In one or more embodiments of this embodiment, the reduction of the azide group to a primary amine group is by: and (3) uniformly dispersing the covalent organic framework material precursor layer, adding triphenylphosphine, and reacting at normal temperature. The normal temperature is 20-25 ℃. The reduction of the azide group to a primary amine group is carried out by the Staudinger reaction (Staudinger reduction), which is a reaction between azide and phosphine (e.g., triphenylphosphine) or phosphite to give an iminophosphorane intermediate, which is then hydrolyzed to give the corresponding amine and phosphine oxide (e.g., triphenylphosphine oxide). Among them, triphenylphosphine is used with a better effect.
In this series of examples, the solvent in which the covalent organic framework material precursor layer is dispersed is methanol, dichloromethane, tetrahydrofuran or N, N-dimethylformamide.
In the series of embodiments, the ratio of the covalent organic framework material precursor layer to triphenylphosphine is 100-300 mg: 0.7 to 2.6 g.
In one or more embodiments of this embodiment, the ferroferric oxide nanoparticles are prepared by a solvothermal method.
In the series of embodiments, the process for preparing the ferroferric oxide nano particles by the solvothermal method comprises the following steps: adding soluble ferric ion salt, sodium acetate and sodium citrate into an ethylene glycol solution, dissolving to obtain a clear solution, carrying out solvothermal reaction on the clear solution at 180-220 ℃, and reacting for 5-12 h to obtain the ferroferric oxide nanoparticles.
Wherein, the soluble ferric ion salt is one of ferric chloride, ferric acetate, ferric nitrate and ferric sulfate.
In the series of embodiments, the volume ratio of the ferric ion salt to the glycol can be (1-8) g: (25-200) mL.
In the series of embodiments, the molar ratio of ferric ions, sodium acetate and sodium citrate is 1-5:10-30: 0-2. The sodium citrate is different from 0.
In a third embodiment of the invention, the application of the magnetic covalent organic framework material for detecting the perfluorinated compounds is provided.
In one or more embodiments of this embodiment, the perfluorinated compound is PFBS (perfluorobutane sulfonate), PFHpA (perfluoroheptanoic acid), PFOA, PFHxS (perfluorohexyl sulfonic acid), PFNA (perfluorononanoic acid), PFDA (perfluorodecanoic acid), PFOS, PFUdA (perfluoroundecanoic acid), PFDoA (perfluorododecanoic acid).
In a fourth embodiment of the present invention, a method for enriching perfluoro compounds in wastewater is provided, wherein the magnetic covalent organic framework material is added into wastewater containing perfluoro compounds, and after a period of oscillation, magnetic hysteresis separation is performed, and the separated magnetic covalent organic framework material is eluted.
In one or more embodiments of this embodiment, the eluent is methanol, ethanol, acetone, or acetonitrile. When methanol or acetone is selected, the elution effect is better.
In a fifth embodiment of the present invention, a method for detecting perfluorinated compounds in wastewater is provided, wherein the mixed solution eluted by the enrichment method is dried by nitrogen and dissolved, and a sample after dissolution is analyzed by liquid chromatography tandem mass spectrometry.
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.
The experimental methods used in the examples are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples are commercially available unless otherwise specified.
Example 1
Synthesis of 2, 5-bis (2- (2-azidoethoxy) ethoxy) -1, 4-benzenedicarboxaldehyde.
(1) To a 50mL round bottom flask was added 2- (2-chloroethoxy) ethanol (4g,32mmol), deionized water (20mL), and then to the above solution was neutralized sodium azide (5.2g,80mmol,2.5 eq). After stirring at 80 ℃ for 18 hours under nitrogen, it was poured into 35mL of sodium hydroxide solution (5% (W/V)), and extracted with ethyl acetate (3X 35 mL). The organic phase was dried over anhydrous sodium sulfate and spin-dried to give 2- (2-azidoethoxy) ethanol as an oil.
(2) To a 100mL round bottom flask was added 2- (2-azidoethoxy) ethanol (2g,15.3mmol), dried dichloromethane (20mL) under nitrogen, then to the above solution was added triethylamine (2.7mL,18.4mmol,1.5eq), cooled to 0 deg.C and p-toluenesulfonyl chloride (3.48g,18.4mmol,1.2eq) was added. The reaction mixture was stirred at 0 ℃ for 1 hour, warmed to room temperature and stirred for 17 hours to end the reaction. Then, the reaction mixture was washed with sodium hydrogencarbonate solution (3 × 80mL), water (3 × 80mL) and saturated brine (3 × 80mL), and the organic phase was dried over anhydrous sodium sulfate and spin-dried to give a crude product, which was then purified by column chromatography (petroleum ether/ethyl acetate ═ 5:1) to give 2- (2-azidoethoxy) ethyl p-toluenesulfonate as a colorless oil.
(3) To a 100mL round bottom flask was added 2, 5-dihydroxyterephthalaldehyde (0.4g,2.4mmol), 2- (2-azidoethoxy) ethyl p-toluenesulfonate (1.64g,5.7mmol,2.4eq), dried N, N-dimethylformamide (40mL) under nitrogen, and then to the above solution was added anhydrous potassium carbonate (2.6g,1.93 mmol). The reaction mixture was stirred at 80 ℃ for 18 h, diluted with water (100mL) and extracted with hot ethyl acetate (5X 60 mL). The combined organic phases were dried over anhydrous sodium sulfate, filtered and spun to give the crude product, which was then purified by column chromatography (petroleum ether/ethyl acetate 3:2) to give 2, 5-bis (2- (2-azidoethoxy) ethoxy) -1, 4-benzenedicarboxaldehyde as a yellow solid.
And (3) synthesizing ferroferric oxide nano particles.
4.0g of ferric chloride hexahydrate, 0.75g of trisodium citrate dihydrate and 6g of anhydrous sodium acetate are weighed, and dissolved and dispersed in 100mL of glycol solution by ultrasonic wave to obtain a homogeneous solution. The solution was transferred to 2 100mL autoclave and heated to 200 ℃ for 12 h. And washing the obtained ferroferric oxide nano particles with water and absolute ethyl alcohol for 3 times in sequence, and drying at room temperature in vacuum overnight.
Synthesis of magnetic covalent organic framework materials.
(1) Dispersing the synthesized 150mg ferroferric oxide nanoparticles in 60mL dimethyl sulfoxide, adding 1,3, 5-tri (4-aminophenyl) benzene (106mg,0.3mmol), terephthalaldehyde (30mg,0.225mmol) and 2, 5-bis (2- (2-azidoethoxy) ethoxy) -1, 4-phthalaldehyde (88mg,0.225mmol), carrying out ultrasonic treatment at room temperature for 5 minutes to uniformly disperse the ferroferric oxide nanoparticles, adding 2mL acetic acid while carrying out ultrasonic treatment, and continuing ultrasonic treatment for 10 min. After standing for 30 minutes, separating the obtained brown precipitate by using a magnet, then respectively washing the brown precipitate by using tetrahydrofuran and methanol for three times, and performing vacuum drying at room temperature overnight to obtain the magnetic covalent organic framework material of the azido group.
(2) The synthesized 150mg azido magnetic covalent organic framework material is dispersed in 10mL absolute methanol, then 1.3g triphenylphosphine is added, after oscillation for 24h at normal temperature, the material is recovered by a magnet, then extracted by acetone and methanol for 24h, and then dried in vacuum overnight at 50 ℃ to obtain the magnetic covalent organic framework material of primary amino.
FIG. 1A is a transmission electron microscope image of the ferroferric oxide nanoparticles synthesized in the examples, and it can be seen from the image that the particle size of the ferroferric oxide nanoparticles is about 200nm and the dispersibility is good. FIG. 1B is a transmission electron micrograph of azido magnetic covalent organic framework material, and FIG. 1C is a transmission electron micrograph of primary amino magnetic covalent organic framework material, which shows that it has an obvious core-shell structure, indicating that the magnetic nanoparticles successfully coat the covalent organic framework shell.
Fig. 2 is a picture of the magnetic covalent organic framework material of the primary amine group synthesized in the example before (a) and after (B) the application of the magnetic field after being dispersed in an aqueous solution. Before the external magnetic field is applied, as shown in fig. 2A, the magnetic covalent organic framework material of the primary amine group is uniformly dispersed in the aqueous solution, and after the external magnetic field is applied, as shown in fig. 2B, the magnetic covalent organic framework material of the primary amine group is adsorbed to the side where the magnet is placed, which indicates that the prepared magnetic covalent organic framework material has magnetism.
FIG. 3 is an infrared spectrum of the ferroferric oxide nanoparticles (A), the azido magnetic covalent organic framework material (B) and the primary amine magnetic covalent organic framework material (C) synthesized in the examples. IR spectrum of B showed 1613cm-1A strong absorption peak appears, which indicates that 1,3, 5-tri (4-aminophenyl) benzene and terephthalaldehyde building monomer form imine bond (-C ═ N-); 2097cm-1Is a characteristic peak of the azide group, and indicates that the magnetic covalent organic framework material has the azide group. Comparing the infrared spectrums of B and C, it is obvious that the infrared spectrum of C is 2097cm-1There is no absorption peak, confirming that all azide groups of the magnetic covalent organic framework material are reduced to primary amine groups.
The magnetic covalent organic framework materials prepared in the examples were used for enrichment detection of perfluorosulfonic acid (PFSA) and perfluorocarboxylic acid (PFCA).
25mL of sample solution (1ppb) was added to a glass bottle, and 2 to 20mg of the primary amino magnetic covalent organic framework material was added to the solution. The mixture solution was shaken at room temperature for 40 min. The adsorbent was separated from the aqueous phase by means of an external magnet outside the glass vial and the supernatant was discarded completely. And (3) eluting the adsorbed magnetic covalent organic framework material of the primary amino group by 2mL of methanol (ultrasonic treatment for 3min), blowing the mixed solution of the methanol and the perfluorinated compounds by nitrogen, and then re-dissolving the mixed solution by 250 mu L of methanol. The re-dissolved sample was injected into HPLC-MS/MS for analysis. The enrichment effect of the magnetic covalent organic framework material with primary amine groups on the perfluorinated compounds is evaluated by calculating the recovery rate, and the result is shown in fig. 4. The magnetic covalent organic framework material of the used primary amine groups was ultrasonically washed twice with methanol before being used again. FIG. 4 shows the recovery rates of nine kinds of perfluoro carboxylic acids and perfluoro sulfonic acids when the amount of the primary amino magnetic covalent organic framework material is 20mg, which is shown in Table 1, and shows that the primary amino magnetic covalent organic framework material has a good enrichment effect on perfluorinated compounds.
TABLE 120 mg recovery of nine perfluorocarboxylic acids and perfluorosulfonic acids from magnetic covalent organic framework materials containing primary amino groups
| Name of Compound | Recovery rate |
| PFBS | 33.41406 |
| PFHpA | 36.4699 |
| PFOA | 93.87928 |
| PFHxS | 72.85123 |
| PFNA | 114.58703 |
| PFDA | 116.94874 |
| PFOS | 84.43923 |
| PFUdA | 117.52992 |
| PFDoA | 115.86769 |
Chromatographic mass spectrometry conditions: a chromatographic column: eclipse XDB C18 column (150 mm. times.2.1 mm,3.5 μm, Agilent Technologies, Santa Clara, Calif., USA); mobile phase: the organic phase was methanol and the aqueous phase was ultrapure water containing 5mmol/L ammonium acetate. The elution gradient program started with 10% organic phase, increased to 40% organic phase in 1.5 min, then to 95% organic phase in 10.5 min, and held for 1 min. Finally, the organic phase was reduced to 10% in 1 minute and kept for 5 minutes. The flow rate was 0.3mL/min, the amount of sample was 10. mu.L, and the column oven was set at 40 ℃.
TABLE 2 Mass Spectrometry setup parameters for nine perfluorocarboxylic acids and perfluorosulfonic acids in HPLC tandem Mass Spectrometry MRM mode
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 (10)
1. A magnetic covalent organic framework material is characterized by being of a core-shell structure, wherein the core-shell structure takes ferroferric oxide nano particles as a core and a covalent organic framework as a shell, the covalent organic framework is formed by connecting 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde derivatives through carbon-nitrogen double bonds, and the terephthalaldehyde derivatives are terephthalaldehyde of which benzene rings are connected with primary amino groups through chemical bonds.
2. The magnetic covalent organic framework material of claim 1, wherein the ratio of ferroferric oxide nanoparticles, 1,3, 5-tris (4-aminophenyl) benzene, and total terephthalaldehyde is 100-300 mg: 0.2-0.6 mmol: 0.3-0.9 mmol;
or the total molar amount of the terephthalaldehyde derivatives is 1-100%.
3. The magnetic covalent organic framework material of claim 1, wherein the primary amine groups are attached through
To the benzene ring of terephthalaldehyde;
or, the benzene ring of the benzene dicarbaldehyde is connected with two primary amine groups; preferably, two primary amine groups of one phthalaldehyde are located at the 2-and 5-positions of the benzene ring, respectively.
4. A preparation method of a magnetic covalent organic framework material is characterized in that 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde intermediates are used as raw materials and are subjected to covalent connection on the surfaces of ferroferric oxide nanoparticles under the catalytic action of acetic acid to obtain a precursor layer of the covalent organic framework material containing azido; then reducing the azide groups of the covalent organic framework material precursor layer into primary amine groups to generate a magnetic covalent organic framework material containing the primary amine groups; the terephthalaldehyde intermediate is terephthalaldehyde with benzene rings connected with azido groups through chemical bonds.
5. The method of claim 4, wherein the covalent linking is performed by: adding 1,3, 5-tri (4-aminophenyl) benzene, terephthalaldehyde and terephthalaldehyde intermediate into ferroferric oxide nanoparticle dispersion liquid, uniformly dispersing, adding acetic acid, uniformly mixing, and reacting at room temperature;
or the ratio of the ferroferric oxide nanoparticles, the 1,3, 5-tri (4-aminophenyl) benzene and the total terephthalaldehyde is 100-300 mg: 0.2-0.6 mmol: 0.3-0.9 mmol;
or the intermediate of the terephthalaldehyde is 1 to 100 percent of the total molar weight of the total terephthalaldehyde.
6. The method of claim 4, wherein the step of reducing azide groups to primary amine groups comprises: uniformly dispersing a covalent organic framework material precursor layer, adding triphenylphosphine, and reacting at normal temperature;
preferably, the solvent in which the covalent organic framework material precursor layer is dispersed is methanol, dichloromethane, tetrahydrofuran or N, N-dimethylformamide;
preferably, the ratio of the covalent organic framework material precursor layer to triphenylphosphine is 100-300 mg: 0.7 to 2.6 g.
7. The method according to claim 4, wherein the intermediate terephthalaldehyde is 2, 5-bis (2- (2-azidoethoxy) ethoxy) -1, 4-benzenedicarboxaldehyde;
or the ferroferric oxide nano particles are prepared by a solvothermal method;
preferably, the process for preparing the ferroferric oxide nano particles by the solvothermal method comprises the following steps: adding soluble ferric ion salt, sodium acetate and sodium citrate into an ethylene glycol solution, dissolving to obtain a clear solution, carrying out solvothermal reaction on the clear solution at the temperature of 180-220 ℃, and reacting for 5-12 h to obtain ferroferric oxide nanoparticles;
preferably, the volume ratio of the mass of the ferric ion salt to the glycol can be 1-8: 25-200, g: mL;
preferably, the molar ratio of ferric ions, sodium acetate and sodium citrate is 1-5:10-30: 0-2.
8. Use of the magnetic covalent organic framework material according to any one of claims 1 to 3 or the magnetic covalent organic framework material obtained by the preparation method according to any one of claims 4 to 7 for detecting perfluorinated compounds.
9. A method for enriching perfluoro compounds in wastewater, which is characterized in that the magnetic covalent organic framework material of any claim 1 to 3 or the magnetic covalent organic framework material obtained by the preparation method of any claim 4 to 7 is added into wastewater containing perfluoro compounds, after oscillation for a period of time, hysteresis separation is carried out, and the separated magnetic covalent organic framework material is eluted;
preferably, the eluent is methanol, ethanol, acetone or acetonitrile.
10. A method for detecting perfluorinated compounds in wastewater, which is characterized in that the mixed solution eluted by the enrichment method of claim 9 is dissolved after being dried by nitrogen, and a sample after dissolution is analyzed by liquid chromatography-tandem mass spectrometry.
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