CN109894082B - Preparation method and application of nanoflowers covalent organic framework composite material - Google Patents
Preparation method and application of nanoflowers covalent organic framework composite material Download PDFInfo
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- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
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Images
Abstract
The invention discloses a preparation method and application of a nanoflower covalent organic framework composite material. The invention adopts a two-step heterogeneous nucleation method to prepare the nanoflowers type ion covalent organic framework composite material, the existence of heterogeneous nuclei inhibits the rapid precipitation of early amorphous polymers and guides the crystal growth of covalent organic frameworks, compared with a hydrothermal method, the synthesis time is greatly shortened, and simultaneously, functional groups modified on the surface of the material are more uniform; the covalent organic framework composite material is prepared by adopting amine monomers containing positive charges, and can generate electrostatic interaction with negative charge groups of target compound molecules, so that the selective enrichment of the nonsteroidal anti-inflammatory drugs in a water sample is realized.
Description
Technical Field
The invention relates to preparation and application of a covalent organic framework composite material, in particular to a preparation method of a nanoflowers type ionic covalent organic framework composite material and application of the nanoflowers type ionic covalent organic framework composite material as a solid-phase extraction material
Background
Covalent Organic Frameworks (COFs) are covalently bonded crystalline porous materials composed of light elements such as C, H, O, N and B. Covalent organic frameworks have attracted considerable attention since their first report in 2005. These materials have quite attractive properties including high specific surface area, excellent thermal stability, high porosity and low density [1 ]. Furthermore, covalent organic frameworks are more stable in water and acidic media than metal organic frameworks. Due to these unique properties, covalent organic frameworks are considered promising adsorbent materials with good capacity.
Most conventional molecularly imprinted covalent organic frameworks mainly contain a large number of pi-pi covalent bonds, and extract non-steroidal anti-inflammatory drugs through strong hydrophobic interactions, pi-pi interactions and molecular specific recognition, resulting in their affinity for some hydrophobic interferents and their inability to undergo complete matrix elimination [2 ]. Researches show that the introduction of hydrophilic functional groups on the surface of the molecularly imprinted polymer not only can improve the hydrophilicity of the polymer and improve the extraction efficiency, but also can provide charge attraction and enhance the imprinting effect. Puoci et al introduce polar hydrophilic functional groups by using the ring-opening reaction of glycidyl methacrylate on the surface of a molecularly imprinted polymer, apply the polar hydrophilic functional groups to the extraction of acetaminophen in China, which has better selectivity [3 ]. Zhu et al use hydrophilic propyl triethoxy silane as monomer to react with ethylene glycol dimethacrylate and gamma-methacryl to prepare molecularly imprinted polymer, which can selectively extract chlorogenic acid [4 ]. Inspired by these documents, we hope to introduce hydrophilic monomers to synthesize a molecularly imprinted covalent organic framework to improve the selectivity of the extraction material.
Covalent organic framework composites tend to agglomerate during preparation and are generally prepared as composites for use [5 ]. The conventional silica matrix has a narrow pH range, which limits the range of applications of the composite. While the specific surface area of the spherical matrix is smaller. To solve these problems, we propose a novel matrix.
Reference to the literature
[1]Y.B.Zhang,J.Su,H.Furukawa,Y.Yun,F.Gandara,A.Duong,X.Zou,O.M.Yaghi,Single-crystal structure of a covalent organic framework,J Am Chem Soc,135(2013)16336-16339.
[2]W.Ji,R.Sun,Y.Geng,W.Liu,X.Wang,Rapid,low temperature synthesis ofmolecularly imprinted covalent organic frameworks for the highly selectiveextraction of cyano pyrethroids from plant samples,Anal.Chim.Acta,1001(2018)179-188.
[3]F.Puoci,F.Iemma,G.Cirillo,M.Curcio,O.I.Parisi,U.G.Spizzirri,N.Picci,New restricted access materials combined to molecularly imprintedpolymers for selective recognition/release in water media,Eur.Polym.J.,45(2009)1634-1640.
[4]W.Tang,G.Li,K.H.Row,T.Zhu,Preparation of hybrid molecularlyimprinted polymer with double-templates for rapid simultaneous purificationof theophylline and chlorogenic acid in green tea,Talanta,152(2016)1-8.
[5]R.Wang,Z.Chen,A covalent organic framework-based magnetic sorbentfor solid phase extraction of polycyclic aromatic hydrocarbons,and itshyphenation to HPLC for quantitation,Microchim.Acta,184(2017)3867-3874.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a nanoflowers type ion covalent organic framework composite material through a large number of experimental screens. Aims to realize the rapid synthesis and application of the covalent organic framework composite material.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of a nanoflower covalent organic framework composite material.
As a further improvement, the preparation method comprises the following specific preparation steps:
1) dissolving an aldehyde monomer in NH2-SnO2The suspension is stirred and reacts in dioxane solution at room temperature;
2) adding another amine monomer and acetic acid serving as a catalyst into the solution obtained in the step 1), and stirring at room temperature for reaction;
3) diluting the solution obtained in the step 2), and adding higher-concentration aldehyde monomers, amine monomers and catalyst acetic acid;
4) heating and refluxing for reaction to generate a coating on the surface of the tin dioxide;
5) and (4) centrifugally separating the solid obtained in the step 4), washing an ethanol/acetic acid mixture, and drying to obtain the nanoflowers covalent organic framework composite material.
As a further improvement, in the step 1) of the invention, the concentration of the aldehyde monomer in the suspension is 0.04mol L-1The reaction time was 1 hour.
As a further improvement, in the step 2) of the invention, the concentration of the amine monomer in the suspension is 0.06mol L-1The reaction time was 10 minutes.
As a further improvement, in the step 3) of the invention, the concentrations of the aldehyde monomer and the amine monomer in the dioxane solution are respectively 0.05mol L-1And 0.75mol L-1The concentration of the catalyst in the dioxane solution is 3mol L-1。
As a further improvement, in the step 4) of the present invention, the reaction time is 3 hours, and the reaction temperature is 120 ℃.
As a further improvement, in the step 5) of the present invention, the volume concentration ratio of the ethanol/acetic acid mixture is 98/2.
As a further improvement, the substrate used for the preparation according to the invention is aminated tin dioxide.
As a further improvement, the monomer used for the preparation of the invention is an amine organic substance containing positive ions.
The invention has the following advantages and effects:
1. the invention adopts a two-step heterogeneous nucleation method to prepare the nanoflowers type ion covalent organic framework composite material, the existence of heterogeneous nuclei inhibits the rapid precipitation of early amorphous polymers and guides the crystal growth of covalent organic frameworks, compared with a hydrothermal method, the synthesis time is greatly shortened, and simultaneously, functional groups modified on the surface of the material are more uniform;
2、NH2-SnO2the amino group reacts with aldehyde group of trimesic aldehyde through Schiff base reactionIt should be noted that, after adding a low concentration of bromomephenanthridine solution, schiff base reaction occurs between trimesic aldehyde and bromomephenanthridine, thus forming a thin amorphous imine-linked polymer on the surface of the silica particles, and by using the amorphous imine-linked polymer as a seed, monomers are added to the seed solution to synthesize an ionic covalent organic framework on the seed surface, which growth benefits are mainly from three points: 1) the growth of imine-type covalent organic frameworks is generally a relatively lengthy process in which an amorphous polymer is formed and then slowly transforms into a crystalline form. In this experiment, the presence of heterogeneous cores inhibits rapid precipitation of early amorphous polymers. 2) The composition of the amorphous imine-linked polymer is consistent with the monomer, which allows the monomer to be easily attracted to the surface of the heterogeneous core and promotes crystallization of the covalent organic framework during growth. 3) And the residual aldehyde and amino groups on the surface of the amorphous imine-linked polymer seed can direct the crystal form growth of the covalent organic framework.
3. The nano flower type tin dioxide is used as the matrix to prepare the composite material, so that the composite material has larger specific surface area.
4. The covalent organic framework composite material is prepared by adopting amine monomers containing positive charges, and can generate electrostatic interaction with negative charge groups of target compound molecules, so that the selective enrichment of the nonsteroidal anti-inflammatory drugs in a water sample is realized.
Drawings
FIG. 1 is a schematic diagram of a self-made nanoflowers type ionic covalent organic framework composite material;
FIG. 2 is a schematic view of a device for extracting and separating non-steroid anti-inflammatory drugs in a water sample by using a novel nanoflowers type ion covalent organic framework composite material.
Detailed Description
The invention discloses a preparation method of a nanoflower covalent organic framework composite material.
The preparation method comprises the following specific steps:
6) dissolving an aldehyde monomer in NH2-SnO2Suspending liquid, dioxane solution, stirring at room temperature for reaction, wherein the concentration of aldehyde monomer in the suspending liquid is 0.04mol L-1The reaction time was 1 hour.
7) Adding another amine monomer and acetic acid serving as a catalyst into the solution obtained in the step 1), and stirring at room temperature for reaction; the concentration of the amine monomer in the suspension is 0.06mol L-1The reaction time was 10 minutes.
8) Diluting the solution obtained in the step 2), and adding higher-concentration aldehyde monomers, amine monomers and catalyst acetic acid; the concentrations of the aldehyde monomer and the amine monomer in the dioxane solution are respectively 0.05mol L-1And 0.75mol L-1The concentration of the catalyst in the dioxane solution is 3mol L-1。
9) Heating and refluxing for reaction, and generating a coating on the surface of the tin dioxide, wherein the reaction time is 3 hours, and the reaction temperature is 120 ℃.
10) And (3) centrifugally separating the solid obtained in the step 4), washing and drying an ethanol/acetic acid mixture to obtain the nanoflowers covalent organic framework composite material, wherein the volume concentration ratio of the ethanol/acetic acid mixture is 98/2.
The technical scheme of the invention is further explained by combining the attached drawings of the specification:
the invention prepares a nano flower type ion covalent organic framework composite material, obtains a novel extraction material through heterogeneous nucleation reaction, selectively enriches the non-steroid anti-inflammatory drug in a water sample through simple solid phase extraction, and has high enrichment efficiency. And then injecting a sample in a high performance liquid chromatography, separating and simultaneously analyzing by using an ultraviolet detector.
Fig. 1 is a schematic diagram of a preparation of a self-made nanoflowers type ionic covalent organic framework composite material, and the specific preparation process is as follows:
1g of triton 100 was dissolved in 30mL of deionized water and stirred for 10min to obtain a homogeneous solution. Another beaker was taken and 30mL of deionized water, 0.564g of stannous chloride hydrate and 0.838g of sodium citrate hydrate were added,stirring for 10min to obtain a clear solution. The two solutions were then mixed and after 5min of further stirring, 0.4mL of tetrapropylammonium hydroxide was added. After stirring the above solution for 10min, 27mL of the solution was transferred to a 50mL autoclave and reacted at 180 ℃ for 5 h. The deposits at the bottom of the reactor were washed 3 times with ethanol and deionized water, respectively. And finally, drying the obtained stannic oxide product in a 60 ℃ oven. 1g SnO by sonication2Dispersed in 180mL of ethanol. A mixture of 300. mu.L of propyltriethoxysilane and 20mL of ethanol was slowly added to the SnO under ultrasonic conditions2In solution. Then, refluxed at 70 ℃ for another 4 hours to make the amino-functionalized tin dioxide (NH)2-SnO2) A surface. The surface-modified particles were washed three times with ethanol and dried under atmospheric air.
In step 1, trimesic aldehyde (TFB,83.98mg) was dissolved in 13mL NH2-SnO2Suspension (100 mgmL)-1Dioxane solution) and stirred at room temperature for 1 hour. Then, bromomethylphenanthridine (DB, 197.70mg) and 200. mu.L acetic acid (3mol L)-1) Is added to the mixture. After 10 minutes of reaction, heterogeneous nuclei were formed and diluted to 50mgmL with dioxane-1. For step 2, trimesic aldehyde (210.6mg) and bromophenanthridine (494.3mg) were dissolved in 13mL heterogeneous nuclear solution (50mg mL), respectively-1) In (1). The two solutions were mixed and 1.17mL of acetic acid and 268.2mg of ibuprofen were added. The reaction mixture was transferred to a 50mL round bottom flask and maintained at reflux at 120 ℃ for 3 hours. The template molecules in the resulting nanocomposite were removed by washing several times with an ethanol/acetic acid mixture (98/2, v/v). Finally, molecularly imprinted covalent organic framework composite (MI-IC-COF @ SnO)2) Drying in the atmosphere.
FIG. 2 is a schematic view of a device for extracting and separating non-steroid anti-inflammatory drugs from a water sample by using a novel nanoflowers type ion covalent organic framework composite material, wherein the process of extracting aromatic amine from the water sample by using the novel nanoflowers type ion covalent organic framework composite material is as follows:
first step, enrichment: 10mg of MI-IC-COF @ SnO2Directly dispersed into 10mL of water sample. The mixture solution was sonicated for 5 minutes, thenCentrifuge at 6400rpm for 4 minutes to separate the two phases. After removal of the supernatant, 0.5mL of methanol containing 1% acetic acid was added and sonicated for 5 minutes to desorb the nsaid from the separated adsorbent. Finally, 25. mu.L of the resulting solution was injected into the HPLC-UV system.
And a second step of analysis: the analysis of the nsaids was performed on the Ultimate 3000HPLC system. Analytes were isolated using a Hypersil GOLD C18 column (250 mm. times.4.6 mm, i.d.5.0 μm) at 40 ℃. A mobile phase consisting of 1% acetic acid buffer solution (A) and methanol (B) was mixed at 1.0mLmin-1And (4) pumping. The gradient program was chosen as follows: 0min, 20% B; 0-4 minutes, 20-80% B; 4-12 minutes, 80% B; 12-20 minutes, 80-20% B. Chromatographic data for the analyte were collected at 225nm, 255nm and 277 nm.
Finally, it should also be noted that the above-mentioned list is only a specific embodiment of the invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible, and all variations that can be derived or suggested by a person skilled in the art from the disclosure of the present invention should be considered as the protection scope of the present invention.
Claims (4)
1. A method for preparing a nanoflower covalent organic framework composite material is characterized in that a low-concentration reaction monomer is added into a suspension solution containing a substrate step by step to generate amorphous heterogeneous cores, then a high-concentration reaction monomer and a catalyst are added, and an aldehyde-amine condensation reaction is carried out under a heating reflux condition to obtain the covalent organic framework composite material, wherein the substrate is aminated tin dioxide, and the specific preparation steps are as follows:
1) dissolving an aldehyde monomer in NH2-SnO2Stirring the mixture at room temperature for reaction in the dioxane suspension;
2) adding another amine monomer and acetic acid serving as a catalyst into the solution obtained in the step 1), and stirring at room temperature for reaction;
3) diluting the solution obtained in the step 2), and adding higher-concentration aldehyde monomers, amine monomers and catalyst acetic acid;
4) heating and refluxing for reaction to generate a coating on the surface of the tin dioxide;
5) centrifugally separating the solid obtained in the step 4), washing the solid with an ethanol/acetic acid mixture, and drying to obtain a nanoflowers type covalent organic framework composite material;
in the step 1), the concentration of the aldehyde monomer in the suspension is 0.04mol L-1The reaction time is 1 hour;
in the step 2), the concentration of the amine monomer in the suspension is 0.06mol L-1The reaction time is 10 minutes;
in the step 3), the concentrations of the aldehyde monomer and the amine monomer in the dioxane solution are respectively 0.05mol L-1And 0.75mol L-1The concentration of the catalyst in the dioxane solution is 3mol L-1；
In the step 4), the reaction time is 3 hours, and the reaction temperature is 120 ℃.
2. The method for preparing a nanofilamented covalent organic framework composite material according to claim 1, wherein in the step 5), the volume concentration ratio of the ethanol/acetic acid mixture is 98/2.
3. The method for preparing nanoflowers covalent organic framework composite materials according to any of claims 1-2, wherein the monomers used for preparation are amine organic compounds containing positive ions.
4. The use of the nanoflowers prepared by the method of preparing the covalent organic framework composites of claims 1-2 to extract and separate non-steroidal anti-inflammatory drugs from water samples.
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| CN106083909A (en) * | 2016-06-24 | 2016-11-09 | 兰州大学 | A kind of preparation method of covalent organic frame material monocrystalline |
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