CN111171369B - Covalent organic framework nanotube and preparation method and application thereof - Google Patents
Covalent organic framework nanotube and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a covalent organic framework nanotube and a preparation method and application thereof. The method uses the silicon dioxide nanowire as a hard template, and can deposit the silicon dioxide nanowire on the surface of materials such as stainless steel wires and the like by soaking and extracting to form a silicon dioxide nanowire film; and taking the dispersed silicon oxide nano-wires or the deposited silicon dioxide nano-wire film as a substrate, growing a COF film in situ, etching the silicon oxide nano-wire template to obtain the dispersed COF nano-tubes and the COF nano-tube film modified stainless steel wires respectively. The abundant micropores of the COF enable the material to have a high specific surface area, and the hollow pipeline structure provides a rapid substance transmission channel for molecules, so that the COF is an ideal separation and enrichment material and can be used for effectively enriching trace organic pollutants in a solution. The stainless steel wire modified by the COF nanotube film can be used as a stainless steel wire solid phase micro-extraction head and is used as a pretreatment material for quantitative enrichment and purification of hazardous substances.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a Covalent Organic Framework (COF) nanotube and a preparation method and application thereof.
Background
Covalent organic framework materials (COFs) are organic porous materials with periodic network structures and connected by covalent bonds, and have uniform pore channel structures. The material is prepared by reversible reaction synthesis under thermodynamic control, and can accurately control the structural properties such as geometric structure, aperture, three-dimensional orientation and the like of the material1COFs have various structures2Low density of3High specific surface area4And excellent thermal and chemical stability5And permanent void fraction6It can be used in water or organic solvent. COFs have attracted extensive attention at present due to their superior properties and are used in separations7And enriching the mixture8Catalysis, the9Energy storage and transportation10And sensing11And so on in a number of areas. COFs have wide application in the field of separation and enrichment, but mainly focus on preparing 2D sheet materials12Magnetic composite material13And a film14And the like. However, the COFs materials synthesized by the conventional laboratory method are all polycrystalline powder, a continuous and uniform COFs film cannot be obtained, and the polycrystalline powder of the COFs materials is difficult to dissolve and disperse, so that the COFs materials have insufficient film forming stability by the conventional methods of suspension coating, solvent volatilization and the like15。
The invention uses silicon dioxide nanometer line and nanometer line film as template, and grows COF nanometer tube and nanometer tube film, which has good film forming property and stable mechanical property, and can be used to separate and enrich various organic pollutants (such as DDT). DDT is also called dichlorodiphenyltrichloroethane, has a chemical name of bis-p-chlorophenyltrichloroethane, is widely used in pesticides, can migrate for a long distance through various environmental media (air, water, organisms and the like) and exist in the environment for a long time, has long-term residue, biological accumulation, semi-volatility and high carcinogenicity, and has serious harm to human health and environment. Because DDT has low molecular weight, a benzene ring structure and extremely strong hydrophobicity, the DDT has high affinity with COFs materials, and therefore, the COFs tube and film which have high specific surface area and can be recycled can provide enough contact area and contact sites for the enrichment of DDT so as to improve the enrichment efficiency of DDT, and meanwhile, the DDT can adapt to various different experimental conditions and can be recycled. The preparation method can be used for regulating and controlling the adsorption performance of the COFs tube membrane material by preparing different COFs materials and regulating and controlling the thickness of the COF tube wall, thereby having wide application prospect in the field of organic pollutant separation and enrichment.
Reference to the literature
1.G. Zhang, M. Tsujimoto, D. Packwood, N. T. Dong, Y. Nishiyama, K. Kadota, S. Kitagawa and S. Horike,J. Am. Chem. S0℃., 2018, 140, 2602-2609.
2.Z. F. Pang, T. Y. Zhou, R. R. Liang, Q. Y. Qi and X. Zhao,Chem. Sci., 2017, 8, 3866-3870.
3.C. S. Diercks and O. M. Yaghi, Science, 2017, 355, eaal1585.
4.J. Zhang, X. Han, X. W. Wu, Y. Liu and Y. Cui, J. Am. Chem.S0℃., 2017, 139, 8277-8285.
5.Q. R. Fang, Z. B. Zhuang, S. Gu, R. B. Kaspar, J. Zheng, J. H. Wang, S. L. Qiu and Y. S. Yan, Nat. Commun., 2014,5, 4503.
6.H. Xu, S. S. Tao and D. L. Jiang, Nat. Mater., 2016, 15,722-726.
7.H. L. Qian, C. X. Yang and X. P. Yan, Nat. Commun., 2016, 7, 12104.
8.Y. F. Zeng, R. Y. Zou, Z. Luo, H. C. Zhang, X. Yao, X. Ma,R. Q. Zou and Y. L. Zhao, J. Am. Chem. S0℃., 2015, 137, 1020-1023.
9.S. Lin, C. S. Diercks, Y. B. Zhang, N. Kornienko,E. M. Nichols, Y. B. Zhao, A. R. Paris, D. Kim, P. Yang,O. M. Yaghi and C. J. Chang, Science, 2015, 349, 1208-1213.
10.J. H. Sun, A. Klechikov, C. Moise, M. Prodana,M. Enachescu and A. V. Talyzin, Angew. Chem., Int. Ed.,2018, 57, 1034-1038.
11.S. Dalapati, S. B. Jin, J. Gao, Y. H. Xu, A. Nagai andD. L. Jiang, J. Am. Chem. S0℃., 2013, 135, 17310-17313.
12.Kunh.P, Kruger. K,Thomas. A,et a1. Chem. Commun.,2008,44, 5815-5817.
13.W. Zhang, F.Liang,C. Li,et a1.J. Hazard. Mater.,2011,86, 984-990.
14.H. Lu,C. Wang,J. Chen,Chem. Commun.,2015,51, 15562-15565.
15.A novel reverse osmosis membrane with PAMAM/TMC for effective oily salinewaterseparation,AIChE Annual Meeting, Oral Presentation, Salt Lake City, USA, 2015.。
Disclosure of Invention
The invention aims to provide a Covalent Organic Framework (COF) nanotube with good film-forming performance and stable mechanical performance, and a preparation method and application thereof.
According to the preparation method of the Covalent Organic Framework (COF) nanotube, a silicon dioxide nanowire is used as a removable template to grow the COF; and depositing the silicon dioxide nanowires on the surface of the stainless steel wire, growing COF in situ by taking the silicon dioxide nanowires as a substrate, and etching off the silicon oxide nanowire template to obtain the COF nanotubes and the COF nanotube film-modified stainless steel wire respectively. The COF nanotube and the stainless steel wire modified by the nanotube film can be used as a solid phase microextraction head of the stainless steel wire and a pretreatment material for quantitatively enriching and purifying hazardous substances.
The preparation method of the Covalent Organic Framework (COF) nanotube provided by the invention comprises the following specific steps:
(1) mixing Aminopropylsilane (APTES) modified silicon dioxide nanowires, ternary aldehyde, glacial acetic acid and dioxane in a certain proportion, and performing high-temperature tube sealing reaction; obtaining a ternary aldehyde modified silicon dioxide nanowire; wherein:
the ternary aldehyde is one of trialdehyde phloroglucinol and mesitylene formaldehyde;
the mass ratio of the APTES modified silicon dioxide nanowire to the ternary aldehyde is 1: (0.1-10);
the mass ratio of the APTES modified silicon dioxide nanowire to the glacial acetic acid is 1: (1-10);
the mass ratio of the APTES modified silicon dioxide nanowire to the dioxane is 1: (10-1000);
the reaction temperature of the sealed tube is 100-200 ℃, and the reaction time of the sealed tube is 1-3 hours;
(2) mixing the ternary aldehyde modified silicon dioxide nanowire obtained in the step (1), ternary aldehyde, benzidine, glacial acetic acid and dioxane in a certain proportion, and carrying out high-temperature tube sealing reaction; obtaining a COF nanotube film; wherein:
the ternary aldehyde is one of trialdehyde phloroglucinol and mesitylene formaldehyde;
the benzidine is one of 3,3 '-dimethylbenzidine and 3,3' -diethylbenzidine, and 2,2 '-dimethylbenzidine and 2,2' -diethylbenzidine;
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the ternary aldehyde is 1: (0.01-5);
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the benzidine is 1: (0.01-5);
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the glacial acetic acid is 1: (0.01-10);
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the dioxane is 1: (10-1000)
The tube sealing reaction temperature is 100-200 ℃, and the tube sealing reaction time is 72-96 hours;
(3) etching away the silicon dioxide nanowire template in the silicon oxide/COF composite nanowire obtained in the step (3) by using hydrofluoric acid (HF) or sodium hydroxide solution to obtain a hollow Covalent Organic Framework (COF) nanotube; wherein:
the concentration of the hydrofluoric acid (HF) or sodium hydroxide solution is 1-5M; the treatment time of hydrofluoric acid (HF) or sodium hydroxide solution is 10-30 minutes.
In the present invention, the thickness of the COF tube film is controlled by the variation in the thickness of the silicon oxide nanowire film as a template.
In the invention, the reaction temperature of the sealed tube is 100-200 ℃, and nitrogen or inert gas is used for protection.
In the invention, before the step (1), APTES modified silicon dioxide nanowires can be deposited on stainless steel wires by a 'soaking-taking-out' method, wherein the stainless steel wires are pretreated by hydrofluoric acid (HF) solution (the concentration of the hydrofluoric acid solution is 1-5M; the treatment time of the hydrofluoric acid solution is 10-20 minutes), and are solidified by tetrabutyl titanate; then, the stainless steel wire is placed in the solution statically, a COF film is grown on the silicon oxide nanowire film in situ, and the COF nanotube film can be obtained after the silicon oxide nanowire film template is etched away. Then, the operations of the steps (1), (2) and (3) are carried out.
The Covalent Organic Framework (COF) nanotube obtained by the preparation method of the COF tube provided by the invention has a hollow tubular structure with a large number of micropores, 1-2 nanometer micropores, macropores with the size of about 80 nm are generated after the nanowires are removed, and the specific surface area of the COF tube can reach 900 m2Has good adsorption performance per gram. Is an ideal separation and enrichment material and can be used as a pretreatment material for quantitative enrichment and purification of hazardous substances. The specific method is as follows.
Flowing a sample to be detected containing DDT through a COF tube film, so that low-concentration DDT in the solution can be enriched; with acetone/n-hexane = 1: 3 may elute the adsorbed DTT.
The material has particularly strong affinity to hydrophobic pollutants, particularly aromatic substances, 100% of equilibrium adsorption can be achieved in 1 minute under 10% of loading capacity, 100% of equilibrium adsorption can be achieved in 5 minutes under 60% of loading capacity, the limit loading capacity can be 800 mg/g, more than 90% of enrichment absorption can be achieved on a sample with DDT concentration of 10 mug/L, the material can be recycled for many times after adsorbed molecules are desorbed, and the recycling rate can be more than 85%.
The method has simple process and safe operation, and is easy for industrial scale-up production.
Drawings
Fig. 1 is a transmission electron micrograph of COF tube films at different stages. Wherein, (a) is a transmission electron microscope image of the silicon oxide nanowire; (b) a transmission electron microscope image of the COF modified silicon oxide nanowire is shown; (c) a transmission electron microscope image of the COF tube with the silicon oxide template removed is shown; (d) is a transmission electron microscope picture of a COF nanotube film wrapped on a stainless steel wire. The thickness of the COF tube film can be controlled with the variation of the thickness of the silicon oxide nanowire film used as the template.
FIG. 2 shows XRD diffraction pattern and infrared spectrum of the material prepared by the present invention. Wherein (a) is XRD diffraction patterns of silicon oxide Nanowires (NW) and COF modified silicon oxide nanowires (NW-COF), and a characteristic peak of crystal lattice at low-angle COF can be obviously seen in reference to amorphous NW; (b) the infrared spectra of silicon oxide nanowires, Aminopropylsilane (APTES) modified silicon dioxide nanowires (NW-APTES), COF modified silicon oxide nanowires (NW-COF) and COF tubes, wherein the COF has characteristic benzene ring C = C peak and amine C-N peak, and the silicon oxide nanowires have characteristic Si-O peak.
FIG. 3 is N of the material of the present invention2Adsorption-desorption curve diagram and pore volume-pore diameter curve diagram. Wherein (a) is N of COF tube2And (b) is a pore volume-pore diameter curve chart of the COF tube, and the material pore channel is mainly COF micropores with the diameter of 1-2 nm.
FIG. 4 is a graph of the performance of the material of the present invention. Wherein (a) is an adsorption-time curve graph and a desorption-time curve graph of a COF modified silicon oxide nanowire (NW-COF) and a COF tube. Dispersing 1mg of material in 10 ml of deionized water, adding 10,30 and 60 mug/ml of DDT (load amount is 10,30 percent and 60 percent) respectively, shaking at room temperature, centrifuging for 5min, 30 min, 1 h and 2 h respectively, and taking supernatant to measure the material adsorption value through GC-MS; (b) desorption-time profiles for COF modified silicon oxide nanowires (NW-COF) and COF tubes. 1mg of DDT-adsorbed material was purified with acetone/n-hexane = 1: and 3, eluting with the mixed solvent, centrifuging at different times, taking out desorption liquid, and measuring the desorption value of the material by using GC-MS.
FIG. 5 is a graph of the performance of the material of the present invention in adsorbing DDT. Wherein (a) is an adsorption capacity isotherm diagram of a COF tube on DDT, namely the COF tube has the enrichment effect on DDT with different concentrations (1-20 mug/L), the COF tube material is 1mg, the enrichment volume is 100ml, and the adsorption efficiency is the ratio of the loading amount of the material on the DDT to the DDT content of a sample; (b) the cycle recovery rate under multiple use of the COF tube is shown.
Detailed Description
The invention will be further explained with reference to the drawings and examples, which will be better understood. Wherein the given figures 1, 2, 3 are the results of example 1 and example 2.
Example 1: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The obtained COF tube was dispersed in acetone to prepare a 0.001 g/mL solution, and a COF tube self-assembled film was prepared by suction filtration using a sand core suction filtration funnel having a diameter of 0.5 cm.
Example 2: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate was removed after 5 minutes of soaking in 5M HF to form a hollow COF tube. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 3: the method comprises the following steps of (1) carrying out APTES modified silicon dioxide nanowire treatment on trimesic aldehyde, glacial acetic acid and dioxane in a ratio of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing the silicon dioxide nanowire modified by the trimesic aldehyde with the trimesic aldehyde, 3,3' -dimethylbenzidine, glacial acetic acid and dioxane in a ratio of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 4: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -diethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 5: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 2,2' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 6: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 7: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 2,2' -diethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 8: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 0.2: 2: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 0.1: 0.15: 0.5: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 9: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 0.4: 4: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 0.2: 0.3: 1: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 10: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 0.8: 8: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 0.4: 0.6: 2: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. The obtained COF tube was dispersed in acetone to prepare a 0.001 g/mL solution, and the COF nanotube self-assembled film was prepared by suction filtration using a sand core suction filtration funnel having a diameter of 0.5 cm.
Example 11: the method comprises the following steps of mixing APTES modified silicon dioxide nanowires, trialdehyde phloroglucinol, glacial acetic acid and dioxane in a proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 0.8: 1.2: 2: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 72 hours, and washing the mixture with acetone and methanol once. The silicon dioxide substrate can be removed after soaking in 5M HF for 5 minutes, and a hollow COF pipe can be formed. And dispersing the obtained COF tube in acetone to prepare 0.001 g/mL solution, and performing suction filtration by using a sand core suction filtration funnel with the diameter of 0.5 cm to prepare the COF nanotube self-assembled film.
Example 12: through a soaking-extracting method, the APTES modified silicon dioxide nanowires are deposited on the surfaces of stainless steel wires and other materials, and the stainless steel wire substrate wrapped by the silicon oxide nanowire film is obtained. And standing the steel wire in the solution, growing a COF film on the deposited silicon oxide nanowire film in situ, and etching the silicon oxide nanowire film template to obtain the COF nanotube film. The APTES modified silicon dioxide nanowire, trialdehyde phloroglucinol, glacial acetic acid and dioxane which are treated in the proportion of 1: 1: 10: 1000, sealing the tube at 130 ℃ under inert atmosphere for reaction for 1 hour, and washing with tetrahydrofuran and dioxane once respectively. Dispersing the material in dioxane, mixing silica nanometer line modified by trialdehyde phloroglucinol with trialdehyde phloroglucinol, 3,3' -dimethyl benzidine, glacial acetic acid, and dioxane in the proportion of 1: 1: 1.5: 5: 1000, sealing the tube at 130 ℃ under an inert atmosphere for reaction for 72 hours, washing the mixture with acetone and methanol once, and then soaking the mixture in 5M HF for 5 minutes to remove the silicon dioxide substrate.
Adsorption Performance test
The COF modified silicon oxide nanowire (NW-COF) prepared in example 1 and the COF tube prepared in example 2 were respectively taken and dispersed in 10 ml of deionized water, wherein the deionized water contains 10,30 and 60 mu g/ml of DDT (corresponding to the loading amount of the DDT in the COF being 10,30 and 60%), the materials were shaken at room temperature, the adsorption value of the materials on the DTT was measured by GC-MS after centrifugation at 5min, 30 min, 1 h and 2 h, and the supernatant was dried at 60 ℃ and then dissolved in acetone. The DDT-adsorbing material obtained above was purified by distillation using acetone/n-hexane = 1: 3, eluting with the mixed solvent, dispersing the material in the eluent, oscillating at room temperature, centrifuging according to different time, taking the eluent, and measuring the desorption value by GC-MS. The GC-MS analysis conditions were as follows, column: capillary column DB-1701 (30 m 0.32mm 0.25 μm); carrier gas: high-purity nitrogen with purity of 99.999 percent and 30 ml/min; the column temperature adopts programmed temperature rise, firstly 60 ℃ is kept for 2min, then the temperature is raised to 180 ℃ at the speed of 20 ℃/min, then the temperature is kept for 7min, then the temperature is raised to 230 ℃ at the speed of 10 ℃/min, then the temperature is kept for 4min, then the temperature is raised to 270 ℃ at the speed of 20 ℃/min, and then the column flow rate is kept for 5 min: 3ml/min, constant pressure; sample inlet temperature: 250 ℃; a detector: an ECD; detector temperature: 300 ℃; sample introduction amount: 1 mul. The results are shown in FIG. 4.
And (3) respectively taking 1mg of the COF modified silicon oxide nanowire (NW-COF) prepared in example 1 and the COF tube prepared in example 2, performing suction filtration to form a film, simulating an organic pollutant residual sample by using 100ml of DDT solution with the concentration of 1-20 mug/L, enabling the DDT solution to pass through the film material, and measuring the content of DDT in the filtrate at the flow rate of 5ml/min to obtain a material adsorption value. And (3) eluting the membrane material by using 50ml of n-hexane eluent at the flow rate of 5ml/min, measuring the content of DDT in the n-hexane eluent, and calculating the recovery rate of the material after each use by using the desorption/adsorption = the recovery rate. The measurement is carried out by repeating the cycle for 1 to 10 times according to the scheme, and the result is shown in figure 5.
Claims (4)
1. A preparation method of a covalent organic framework nanotube is characterized by comprising the following specific steps:
(1) mixing APTES modified silicon dioxide nanowires, ternary aldehyde, glacial acetic acid and dioxane in a certain proportion, and carrying out high-temperature tube sealing reaction; obtaining a ternary aldehyde modified silicon dioxide nanowire; wherein:
the ternary aldehyde is one of trialdehyde phloroglucinol and mesitylene formaldehyde;
the mass ratio of the APTES modified silicon dioxide nanowire to the ternary aldehyde is 1: (0.1-10);
the mass ratio of the APTES modified silicon dioxide nanowire to the glacial acetic acid is 1: (1-10);
the mass ratio of the APTES modified silicon dioxide nanowire to the dioxane is 1: (10-1000);
the reaction temperature of the sealed tube is 100-200 ℃, and the reaction time of the sealed tube is 1-3 hours;
(2) mixing the ternary aldehyde modified silicon dioxide nanowire obtained in the step (1), ternary aldehyde, benzidine, glacial acetic acid and dioxane in a certain proportion, and carrying out high-temperature tube sealing reaction; obtaining a COF nanotube film; wherein:
the ternary aldehyde is one of trialdehyde phloroglucinol and mesitylene formaldehyde;
the benzidine is one of 3,3 '-dimethylbenzidine and 3,3' -diethylbenzidine, and 2,2 '-dimethylbenzidine and 2,2' -diethylbenzidine;
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the ternary aldehyde is 1: (0.01-5);
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the benzidine is 1: (0.01-5);
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the glacial acetic acid is 1: (0.01-10);
the mass ratio of the ternary aldehyde modified silicon dioxide nanowire to the dioxane is 1: (10-1000);
the reaction temperature of the sealed tube is 100-200 ℃; the tube sealing reaction time is 72-96 hours;
(3) etching away the silicon dioxide nanowire template in the COF nanotube film obtained in the step (2) by using hydrofluoric acid or sodium hydroxide solution to obtain a hollow covalent organic framework nanotube; wherein:
the concentration of the hydrofluoric acid or sodium hydroxide solution is 1-5M; the treatment time of hydrofluoric acid or sodium hydroxide solution is 10-30 minutes.
2. The method of claim 1, wherein the temperature of the tube sealing reaction is 100-200 ℃ and is protected with nitrogen.
3. The covalent organic framework nanotube obtained by the preparation method of claim 1 or 2 is a hollow tubular structure with a large number of micropores and a specific surface area of 900 m2Has good adsorption performance per gram.
4. Use of the covalent organic framework nanotubes of claim 3 as pretreatment materials for quantitative enrichment and purification of hazardous substances.
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