CN116024813A - Preparation method of pyrenyl COF composite fiber and application of photocatalysis antibacterial and mustard gas degradation simulator - Google Patents
Preparation method of pyrenyl COF composite fiber and application of photocatalysis antibacterial and mustard gas degradation simulator Download PDFInfo
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Images
Abstract
The invention discloses a preparation method of pyrenyl COF composite fiber and application of a photocatalytic antibacterial and mustard degrading simulator, wherein 1,3,6, 8-tetra (4' -aldehyde benzene) pyrene and 2, 6-diaminoanthracene are utilized to synthesize a stable COF connected with two-dimensional imine bonds through a solvothermal method, the COF is loaded on modified non-woven fabrics grafted with acrylic acid through photoinitiated radiation, and carboxyl of the acrylic acid and amino in the COF are utilized to perform an amide reaction to prepare the COF composite fiber with strong visible light absorption, and the COF composite fiber has high photocatalytic activity on gram-positive bacillus subtilis and gram-negative escherichia coli with the antibacterial rate of more than 99% under visible light and on detoxification of sulfur mustard simulants; the degradation rate to 2-CEES remains unchanged by more than 99% after at least 5 cycles of decontamination cycle. The fabric has great application potential in the aspect of biochemical protection.
Description
Technical Field
The invention relates to the field of composite fiber material products, in particular to a preparation method of pyrenyl COF composite fibers and application of a photocatalytic antibacterial and mustard degrading simulator.
Background
With TiO 2 The photocatalysis technology based on the materials shows good elimination effect in biological anti/antibacterial antiviral activity and chemical toxin disinfection, but TiO 2 The problems of narrow absorption spectrum light, poor performance under visible light and the like exist, and the method is difficult to adapt to the rapid and efficient elimination of biochemical poison toxins in various environments. The key point of research is to develop a novel photocatalytic system, which is more and more paid attention to as a novel photocatalyst with design flexibility, compared with other materials, covalent organic framework materials (Covalent Organic Framework, COF) which have the characteristics of precisely controllable structure and compositionSo that the catalyst can be used in various environments and has been shown to be very high in photocatalytic degradation of various biochemical pollutants. By means of excellent sterilizing and disinfecting performances of the COF material, the COF material is compounded with materials such as fiber and the like, and the prepared protective clothing and mask fabric have great application potential in the aspect of biochemical protection.
Disclosure of Invention
The invention provides a preparation method of pyrenyl COF composite fiber and application of photocatalysis antibacterial and degradation mustard gas simulator, the pyrenyl COF of the invention has flexible design, high stability and simple operation of grafting to fiber materials, the COF composite fiber of the invention has the antibacterial rate of more than 99 percent to gram positive bacillus subtilis and gram negative escherichia coli under simulated sunlight in illumination for 60min, has the photocatalysis activity of rapidly degrading mustard gas simulator 2-CEES into nontoxic sulfoxide compound, and the photocatalytic oxidation of the mustard gas simulator 2-CEES into nontoxic sulfoxide compound CEESO in 4 h, wherein the degradation rate is more than 99 percent and half-life t 1/2 Less than or equal to 90 min; the degradation rate of the COF composite fiber to 2-CEES is still kept to be more than 99% stable after at least 5 periods of photocatalytic decontamination. The COF composite fiber material has good application progress in the aspects of photocatalysis elimination of biochemical toxicants and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of pyrenyl COF composite fiber, which comprises the following steps of;
1) Washing the non-woven fabric fiber with acetone and NaOH solution to remove surface impurities and oily substances, washing the non-woven fabric fiber with clear water for multiple times, drying the non-woven fabric fiber for later use, weighing 0.3 g benzophenone, dissolving the benzophenone in 20 mL absolute ethyl alcohol, adding 100 mL of 40 volume percent acrylic acid monomer aqueous solution, uniformly stirring the mixture at 25-35 ℃, and then adding the non-woven fabric fiber to dip the non-woven fabric fiber at the temperature for 0.5-1 h;
2) Taking out the impregnated non-woven fabric fibers, draining liquid, placing the non-woven fabric fibers under a 365 nm ultraviolet lamp, radiating the front and back surfaces by 0.5 h respectively, then taking out the non-woven fabric fibers, ultrasonically cleaning the non-woven fabric fibers in absolute ethyl alcohol, washing the non-woven fabric fibers for multiple times by using clear water, and drying the non-woven fabric fibers for later use;
3) Adding 20.4 mg of 1,3,6, 8-tetra (4' -aldehyde benzene) pyrene and 13.8mg of 2, 6-diaminoanthracene or 2, 6-diaminoanthraquinone into a 5 mL glass tube, adding mixed solution of o-dichlorobenzene and ethanol, carrying out ultrasonic treatment on the suspension at room temperature until the monomers are completely dispersed, then adding catalyst glacial acetic acid, carrying out ultrasonic treatment for 5 minutes, freezing the solution in a liquid nitrogen bath, vacuumizing, thawing in a water bath, repeatedly freezing, vacuumizing and thawing for three times, carrying out flame sealing on the glass tube, and then placing the glass tube into an oven for reaction at 120 ℃ for 3 days;
4) Extracting the solid obtained in the step 3) with tetrahydrofuran and acetone Soxhlet respectively to obtain 12 h, and activating the 12 h in a vacuum drying oven at 70 ℃ to obtain COF reddish brown powder;
5) Dispersing COF powder in an ethanol solvent, carrying out ultrasonic treatment at room temperature until the dispersion is uniform, immersing the acrylic acid grafted non-woven fabric fiber obtained in the step 2) in the ethanol solvent, and immersing the non-woven fabric fiber at room temperature for 24 h; taking out, washing with absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 70 ℃ to obtain the pyrenyl COF composite fiber material.
Further, the non-woven fabric fibers in the step 1) are made of polypropylene, polyacrylonitrile, polyamide and PET fiber materials.
Further, the nonwoven fabric in the step 1) is cut into a size of 5×5 cm, the concentration of benzophenone is 2.5 g/L, the volume ratio of acrylic acid to deionized water=4:6, and the concentration of NaOH solution is 0.1 mol/L.
Further, the ultraviolet lamp wavelength in step 2) is 365 and nm.
Further, in the step 3), the amount of the mixed solution of o-dichlorobenzene and ethanol is 1mL, the volume ratio of o-dichlorobenzene to ethanol=0.4:0.1, and the amount of glacial acetic acid catalyst is 0.1mL.
Further, the concentration of COF in step 5) was 1 mg/mL.
Application: the pyrenyl COF composite fiber material is used for preparing protective clothing and mask fabrics in photocatalysis antibacterial and mustard gas degradation simulators.
The pyrenyl COF material prepared by the invention has the following structure:
the beneficial effects of the invention are as follows:
the invention utilizes 1,3,6, 8-tetra (4' -aldehyde benzene) pyrene and 2, 6-diaminoanthracene to synthesize stable two-dimensional imine bond-connected DA-Py-COF through a solvothermal method, the COF is loaded on modified non-woven fabric fiber grafted with acrylic acid through photoinitiated radiation, carboxyl of the acrylic acid and amino in the COF are utilized to carry out amide reaction to prepare the COF composite fiber with strong visible light absorption, experiments prove that the COF composite fiber of the invention has good photocatalytic activity to gram positive bacillus subtilis and gram negative escherichia coli with the antibacterial rate reaching more than 99% in 60min of illumination and to detoxification of sulfur mustard simulant, the degradation rate is more than 99% and the half life of the COF composite fiber is t, and the mustard simulator 2-CEES is photo-catalyzed and oxidized into CEESO in 4 h 1/2 Less than or equal to 90 min; the degradation rate of the COF composite fiber to 2-CEES is still kept to be more than 99% stable after at least 5 periods of photocatalytic decontamination. The COF composite fiber material has great application potential in the aspect of biochemical protection of protective clothing and gauze mask fabrics.
Drawings
FIG. 1 is an XRD and ultraviolet spectrum of COF powder;
fig. 2 (a) is a drawing of a modified polypropylene nonwoven fabric; (b) is a COF composite fiber map;
FIG. 3 is an experimental diagram of the antibacterial effect of COF composite fiber on Escherichia coli;
FIG. 4 is an experimental diagram of the antibacterial condition of COF composite fiber against Bacillus subtilis;
FIG. 5 is a graph of activity of COF composite fiber degrading mustard simulator;
FIG. 6 shows that the degradation rate of COF composite fiber after 5 cycles of degrading mustard gas simulator remains more than 99% stable.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
1) Washing polypropylene non-woven fabric with acetone and NaOH solution successively to remove surface impurities and oily substances, washing the non-woven fabric with clear water for multiple times, drying the non-woven fabric for later use, weighing 0.3 g benzophenone, dissolving the benzophenone in 20 mL absolute ethyl alcohol, stirring and dissolving the benzophenone, then adding 100 mL of 40 volume percent of aqueous solution of acrylic acid monomer, stirring the mixture uniformly at 25 ℃, and then adding the polypropylene non-woven fabric to dip 0.5 h at the temperature;
2) Taking out the impregnated non-woven fabric, draining liquid, placing the non-woven fabric under a 365 nm ultraviolet lamp, radiating the front and back surfaces by 0.5 h respectively, then taking out the non-woven fabric, ultrasonically cleaning the non-woven fabric in absolute ethyl alcohol, washing the non-woven fabric for a plurality of times by using clear water, and drying the non-woven fabric for later use;
3) 20.4 mg of 1,3,6, 8-tetra (4' -aldehyde benzene) pyrene and 13.8mg of 2, 6-diaminoanthracene are added into a 5 mL glass tube, 0.8 mL o-dichlorobenzene and 0.2 mL ethanol are added, the suspension is subjected to ultrasonic treatment at room temperature until the monomers are completely dispersed, then 0.1mL glacial acetic acid is added, ultrasonic treatment is carried out for 5 minutes, a liquid nitrogen bath is used for freezing the solution, then vacuum pumping is carried out, then water bath thawing is carried out, freezing-vacuumizing-thawing is repeated three times, the glass tube is subjected to flame sealing, and then the glass tube is placed into an oven for reaction at 120 ℃ for 3 d;
4) Extracting the solid obtained in the step 3) with tetrahydrofuran and acetone Soxhlet respectively to obtain 12 h, and activating the 12 h in a vacuum drying oven at 70 ℃ to obtain COF reddish brown powder;
as shown in FIG. 1, the XRD pattern shows that the COF powder has better crystallinity at 3.26 degrees by a stronger diffraction peak, and the ultraviolet spectrum shows that the COF powder has strong and wide light absorption in the ultraviolet-visible light range (200-800 nm) and near infrared.
5) Dispersing COF powder in an ethanol solvent at a concentration of 1 mg/mL, carrying out ultrasonic treatment at room temperature until the dispersion is uniform, immersing the acrylic-grafted polypropylene non-woven fabric fiber obtained in the step 2) in the ethanol solvent, immersing the non-woven fabric fiber for 24 hours at room temperature, washing the non-woven fabric fiber with absolute ethyl alcohol for 3 times, and drying the non-woven fabric fiber in a vacuum drying oven at 70 ℃ to obtain the pyrenyl COF composite fiber material (figure 2).
Example 2 antibacterial test of COF composite fiber
The method comprises the steps of recovering and passaging bacillus subtilis and escherichia coli (the third generation strains are used in the invention), respectively taking a certain amount of bacillus subtilis and escherichia coli, putting the bacillus subtilis and escherichia coli into respective liquid culture mediums (the bacillus subtilis and escherichia coli are cultured by nutrient agar), culturing the bacillus subtilis and escherichia coli in an incubator for 18 h, measuring the OD value of the corresponding strains by an enzyme-labeling instrument, then respectively taking 1mL bacteria liquid, putting the bacteria liquid into a glass test tube filled with 9 mL sterile water, diluting the bacteria liquid to a proper bacteria liquid concentration by a 10-fold dilution method, cutting the COF composite fiber to the right size, putting the COF composite fiber into a 24-pore plate, respectively taking the bacteria liquid 1mL with proper times to illuminate the 24-pore plate at the bottom, respectively illuminating the liquid for 0min, illuminating for 10 min, illuminating for 30 min, illuminating for 60min, taking 100 mu L, coating the liquid onto a solid culture medium, culturing the liquid in the incubator for 24 h, and observing photographing records, and the conditions under blank control and dark conditions.
As shown in fig. 3 and 4, the antibacterial rate of the COF composite fiber provided by the invention on gram-positive bacillus subtilis and gram-negative escherichia coli under simulated sunlight can reach more than 99% within 60 min.
Example 3 degradation mustard simulator test of COF composite fiber
After 200 mL deionized water and 20. Mu.L of mustard simulator (2-CEES) were added to the reactor, the mustard simulator was uniformly dispersed on a magnetic stirrer, and 2.5. 2.5 mL samples were taken. Then, the composite fiber loaded with 10 mg of COF is immersed in a reactor, and is placed in an ultrasonic device for ultrasonic treatment until the catalyst is uniformly dispersed in the solution, and then the reactor is placed on a magnetic stirrer for stirring so as to carry out adsorption balance. After 1 hour, 2.5. 2.5 mL liquid was taken out with a syringe to ensure adsorption equilibrium. Placing a xenon lamp to make the illumination of the xenon lamp be full-wave band, sampling 2.5 mL every 4 th h, filtering the catalyst in the solution by using an organic filter head, taking the solution filtered by 2 mL, and adding 3 mL chromatographic pure dichloromethane into all the solutions to be detected for extraction. Shaking and vibrating to uniformly mix the materials, standing, layering, taking down the liquid layer by using a syringe, and detecting the residual reaction product by using high performance liquid chromatography.
Example 4 COF Complex fiber degradation mustard simulator decontamination cycle test
After carrying out a degradation experiment on the COF composite fiber for photocatalytic degradation of 2-CEES, carrying out a large amount of deionized water to wash the COF composite fiber subjected to the degradation experiment to remove undegraded 2-CEES and CEESO, drying in an oven, detecting the residual reaction product by using high performance liquid chromatography according to the method of embodiment 3, and repeatedly using for 5 times.
As shown in FIG. 5, COF composite fiber degrading mustard simulator, 2-CEES was converted to CEESO in 4 hours, with conversion greater than 99%, half-life t 1/2 Less than or equal to 90 min; the degradation rate to 2-CEES remained unchanged for more than 99% after at least 5 cycles of photocatalytic decontamination of COF composite fibers (fig. 6).
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. The preparation method of the pyrenyl COF composite fiber is characterized by comprising the following steps of;
1) Washing non-woven fabric fibers with acetone and NaOH solution successively to remove surface impurities, washing the non-woven fabric fibers with clear water for multiple times, drying the non-woven fabric fibers for later use, weighing a certain amount of benzophenone, dissolving the benzophenone in 20 mL absolute ethyl alcohol, adding 40% acrylic acid aqueous solution 100 mL in volume percent concentration, stirring the mixture at 25-35 ℃, and adding the non-woven fabric fibers to impregnate the non-woven fabric fibers at the temperature of 0.5-1 h;
2) Taking out the impregnated non-woven fabric fibers, draining liquid, and then placing the non-woven fabric fibers under an ultraviolet lamp, wherein the front side and the back side of the non-woven fabric fibers are respectively irradiated by 0.5 to h; then taking out the mixture from absolute ethyl alcohol, ultrasonically cleaning the mixture, washing the mixture for a plurality of times by clear water, and drying the mixture for later use;
3) Adding 20.4 mg of 1,3,6, 8-tetra (4' -aldehyde benzene) pyrene and 13.8mg of amino compound into a glass tube, adding a mixed solution of o-dichlorobenzene and ethanol, carrying out ultrasonic treatment on the suspension at room temperature until the monomers are completely dispersed, then adding anhydrous acetic acid serving as a catalyst, carrying out ultrasonic treatment for 5 minutes, freezing the solution in a liquid nitrogen bath, vacuumizing, thawing in a water bath, repeating for three times, carrying out flame sealing on the glass tube, and then placing the glass tube into an oven for reaction at 120 ℃ for 3 days;
4) Extracting the solid obtained in the step 3) with tetrahydrofuran and acetone Soxhlet respectively for 12 hours, and drying in a vacuum drying oven at 70 ℃ for 12 h to obtain COF reddish brown powder;
5) Dispersing the obtained COF powder in an ethanol solvent, carrying out ultrasonic treatment at room temperature until the dispersion is uniform, immersing the non-woven fabric fiber grafted with acrylic acid, which is obtained in the step 2), into the non-woven fabric fiber, immersing the non-woven fabric fiber at room temperature for 24 hours, washing the non-woven fabric fiber with absolute ethyl alcohol for 3 times, and drying the non-woven fabric fiber in a vacuum drying oven at 70 ℃ to obtain the pyrenyl COF composite fiber.
2. The method for preparing pyrenyl COF composite fiber according to claim 1, wherein: the non-woven fabric fibers in the step 1) are made of polypropylene, polyacrylonitrile, polyamide and PET fiber materials.
3. The method for preparing pyrenyl COF composite fiber according to claim 1, wherein: the amount of benzophenone in step 1) was 0.3. 0.3 g.
4. The method for preparing pyrenyl COF composite fiber according to claim 1, wherein: the ultraviolet lamp wavelength in step 2) was 365 and nm.
5. The method for preparing pyrenyl COF composite fiber according to claim 1, wherein: the dosage of the mixed solution of the o-dichlorobenzene and the ethanol in the step 3) is 1mL, the volume ratio of the o-dichlorobenzene to the ethanol is 0.4:0.1, and the dosage of the anhydrous acetic acid serving as a catalyst is 0.1mL.
6. The method for preparing pyrenyl COF composite fiber according to claim 1, wherein: the amino compound in the step 3) is 2, 6-diaminoanthracene or 2, 6-diaminoanthraquinone.
7. The method for preparing pyrenyl COF composite fiber according to claim 1, wherein: the concentration of COF in step 5) was 1 mg/mL.
8. Pyrenyl COF composite fiber material prepared by the preparation method according to any one of claims 1 to 7.
9. Use of pyrenyl COF composite fiber material as claimed in claim 8 to produce protective clothing and mask fabrics in photocatalytic antibacterial and mustard degradation simulators.
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