CN111188196B - Preparation and application of graphene composite fiber non-woven fabric for catalytic degradation of neurogenic chemical warfare agent - Google Patents

Preparation and application of graphene composite fiber non-woven fabric for catalytic degradation of neurogenic chemical warfare agent Download PDF

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CN111188196B
CN111188196B CN202010060019.0A CN202010060019A CN111188196B CN 111188196 B CN111188196 B CN 111188196B CN 202010060019 A CN202010060019 A CN 202010060019A CN 111188196 B CN111188196 B CN 111188196B
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杨冬芝
宋林娜
王雪娇
于中振
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Beijing University of Chemical Technology
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Abstract

Preparation and application of graphene composite fiber non-woven fabric for catalytic degradation of neurogenic chemical warfare agents belong to the field of chemical defense. Taking graphene fiber as a carrier, and carrying out solvothermal synthesis on Metal Organic Framework (MOFs) nanoparticles on the surface of the fiber, wherein the diameter of the graphene fiber is 20-100 mu m, and the MOFs catalyst is UiO-66-NH2The particle size is 50-400 nm, and the composite fiber non-woven fabric is graphene @ UiO-66-NH2The thickness is 50 to 300 μm. The composite material is prepared by wet spinning and subsequent vacuum filtration, and has high-efficiency photothermal conversion effect. Under simulated sunlight, graphene @ UiO-66-NH2The half-life period of catalytic degradation of methylparathion which is the optimal simulant of the nerve agent soman is 1.6min, and the methylparathion can be almost completely degraded within 20min, thereby showing the excellent capability of rapidly catalyzing and degrading the nerve chemical warfare agent.

Description

Preparation and application of graphene composite fiber non-woven fabric for catalytic degradation of neurogenic chemical warfare agent
The technical field is as follows:
the invention relates to a preparation method and application of a graphene composite fiber non-woven fabric with a photo-thermal enhancement effect for ultra-fast catalytic degradation of a neurogenic chemical warfare agent, and belongs to the field of chemical defense.
Background art:
highly toxic neurochemical Warfare Agents (CWArfare, CWAs) containing a phosphate ester bond, such as tabun (GA), sarin (GB), soman (GD) and Vietxus (VX), are characterized by strong toxicity, fast action, and toxic action to the human body by contact or respiration. Although the use of chemical weapons has been prohibited internationally, there are still a large number of chemical weapons being produced that pose a global threat. Currently, the use of activated carbon as an intermediate layer or coating of material to adsorb chemical warfare agents is the primary protection strategy. For example, chinese patent document CN107584824A discloses a multifunctional breathable gas suit and a method for preparing the same, which can effectively adsorb CWAs molecules, but cannot digest chemical warfare agents, and may generate a threat of secondary pollution. Therefore, there is a need to develop composite materials capable of neutralizing nerve agents to achieve chemical protection. Therefore, it is urgent to design and develop a novel chemical protective material having the ability to adsorb and catalytically degrade nerve agents.
CN101622195A discloses a metal oxide fiber and nanofiber, their preparation method and their use for the absorption and decomposition of chemical warfare agents and other toxic chemicals. Compared with the activated carbon, the metal oxide fiber has larger specific surface area and can play a certain chemical protection role, but has slower digestion effect on CWAs, and is obviously different from the activated carbon.
CN108559100A discloses a metal ion-guided carboxylic acid ligand functionalized polyacid compound, a preparation method thereof and application of the polyacid compound in catalytic degradation of a neurogenic chemical warfare agent.
CN109261212A discloses a polyniobium oxygen cluster-bimetal hydroxide compound, a preparation method thereof and a method for heterogeneous catalytic degradation of chemical warfare agent analogues, wherein layered magnesium aluminum bimetal hydroxide, layered multi-niobium oxygen cluster anions and interlayer water molecules of the compound can realize catalytic hydrolysis of ethyl chlorophosphate which is an optimal analogue of nerve agent sarin, but the compound has low specific surface area, adsorption capacity and few active sites, so that the application of the compound in chemical protection materials is limited, and the compound is obviously different from the compound.
Metal Organic Frameworks (MOFs) have attracted considerable attention as a crystalline porous material in the field of catalytic degradation chemical warfare agents. CN108310982A discloses a chemical warfare agent self-disinfection metal-organic framework fiber filter membrane and a preparation method thereof, wherein a self-supporting MOFs fiber membrane structure can reduce the agglomeration phenomenon of MOFs nano-particles to a certain extent and shows a certain catalytic degradation performance, UiO-66-NH2The half-life period of the optimal simulant dimethy ether for catalyzing and degrading nerve agent soman by the fibrous membrane is 2.4min, but the preparation method of the fibrous membrane is relatively complex, so that the preparation method is limited in practical application, and the preparation method is obviously not limited to the methodThe same is true.
CN109603910A discloses a preparation method and application of a photothermal enhanced degradation chemical warfare agent simulant nano core-shell compound and a composite fiber membrane thereof, and dopamine @ UiO-66-NH is improved under the action of near-infrared laser2The composite fiber membrane has the fastest degradation half-life period of 1.8min for the catalytic degradation of the dimethomorph, but the dopamine @ UiO-66-NH of the composite fiber membrane2The MOFs catalytic active sites in the composite fiber fabric cannot be fully utilized, and the method is obviously different from the method. In view of the above, the development of a protective material for digesting chemical warfare agents that is highly efficient and active site efficient remains a significant challenge.
The graphene composite fiber non-woven fabric for ultra-fast catalytic degradation of the nerve chemical warfare agent is characterized in that the graphene composite fiber non-woven fabric with fast photothermal conversion efficiency is prepared by adopting simple wet spinning and subsequent vacuum filtration, and the graphene composite fiber non-woven fabric capable of fast digesting the nerve chemical agent is prepared by thermally synthesizing MOFs nano-particles on the surface of the fiber through a solvent. Under the illumination condition, the graphene fiber has excellent photo-thermal conversion efficiency and broad-spectrum adsorption capacity, so that the ultra-fast catalytic degradation of the nerve chemical warfare agent is realized, the fastest degradation half-life period can reach 1.6min, the nerve chemical warfare agent can be almost completely degraded within 20min, the excellent ability of fast digesting the nerve agent is embodied, and the graphene fiber has strong competitive advantage in the field of catalytic degradation of the chemical warfare agent. The invention provides a feasible strategy for the design of chemical warfare agent protective materials, and has great application prospect in the field of chemical defense.
The invention content is as follows:
the invention provides a preparation method and application of a graphene composite fiber non-woven fabric for ultra-fast catalytic degradation of a neurogenic chemical warfare agent, aiming at overcoming the problems of complicated preparation process of an efficient chemical protective material, low utilization rate of MOFs catalyst in a composite system and the like, so as to achieve the purpose of fast catalytic degradation of the neurogenic chemical warfare agent. The composite fiber non-woven fabric prepared by the invention can quickly convert absorbed light energy into heat energy under the illumination condition, effectively improve the temperature of local environment in a system, and further improve the reaction rate and the conversion rate of catalytic degradation of the neurochemical warfare agent.
The technical scheme of the invention is as follows:
a graphene composite fiber non-woven fabric for ultra-fast catalytic degradation of a nerve chemical warfare agent is prepared by taking the graphene composite fiber non-woven fabric with excellent photothermal conversion efficiency as a carrier, adopting a wet spinning and subsequent vacuum filtration method, and thermally synthesizing MOFs nano particles on the surface of a fiber through a solvent to prepare the graphene composite fiber non-woven fabric with the ultra-fast catalytic degradation of the nerve agent. Wherein the diameter of graphene fiber in the graphene oxide fiber non-woven fabric is 20-100 mu m, and the MOFs catalyst is UiO-66-NH2The particle size is 50-400 nm, and the composite fiber non-woven fabric is graphene @ UiO-66-NH2(GF@UiO-66-NH2) The thickness is 50-300 μm; graphene @ UiO-66-NH2Medium UiO-66-NH2The loading amount of (A) is 8-34 wt%.
GF @ UiO-66-NH in the present invention2The schematic flow chart, digital photograph and scanning electron microscope pictures with different magnifications of the composite fiber non-woven fabric are respectively shown in figures 1 and 2. The preparation process comprises the following steps:
(1) preparation of graphene fiber non-woven fabric
Preparing graphene oxide fibers by using the graphene oxide aqueous dispersion as a spinning stock solution and adopting a continuous wet spinning method, standing at room temperature, and drying in vacuum; dispersing the dried fibers in an ethanol aqueous solution, chopping the fibers into short fibers with the length of 1-7 mm by adopting a high-speed shearing and stirring method to prepare short fiber ethanol aqueous dispersion, carrying out vacuum filtration, drying at room temperature, then preparing graphene oxide fiber non-woven fabric, and partially reducing the graphene oxide fiber non-woven fabric to prepare the graphene fiber non-woven fabric;
(2) preparation of composite fiber fabrics
Weighing a proper amount of zirconium salt and an organic ligand 2-amino terephthalic acid, respectively dissolving in N, N-dimethylformamide,fully mixing, adding a regulator, and uniformly stirring; soaking the graphene fiber non-woven fabric prepared in the step (1) in the mixed solution, and standing at room temperature to enable the graphene fiber non-woven fabric to fully adsorb zirconium ions in the mixed solution; putting the system into a reaction kettle for solvothermal synthesis reaction to obtain GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange; and (5) drying in vacuum to obtain the graphene composite fiber non-woven fabric with the ultra-fast catalytic degradation function.
Preferably, the concentration of the graphene oxide aqueous dispersion in the step (1) is 5-30 mg/mL, and the dosage of the partially reduced graphene oxide fiber non-woven fabric is 20 mg. The spinning process in the step (1) selects KOH, NaOH and CaCl2、CuSO4One or two of the salt solutions are coagulating baths with the concentration of 5-20 wt%. The graphene oxide fiber in the step (1) is kept standing for 8-24 hours at room temperature, vacuum drying time is 2-24 hours, and drying temperature is 20-100 ℃.
The volume ratio of ethanol to water in the ethanol-water dispersion liquid of the graphene oxide-dried fiber in the step (1) is 1: (0.34-3).
Reducing agents selected for partially reducing the graphene oxide fiber non-woven fabric in the step (1) are hydriodic acid, hydrazine hydrate, ascorbic acid and sodium borohydride, and the mass ratio of the consumption of the reducing agents to the consumption of the graphene oxide fiber non-woven fabric is 1:1, under the condition of room temperature, the reduction time is 6-12 h, and the amount of a reducing agent and the reaction time are controlled to reduce the graphene oxide fiber non-woven fabric part.
The zirconium salt in the step (2) comprises zirconium nitrate, zirconium acetate, zirconium chloride and zirconium oxychloride.
The regulator in the step (2) comprises formic acid (with the concentration of 98%), benzoic acid (with the concentration of 99%), hydrochloric acid (with the concentration of 37%), hydrofluoric acid (with the concentration of 40%), glacial acetic acid (with the concentration of 99%) and ammonia water (with the concentration of 25-28%).
The mass ratio of the graphene fiber non-woven fabric in the step (2) to the zirconium salt is 1: (1-17), wherein the molar ratio of the zirconium salt to the organic ligand 2-amino terephthalic acid is 1:1, the volume ratio of the regulator to the N, N-dimethylformamide is 1: (10-20), and soaking the graphene fiber non-woven fabric for 3-72 hours.
The solvothermal synthesis temperature in the step (2) is 80-140 ℃, the synthesis time is 12-72 hours, and the solvent exchange time is 8-72 hours.
GF @ UiO-66-NH in the step (2)2The drying temperature of the composite fiber non-woven fabric is 80-150 ℃, and the drying time is 8-36 h.
The composite fiber fabric is applied to the catalytic degradation of the neurochemical warfare agent.
The method specifically comprises the following steps: placing the prepared composite fiber non-woven fabric into a reactor, adding 0-0.6M (preferably 0.45M) of N-ethylmorpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with a light source for illumination treatment; a nerve agent such as soman or its best analog, methyl paraoxon (DMNP), is added to the reactor, and catalytic degradation is carried out with constant stirring, preferably 0.8-1.5mL per 20mg of composite fiber nonwoven fabric corresponding to N-ethylmorpholine buffer.
The light source is an ultraviolet light source, a simulated sunlight light source and an infrared light source, and the illumination intensity is 0.1-1W-cm-2(1-10 sunlight equivalent, preferably 6 sunlight equivalent), and the illumination time is 30-120 min.
In the preparation and application of the graphene composite fiber non-woven fabric for ultra-fast catalytic degradation of the neurogenic chemical warfare agent, which are provided by the invention, the GF @ UiO-66-NH is described in the step (3)2The mol amount of the MOFs catalyst on the composite fabric is 4-16 mol% of that of the nerve agent.
The principle of the invention is as follows:
(1) selecting graphene fibers with excellent photo-thermal conversion efficiency as MOFs catalyst carriers and utilizing good broad-spectrum adsorption capacity of the graphene fibers; namely, under the same amount of MOFs and the same catalysis condition, the composite material of the invention has better catalysis effect than that of the MOFs only.
(2) The surface of the partially reduced graphene oxide fiber is provided with negative charges, can induce zirconium ions to perform heterogeneous nucleation on the surface of the fiber, and further grows into UiO-66-NH with efficient catalytic degradation effect2The nano particles can better inhibit the stacking among the particles, and the fiber structure can expose more catalytic active sites;
(3) by utilizing the excellent photo-thermal conversion efficiency of the graphene fiber, the light energy is quickly converted into heat energy and transferred to UiO-66-NH2The catalyst can quickly raise the temperature of the reaction system and improve the catalytic degradation efficiency of the composite fabric.
Drawings
Fig. 1 is a schematic flow chart of the preparation of the graphene composite fiber nonwoven fabric according to the present invention.
Fig. 2 is a digital photograph and scanning electron microscope pictures of different magnifications of the graphene composite fiber nonwoven fabric manufactured by the present invention.
FIG. 3 shows GF, GF @ UiO-66-NH prepared in example 32And UiO-66-NH2X-ray diffraction pattern of the powder.
FIG. 4 shows UiO-66-NH prepared in example 32Conversion-time relationship plots for powder catalyzed degradation of DMNP in the absence of light and simulated sunlight.
FIG. 5 is GF @ UiO-66-NH prepared in example 32Conversion rate-time relationship diagram for catalytic degradation of DMNP in the absence of illumination and simulated sunlight.
Detailed Description
The present invention will be further described in the following examples, which are illustrative, not restrictive and are not intended to limit the scope of the invention.
Example 1
(1) Preparing a graphene fiber non-woven fabric: carrying out continuous wet spinning by taking graphene oxide water dispersion liquid with the concentration of 5mg/mL as spinning stock solution and 5 wt% of KOH solution as a coagulating bath to prepare graphene oxide fibers, standing at room temperature for 8 hours, and then carrying out vacuum drying at 60 ℃ for 2 hours; dispersing the dried fibers in ethanol water dispersion liquid (volume ratio is 3: 1), crushing the fibers into short fibers by using a high-speed shearing stirrer, obtaining short fiber dispersion liquid, carrying out vacuum filtration, drying at room temperature, obtaining graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using hydroiodic acid to obtain graphene fiber non-woven fabric, wherein the diameter of each graphene fiber non-woven fabric is 20 micrometers, the reaction time is 6 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to the hydroiodic acid is 1: 1.
(2) preparing a composite fiber fabric: weighing 37mg of zirconium nitrate and 16mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving in 13.3mL of N, N-dimethylformamide, mixing, adding 2.66mL of formic acid, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 3 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at the temperature of 80 ℃ for 72 hours; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 8 hours; drying the obtained composite fiber fabric in a vacuum oven at 150 ℃ for 8h to obtain GF @ UiO-66-NH with catalytic degradation function2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 8.5 wt% of the composite fabric).
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0.3M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and irradiating with ultraviolet light source at intensity of 0.1W cm for 30min-2(1 sunlight equivalent); to the reactor was added 4. mu.L of DMNP (GF @ UiO-66-NH)2The molar quantity of the MOFs catalyst on the composite fabric is 4mol percent of that of the DMNP, the catalytic degradation is carried out by continuously stirring, 20 mu L of samples are taken at regular intervals, the samples are dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by using UV-vis. Prepared GF @ UiO-66-NH2The half-life period of DMNP catalyzed and degraded by the composite fabric is 8.6min, and the conversion rate is 78%.
Example 2
(1) Preparing a graphene fiber non-woven fabric: taking graphene oxide water dispersion with the concentration of 30mg/mL as spinning stock solution, taking mixed solution of 15 wt% of KOH and NaOH as coagulating bath, continuously performing wet spinning to prepare graphene oxide fibers, standing at room temperature for 24 hours, and then performing vacuum drying at 100 ℃ for 24 hours; dispersing the dried fibers in an ethanol water solution (volume ratio is 1:1), crushing the fibers into short fibers by using a high-speed shearing stirrer to obtain a short fiber dispersion liquid, carrying out vacuum filtration, drying at room temperature to obtain a graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using hydrazine hydrate to obtain a graphene fiber non-woven fabric, wherein the diameter of each graphene fiber non-woven fabric is 100 microns, the reaction time is 10 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to the hydrazine hydrate is 1: 1.
(2) preparing a composite fiber fabric: weighing 56mg of zirconium acetate and 31mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving in 26.6mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 24 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at the temperature of 140 ℃ for 12 hours; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 72 hours; drying the obtained composite fiber fabric in a vacuum oven at 80 ℃ for 36h to obtain GF @ UiO-66-NH with catalytic degradation function2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 17 wt% of the composite fabric).
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0.6M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and treating with simulated sunlight for 60min at illumination intensity of 0.3W cm-2(3 solar equivalent); to the reactor was added 4. mu.L of DMNP (GF @ UiO-66-NH)2The molar quantity of the MOFs catalyst on the composite fabric is 8mol percent of that of the DMNP), the catalytic degradation is carried out by continuously stirring, 20 mu L of samples are taken at regular intervals, the samples are dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by using UV-vis. Prepared GF @ UiO-66-NH2The half-life period of DMNP catalyzed and degraded by the composite fabric is 4.2min, and the conversion rate is 90%.
Example 3
(1) Preparing a graphene fiber non-woven fabric: taking graphene oxide water dispersion with the concentration of 20mg/mL as spinning solution and 10 wt% of CaCl2Taking the solution as a coagulating bath, carrying out continuous wet spinning to obtain graphene oxide fibers, standing at room temperature for 12 hours, and then carrying out vacuum drying at 60 ℃ for 6 hours; dispersing the dried fibers in an ethanol water solution (volume ratio is 1: 3), crushing the fibers into short fibers by using a high-speed shearing stirrer to obtain a dispersion liquid of the short fibers, carrying out vacuum filtration, drying at room temperature to obtain a graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using ascorbic acid to obtain the graphene fiber non-woven fabric, wherein the diameter of the graphene fiber non-woven fabric is 80 microns, the reaction time is 8 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to hydrazine hydrate is 1: 1. the X-ray diffraction spectrum of the prepared graphene fiber is shown in figure 3.
(2) Preparing a composite fiber fabric: weighing 80mg of zirconium chloride and 62mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 12 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 24 hours; drying the obtained composite fiber fabric in a vacuum oven at 120 ℃ for 24 hours to obtain GF @ UiO-66-NH with catalytic degradation function2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 26 wt% of the composite fabric). Prepared GF @ UiO-66-NH2The X-ray diffraction spectrum of the composite fabric is shown in figure 3.
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0.45M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and performing illumination treatment with infrared light source for 120min at illumination intensityIs 0.6 W.cm-2(6 solar equivalents); to the reactor was added 4. mu.L of DMNP (GF @ UiO-66-NH)2The molar quantity of the MOFs catalyst on the composite fabric is 12 mol% of that of the DMNP), the catalytic degradation is carried out by continuously stirring, 20 mu L of samples are taken at regular intervals, the samples are dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by UV-vis, such as a catalytic process conversion rate-time curve shown in FIG. 5. Prepared GF @ UiO-66-NH2The half-life period of DMNP catalyzed and degraded by the composite fabric is 1.6min, and the conversion rate is 99%.
Example 4
(1) Preparing a graphene fiber non-woven fabric: taking graphene oxide water dispersion with the concentration of 10mg/mL as spinning solution and 20 wt% of CaCl2And CuSO4The mixed solution is coagulating bath, and the graphene oxide fiber is prepared by continuous wet spinning, stands for 12 hours at room temperature, and is dried for 6 hours in vacuum at 60 ℃; dispersing the dried fibers in an ethanol water solution (volume ratio is 1: 3), crushing the fibers into short fibers by using a high-speed shearing stirrer, obtaining a dispersion liquid of the short fibers, carrying out vacuum filtration, drying at room temperature, obtaining graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using sodium borohydride to obtain the graphene fiber non-woven fabric, wherein the diameter of the graphene fiber non-woven fabric is 80 microns, the reaction time is 8 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to hydrazine hydrate is 1: 1. the X-ray diffraction spectrum of the prepared graphene fiber is shown in figure 3.
(2) Preparing a composite fiber fabric: weighing 160mg of zirconium chloride and 124mg of 2-amino terephthalic acid (the molar ratio is 1:1) and respectively dissolving in 15mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 3 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at 100 ℃ for 36 hours; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 36 hours; drying the obtained composite fiber fabric in a vacuum oven at 150 ℃ for 12h to obtain the composite fiber fabric with the catalytic degradation functionGF @ UiO-66-NH2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 34 wt% of the composite fabric).
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and irradiating with ultraviolet light source at intensity of 0.1W cm for 30min-2(1 sunlight equivalent); to the reactor was added 4. mu.L of DMNP (GF @ UiO-66-NH)2The molar quantity of the MOFs catalyst on the composite fabric is 16mol percent of that of the DMNP), the catalytic degradation is carried out by continuously stirring, 20 mu L of samples are taken at regular intervals, the samples are dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by using UV-vis. Prepared GF @ UiO-66-NH2The half-life period of DMNP catalytically degraded by the composite fabric is 32.1min, and the conversion rate is 36%.
Example 5
(1) Preparing a graphene fiber non-woven fabric: taking graphene oxide water dispersion with the concentration of 30mg/mL as spinning stock solution, taking mixed solution of 15 wt% of KOH and NaOH as coagulating bath, continuously performing wet spinning to prepare graphene oxide fibers, standing at room temperature for 24 hours, and then performing vacuum drying at 100 ℃ for 24 hours; dispersing the dried fibers in an ethanol water solution (volume ratio is 1:1), crushing the fibers into short fibers by using a high-speed shearing stirrer to obtain a short fiber dispersion liquid, carrying out vacuum filtration, drying at room temperature to obtain a graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using hydrazine hydrate to obtain a graphene fiber non-woven fabric, wherein the diameter of each graphene fiber non-woven fabric is 100 microns, the reaction time is 10 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to the hydrazine hydrate is 1: 1.
(2) preparing a composite fiber fabric: weighing 61mg of zirconium oxychloride and 62mg of 2-amino terephthalic acid (the molar ratio is 1:1) to respectively dissolve in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of glacial acetic acid, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 24 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at the temperature of 140 ℃ for a period of timeIs 12 h; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 72 hours; drying the obtained composite fiber fabric in a vacuum oven at 80 ℃ for 36h to obtain GF @ UiO-66-NH with catalytic degradation function2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 26 wt% of the composite fabric).
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0.6M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and treating with simulated sunlight for 60min at illumination intensity of 0.3W cm-2(3 solar equivalent); to the reactor was added 4. mu.L of DMNP (GF @ UiO-66-NH)2The mol weight of the MOFs catalyst on the composite fabric is 12 mol% of that of the DMNP, the catalytic degradation is carried out by continuously stirring, 20 mu L of samples are taken at regular intervals, the samples are dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by using UV-vis. Prepared GF @ UiO-66-NH2The half-life period of DMNP catalyzed and degraded by the composite fabric is 4.6min, and the conversion rate is 99%.
Example 6
(1) Preparing a graphene fiber non-woven fabric: taking graphene oxide water dispersion with the concentration of 20mg/mL as spinning solution and 10 wt% of CaCl2Taking the solution as a coagulating bath, carrying out continuous wet spinning to obtain graphene oxide fibers, standing at room temperature for 12 hours, and then carrying out vacuum drying at 60 ℃ for 6 hours; dispersing the dried fibers in an ethanol water solution (volume ratio is 1: 3), crushing the fibers into short fibers by using a high-speed shearing stirrer to obtain a dispersion liquid of the short fibers, carrying out vacuum filtration, drying at room temperature to obtain a graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using ascorbic acid to obtain the graphene fiber non-woven fabric, wherein the diameter of the graphene fiber non-woven fabric is 80 microns, the reaction time is 8 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to hydrazine hydrate is 1: 1.
(2) preparing a composite fiber fabric: weighing 336mg of zirconium acetate and 2-ammoniaRespectively dissolving 186mg of terephthalic acid (the molar ratio is 1:1) in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 12 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 24 hours; drying the obtained composite fiber fabric in a vacuum oven at 120 ℃ for 24 hours to obtain GF @ UiO-66-NH with catalytic degradation function2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 34 wt% of the composite fabric).
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0.45M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and performing illumination treatment with infrared light source at illumination intensity of 0.2W cm for 90min-2(2 solar equivalents); to the reactor was added 4. mu.L of DMNP (GF @ UiO-66-NH)2The molar quantity of the MOFs catalyst on the composite fabric is 16 mol% of that of the DMNP), the catalytic degradation is carried out by continuously stirring, 20 mu L of samples are taken at regular intervals, the samples are dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by UV-vis, such as a catalytic process conversion rate-time curve shown in FIG. 5. Prepared GF @ UiO-66-NH2The half-life period of DMNP catalyzed and degraded by the composite fabric is 2.8min, and the conversion rate is 99%.
Example 7
(1) Preparing a graphene fiber non-woven fabric: taking graphene oxide water dispersion with the concentration of 20mg/mL as spinning solution and 10 wt% of CaCl2Taking the solution as a coagulating bath, carrying out continuous wet spinning to obtain graphene oxide fibers, standing at room temperature for 12 hours, and then carrying out vacuum drying at 60 ℃ for 6 hours; dispersing the dried fiber in ethanol water solution (volume ratio of 1: 3), mincing into short fiber with high speed shearing blender to obtain short fiber dispersion, vacuum filteringAnd drying at room temperature to obtain a graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using ascorbic acid to obtain the graphene fiber non-woven fabric, wherein the diameter of the graphene fiber non-woven fabric is 80 microns, the reaction time is 8 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to hydrazine hydrate is 1: 1.
(2) preparing a composite fiber fabric: weighing 147mg of zirconium nitrate and 62mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of hydrofluoric acid, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 12 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 24 hours; drying the obtained composite fiber fabric in a vacuum oven at 120 ℃ for 24 hours to obtain GF @ UiO-66-NH with catalytic degradation function2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 26 wt% of the composite fabric).
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0.6M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and performing illumination treatment with infrared light source at illumination intensity of 1W cm for 60min-2(10 solar equivalents); to the reactor was added 4. mu.L of soman (GF @ UiO-66-NH)2The mol weight of the MOFs catalyst on the composite fabric is 12 mol% of the soman mol weight), the catalytic degradation is carried out by continuously stirring, 20 mu L of sample is taken at regular intervals, the sample is dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by UV-vis, such as the conversion rate-time curve of the catalytic process shown in FIG. 5. Prepared GF @ UiO-66-NH2The half-life period of the composite fabric catalytic degradation soman is 1.8min, and the conversion rate is 99%.
Example 8
(1) Preparing a graphene fiber non-woven fabric: at a concentration of 20mg/mL graphene oxide water dispersion liquid is used as spinning stock solution, and 10 wt% CaCl2Taking the solution as a coagulating bath, carrying out continuous wet spinning to obtain graphene oxide fibers, standing at room temperature for 12 hours, and then carrying out vacuum drying at 60 ℃ for 6 hours; dispersing the dried fibers in an ethanol water solution (volume ratio is 1: 3), crushing the fibers into short fibers by using a high-speed shearing stirrer to obtain a dispersion liquid of the short fibers, carrying out vacuum filtration, drying at room temperature to obtain a graphene oxide fiber non-woven fabric, partially reducing the graphene oxide fiber non-woven fabric by using ascorbic acid to obtain the graphene fiber non-woven fabric, wherein the diameter of the graphene fiber non-woven fabric is 80 microns, the reaction time is 8 hours, and the mass ratio of the graphene oxide fiber non-woven fabric to hydrazine hydrate is 1: 1. the X-ray diffraction spectrum of the prepared graphene fiber is shown in figure 3.
(2) Preparing a composite fiber fabric: weighing 31mg of zirconium oxychloride and 31mg of 2-amino terephthalic acid (the molar ratio is 1:1) and respectively dissolving in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of ammonia water, and uniformly stirring; soaking the graphene fiber non-woven fabric (20mg) prepared in the step (1) in the mixed solution for 12 hours, and placing the mixture in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, the surface load UiO-66-NH is obtained2GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange for 24 hours; drying the obtained composite fiber fabric in a vacuum oven at 120 ℃ for 24 hours to obtain GF @ UiO-66-NH with catalytic degradation function2Composite fiber nonwoven fabric (UiO-66-NH)2Loading was 26 wt% of the composite fabric). Prepared GF @ UiO-66-NH2The X-ray diffraction spectrum of the composite fabric is shown in figure 3.
(3) The application of the DMNP catalyzed and degraded by the composite fiber fabric comprises the following steps: GF @ UiO-66-NH prepared in the step (2)2Placing the composite fiber non-woven fabric into a reactor, adding 1mL of 0.45M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with light source, and performing illumination treatment with infrared light source at illumination intensity of 0.6W cm for 120min-2(6 solar equivalents); to the reactor was added 4. mu.L of DMNP (GF @ UiO-66-NH)2MOF on composite fabricsThe molar amount of the s catalyst was 12 mol% of the molar amount of the DMNP), the catalytic degradation was performed while continuing the stirring, 20. mu.L of the sample was taken at regular intervals, dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution was measured by UV-vis as shown in the conversion rate-time curve of the catalytic process in FIG. 5. Prepared GF @ UiO-66-NH2The half-life period of DMNP catalyzed and degraded by the composite fabric is 2.5min, and the conversion rate is 99%.
GF @ UiO-66-NH prepared by the invention2Performance of composite fabrics for catalytic degradation of soman and DMNP is determined by obtaining pure UiO-66-NH under the same conditions as in examples 1 to 8 above2The powder catalysts were evaluated as controls, as in comparative examples 1 to 8.
Comparative example 1
The procedure is as in example 1, (1) UiO-66-NH2Preparation of powder: weighing 37mg of zirconium nitrate and 16mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving the zirconium nitrate and the 2-amino terephthalic acid in 13.3mL of N, N-dimethylformamide, mixing, adding 2.66mL of formic acid, uniformly stirring, and placing in a reaction kettle for solvothermal synthesis reaction at the temperature of 80 ℃ for 72 hours; after the reaction is finished, UiO-66-NH2The powder is washed with N, N-dimethylformamide for three times, further soaked in absolute ethyl alcohol for solvent exchange for 8h, and dried in vacuum at 150 ℃ for 8 h.
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 1.7mg of the powder in a reactor, adding 1mL of 0.3M N-ethylmorpholine buffer solution, and vigorously stirring for 30 min; placing the reactor in a dark box with light source, and irradiating with ultraviolet light source at intensity of 0.1W cm for 30min-2(1 sunlight equivalent); to the reactor was added 4. mu.L of DMNP (UiO-66-NH)2The molar amount of (2) was 4 mol% based on the molar amount of DMNP), and catalytic degradation was carried out while stirring, and 20. mu.L of the sample was dissolved in 10mL of N-ethylmorpholine solution (0.15M) at regular intervals, and the absorbance of the solution was measured by UV-vis. Prepared UiO-66-NH2The half-life period of DMNP catalyzed and degraded by powder is 2.2min, and the conversion rate is 98%.
Comparative example 2
The procedure is as in example 2, (1) UiO-66-NH2Preparation of powder:weighing 56mg of zirconium acetate and 31mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving the zirconium acetate and the 2-amino terephthalic acid in 26.6mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, uniformly stirring, and placing in a reaction kettle for solvothermal synthesis reaction at the temperature of 140 ℃ for 12 hours; after the reaction is finished, UiO-66-NH2The powder is washed with N, N-dimethylformamide three times, further soaked in absolute ethyl alcohol for solvent exchange for 72h, and vacuum dried at 80 ℃ for 36 h.
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 3.4mg of powder in a reactor, adding 1mL of 0.6M N-ethylmorpholine buffer solution, and vigorously stirring for 30 min; placing the reactor in a dark box with light source, and treating with simulated sunlight for 60min at illumination intensity of 0.3W cm-2(3 solar equivalent); to the reactor was added 4. mu.L of DMNP (UiO-66-NH)2The molar amount of (2) was 8 mol% based on the molar amount of DMNP), and catalytic degradation was carried out while stirring, and 20. mu.L of the sample was dissolved in 10mL of N-ethylmorpholine solution (0.15M) at regular intervals, and the absorbance of the solution was measured by UV-vis. Prepared UiO-66-NH2The half-life period of the powder catalytic degradation DMNP is 4.2min, and the conversion rate is 90%.
Comparative example 3
The procedure is as in example 3, (1) UiO-66-NH2Preparation of powder: weighing 80mg of zirconium chloride and 62mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving the zirconium chloride and the 2-amino terephthalic acid in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, uniformly stirring, and placing in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, UiO-66-NH2The powder is washed with N, N-dimethylformamide three times, further soaked in absolute ethyl alcohol for solvent exchange for 24h, and vacuum dried for 24h at 120 ℃.
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 5.2mg of powder in a reactor, adding 1mL of 0.45M N-ethylmorpholine buffer solution, and vigorously stirring for 30 min; placing the reactor in a dark box with light source, and performing illumination treatment with infrared light source at illumination intensity of 0.6W cm for 120min-2(6 Tai)Sunlight equivalent); to the reactor was added 4. mu.L of DMNP (UiO-66-NH)2The molar amount of (2) was 12 mol% of the molar amount of DMNP), and catalytic degradation was carried out while stirring, and 20. mu.L of the sample was dissolved in 10mL of N-ethylmorpholine solution (0.15M) at regular intervals, and the absorbance of the solution was measured by UV-vis. Prepared UiO-66-NH2The half-life period of the powder catalytic degradation DMNP is 1.8min, and the conversion rate is 99%. Prepared UiO-66-NH2The powder has an X-ray diffraction pattern as shown in FIG. 3.
Comparative example 4
The procedure is as in example 4, (1) UiO-66-NH2Preparation of powder: weighing 160mg of zirconium chloride and 124mg of 2-amino terephthalic acid (the molar ratio is 1:1) and respectively dissolving the zirconium chloride and the 2-amino terephthalic acid in 15mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, uniformly stirring, and placing in a reaction kettle for solvothermal synthesis reaction at the temperature of 100 ℃ for 36 hours; after the reaction is finished, UiO-66-NH2The powder is washed with N, N-dimethylformamide three times, further soaked in absolute ethyl alcohol for solvent exchange for 36h, and vacuum dried for 12h at 150 ℃.
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 3.4mg of powder in a reactor, adding 1mL of 0M N-ethyl morpholine buffer solution, and stirring vigorously for 30 min; placing the reactor in a dark box with light source, and irradiating with ultraviolet light source at intensity of 0.1W cm for 30min-2(1 sunlight equivalent); to the reactor was added 4. mu.L of DMNP (UiO-66-NH)2The molar amount of (2) was 16 mol% based on the molar amount of DMNP), and catalytic degradation was carried out while stirring, and 20. mu.L of the sample was dissolved in 10mL of N-ethylmorpholine solution (0.15M) at regular intervals, and the absorbance of the solution was measured by UV-vis. Prepared UiO-66-NH2The half-life period of the powder catalytic degradation DMNP is 28min, and the conversion rate is 40%.
Comparative example 5
The procedure is as in example 5, (1) UiO-66-NH2Preparation of powder: 61mg of zirconium oxychloride and 62mg of 2-amino terephthalic acid (molar ratio is 1:1) are respectively weighed and dissolved in 20mL of N, N-dimethylformamide, mixed and added with 2.66mL of glacial acetic acid, stirred uniformly and placed in a reaction kettle for carrying outCarrying out solvothermal synthesis reaction at 140 ℃ for 12 h; after the reaction is finished, UiO-66-NH2The powder is washed with N, N-dimethylformamide three times, further soaked in absolute ethyl alcohol for solvent exchange for 72h, and vacuum dried at 80 ℃ for 36 h.
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 5.2mg of powder in a reactor, adding 1mL of 0.6M N-ethylmorpholine buffer solution, and vigorously stirring for 30 min; placing the reactor in a dark box with light source, and treating with simulated sunlight for 60min at illumination intensity of 0.3W cm-2(3 solar equivalent); to the reactor was added 4. mu.L of DMNP (UiO-66-NH)2The molar amount of (2) was 12 mol% of the molar amount of DMNP), and catalytic degradation was carried out while stirring, and 20. mu.L of the sample was dissolved in 10mL of N-ethylmorpholine solution (0.15M) at regular intervals, and the absorbance of the solution was measured by UV-vis. Prepared UiO-66-NH2The half-life period of DMNP catalyzed and degraded by powder is 2.7min, and the conversion rate is 99%.
Comparative example 6
The procedure is as in example 6, (1) UiO-66-NH2Preparation of powder: weighing 112mg of zirconium acetate and 62mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving the zirconium acetate and the 2-amino terephthalic acid in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of benzoic acid, uniformly stirring, and placing in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, UiO-66-NH2The powder is washed with N, N-dimethylformamide three times, further soaked in absolute ethyl alcohol for solvent exchange for 24h, and vacuum dried for 24h at 120 ℃.
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 6.8mg of powder in a reactor, adding 1mL of 0.45M N-ethylmorpholine buffer solution, and vigorously stirring for 30 min; placing the reactor in a dark box with light source, and treating with simulated sunlight for 60min at illumination intensity of 0.2W cm-2(2 solar equivalents); to the reactor was added 4. mu.L of DMNP (UiO-66-NH)2The molar amount of (b) is 16 mol% of the molar amount of DMNP), continuously stirring, performing catalytic degradation, and dissolving 20. mu.L of sample in water at regular intervals10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution was measured by UV-vis. Prepared UiO-66-NH2The half-life period of the powder catalytic degradation DMNP is 2.0min, and the conversion rate is 99%.
Comparative example 7
The procedure is as in example 7, (1) UiO-66-NH2Preparation of powder: weighing 147mg of zirconium nitrate and 62mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving the zirconium nitrate and the 2-amino terephthalic acid in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of hydrofluoric acid, uniformly stirring, and placing in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, UiO-66-NH2Washing the powder with N, N-dimethylformamide for three times, further soaking in anhydrous ethanol for solvent exchange for 24h, and vacuum drying at 120 deg.C for 24 h.
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 5.2mg of powder in a reactor, adding 1mL of 0.6M N-ethylmorpholine buffer solution, and vigorously stirring for 30 min; placing the reactor in a dark box with a light source, and treating with simulated sunlight for 60min at an illumination intensity of 1W cm-2(10 solar equivalents); to the reactor was added 4. mu.L of soman (GF @ UiO-66-NH)2The mol weight of the MOFs catalyst on the composite fabric is 12 mol% of the soman mol weight), the catalytic degradation is carried out by continuously stirring, 20 mu L of sample is taken at regular intervals, the sample is dissolved in 10mL of N-ethylmorpholine solution (0.15M), and the absorbance of the solution is detected by UV-vis. Prepared UiO-66-NH2The half-life of powder catalytic degradation soman is 1.7min, and the conversion rate is 99%.
Comparative example 8
The procedure is as in example 8, (1) UiO-66-NH2Preparation of powder: weighing 31mg of zirconium oxychloride and 31mg (the molar ratio is 1:1) of 2-amino terephthalic acid, respectively dissolving the zirconium oxychloride and the 2-amino terephthalic acid in 20mL of N, N-dimethylformamide, mixing, adding 2.66mL of ammonia water, uniformly stirring, and placing in a reaction kettle for solvothermal synthesis reaction at the temperature of 120 ℃ for 24 hours; after the reaction is finished, UiO-66-NH2Washing the powder with N, N-dimethylformamide for three times, further soaking in anhydrous ethanol for solvent exchange for 24 hr, and vacuum drying at 120 deg.C for 24 hr。
(2)UiO-66-NH2Application of powder catalytic degradation of DMNP: weighing the UiO-66-NH prepared in the step (2)2Placing 5.2mg of powder in a reactor, adding 1mL of 0.45M N-ethylmorpholine buffer solution, and vigorously stirring for 30 min; placing the reactor in a dark box with light source, and irradiating with infrared light source at intensity of 0.6W cm for 120min-2(6 solar equivalents); to the reactor was added 4. mu.L of DMNP (UiO-66-NH)2The molar amount of (2) was 12 mol% of the molar amount of DMNP), and catalytic degradation was carried out while stirring, and 20. mu.L of the sample was dissolved in 10mL of N-ethylmorpholine solution (0.15M) at regular intervals, and the absorbance of the solution was measured by UV-vis. Prepared UiO-66-NH2The half-life period of the powder catalytic degradation DMNP is 2.1min, and the conversion rate is 99%.
UiO-66-NH under the condition of existence of simulated sunlight irradiation2Powder and GF @ UiO-66-NH2The conversion rate-time curves of the composite fabric for the catalytic degradation process of DMNP are shown in fig. 4 and 5, respectively. Illumination Condition vs. UiO-66-NH2The rate of powder catalytic degradation of DMNP has little influence, the half-life period under 6 equivalent solar radiation can reach 1.8min, and the performance (t) is slightly better than that under the condition of no illumination1/22.2 min). GF @ UiO-66-NH prepared by the invention2The half-life period of the composite fabric can reach 1.6min under the same 6 equivalent solar radiation, and the half-life period is obviously superior to the performance of the catalyst, so that the GF @ UiO-66-NH prepared by the method has excellent photo-thermal conversion efficiency and broad-spectrum adsorption capacity2The composite fabric achieves the effect of ultra-fast catalytic degradation of the neurogenic chemical warfare agent, and has great development potential in the field of novel chemical protective materials.

Claims (12)

1. The graphene composite fiber non-woven fabric for ultra-fast catalytic degradation of the neurogenic chemical warfare agent is characterized in that graphene fibers are used as a carrier, MOFs nanoparticles are thermally synthesized on the surface of the fibers through a solvent, the diameter of each graphene fiber of the graphene oxide fiber non-woven fabric is 20-100 micrometers, and the MOFs catalyst is UiO-66-NH2The particle size is 50-400 nm, and the composite fiber non-woven fabric is graphene @ UiO-66-NH2I.e. GF @ UiO-66-NH2The thickness is 50-300 μm; graphene @ UiO-66-NH2Medium UiO-66-NH2The loading amount of (A) is 8-34 wt%.
2. The method for preparing the graphene composite fiber non-woven fabric for ultra-fast catalytic degradation of the neurochemical warfare agent according to claim 1, which comprises the following steps:
(1) preparation of graphene fiber non-woven fabric
Preparing graphene oxide fibers by using the graphene oxide aqueous dispersion as a spinning stock solution and adopting a continuous wet spinning method, standing at room temperature, and drying in vacuum; dispersing the dried fibers in an ethanol aqueous solution, chopping the fibers into short fibers with the length of 1-7 mm by adopting a high-speed shearing and stirring method to prepare short fiber ethanol aqueous dispersion, carrying out vacuum filtration, drying at room temperature, then preparing graphene oxide fiber non-woven fabric, and partially reducing the graphene oxide fiber non-woven fabric to prepare the graphene fiber non-woven fabric;
(2) preparation of composite fiber fabrics
Weighing a proper amount of zirconium salt and an organic ligand 2-amino terephthalic acid, respectively dissolving in N, N-dimethylformamide, fully mixing, adding a regulator, and uniformly stirring; soaking the graphene fiber non-woven fabric prepared in the step (1) in the mixed solution, and standing at room temperature to enable the graphene fiber non-woven fabric to fully adsorb zirconium ions in the mixed solution; putting the system into a reaction kettle for solvothermal synthesis reaction to obtain GF @ UiO-66-NH2Washing the composite fabric with N, N-dimethylformamide for three times, and further soaking the composite fabric in absolute ethyl alcohol for solvent exchange; and (5) drying in vacuum to obtain the graphene composite fiber non-woven fabric with the ultra-fast catalytic degradation function.
3. The method according to claim 2, wherein the concentration of the graphene oxide aqueous dispersion in the step (1) is 5-30 mg/mL, and the dosage of the partially reduced graphene oxide fiber non-woven fabric is 20 mg; the spinning process in the step (1) selects KOH, NaOH and CaCl2、CuSO4One or two of the salt solutions are coagulating baths with the concentration of 5-20 wt%; standing the graphene oxide fiber in the step (1) at room temperature for 8-24 h, vacuum drying for 2-24 h, and drying at 20-100 ℃; the volume ratio of ethanol to water in the ethanol-water dispersion liquid of the graphene oxide-dried fiber in the step (1) is 1: (0.34-3).
4. The method according to claim 2, wherein the reducing agent selected for partially reducing the graphene oxide fiber non-woven fabric in the step (1) is hydroiodic acid, hydrazine hydrate, ascorbic acid, and sodium borohydride, and the mass ratio of the amount of the reducing agent to the amount of the graphene oxide fiber non-woven fabric is 1:1, under the condition of room temperature, the reduction time is 6-12 h, and the amount of a reducing agent and the reaction time are controlled to reduce the graphene oxide fiber non-woven fabric part.
5. The method of claim 2 wherein said zirconium salt of step (2) comprises zirconium nitrate, zirconium acetate, zirconium chloride, and zirconium oxychloride; the regulator in the step (2) comprises one of formic acid (with the concentration of 98%), benzoic acid (with the concentration of 99%), hydrochloric acid (with the concentration of 37%), hydrofluoric acid (with the concentration of 40%), glacial acetic acid (with the concentration of 99%) and ammonia water (with the concentration of 25-28%).
6. The method according to claim 2, wherein the mass ratio of the graphene fiber nonwoven fabric in the step (2) to the zirconium salt is 1: (1-17), wherein the molar ratio of the zirconium salt to the organic ligand 2-amino terephthalic acid is 1:1, the volume ratio of the regulator to the N, N-dimethylformamide is 1: (10-20), and soaking the graphene fiber non-woven fabric for 3-72 hours.
7. The method according to claim 2, wherein the solvothermal synthesis temperature in the step (2) is 80-140 ℃, the synthesis time is 12-72 hours, and the solvent exchange time is 8-72 hours.
8. Use of the graphene composite fiber nonwoven fabric of claim 1 for catalytic degradation of a neurochemical warfare agent.
9. Use according to claim 8, characterized in that it comprises in particular the following: placing the prepared composite fiber non-woven fabric into a reactor, adding 0-0.6M N-ethyl morpholine buffer solution, and violently stirring for 30 min; placing the reactor in a dark box with a light source for illumination treatment; the catalytic degradation is carried out by adding a nerve agent such as soman or its best mimic methyl paraoxon (DMNP) to the reactor with constant stirring, 0.8-1.5mL per 20mg of composite fiber nonwoven fabric corresponding to N-ethylmorpholine buffer.
10. Use according to claim 9, characterized in that it comprises in particular the following: 0.45M N-ethylmorpholine buffer was added.
11. The use according to claim 9, wherein the light source is an ultraviolet light source, a simulated solar light source, an infrared light source, and the illumination intensity is 0.1 to 1W-cm-2The illumination time is 30-120 min.
12. Use according to claim 9, characterized in that GF @ UiO-66-NH2The molar weight of the MOFs catalyst on the composite fabric is 4-16% of that of the nerve agent.
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