CN112452165A - Ag/AgBr/AgVO3Composite nanofiber filtering membrane and preparation method and application thereof - Google Patents

Ag/AgBr/AgVO3Composite nanofiber filtering membrane and preparation method and application thereof Download PDF

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CN112452165A
CN112452165A CN202011413088.1A CN202011413088A CN112452165A CN 112452165 A CN112452165 A CN 112452165A CN 202011413088 A CN202011413088 A CN 202011413088A CN 112452165 A CN112452165 A CN 112452165A
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agvo
agbr
solution
pan
composite
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CN112452165B (en
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岳一莹
侯凯阳
顾佳敏
韩景泉
蒋剑春
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Nanjing Forestry University
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Nanjing Forestry University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J35/39—
    • B01J35/59—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention belongs to the field of polymer composite materials, and discloses a polyacrylonitrile/cellulose acetate-silver/silver bromide/silver metavanadate composite fiber membrane, and a preparation method and application thereof. The fiber membrane is prepared by the following method: a. preparing silver metavanadate; b. preparing a silver/silver bromide/silver metavanadate composite photocatalyst; c. preparing polyacrylonitrile/cellulose acetate-silver/silver bromide/silver metavanadate electrostatic spinning solution, and preparing the nanofiber membrane by an electrostatic spinning technology. The fiber membrane is used as a carrier of the photocatalyst to realize the recycling of the photocatalyst, and is expected to be better applied in the future.

Description

Ag/AgBr/AgVO3Composite nanofiber filtering membrane and preparation method and application thereof
Technical Field
The invention belongs to the field of polymer composite materials. In particular to Ag/AgBr/AgVO based on electrostatic spinning technology3Composite nanofiber membrane and preparation method and application thereof
Background
With the development of the industry in China, a large amount of industrial wastewater is generated, and the untreated wastewater is discharged into rivers and even underground water, so that the functions of purifying rivers and underground water bodies are greatly reduced, and the environment is seriously damaged. The traditional organic matter treatment methods (adsorption, filtration, biochemical treatment, etc.) are not ideal in effect, so that an environment-friendly and efficient treatment method is urgently needed.
The photocatalysis technology is efficient, green, energy-saving and no secondary pollution, and has wide application prospect in many fields. The technology has excellent treatment effect on organic dye in water, and has the advantages of energy conservation, reusability and the like, and the treatment process is simple and the reaction process is easy to control. Wherein, the selection of the photocatalyst is the key point of the photocatalysis technology, AgVO3As a typical silver vanadate, the silver vanadate has huge potential in the field of photocatalysis due to the advantages of unique electronic structure, good crystallinity, strong visible light absorption and the like. However, AgVO is required to achieve high photocatalytic activity because of its rapid electron-hole pair recombination3And other semiconductor materials to form a heterojunction to enhance the photocatalytic performance. However, the photocatalyst is various, and one suitable for AgVO is urgently needed to be screened3Composite semiconductor materialThe material enhances the photocatalytic performance of silver metavanadate and improves the treatment capacity of dye wastewater.
In addition, the powdery photocatalyst is widely used in the practical use of wastewater treatment, and has the problems of easy aggregation, reduced catalytic performance, difficult recovery and easy secondary pollution.
The electrostatic spinning technology is a simple method for obtaining continuous nano-fibers, the diameter of the spun fibers is 10nm-10 mu m, the porosity, the pore diameter and the pore diameter distribution of the fiber membranes can be controlled by adjusting the fiber diameter and the thickness of the fiber membranes, and a spinning device commonly used for electrostatic spinning mainly comprises an injector, a spinning assembly, a high-voltage power supply and a receiver. The spin pack assembly is connected to a high voltage and the receiver is grounded, and when the force of the electric field is large enough, the polymer droplets overcome the surface tension to form jet streams. The solvent evaporates or solidifies during the trickle-spray process and eventually lands on the receiver, forming a fibrous film. The nano-fiber membrane material has high specific surface area and porosity due to the fact that the nano-fiber membrane material is a membrane material consisting of nano-fibers. Compared with the traditional water treatment material, the separation efficiency of the water treatment material in the oil-water separation, dye and heavy metal removal process is greatly improved, the energy consumption in the separation process is reduced, the secondary pollution is also avoided, and the water treatment material becomes a novel sewage treatment material.
Polyacrylonitrile (PAN) is a linear high molecular polymer which is obtained by radical polymerization of acrylonitrile monomer dissolved in polar organic solvents such as dimethylformamide and dimethyl sulfoxide. The raw materials are easy to obtain, cheap and have certain mechanical properties, so that the fiber membrane is often prepared. PAN membrane prepared based on electrostatic spinning technology has good separation effect in water and is often used for water treatment, but due to poor mechanical property, the PAN membrane can not be recycled.
At present, no composite catalytic fiber membrane with good mechanical property and catalytic property exists in the market.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide PAN/CA-Ag/AgBr/AgVO based on an electrostatic spinning process3Composite nanofiber membrane and preparation method thereofThe filtering function of the fiber membrane is combined with the catalyzing function of the photocatalyst, so that the high-efficiency treatment of the wastewater containing organic matters is realized, and meanwhile, the mechanical property of the fiber membrane can be enhanced by adding the catalyst, so that the recycling of the composite catalytic fiber membrane in the wastewater treatment is realized.
The purpose of the invention is realized by the following technical scheme:
the first purpose of the invention is to provide PAN/CA-Ag/AgBr/AgVO3A method of making a composite nanofiber membrane, the method comprising the steps of:
a. preparation of AgVO3；
b. Preparation of Ag/AgBr/AgVO3A composite photocatalyst;
c. dissolving Polyacrylonitrile (PAN) and Cellulose Acetate (CA) in N, N-dimethylformamide, and adding the Ag/AgBr/AgVO prepared in the step b3Compounding photocatalyst to prepare electrostatic spinning solution, and preparing the composite nanofiber membrane by an electrostatic spinning process.
Further, AgVO in step a3The preparation method adopts a hydrothermal method, and comprises the following specific steps:
1) taking silver nitrate (AgNO) with equal molar mass3) And ammonium metavanadate, wherein silver nitrate and ammonium metavanadate are respectively dissolved in deionized water to respectively prepare a silver nitrate solution and an ammonium metavanadate solution, the silver nitrate solution and the ammonium metavanadate solution have the same concentration, and the concentration ranges of the silver nitrate solution and the ammonium metavanadate solution are both 20-50 mmol.L-1(ii) a Dropwise adding a silver nitrate solution into a sodium molybdate solution, adjusting the pH value of the sodium molybdate solution to 6.0-8.0 by using 1mol/L ammonia water and nitric acid, and stirring for 2-4 h in the dark to obtain a mixed solution;
2) carrying out hydrothermal synthesis reaction on the mixed solution obtained in the step 1), wherein the hydrothermal synthesis reaction condition is that the mixed solution is reacted for 6-10 hours at the temperature of 140-180 ℃, after the reaction is finished and cooled, washing the mixed solution for 3-5 times by using deionized water and absolute ethyl alcohol, and drying the washed mixed solution to remove redundant water or ethyl alcohol to prepare AgVO3。
Further, Ag/AgBr/AgVO in the step b3The preparation method of the composite photocatalyst adopts an in-situ growth method, and comprises the following specific steps:
1) taking silver nitrate (AgNO)3) And AgVO prepared in step a3Said AgVO3And AgNO3The molar ratio of (A) to (B) is 0.5-1.2: 1; mixing the AgVO3And AgNO3Dissolving in purified water to obtain AgVO3-AgNO3Solution of said AgVO3-AgNO3In solution, AgVO3And AgNO3Has a molar concentration of 10 to 30 mmol.L-1；
Separately mixing with AgNO3Dissolving equimolar NaBr in purified water to prepare a NaBr solution; the concentration of NaBr in the NaBr solution is 10-30 mmol.L-1；
2) Dropwise adding the NaBr solution prepared in the step 1) into AgVO3-AgNO3In the solution, AgBr-AgVO is obtained3A reaction system;
AgBr-AgVO3The reaction system is irradiated for 4-8 hours under visible light, and the illumination intensity is 160mW cm-2Depositing on AgVO3The AgBr on the surface generates silver nano particles under visible light to form an Ag/AgBr compound to obtain Ag-AgBr-AgVO3A reaction system;
3) the Ag-AgBr-AgVO obtained in the step 2) is added3Centrifuging a reaction system, collecting precipitate, cleaning for 3-5 times by using deionized water and absolute ethyl alcohol, and drying to remove redundant water or ethyl alcohol to obtain Ag/AgBr/AgVO3A composite photocatalyst of Ag/AgBr/AgVO3Ag/AgBr compound and AgVO in composite photocatalyst3In a molar ratio of 0.5 to 1.2: 1.
Further, in step c, PAN/CA-Ag/AgBr/AgVO3The preparation method of the membrane adopts an electrostatic spinning process, and comprises the following specific steps:
1) dissolving Polyacrylonitrile (PAN) and Cellulose Acetate (CA) in N, N-dimethylformamide, and stirring overnight to form a uniform spinning solution, wherein the mass percentage concentration of polyacrylonitrile in the spinning solution is 6-8%, and the mass percentage concentration of cellulose acetate is 0.8-1.2%;
2) c, enabling the Ag/AgBr/AgVO obtained in the step b to be3Adding the composite photocatalyst into the spinning solution obtained in the step 1), and stirringStirring overnight to uniformly distribute the composite catalyst, and preparing electrostatic spinning solution; the Ag/AgBr/AgVO3The mass ratio of the composite photocatalyst to the polyacrylonitrile is 1: 8-1: 6;
3) obtaining PAN/CA-Ag/AgBr/AgVO from the electrostatic spinning solution prepared in the step 2) by adopting an electrostatic spinning process3Compounding the nanofiber membrane primary product;
preferably, the electrostatic spinning conditions comprise that the flow rate is 1.2-1.8 mL/h, the strength of a high-voltage power supply is 17-23 KV, the receiving distance of a roller is 7-12 cm, and the rotating speed of a roller of a receiver is 60-100 rpm;
4) drying the composite nanofiber membrane primary product prepared in the step 3) for 1-3 hours at the temperature of 60-80 ℃ to obtain the composite nanofiber membrane primary product.
The second purpose of the invention is to provide PAN/CA-Ag/AgBr/AgVO3A composite nanofiber membrane of PAN/CA-Ag/AgBr/AgVO3The composite nanofiber membrane is prepared by the preparation method.
Further, the fiber membrane is formed by fixing the composite photocatalyst on the nanofiber membrane;
the composite photocatalyst comprises Ag/AgBr compound and AgVO3The nanofiber membrane comprises cellulose acetate and polyacrylonitrile;
in the composite photocatalyst, Ag/AgBr compound and AgVO3The molar ratio of (A) to (B) is 0.5-1.2: 1;
in the nanofiber membrane, the mass ratio of cellulose acetate to polyacrylonitrile is 1: 10-1: 5;
the mass ratio of the composite photocatalyst to polyacrylonitrile is 1: 8-1: 6.
It is a third object of the present invention to provide the aforementioned PAN/CA-Ag/AgBr/AgVO3The application of the composite nanofiber membrane in wastewater treatment.
Further, the wastewater is wastewater containing organic pollutants. In a particular embodiment, the main pollutant in the wastewater containing organic pollutants is dye, and in a particular embodiment, the main pollutant in the wastewater containing organic pollutants is rhodamine B.
The invention selects AgBr and AgVO3The AgBr photocatalyst has the advantages of simple operation method, mild reaction conditions, low energy consumption and wide application range, and is very suitable for preparing efficient and stable photocatalysts. Depositing AgBr on AgVO3On the surface of the nano rod, AgBr can generate silver nano particles under light to form a ternary heterojunction, and the Ag/AgBr/AgVO is prepared3A composite photocatalyst is provided. Meanwhile, the invention also defines the dosage ratio of the three components, and the composite catalyst has high-efficiency photocatalytic capability within the dosage ratio range defined by the invention.
However, due to Ag/AgBr/AgVO3The composite photocatalyst is a powdery solid, is easy to gather in the using process and is not beneficial to the performance of the photocatalyst, and the powder is difficult to recover and is easy to cause secondary pollution to water. Therefore, the invention uses Ag/AgBr/AgVO3The composite photocatalyst is fixed on a Polyacrylonitrile (PAN) nanofiber membrane based on an electrostatic spinning technology, so that the problem of easy agglomeration of the composite photocatalyst is solved; Ag/AgBr/Ag2MoO4The surface of the composite catalyst contains a large number of functional groups which can be combined with groups such as cyano-group of polyacrylonitrile and the like, so that the mechanical property of the nanofiber membrane is improved, and the mechanical property of the fiber membrane is improved. The Cellulose Acetate (CA) is introduced into the fiber membrane, is a cellulose derivative, is easily soluble in organic solvents, is rich in raw materials and low in cost, can further improve the mechanical property of the fiber membrane, realizes the recycling of the materials, and can be recycled.
The technical scheme of the invention has the following beneficial effects:
1. the invention creatively prepares PAN/CA-Ag/AgBr/AgVO3The composite fiber membrane is characterized in that the composite catalyst is dispersed on the PAN/CA fiber membrane by adopting an electrostatic spinning technology, so that the catalyst can be uniformly dispersed, the agglomeration of catalyst nanoparticles is overcome, and the dispersibility of the catalyst is increased, thereby improving the Ag/AgBr/AgVO3The catalytic performance of the catalyst. The photocatalysis of the photocatalyst and the filtration of the fiber membrane are combined to realize the high-efficiency treatment of the dye wastewater.
2. The polyacrylonitrile has the characteristics of good spinnability, low toxicity, good chemical stability, good light resistance and weather resistance and the like, and is beneficial to keeping the integrity of the structure of the electrostatic spinning membrane in the filtering process;
3. the cellulose acetate can improve the mechanical strength of the fiber membrane and is beneficial to the cyclic utilization of the fiber membrane. In addition, the cellulose acetate is a biomass material, has biocompatibility and cannot cause secondary pollution to water.
4.Ag/AgBr/AgVO3The function of the composite catalyst is as follows: Ag/AgBr/AgVO3As an inorganic nano particle, the functional group on the surface of the inorganic nano particle can be combined with the group on the fiber membrane, thereby improving the mechanical strength of the nano fiber membrane. In addition, Ag/AgBr/AgVO3As an efficient photocatalyst, the photocatalyst can rapidly degrade dye molecules in a dye solution to achieve the aim of purifying water.
5. The invention creatively prepares PAN/CA-Ag/AgBr/AgVO3The fiber membrane combines the filtering action of the nanofiber membrane with the photosynthesis of the photocatalyst, so that the high-speed treatment of the dye wastewater is realized, and the mechanical strength of the dye wastewater is enhanced by adding the cellulose acetate. Thus PAN/CA-Ag/AgBr/AgVO3The fiber membrane not only has excellent photocatalytic performance, but also has good recycling performance. The novel nano composite material can be used for preparing various novel catalyst materials with high catalytic performance and easy recovery, is expected to be applied to the field of wastewater treatment, meets the requirement of sustainable development, is easy to widely popularize and apply, and realizes industrial production.
6. The fiber membrane obtained by the invention is easy to carry, plays a good role in separating in wastewater treatment, and contains Ag/AgBr/AgVO3Therefore, the fiber membrane can catalyze and degrade pollutants in the sun, and has obvious effect on wastewater treatment.
Drawings
FIG. 1 shows PAN/CA-Ag/AgBr/AgVO prepared in example 13Nanofiber membrane, PAN/CA nanofiber membrane prepared in comparative example 2, and PAN/CA-AgVO prepared in comparative example 33Separating rhodamine B image by a nanofiber membrane.
FIG. 2 is P prepared in example 1AN/CA-Ag/AgBr/AgVO3Nanofiber membrane, PAN/CA-AgVO prepared in comparative example 33And (3) a graph of the degradation effect of the nanofiber membrane on rhodamine B. Wherein the content of the first and second substances,
FIG. 2a shows PAN/CA-AgVO3Graph of dye color change over time when rhodamine B dye solutions were processed with the membrane.
FIG. 2b shows PAN/CA-Ag/AgBr/AgVO3Graph of dye color change over time when processing rhodamine B dye solutions.
FIG. 3 shows the PAN nanofiber membrane prepared in comparative example 1, CA, PAN/CA-Ag/AgBr/AgVO prepared in example 13Infrared spectra of the membrane, the PAN/CA nanofiber membrane prepared in comparative example 2;
FIG. 4 shows PAN/CA-Ag/AgBr/AgVO prepared in example 13Active substance capture profile of nanofiber membrane;
FIG. 5 shows the PAN nanofiber membrane prepared in comparative example 1, the PAN/CA-Ag/AgBr/AgVO prepared in example 13Water flux plots for nanofiber membranes, PAN/CA nanofiber membrane prepared in comparative example 2;
FIG. 6 shows the PAN nanofiber membrane prepared in comparative example 1, the PAN/CA-Ag/AgBr/AgVO prepared in example 13Mechanical property test charts of the nanofiber membrane and the PAN/CA nanofiber membrane prepared in comparative example 2;
FIG. 7 shows PAN/CA-Ag/AgBr/AgVO prepared in example 13Cyclability profile of nanofiber membrane.
FIG. 8 shows PAN/CA-Ag/AgBr/AgVO prepared in example 13Nanofiber membrane and PAN/CA-Ag/AgBr/AgVO prepared in comparative example 43Degradation of the nanofiber membrane 3 is compared.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claimed invention.
Abbreviations in the following examples:
ag represents silver;
AgBr represents silver bromide;
AgVO3represents silver metavanadate;
PAN represents polyacrylonitrile;
CA represents cellulose acetate;
RhB represents rhodamine B.
EXAMPLE 1 preparation of PAN/CA-Ag/AgBr/AgVO3Film
Step one, AgVO3The preparation method of the catalyst adopts a hydrothermal method, and comprises the following specific steps:
1) weighing 1mmol of silver nitrate (AgNO)3) Added to 40mL of deionized water and stirred to dissolve completely, which was designated as solution a. An additional 1mmol of ammonium metavanadate was weighed into 40mL of deionized water and stirred to obtain solution B. The solution A was slowly dropped into the solution B dropwise, the pH thereof was adjusted to 7.0 using 1mol/L ammonia water and nitric acid, and the mixture was stirred in the dark for 3 hours to obtain a mixed solution.
2) The mixture was transferred to a 100mL autoclave, placed in an oven, and subjected to hydrothermal synthesis reaction at 160 ℃ for 8 hours. After natural cooling, washing with deionized water and absolute ethyl alcohol for 3-5 times, drying to remove excess water or ethyl alcohol, and preparing to obtain AgVO3。
Step two, Ag/AgBr/AgVO3The preparation method of the composite photocatalyst adopts an in-situ growth method, and comprises the following specific steps:
taking 1mmol of AgVO obtained in the first step3Adding into 50mL of purified water, and adding 1mmol of silver nitrate, namely AgVO3And AgNO3In a molar ratio of 1: 1;
stirring to mix them uniformly, preparing to obtain AgVO3-AgNO3Solution of said AgVO3-AgNO3In solution; AgVO (AgVO)3And AgNO3Has a molar concentration of 20 mmol.L-1；
Adding 1mmol NaBr into 50mL of purified water, stirring, and preparing to obtain NaBr solution, wherein the molar concentration of NaBr is 20 mmol.L-1。
Adding NaBr solution dropwise to AgVO3-AgNO3In the solution, AgBr-AgVO is obtained3A reaction system; AgBr-AgVO3Irradiating the reaction system for 5 hours under visible light to deposit on AgVO3The AgBr on the surface generates silver nano particles under visible light to form an Ag/AgBr compound. Centrifuging, collecting precipitate, washing with deionized water and absolute ethyl alcohol for 3-5 times, and drying to obtain Ag/AgBr/AgVO3A composite photocatalyst of Ag/AgBr/AgVO3Ag/AgBr compound and AgVO in composite photocatalyst3In a 1:1 molar ratio.
Step three, PAN/CA-Ag/AgBr/AgVO3The preparation method of the composite membrane adopts an electrostatic spinning process and comprises the following specific steps:
1) adding 1.75g of polyacrylonitrile and 0.25g of cellulose acetate into 23g N, N-dimethylformamide, and stirring overnight to form a uniform spinning solution, wherein the mass fraction of polyacrylonitrile in the spinning solution is 7%, and the mass fraction of cellulose acetate is 1%.
2) Then 0.25g of Ag/AgBr/AgVO prepared in the second step3Adding the composite photocatalyst into the spinning solution obtained in the step 1), and stirring overnight to ensure that the composite photocatalyst is uniformly distributed, namely an electrostatic spinning solution;
3) injecting the electrostatic spinning solution obtained in the step 1) into an injector, and obtaining PAN/CA-Ag/AgBr/AgVO by selecting JDF05 type electrostatic spinning equipment3Compounding the fiber membrane primary product; the conditions of electrostatic spinning are that the flow rate is 1.6mL/h, the strength of a high-voltage power supply is 19KV, the receiving distance of a roller is 9cm, and the rotating speed of a roller of a receiver is 80 rpm.
4) Drying the fiber membrane primary product prepared in the step 3) at 60 ℃ for 2h to obtain the composite nanofiber membrane.
In the composite photocatalyst, Ag/AgBr compound and AgVO3In a molar ratio of 1: 1;
in the nanofiber membrane, the mass ratio of cellulose acetate to polyacrylonitrile is 1: 7;
the mass ratio of the composite photocatalyst to polyacrylonitrile is 1: 7.
EXAMPLE 2 preparation of PAN/CA-Ag/AgBr/AgVO3Membrane 2
Step one, AgVO3The preparation method of the catalyst adopts a hydrothermal method, and comprises the following specific steps:
1) weighing 1mmol of silver nitrate (AgNO)3) Added to 40mL of deionized water and stirred to dissolve completely, which was designated as solution a. An additional 1mmol of ammonium metavanadate was weighed into 40mL of deionized water and stirred to obtain solution B. The solution A was slowly dropped into the solution B dropwise, the pH thereof was adjusted to 7.0 using 1mol/L ammonia water and nitric acid, and the mixture was stirred in the dark for 3 hours to obtain a mixed solution.
2) The mixture was transferred to a 100mL autoclave, placed in an oven, and subjected to hydrothermal synthesis reaction at 160 ℃ for 8 hours. After natural cooling, washing with deionized water and absolute ethyl alcohol for 3-5 times, drying to remove excess water or ethyl alcohol, and preparing to obtain AgVO3。
Step two, Ag/AgBr/AgVO3The preparation method of the composite photocatalyst adopts an in-situ growth method, and comprises the following specific steps:
taking 1mmol of AgVO obtained in the first step3Adding into 50mL of purified water, and adding 1mmol of silver nitrate, namely AgVO3And AgNO3In a molar ratio of 1: 1;
stirring to mix them uniformly, preparing to obtain AgVO3-AgNO3Solution of said AgVO3-AgNO3In solution, the AgVO3And AgNO3Has a molar concentration of 20 mmol.L-1；
Adding 0.8mmol of NaBr into 50mL of purified water, stirring, and preparing to obtain NaBr solution, wherein the molar concentration of NaBr is 16 mmol.L-1；。
Adding NaBr solution dropwise to the AgVO3-AgNO3In the solution, AgBr-AgVO is obtained3A reaction system; AgBr-AgVO3Irradiating the reaction system for 5 hours under visible light to deposit on AgVO3The AgBr on the surface generates silver nano particles under visible light to form an Ag/AgBr compound. Centrifuging, collecting precipitate, washing with deionized water and absolute ethyl alcohol for 3-5 times, and drying to obtain Ag/AgBr/AgVO3A composite photocatalyst of Ag/AgBr/AgVO3Ag in composite photocatalystAgBr Complex and AgVO3In a molar ratio of 0.8: 1.
Step three, PAN/CA-Ag/AgBr/AgVO3The preparation method of the composite membrane adopts an electrostatic spinning process and comprises the following specific steps:
1) adding 1.75g of polyacrylonitrile and 0.25g of cellulose acetate into 23g N, N-dimethylformamide, and stirring overnight to form a uniform spinning solution, wherein the mass fraction of polyacrylonitrile in the spinning solution is 7%, and the mass fraction of cellulose acetate is 1%.
2) Then 290mg of Ag/AgBr/AgVO prepared in the second step3Adding the composite photocatalyst into the spinning solution obtained in the step 1), and stirring overnight to ensure that the composite photocatalyst is uniformly distributed, namely the electrostatic spinning solution;
3) injecting the electrostatic spinning solution obtained in the step 1) into an injector, and obtaining PAN/CA-Ag/AgBr/AgVO by selecting JDF05 type electrostatic spinning equipment3A composite film primary product; the conditions of electrostatic spinning are that the flow rate is 1.6mL/h, the strength of a high-voltage power supply is 20KV, the receiving distance of a roller is 10cm, and the rotating speed of a roller of a receiver is 80 rpm.
4) Drying the fiber membrane primary product prepared in the step 3) at 60 ℃ for 2h to obtain the composite nanofiber membrane.
In the composite photocatalyst, Ag/AgBr compound and AgVO3In a molar ratio of 0.8: 1;
in the nanofiber membrane, the mass ratio of cellulose acetate to polyacrylonitrile is 1: 7;
the mass ratio of the composite photocatalyst to polyacrylonitrile is 1: 6.
Comparative example 1 preparation of PAN nanofiber Membrane
1) Adding 1.75g of polyacrylonitrile into 23.25g N, N-dimethylformamide, and stirring overnight to form a uniform spinning solution, wherein the mass fraction of polyacrylonitrile in the prepared spinning solution is 7%.
2) And (2) injecting the spinning solution obtained in the step 1) into an injector, and selecting JDF05 type electrostatic spinning equipment, wherein the electrostatic spinning conditions are that the flow rate is 1.6mL/h, the strength of a high-voltage power supply is 19KV, the receiving distance of a roller is 9cm, and the rotating speed of a receiver roller is 80rpm, so as to obtain a fiber membrane primary product.
3) Drying the fiber membrane primary product prepared in the step 2) at 60 ℃ for 2h to obtain the PAN nanofiber membrane.
Comparative example 2 preparation of PAN/CA composite nanofiber Membrane
1) Adding 1.75g of polyacrylonitrile and 0.25g of cellulose acetate into 23g N, N-dimethylformamide, and stirring overnight to form a uniform spinning solution, wherein the mass fraction of polyacrylonitrile in the spinning solution is 7%, and the mass fraction of cellulose acetate is 1%.
2) And (2) injecting the spinning solution obtained in the step 1) into an injector, and selecting JDF05 type electrostatic spinning equipment, wherein the electrostatic spinning conditions are that the flow rate is 1.6mL/h, the strength of a high-voltage power supply is 19KV, the receiving distance of a roller is 9cm, and the rotating speed of a receiver roller is 80rpm, so as to obtain a fiber membrane primary product.
3) Drying the fiber membrane primary product prepared in the step 2) at 60 ℃ for 2h to obtain the PAN/CA composite nanofiber membrane.
COMPARATIVE EXAMPLE 3 preparation of PAN/CA-AgVO3Film
Step one, AgVO3The preparation method of the catalyst adopts a hydrothermal method, and comprises the following specific steps:
1) weighing 1mmol of silver nitrate (AgNO)3) Added to 40mL of deionized water and stirred to dissolve completely, which was designated as solution a. An additional 1mmol of ammonium metavanadate was weighed into 40mL of deionized water and stirred to obtain solution B. The solution A was slowly dropped into the solution B dropwise, the pH thereof was adjusted to 7.0 using 1mol/L ammonia water and nitric acid, and the mixture was stirred in the dark for 3 hours to obtain a mixed solution.
2) The mixture was transferred to a 100mL autoclave, placed in an oven, and subjected to hydrothermal synthesis reaction at 160 ℃ for 8 hours. After natural cooling, washing with deionized water and absolute ethyl alcohol for 3-5 times, drying, and preparing to obtain AgVO3。
Step two, PAN/CA-AgVO3The preparation method of the composite membrane adopts an electrostatic spinning process and comprises the following specific steps:
1) adding 1.75g of polyacrylonitrile and 0.25g of cellulose acetate into 23g N, N-dimethylformamide, and stirring overnight to form a uniform spinning solution, wherein the mass fraction of polyacrylonitrile in the spinning solution is 7%, and the mass fraction of cellulose acetate is 1%.
2) 0.25g of AgVO prepared in step one is subsequently added3Adding a photocatalyst into the spinning solution obtained in the step 1), adding the catalyst into the spinning solution, and stirring overnight to uniformly distribute the composite catalyst, thereby obtaining an electrostatic spinning solution;
3) injecting the electrostatic spinning solution obtained in the step 1) into an injector, and obtaining PPAN/CA-AgVO by selecting JDF05 type electrostatic spinning equipment3Compounding the fiber membrane primary product; the conditions of electrostatic spinning are that the flow rate is 1.6mL/h, the strength of a high-voltage power supply is 19KV, the receiving distance of a roller is 9cm, and the rotating speed of a roller of a receiver is 80 rpm.
4) Drying the fiber membrane primary product prepared in the step 3) at 60 ℃ for 2h to obtain the composite nanofiber membrane.
COMPARATIVE EXAMPLE 4 preparation of PAN/CA-Ag/AgBr/AgVO3Membrane 3
Step one, AgVO3The preparation method of the catalyst adopts a hydrothermal method, and comprises the following specific steps:
1) weighing 1mmol of silver nitrate (AgNO)3) Added to 40mL of deionized water and stirred to dissolve completely, which was designated as solution a. An additional 1mmol of ammonium metavanadate was weighed into 40mL of deionized water and stirred to obtain solution B. The solution A was slowly dropped into the solution B dropwise, the pH thereof was adjusted to 7.0 using 1mol/L ammonia water and nitric acid, and the mixture was stirred in the dark for 3 hours to obtain a mixed solution.
2) The mixture was transferred to a 100mL autoclave, placed in an oven, and subjected to hydrothermal synthesis reaction at 160 ℃ for 8 hours. After natural cooling, washing with deionized water and absolute ethyl alcohol for 3-5 times, drying to remove excess water or ethyl alcohol, and preparing to obtain AgVO3。
Step two, Ag/AgBr/AgVO3The preparation method of the composite photocatalyst adopts an in-situ growth method, and comprises the following specific steps:
taking 1mmol of AgVO obtained in the first step3Adding into 50mL of purified water, and adding 2mmol of silver nitrate, namely AgVO3And AgNO3In a molar ratio of 1: 2;
stirring to mix them uniformly, preparing to obtain AgVO3-AgNO3Solution of said AgVO3-AgNO3AgVO in solution3And AgNO3The molar concentrations of (A) and (B) are respectively 20 and 40 mmol.L-1；
Adding 2mmol of NaBr into 50mL of purified water, stirring, and preparing to obtain NaBr solution, wherein the molar concentration of NaBr is 40 mmol.L-1。
Adding NaBr solution dropwise to the AgVO3-AgNO3In the solution, AgBr-AgVO is obtained3A reaction system; AgBr-AgVO3Irradiating the reaction system for 5 hours under visible light to deposit on AgVO3The AgBr on the surface generates silver nano particles under visible light to form an Ag/AgBr compound. Centrifuging, collecting precipitate, washing with deionized water and absolute ethyl alcohol for 3-5 times, and drying to obtain Ag/AgBr/AgVO3A composite photocatalyst of Ag/AgBr/AgVO3Ag/AgBr compound and AgVO in composite photocatalyst3In a molar ratio of 2: 1.
Step three, PAN/CA-Ag/AgBr/AgVO3The preparation method of the composite membrane adopts an electrostatic spinning process and comprises the following specific steps:
1) adding 1.75g of polyacrylonitrile and 0.25g of cellulose acetate into 23g N, N-dimethylformamide, and stirring overnight to form a uniform spinning solution, wherein the mass fraction of polyacrylonitrile in the spinning solution is 7%, and the mass fraction of cellulose acetate is 1%.
2) Then 0.175g of Ag/AgBr/AgVO prepared in the second step3Adding the composite photocatalyst into the spinning solution obtained in the step 1), and stirring overnight to ensure that the composite photocatalyst is uniformly distributed, namely an electrostatic spinning solution;
3) injecting the electrostatic spinning solution obtained in the step 1) into an injector, and obtaining PAN/CA-Ag/AgBr/AgVO by selecting JDF05 type electrostatic spinning equipment3Compounding the fiber membrane primary product; the conditions of electrostatic spinning are that the flow rate is 1.5mL/h, the strength of a high-voltage power supply is 20KV, the receiving distance of a roller is 10cm, and the rotating speed of a roller of a receiver is 70 rpm.
4) Drying the fiber membrane primary product prepared in the step 3) at 60 ℃ for 2h to obtain the PAN/CA-Ag/AgBr/AgVO3 membrane 3.
In the composite photocatalyst, Ag/AgBr compound and AgVO3In a molar ratio of 2: 1;
in the nanofiber membrane, the mass ratio of cellulose acetate to polyacrylonitrile is 1: 7;
the mass ratio of the composite photocatalyst to polyacrylonitrile is 1: 10.
Examples of the experiments
1) The PAN/CA-Ag/AgBr/AgVO prepared in example 1 was taken3Nanofiber membrane, PAN/CA nanofiber membrane prepared in comparative example 2, and PAN/CA-AgVO prepared in comparative example 33The nano fiber membrane samples (all circular membranes with the diameter of 7 cm) are placed in a photocatalytic reactor, a rhodamine B dye blank control without the fiber membrane samples is additionally arranged, 450mL of prepared rhodamine B solution with the concentration of 10mg/L is added in a water tank, a peristaltic pump is started, the rotating speed is 10r/s, and the photocatalytic reactor is placed under a 250w xenon lamp to start photocatalytic reaction. In the reaction process, the reaction temperature is kept at room temperature, the sampling is carried out every 30min for the first 2h, and every 1h for the second 3h, and the sampling is carried out for 5 h. The corresponding value of absorbance a at the uv maximum absorption wavelength 554 for the sample was recorded.
The degradation rate formula is as follows: eta (%) ═ a0-A)/A0×100％
Eta-rhodamine B degradation rate;
a-absorbance after degradation;
A0-absorbance before degradation of rhodamine B.
And drawing a visible light catalytic activity diagram (figure 1) of different catalyst samples for degrading rhodamine B according to the obtained degradation rate.
As can be seen from fig. 1, within 5 hours of light irradiation, the degradation of RhB itself was negligible (control group "RhB-visible light" in fig. 1). The removal rate of RhB after 5h of the PAN/CA nanofiber membrane prepared in comparative example 2 is about 15%, and the PAN/CA-AgVO prepared in comparative example 33And PAN/CA-Ag/AgBr/AgVO prepared in example 13The removal rate of RhB was 21% and 92%, respectively. This is because of the Ag/AgBr/AgVO3For the photocatalyst, Ag/AgBr/AgVO3The photocatalyst has SPR effectAnd can absorb more visible light, so PAN/CA-Ag/AgBr/AgVO prepared in example 13The photocatalytic degradation efficiency of the RhB dye solution is obviously improved.
2) Observation of PAN/CA-Ag/AgBr/AgVO prepared in example 13Nanofiber membrane, PAN/CA-AgVO prepared in comparative example 33The degradation effect of the nanofiber membrane rhodamine B is the same as that of experiment 1) except for the sample and the sampling time, the rhodamine B sample is taken at 0 hour, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 3 hours, 4 hours and 5 hours respectively, and the sample is put into a test tube to observe the color change.
The results show that: relative to PAN/CA-AgVO3，PAN/CA-Ag/AgBr/AgVO3The RhB color change of the film treatment is obvious, the red color gradually becomes lighter from the beginning to be colorless, and the PAN/CA-Ag/AgBr/AgVO of the invention is shown3The composite fiber membrane has better catalytic performance under visible light.
3) The PAN nanofiber membrane prepared in comparative example 1, CA, PAN/CA-Ag/AgBr/AgVO prepared in example 1 were taken3Infrared spectroscopic analysis was performed on the membrane and the PAN/CA nanofiber membrane prepared in comparative example 2.
The infrared spectrum (fig. 3) shows: the characteristic peak contained in PAN is about 2239cm-1This is caused by C xi N stretching. The peak at 1730cm-1 is due to stretching vibration of C ═ O. At 2934cm-1And 1452cm-1Two peaks at (C) belong to CH respectively2C-H stretching and C-H bending of the groups. CA at 1218cm-1、1027cm-1、1364cm-1And 1730cm-1Absorption peaks near the absorption peaks are C-O stretching vibration, C-C skeleton vibration and-OCOCH3Radical vibration and C ═ O stretching vibration. The IR chromatogram of PAN/CA shows characteristic peaks that can be found in the individual IR spectra of both PAN and CA, which demonstrates the success of PAN/CA fiber preparation. In the range of 1000 to 500cm-1In the infrared spectral peak range of PAN/CA-Ag/AgBr/AgVO3The composite membrane and the PAN/CA membrane showed significant differences. Bending vibration in this range is likely to be associated with V-O-V and VO of the photocatalyst3The groups are related. These results confirm PAN/CA-Ag/AgBr/AgVO3And (4) successfully preparing the composite membrane.
4) PAN/CA-Ag/AgBr/AgVO prepared in example 13Active substance trapping experiment of nanofiber membrane
The experimental method comprises the following steps: except that TEMPOL (2 mmol. L) is added into the rhodamine B dye solution before the experiment-1) tert-Butanol (10 mmol. L)-1)、EDTA(10mmol·L-1) And K2Cr2O7(10mmol·L-1) Respectively as. O2 -、·OH、h+And e-To define the active substance. Otherwise the operation was the same as in experiment 1), and the experimental sample was PAN/CA-Ag/AgBr/Ag prepared in example 12MoO4And (3) a membrane.
The experimental results show that: the addition of EDTA and TEMPOL greatly reduces the photocatalytic efficiency, which shows that+And O2 -Plays a major role in the photocatalytic process. Adding TB (tert-butanol) and K2Cr2O7The photocatalytic efficiency of (A) was very high, and it was found that the effect of OH and e-in the photocatalytic activity was very weak. In the photocatalytic process, h is mainly+And O2 -And occupies a dominant position. 5) PAN nanofiber membrane prepared in comparative example 1, PAN/CA-Ag/AgBr/AgVO prepared in example 13Water flux measurements of membranes, PAN/CA nanofiber membranes prepared in comparative example 2.
The experimental method comprises the following steps: in practical use, the composite fiber membrane is used for treating sewage in a filtration mode, and the water flux is also one of the factors for considering the sewage treatment effect. The filtration of this experiment was normally performed under gravity separation without any external pressure. And loading the prepared composite fiber membrane on a filtering device. Before filtration, the fibers were soaked in deionized water and water was then fed through the upper end of the filter. The permeation flux of the fibers was tested through the effective filtration zone of the fiber membrane. The water flux of the fiber membrane was calculated using the following formula:
Figure BDA0002819424780000131
j-water flux(L/(m2·h))；
Q-volume of permeated water (L);
effective area (m) of A-fiber Membrane2)；
T-test time (h).
As shown in FIG. 5, the PAN nanofiber membrane has a water flux of 302 L.m-2·h-1This is related to the hydrophilicity of PAN fibers. After the CA is added into the electrospinning solution, the water flux of the PAN/CA nano composite material is controlled to be 302 L.m-2·h-1Reduced to 271 L.m-2·h-1Compared with pure PAN nanofiber membrane, the reduction is 10%. Wherein, PAN/CA-Ag/AgBr/AgVO3Has a minimum water flux of 196.4 L.m-2·h-1. Meanwhile, due to the loading of Ag/AgBr/AgVO3Photocatalyst, composite membrane pair PAN/CA-Ag/AgBr/AgVO3The rejection rate of (a) is slightly increased, which may be due to adsorption of dye molecules on the fiber surface by the nanoparticles.
6) PAN nanofiber membrane prepared in comparative example 1, PAN/CA-Ag/AgBr/AgVO prepared in example 13Membrane, PAN/CA nanofiber membrane prepared in comparative example 2 mechanical property test
The experimental method comprises the following steps: at 1mm min on a TY8000 series material testing machine-1Tensile speed of (2) the mechanical strength of the film was tested.
The experimental results show that: the tensile stress (2.0MPa) of PAN nanofiber is poor, and the requirement of practical application cannot be met. The stress of PAN/CA fiber is obviously higher than that of pure PAN membrane, is 2.45MPa, and is increased by 22.5%. Adding Ag/AgBr/AgVO3The catalyst enters a spinning solution, PAN/CA-Ag/AgBr/AgVO3The membrane stress increases due to the high specific surface area and excellent dispersion of the catalyst, thereby transferring the PAN/CA fibers and fiber stress to the catalyst itself. PAN/CA-Ag/AgBr/AgVO3The film has good mechanical property and wide application prospect.
7) PAN/CA-Ag/AgBr/AgVO prepared in example 13Nanofiber membrane cyclability experiment
The experimental method comprises the following steps: the fiber membrane which is circulated once in the experiment 1) is taken out, then 450mL of 10mg/L rhodamine B solution is added, the second circulation is carried out under the same condition, 5 circulations are continuously carried out totally, after each filtration, the fiber is soaked in deionized water for 15 minutes, and then is washed by the deionized water for the next use.
The results show that: PAN/CA-PAN/CA-Ag/AgBr/AgVO loaded with catalyst3The degradation rate of the composite membrane after 5 times of circulation is still more than 80 percent, which proves that the composite membrane can be recycled.
8) PAN/CA-Ag/AgBr/AgVO prepared in example 13Nano fiber film and PAN/CA-Ag/AgBr/AgVO prepared in comparative example 43Comparison of catalytic effects of nanofiber membrane 3:
the experimental method comprises the following steps: comparative example 1 PAN/CA-Ag/AgBr/AgVO3Nano fiber film and PAN/CA-Ag/AgBr/AgVO prepared in comparative example 43The nanofiber membrane 3 is used for degrading rhodamine B, the test method is the same as that of experiment 1 except for the sample and the sampling time, the rhodamine B sample is taken when the sampling time is 0 hour, 1 hour, 2 hours, 3 hours, 4 hours and 5 hours respectively, and the absorbance of the rhodamine B sample is measured.
The results show that: PAN/CA-Ag/AgBr/AgVO prepared in comparative example 43Compared with the catalytic effect of the nanofiber membrane 3, the PAN/CA-Ag/AgBr/AgVO prepared by the method of the invention3The nanofiber membrane is reduced by 41 percent, and it can be seen that the obtained optical composite catalyst can not obtain excellent catalytic effect under any proportion.
Application example
The fiber membrane is adopted to purify water by adopting a filtering mode, a peristaltic pump is used as power for transporting water, and the water inlet flow is less than 30 ml/min-1The light source is natural light, and the usage amount of the fiber film is about 0.6-0.8 g of the fiber film for 1L of water.

Claims (10)

1. PAN/CA-Ag/AgBr/AgVO3A method of making a composite nanofiber membrane, comprising the steps of:
a. preparation of AgVO3；
b. Preparation of Ag/AgBr/AgVO3A composite photocatalyst;
c. polyacrylonitrile (PAN),Dissolving Cellulose Acetate (CA) in N, N-dimethylformamide, and adding the Ag/AgBr/AgVO prepared in the step b3Preparing a composite photocatalyst into an electrostatic spinning solution, and preparing the composite nanofiber membrane through an electrostatic spinning process.
2. The method according to claim 1, wherein AgVO in step a3The preparation method adopts a hydrothermal method, and comprises the following specific steps:
1) respectively dissolving silver nitrate and ammonium metavanadate with equal molar mass in deionized water to prepare a silver nitrate solution and an ammonium metavanadate solution, wherein the silver nitrate solution and the ammonium metavanadate solution have the same concentration, and the concentration ranges from 20mmol to 50 mmol.L-1(ii) a Dropwise adding a silver nitrate solution into an ammonium metavanadate solution, adjusting the pH value of the ammonium metavanadate solution to 6.0-8.0 by using 1mol/L ammonia water and nitric acid, and stirring for 2-4 hours in the dark to obtain a mixed solution;
2) carrying out hydrothermal synthesis reaction on the mixed solution obtained in the step 1), wherein the hydrothermal synthesis reaction condition is that the mixed solution reacts for 6-10 hours at the temperature of 140-180 ℃, after the reaction is finished and cooled, washing the mixed solution for 3-5 times by using deionized water and absolute ethyl alcohol, and drying the washed solution to obtain AgVO3。
3. The method of claim 1, wherein in step b Ag/AgBr/AgVO3The preparation method of the composite photocatalyst adopts an in-situ growth method, and comprises the following specific steps:
1) taking AgNO3And AgVO prepared in step a3Said AgVO3And AgNO3The molar ratio of (A) to (B) is 0.5-1.2: 1; mixing the AgVO3And AgNO3Dissolving in purified water to obtain AgVO3-AgNO3Solution of said AgVO3-AgNO3In solution, AgVO3And AgNO3Has a molar concentration of 10 to 30 mmol.L-1；
Separately mixing with AgNO3Dissolving equimolar NaBr in purified water to prepare a NaBr solution; the molar concentration of NaBr is 10-30 mmol.L-1；
2) Prepared by the step 1)The prepared NaBr solution is added dropwise to AgVO3-AgNO3In the solution, AgBr-AgVO is obtained3A reaction system;
AgBr-AgVO3Irradiating the reaction system for 4-8 hours under visible light to enable AgBr to generate silver nanoparticles under visible light to form an Ag/AgBr compound to obtain Ag-AgBr-AgVO3A reaction system;
3) the Ag-AgBr-AgVO obtained in the step 2) is added3Centrifuging a reaction system, collecting precipitate, cleaning for 3-5 times by using deionized water and absolute ethyl alcohol, and drying to obtain Ag/AgBr/AgVO3A composite photocatalyst of Ag/AgBr/AgVO3Ag/AgBr compound and AgVO in composite photocatalyst3In a molar ratio of 0.5 to 1.2: 1.
4. The method of claim 1, wherein PAN/CA-Ag/AgBr/AgVO is used in step c3The preparation method of the membrane adopts an electrostatic spinning process, and comprises the following specific steps:
1) dissolving polyacrylonitrile and cellulose acetate in N, N-dimethylformamide, and stirring to form a uniform spinning solution, wherein the mass percentage concentration of the polyacrylonitrile in the spinning solution is 6-8%, and the mass percentage concentration of the cellulose acetate in the spinning solution is 0.8-1.2%;
2) c, enabling the Ag/AgBr/AgVO obtained in the step b to be3Adding the composite photocatalyst into the spinning solution obtained in the step 1), and stirring to ensure that the composite photocatalyst is uniformly distributed to prepare an electrostatic spinning solution; the Ag/AgBr/AgVO3The mass ratio of the composite photocatalyst to the polyacrylonitrile is 1: 8-1: 6;
3) obtaining PAN/CA-Ag/AgBr/AgVO from the electrostatic spinning solution prepared in the step 2) by adopting an electrostatic spinning process3Compounding the nanofiber membrane primary product;
4) drying the primary product of the composite nanofiber membrane prepared in the step 3) for 1-3 hours at the temperature of 60-80 ℃ to obtain the composite nanofiber membrane.
5. The method according to claim 4, wherein the electrospinning in step 3) is carried out under conditions of a flow rate of 1.2-1.8 mL/h, a high voltage power source intensity of 17-23 KV, a roller receiving distance of 7-12 cm, and a receiver roller rotation speed of 60-100 rpm.
6. PAN/CA-Ag/AgBr/AgVO3The composite nanofiber membrane is characterized in that the PAN/CA-Ag/AgBr/AgVO3The composite nanofiber membrane is prepared by the preparation method of any claim from 1 to 5.
7. The PAN/CA-Ag/AgBr/AgVO of claim 63The composite nanofiber membrane is characterized in that the composite photocatalyst is fixed on the nanofiber membrane;
the composite photocatalyst comprises Ag/AgBr compound and AgVO3The nanofiber membrane comprises cellulose acetate and polyacrylonitrile.
8. The PAN/CA-Ag/AgBr/AgVO of claim 73The composite nanofiber membrane is characterized in that in the composite photocatalyst, Ag/AgBr compound and AgVO3The molar ratio of (A) to (B) is 0.5-1.2: 1;
in the nanofiber membrane, the mass ratio of cellulose acetate to polyacrylonitrile is 1: 10-1: 5;
the mass ratio of the composite photocatalyst to polyacrylonitrile is 1: 8-1: 6.
9. The PAN/CA-Ag/AgBr/AgVO of claim 63The application of the composite nanofiber membrane in wastewater treatment.
10. Use according to claim 9, wherein the waste water is waste water containing organic contaminants.
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