CN110438664B - Bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection and preparation method thereof - Google Patents
Bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection and preparation method thereof Download PDFInfo
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Abstract
A bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection and a preparation method thereof belong to the technical field of preparation of ray protection materials. Firstly, preparing tungsten oxide nanorod seed crystals through hydrothermal synthesis, then mixing the tungsten oxide nanorod seed crystals with a high molecular solution to prepare an electrospinning precursor solution, obtaining a nanofiber membrane through an electrostatic spinning process, and obtaining the flexible heterogeneous composite nanofiber through a subsequent two-step hydrothermal process. Due to the physical and chemical properties of tungsten and bismuth tungsten oxide and the structural characteristics of the nano fibers, the obtained fiber film has high protection effect on X and gamma rays and can keep low density, the continuous nano fiber material solves the agglomeration problem of powder materials, the introduction of a non-conductive material avoids the interference of electromagnetic shielding effect on radio communication, and the fiber film can be used for photocatalytic degradation of organic pollutants after the life cycle of the fiber film serving as a high-energy ray protection material is finished, so that the fiber film is a novel nano material with good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of ray protection materials, and particularly relates to a green and environment-friendly bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection and a preparation method thereof.
Background
X-rays (λ 0.001 to 100nm) and γ -rays (λ <0.001nm) are electromagnetic waves having a very short wavelength, and are called high-energy rays, which mainly exhibit particle properties when interacting with a substance. With the long-term development of the fields of medical imaging, interventional radiology, nuclear power, aerospace and the like, people have more and more chances of contacting high-energy rays, and the high-energy rays are proved to be harmful to human bodies after being exposed in the fields for a long time, and the existing high-energy ray shielding materials mainly comprise lead plates and lead-containing vulcanized rubber. Lead has strong scattering to low-energy rays in a weak absorption area (40-80 keV), but has poor flexibility, air permeability and comfort, high quality (the weight of whole body protective equipment is more than 15 kg), large thickness (2.5-5 mm), inconvenient movement after being worn for a long time, and easy to cause diseases such as spinal deformation; meanwhile, as a conductor, the electromagnetic shielding effect of the lead simple substance can cause interference to radio communication, and troubles are caused to remote communication and command coordination which depend on radio waves. In addition, lead and its compounds have biological toxicity, cannot contact with skin, and the production process and waste have great environmental pollution, so a light, non-toxic and high-energy ray shielding material is urgently needed to be found to solve the protection requirements of related practitioners. The essence of X/gamma ray is photon, and according to the interaction principle of photon and matter, the element compound with large atomic number has better protective performance to high-energy ray, mainly based on photoelectric effect in X-ray wave band, such as stable compound of heavy nuclear elements such as rare earth elements (lanthanum, gadolinium, erbium, thulium, ytterbium, etc.), tungsten, bismuth, etc.
The nano material is a material with the characteristic size of material components in the nano level (1-100 nm), is in the intermediate field of macroscopic substances, microscopic atoms and molecules, and is in a new structural state. The nano material has a series of special structures, so that the nano material can generate qualitative change in the aspects of physical properties such as light, electricity, magnetism and the like, can absorb high-energy rays more strongly, and is a ray shielding material with great development prospect. For example, yao rong et al disclose a method for preparing X/γ -ray protective powder (chinese patent application No. 201810189502.1), in which the lamellar structure of bismuth tungstate and graphene oxide in the nano-powder prepared by the method plays an effective scattering role, a multi-band gap system formed by nano rare earth tungsten oxide plays a multistage absorption role for X/γ -rays, metal elements play a shielding role for X/γ -rays, and the synergistic effect of multiple effects achieves a high protective effect for X/γ -rays of different energy levels. The Qiu's distance method discloses a novel flexible lead-free radiation protective garment (Chinese patent application No. 201711147296.X), which uses nontoxic environment-friendly materials such as tantalum, tungsten and barium as functional fillers, has the performance of shielding X/gamma rays equivalent to that of lead, and can effectively protect radiation hazards. However, although the currently reported non-toxic light high-energy ray protection material has better performance, most raw materials used in the preparation process are powder or granular, and the problem of agglomeration is difficult to avoid in large-scale production, and the like, and the problem that the material life cycle is finished and the rare heavy metal elements such as rare earth, tungsten, bismuth and the like are recycled is not considered, so that the operability is limited and the use cost is increased; in some reports, conductive materials such as metal simple substances and carbon materials are used as fillers, so that normal radio communication is blocked by an electromagnetic shielding effect in the practical application process.
In recent years, the composite nanofiber membrane material prepared by electrostatic spinning and post-treatment technologies has a good application prospect in many fields due to the advantages of low density, obvious nanoscale effect, good flexibility, easiness in material recovery and the like. The electrostatic spinning technology is a process of forming continuous one-dimensional nano/micron-sized fibers by polymer solution polarization, jet flow splitting formed by a Taylor cone, receiving and solvent volatilization under the action of high-voltage static electricity, and the diameter of the obtained fibers is usually between 100nm and 1000 nm. By combining different technologies such as coaxial electrospinning, calcining, magnetron sputtering, hydrothermal synthesis and the like, organic nanofibers, inorganic nanofibers and organic/inorganic composite nanofibers with different structures can be obtained through electrostatic spinning, and the method can play a great role in the fields of catalysis, energy storage and conversion, sewage treatment and the like. Among them, inorganic/organic composite nanofibers have received much attention because they have both the function of inorganic substances and the flexibility of polymers.
Disclosure of Invention
The invention aims to provide a bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection and a preparation method thereof, which are used for solving the problems that the traditional lead-containing high-energy ray protection material is heavy and has serious pollution in the production process, nano particles in the use of the lead-free high-energy ray protection material are agglomerated and are not easy to recycle, the radio communication is influenced by the electromagnetic shielding effect and the like, so that the effect of a rare heavy nuclear metal element compound is exerted to the maximum extent, and the practicability of the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane is improved.
In order to realize the purpose, the invention provides a preparation method of bismuth tungstate/tungsten oxide/polymer composite nano-fibers for high-energy ray protection. Firstly, preparing tungsten oxide nanorod seed crystals through hydrothermal synthesis, then mixing the tungsten oxide nanorod seed crystals with a high molecular solution to prepare an electrospinning precursor solution, obtaining a nanofiber membrane through an electrostatic spinning process, and obtaining the flexible bismuth tungstate/tungsten oxide/polymer heterogeneous composite nanofiber through a subsequent two-step hydrothermal process. By changing hydrothermal conditions, the inorganic component on the obtained composite nanofiber can have different structures, such as nanospheres, nanosheets and nanorods. The obtained flexible composite nano fiber film can keep low density while having higher protection effect on X and gamma rays due to the physical and chemical properties of tungsten and bismuth tungsten oxide and the structural characteristics of nano fibers, the agglomeration problem of powder materials is solved by the continuous nano fiber material, the interference of electromagnetic shielding effect on radio communication is avoided by introducing no conductive material, and the flexible composite nano fiber film can be used for photocatalytic degradation of organic pollutants after the life cycle of the high-energy ray protection material is finished, so that the flexible composite nano fiber film is a novel nano material with good application prospect.
The invention relates to a preparation method of a bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection, which comprises the following steps:
(1) dissolving tungstate and an auxiliary agent in deionized water, stirring until the tungstate and the auxiliary agent are completely dissolved, preparing a tungstate aqueous solution with the mass fraction of 3-20%, adjusting the pH value to 1-3, then putting the tungstate aqueous solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6-24 h at 140-240 ℃, naturally cooling to room temperature, filtering, ultrasonically crushing, centrifugally screening, washing and drying to obtain tungsten oxide nanorod seeds with the diameter of below 100nm and the length of below 4 mu m;
(2) mixing a polymer with the tungsten oxide nanorod seeds obtained in the step (1), dissolving the mixture in a solvent, and performing ultrasonic dispersion to obtain an electrostatic spinning precursor suspension;
(3) putting the electrostatic spinning precursor suspension obtained in the step (2) into an injector of electrostatic spinning equipment, wherein the diameter of a stainless steel needle head of the injector is 0.6-2 mm, the working voltage of the electrostatic spinning equipment is 10-25 kV, the stainless steel needle head is used as an anode, a planar aluminum foil or a roller wrapped with the aluminum foil is used as a cathode to receive an electric spinning product, the propelling speed of the injector is 0.5-1.5 mL/h, and the distance between the anode and the cathode is 8-25 cm; carrying out electrostatic spinning for 5-15 h to obtain a polymer/tungsten oxide nanorod seed fiber film;
(4) immersing the polymer/tungsten oxide rod seed fiber membrane obtained in the step (3) into 30-70 mL of an alcoholic solution of tungsten salt, wherein the concentration of the tungsten salt is 15-40mmol/L, then transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 2-12 h at 140-240 ℃, naturally cooling to room temperature, and repeatedly washing the obtained product with water and ethanol to obtain a tungsten oxide/polymer composite nanofiber membrane;
(5) and (3) immersing the tungsten oxide/polymer composite nanofiber membrane obtained in the step (4) into 25-75 mL of mixed alcohol solution of bismuth salt, wherein the concentration of bismuth salt is 5-20mmol/L, then transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 2-12 h at 110-220 ℃, naturally cooling to room temperature, and repeatedly washing the obtained product with ethanol and water to obtain the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection.
In the step (1), the tungstate is one of ammonium tungstate, sodium tungstate, potassium tungstate, tungstic acid or ammonium metatungstate;
the auxiliary agent in the step (1) is Triton X-100, oleic acid, NaCl and Na2SO4、KCl、K2SO4、KNO3The molar ratio of the tungstate to the auxiliary agent is 1: (0.3-2);
the polymer in the step (2) is one of polymethyl methacrylate, polystyrene, polyacrylonitrile, sulfonated polyether ether ketone or polyacrylamide;
the solvent in the step (2) is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetone, chloroform, dichloromethane, ethanol and water;
in the step (2), the mass ratio of the polymer to the nanorod seeds to the solvent is 1: (0.1-1.2): (9-19);
the tungsten salt in the step (4) is one of tungsten trichloride, tungsten pentachloride or tungsten hexachloride;
the alcohol in the step (4) is one of ethanol, n-propanol, isopropanol, n-butanol or isobutanol;
the bismuth salt in the step (5) is one of sodium bismuthate, potassium bismuthate, bismuth nitrate or bismuth trichloride;
the mixed alcohol solution in the step (5) is a mixture of two or more of ethanol, n-propanol, n-butanol, ethylene glycol and glycerol;
the bismuth tungstate/tungsten oxide/polymer composite nanofiber obtained in the step (6) is a nanofiber with a multilevel structure, wherein the microscopic morphology of inorganic components is nanospheres, nanorods or nanosheets, and the average diameter of the fiber is 200-900 nm;
the composite nanofiber membrane obtained in the step (6) is flexible, can be folded, and cannot be broken after being repeatedly bent for more than 1000 times;
the composite nanofiber membrane obtained in the step (6) can be applied to the fields of high-energy photon ray protection and photocatalysis.
The bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane is prepared by the method.
The invention has the advantages that:
the invention provides a preparation method of a bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane, which is characterized in that a flexible polymer nanofiber membrane with tungsten oxide seed crystals is used as a precursor template, and a bismuth tungstate/tungsten oxide nano heterostructure is constructed on the flexible polymer nanofiber membrane through subsequent hydrothermal reaction. The bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane provided by the invention can obtain an effect similar to that of the traditional X-ray and gamma-ray protective materials after being accumulated to a certain thickness, avoids using lead which is a material with a large dispute on the aspects of environmental protection and human health, and is low in density, soft and comfortable to wear. Compared with the previously reported lead-free high-energy ray protection material, the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane provided by the invention has the advantages that the fiber is long and continuous, the self-supported fiber membrane can be bent at will and has certain mechanical strength, the functional nanoparticles are uniformly dispersed and are easy to recover after use, the bare oxide nano heterojunction on the surface of the composite nanofiber membrane can be used for photocatalytic pollutant degradation after recovery, and no conductive and magnetic components can interfere with wireless communication signal propagation and the like during wearing, the function of the heavy core material compound with low storage capacity is exerted to the maximum extent, the heavy core material compound can create economic value in the whole life cycle, the use efficiency is high, the environment is friendly, and the operability and the practical applicability are higher. In addition, the structure of the obtained composite nanofiber can be regulated and controlled by changing reaction conditions, the obtained composite nanofiber can load nanorods, nanospheres, nanosheets and the like, the application range and application potential of the material are greatly improved, and the flexible composite nanofiber membrane provided by the invention can be applied to the fields of high-energy ray protection fillers, photocatalysis and the like. Finally, the preparation process shows that the preparation method provided by the invention has the advantages of easily available raw materials, simple and safe operation and easy realization of industrial-grade large-scale production.
Drawings
FIG. 1: photo illustrations of folding, rolling, and recovery of the flexible composite nanofiber membrane obtained in example 1 (left to right: unfolding, folding, unfolding recovery, rolling around a glass rod, unfolding recovery again);
FIG. 2: scanning electron microscope photo of the composite nanofiber membrane obtained in the embodiment 2 shows that the obtained product is a nanofiber loaded with nanosheets, and the diameter of the nanofiber is 580nm on average;
FIG. 3: the composite nanofiber membrane obtained in example 2 is subjected to a catalytic degradation experiment curve for rhodamine B under simulated sunlight, the abscissa is reaction time, and the ordinate is the ratio of the concentration of rhodamine B to the initial concentration during sampling. The specific test method comprises the following steps: immersing the composite nanofiber membrane into 10mg/L rhodamine B solution under the condition of keeping out of the sun, standing for 30 minutes to achieve adsorption and desorption balance, marking as an abscissa zero point, starting a xenon lamp to adjust the irradiation power to 1000W/m2Sampling once every hour, determining the concentration by using an ultraviolet visible absorption spectrum, and setting a reference sample without illumination, wherein the degradation rate of rhodamine B under illumination can reach 99.42% after 4 hours. The results show that the composite nanofiber membrane prepared by the invention can be recovered as a catalyst for photocatalytic sewage treatment after the service cycle of the composite nanofiber membrane as an X-ray shielding material is finished, and has a good photocatalytic degradation effect on typical cationic organic pollutants in water;
FIG. 4: the composite nanofiber films obtained in examples 1, 2 and 3 had a bar graph of the shielding rate of X-rays with an energy of 30keV at a thickness of 100 μm, the shielding rate being defined as the ratio of the difference in dose rate with and without a sample at the same energy to the dose rate without a sample, from which it can be concluded that the composite nanofiber film described in example 2 had the best X-ray shielding properties;
FIG. 5: the relationship curve between the shielding rate of the composite nanofiber membrane obtained in example 2 for the X-rays with energies of 30keV, 48keV, 65keV, 83keV and 100keV and the thickness of the fiber membrane is obtained by using a device as a medium-energy KV reference radiation field (re-filtered narrow spectrum), providing the radiation field by an X-ray machine, measuring the intensity of the radiation by using a PTW-32002 ionization chamber, measuring the sample at a distance of 3m from a radioactive source, wherein the sample is perpendicular to the main beam, the center of the dosimeter, the geometric center of the sample and the main beam are on the same axis, the shielding rate is defined as the ratio of the difference of the dose rates under the same energy and the absence of the sample to the dose rate under the absence of the sample, averaging three times for each energy and thickness test, and the test conditions are in accordance with the national standard GBZ/T147-. The result can show that the composite nanofiber membrane prepared by the invention has better shielding property on X rays in a medical range (30-100 keV), the shielding efficiency is gradually increased along with the increase of the thickness caused by the lamination of the nanofiber membrane, the shielding efficiency is generally reduced along with the increase of the ray energy, but the shielding efficiency of the composite nanofiber membrane on keV 83X rays is slightly higher than that of 65keV X rays due to the absorption of W atom K layer electrons;
FIG. 6: comparative electromagnetic shielding effect curves of the composite nanofiber film (2mm, thickness integrated by stacking of multilayer fiber films) obtained in example 2 and a lead plate (2mm) were plotted, the abscissa being the electromagnetic wave frequency and the ordinate being the shielding effectiveness, defined as SE ═ 20lg (E1/E2) (dB), where: the E1 is the field intensity without shielding, the E2 is the field intensity with shielding, a Mi-electric forty-one institute ZV3672B-S type vector network analyzer is used for testing by using a rectangular waveguide, the frequency band of electromagnetic waves is an X wave band (8-12.4 GHz), a Ku wave band (12-18 GHz) and a K wave band (18-26.5 GHz), and each wave band is tested by using a corresponding rectangular waveguide adapter, so that the result can be obtained.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples, and should not be construed as limiting the scope of the present invention.
Example 1:
(1) dissolving 7mmol of sodium tungstate and 3.5mmol of sodium sulfate in 40mL of deionized water, adjusting the pH to 2 by using 2mol/L HCl solution, then putting the solution into a closed hydrothermal reaction kettle to react for 12 hours at 180 ℃, naturally cooling the solution to room temperature, filtering the obtained solid product, ultrasonically crushing and centrifugally screening nanorods with the diameter less than 100nm and the length less than 4 mu m, washing the nanorods with water and ethanol, and drying the nanorods to obtain tungsten oxide nanorod seeds;
(2) polyacrylonitrile, tungsten oxide nanorod seeds and N, N-dimethylformamide are mixed according to the mass ratio of 1: 0.25: 10.75 stirring for 12h after mixing, and then carrying out ultrasonic treatment for 30min after dissolving polyacrylonitrile so as to uniformly disperse the nanorods in the system and obtain an electrostatic spinning precursor suspension;
(3) putting the electrostatic spinning precursor suspension into an injector of electrostatic spinning equipment, wherein the diameter of a stainless steel needle is 1mm, the working voltage of the electrostatic spinning equipment is 17kV, the stainless steel needle is used as an anode, a planar aluminum foil is used as a cathode for receiving, the propelling speed is 0.5mL/h, and the distance between the two electrodes is 17 cm; carrying out electrostatic spinning for 10h to obtain a tungsten oxide nanorod/polyacrylonitrile nanofiber membrane;
(4) soaking the nanofiber membrane into 60mL of 30mmol/L tungsten chloride ethanol solution, transferring the whole system to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6 hours at 180 ℃, naturally cooling to room temperature, and washing the obtained product with water and ethanol to obtain the tungsten oxide/polymer composite nanofiber membrane;
(5) soaking the tungsten oxide/polymer composite nanofiber membrane obtained in the step (4) into 50mL of 10mmol/L bismuth nitrate ethylene glycol/ethanol (volume ratio is 1: 4) solution, transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6h at 160 ℃, naturally cooling to room temperature, and repeatedly washing the obtained product with ethanol and water to obtain a bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane, wherein the product is a nano-sheet loaded nanofiber membrane, and the average diameter of the fibers is 620 nm;
(6) the average density of the single layer composite nanofiber membrane prepared in this example was 0.669g/cm3The thickness was 100. mu.m. The single-layer composite nanofiber membrane has the advantages that the shielding efficiency of 30keV X-rays can reach 8.86%, the flexibility is good, no fracture phenomenon occurs after the membrane is bent for 1000 times, and no obvious protection efficiency loss exists;
(7) after the composite nanofiber membrane is recovered, the degradation rate of the rhodamine B solution can reach 99.6% after simulated sunlight irradiates for 4 hours, and no obvious efficiency reduction exists within five times of repeated photocatalysis experiments.
Example 2:
(1) dissolving 7mmol of sodium tungstate and 3.5mmol of sodium sulfate in 40mL of deionized water, adjusting the pH to 2 by using 2mol/L HCl solution, then putting the solution into a closed hydrothermal reaction kettle to react for 12 hours at 180 ℃, naturally cooling the solution to room temperature, filtering the obtained solid product, screening nanorods with the diameter less than 100nm and the length less than 4 mu m by ultrasonic crushing and centrifugation, washing the nanorods with water and ethanol, and drying the nanorods to obtain tungsten oxide nanorod seeds;
(2) polyacrylonitrile, tungsten oxide nanorod seeds and N, N-dimethylformamide are mixed according to the mass ratio of 1: 0.25: 10.75 stirring for 12h after mixing to dissolve polyacrylonitrile and then carrying out ultrasonic treatment for 30min to uniformly disperse the nanorods in a system to obtain an electrostatic spinning precursor suspension;
(3) putting the electrostatic spinning precursor suspension into an injector of electrostatic spinning equipment, wherein the diameter of a stainless steel needle is 1.2mm, the working voltage of the electrostatic spinning equipment is 17kV, the stainless steel needle is used as an anode, a planar aluminum foil is used as a cathode for receiving, the propelling speed is 0.5mL/h, and the distance between the two electrodes is 17 cm; carrying out electrostatic spinning for 10h to obtain a tungsten oxide nanorod/polyacrylonitrile nanofiber membrane;
(4) soaking the nanofiber membrane into 60mL of 25mmol/L tungsten chloride ethanol solution, transferring the whole system to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6 hours at 180 ℃, naturally cooling to room temperature, and washing the obtained product with water and ethanol to obtain the tungsten oxide/polyacrylonitrile composite nanofiber membrane;
(5) soaking the tungsten oxide/polymer composite nanofiber membrane obtained in the step (4) into 50mL of 10mmol/L bismuth nitrate ethylene glycol/ethanol (volume ratio is 1: 4) solution, transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6h at 160 ℃, naturally cooling to room temperature, and repeatedly washing the obtained product with ethanol and water to obtain a bismuth tungstate/tungsten oxide/polyacrylonitrile composite nanofiber membrane, wherein the product is a nano-sheet loaded nanofiber membrane, and the average diameter of the fibers is 580 nm;
(6) the average density prepared by the mixture ratio is 0.569g/cm3The single-layer composite nanofiber membrane with the thickness of 100 mu m has the X-ray shielding efficiency of 12.05 percent on 30keV, the X-ray shielding efficiency on 30keV can reach 90.10 percent when the thickness is accumulated to 2mm through the layer-by-layer superposition of the nanofiber membranes, the flexibility is good, no fracture phenomenon occurs after the membrane is bent for 1000 times, and no obvious protection efficiency loss exists;
(7) after the composite nanofiber membrane is recovered, the degradation rate of the rhodamine B solution under the irradiation of simulated sunlight can reach 99.42%, and no obvious efficiency reduction exists within five times of repeated photocatalysis experiments.
Example 3:
(1) dissolving 7mmol of sodium tungstate and 3.5mmol of sodium sulfate in 40mL of deionized water, adjusting the pH to 2 by using 2mol/L HCl solution, then putting the solution into a closed hydrothermal reaction kettle to react for 12 hours at 180 ℃, naturally cooling the solution to room temperature, filtering the obtained solid product, screening nanorods with the diameter less than 100nm and the length less than 4 mu m by ultrasonic crushing and centrifugation, washing the nanorods with water and ethanol, and drying the nanorods to obtain tungsten oxide nanorod seeds;
(2) polyacrylonitrile, tungsten oxide nanorod seeds and N, N-dimethylformamide are mixed according to the mass ratio of 1: 0.25: 10.75 stirring for 12h after mixing to dissolve polyacrylonitrile and then carrying out ultrasonic treatment for 30min to uniformly disperse the nanorods in a system to obtain an electrostatic spinning precursor suspension;
(3) putting the electrostatic spinning precursor suspension into an injector of electrostatic spinning equipment, wherein the diameter of a stainless steel needle is 1mm, the working voltage of the electrostatic spinning equipment is 17kV, the stainless steel needle is used as an anode, a planar aluminum foil is used as a cathode for receiving, the propelling speed is 0.5mL/h, and the distance between the two electrodes is 17 cm; carrying out electrostatic spinning for 10h to obtain a tungsten oxide nanorod/polyacrylonitrile nanofiber membrane;
(4) soaking the nanofiber membrane into 60mL of 25mmol/L tungsten chloride isopropanol solution, transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6 hours at 180 ℃, naturally cooling to room temperature, washing the obtained product with water and ethanol in a reverse mode, and obtaining the tungsten oxide/polyacrylonitrile composite nanofiber membrane;
(5) soaking the tungsten oxide/polyacrylonitrile composite nanofiber membrane obtained in the step (4) into 50mL of ethylene glycol/ethanol (volume ratio is 1: 4) solution of 15mmol/L bismuth nitrate, transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6h at 160 ℃, naturally cooling to room temperature, and repeatedly washing the obtained product with ethanol and water to obtain the bismuth tungstate/tungsten oxide/polyacrylonitrile composite nanofiber membrane, wherein the product is the nanofiber membrane loaded with nanospheres, and the average diameter of the fibers is 370 nm;
(6) the average density of the composite nanofiber membrane prepared by using the proportion is 0.717g/cm3The single-layer fiber film with the thickness of 100 mu m has 9.34 percent of shielding efficiency on the X-ray with 30keV, good flexibility, no fracture phenomenon after being bent for 1000 times and no obvious protection efficiency loss;
(7) after the composite nanofiber membrane is recovered, the degradation rate of the rhodamine B solution under the irradiation of simulated sunlight can reach 98.6%, and no obvious efficiency reduction exists within five times of repeated photocatalysis experiments.
Claims (7)
1. A preparation method of a bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection comprises the following steps:
(1) dissolving tungstate and an auxiliary agent in deionized water, stirring until the tungstate and the auxiliary agent are completely dissolved, preparing a tungstate aqueous solution with the mass fraction of 3-20%, adjusting the pH value to 1-3, then putting the tungstate aqueous solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting at 140-240 ℃ for 6-24 h, naturally cooling to room temperature, filtering, ultrasonically crushing, centrifugally screening, washing and drying to obtain tungsten oxide nanorod seeds with the diameter of below 100nm and the length of below 4 mu m;
(2) mixing a polymer with the tungsten oxide nanorod seeds obtained in the step (1), dissolving the mixture in a solvent, and performing ultrasonic dispersion to obtain an electrostatic spinning precursor suspension;
(3) putting the electrostatic spinning precursor suspension obtained in the step (2) into an injector of electrostatic spinning equipment, wherein the diameter of a stainless steel needle head of the injector is 0.6-2 mm, the working voltage of the electrostatic spinning equipment is 10-25 kV, the stainless steel needle head is used as an anode, a planar aluminum foil or a roller wrapped with the aluminum foil is used as a cathode to receive an electric spinning product, the propelling speed of the injector is 0.5-1.5 mL/h, and the distance between the anode and the cathode is 8-25 cm; carrying out electrostatic spinning for 5-15 h to obtain a polymer/tungsten oxide nanorod seed fiber film;
(4) immersing the polymer/tungsten oxide rod seed fiber membrane obtained in the step (3) into 30-70 mL of an alcoholic solution of tungsten salt, wherein the concentration of the tungsten salt is 15-40mmol/L, then transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 2-12 h at 140-240 ℃, naturally cooling to room temperature, and repeatedly washing the obtained product with water and ethanol to obtain a tungsten oxide/polymer composite nanofiber membrane;
(5) and (3) immersing the tungsten oxide/polymer composite nanofiber membrane obtained in the step (4) into 25-75 mL of bismuth salt mixed alcohol solution, wherein the concentration of bismuth salt is 5-20mmol/L, then transferring the whole system into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 2-12 h at the temperature of 110-220 ℃, naturally cooling to room temperature, and repeatedly washing the obtained product with ethanol and water to obtain the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection.
2. The preparation method of the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (1), the tungstate is one of ammonium tungstate, sodium tungstate or potassium tungstate; the auxiliary agent is Triton X-100, oleic acid, NaCl, Na2SO4、KCl、K2SO4、KNO3The molar ratio of the tungstate to the auxiliary agent is 1: (0.3-2).
3. The preparation method of the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection as claimed in claim 1, wherein the preparation method comprises the following steps: the polymer in the step (2) is one of polymethyl methacrylate, polystyrene, polyacrylonitrile, sulfonated polyether ether ketone or polyacrylamide; the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetone, chloroform, dichloromethane and ethanol; the mass ratio of the polymer to the nanorod seeds to the solvent is 1: (0.1-1.2): (9-19).
4. The preparation method of the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection as claimed in claim 1, wherein the preparation method comprises the following steps: the tungsten salt in the step (4) is one of tungsten trichloride, tungsten pentachloride or tungsten hexachloride; the alcohol is one of ethanol, n-propanol, isopropanol, n-butanol or isobutanol.
5. The preparation method of the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection as claimed in claim 1, wherein the preparation method comprises the following steps: the bismuth salt in the step (5) is one of bismuth nitrate or bismuth trichloride; the mixed alcohol solution is a mixture of two or more of ethanol, n-propanol, n-butanol, ethylene glycol and glycerol.
6. The preparation method of the bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection as claimed in claim 1, wherein the preparation method comprises the following steps: the bismuth tungstate/tungsten oxide/polymer composite nanofiber obtained in the step (5) is a nanofiber with a multilevel structure, wherein the microscopic morphology of inorganic components is nanospheres, nanorods or nanosheets, and the average diameter of the fiber is 200-900 nm.
7. A bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection is characterized in that: is prepared by the method of any one of claims 1 to 6.
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