CN114471732A - Photocatalytic composite nanofiber membrane and preparation method and application thereof - Google Patents

Photocatalytic composite nanofiber membrane and preparation method and application thereof Download PDF

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CN114471732A
CN114471732A CN202210210162.2A CN202210210162A CN114471732A CN 114471732 A CN114471732 A CN 114471732A CN 202210210162 A CN202210210162 A CN 202210210162A CN 114471732 A CN114471732 A CN 114471732A
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nanofiber membrane
hnts
composite
photocatalytic
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汪滨
孙志明
娄耀元
丁姗姗
马佳瑜
金旭
黄楚儿
李秀艳
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Beijing Institute Fashion Technology
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
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Abstract

The invention belongs to the technical field of preparation of nanofiber membranes, and particularly discloses a photocatalytic composite nanofiber membrane as well as a preparation method and application thereof. The invention controls Ag3PO4Preparing a composite spinning solution A and a spraying solution B according to the proportion of the @ HNTs composite particles to the nanofiber stock solution, and then simultaneously carrying out electrostatic spinning and spraying by taking the non-woven fabric as a substrate and the composite spinning solution A and the spraying solution B as raw materials to obtain the photocatalytic composite nanofiber membrane. The photocatalytic composite nanofiber membrane prepared by the method has the functions of adsorbing and photocatalytic degrading organic pollutants in wastewater under the irradiation of visible light, and has good antibacterial property on escherichia coli and staphylococcus aureusCan also play a role in purifying air.

Description

Photocatalytic composite nanofiber membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of nanofiber membranes, in particular to a photocatalytic composite nanofiber membrane and a preparation method and application thereof.
Background
Increasingly serious air and water pollution is a significant threat to human health. The photocatalysis technology is an ideal choice for air purification and water pollution treatment. However, the existing nanometer semiconductor photocatalyst with good catalytic activity has the problems of inconvenient separation and recovery, easy secondary pollution and the like, and the application of the nanometer semiconductor photocatalyst in the field of air purification is limited by the macroscopic form of powder.
Ag3PO4The @ HNTs composite particles (silver phosphate halloysite composite particles) have good catalytic activity, and Ag is not reported in the prior art3PO4Application of @ HNTs composite particles in field of air pollution and water pollution treatment, but due to Ag3PO4The @ HNTs composite particles are still powdery photocatalysts, so that the problems of inconvenience in separation and recovery, high cost, secondary pollution and the like exist when the @ HNTs composite particles are applied to air purification and water pollution treatment.
Therefore, how to provide a photocatalytic composite nanofiber membrane and a preparation method and application thereof in ensuring Ag3PO4Under the premise of high catalytic activity of the @ HNTs composite particles, the avoidance of inconvenience in recovery and separation and secondary pollution caused by the composite particles is a difficult problem to be solved in the field, and is also the key to be applied to purification of VOC (volatile organic compounds) gas pollutants such as formaldehyde in indoor air.
Disclosure of Invention
In view of the above, the invention provides a photocatalytic composite nanofiber membrane, and a preparation method and application thereof, and the invention avoids Ag3PO4The @ HNTs composite particles are difficult to separate and recover, high in treatment cost and easy to cause secondary pollution, and the good air permeability and self-supporting property of the nanofiber membrane are successfully utilized to be used indoorsFree gas-phase formaldehyde in the air is degraded.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a photocatalytic composite nanofiber membrane comprises the following steps:
1) mixing Ag with water3PO4Mixing the @ HNTs composite particles with the nanofiber stock solution to prepare a composite spinning solution A;
2) mixing Ag with water3PO4Mixing the @ HNTs composite particles with the nanofiber stock solution to prepare a spraying solution B;
3) carrying out electrostatic spinning by taking non-woven fabric as a substrate and the composite spinning solution A as a raw material, and spraying by taking the spraying solution B as a raw material to obtain a photocatalytic composite nanofiber membrane;
wherein the electrospinning and spraying are performed simultaneously.
Preferably, the nanofiber stock solution in the step 1) and the nanofiber stock solution in the step 2) are independently polylactic acid solution, polyvinylidene fluoride solution or polyvinylpyrrolidone solution.
Preferably, the mass concentration of the polylactic acid solution is 8-14%, and the solvent is a mixture of N, N-dimethylformamide and dichloromethane; the mass concentration of the polyvinylidene fluoride solution is 10-18%, and the solvent is a mixture of N, N-dimethylformamide and acetone; the mass concentration of the polyvinylpyrrolidone solution is 10-16%, and the solvent is water.
Preferably, Ag in the composite spinning solution A3PO4The mass ratio of the @ HNTs composite particles to the solute in the nanofiber stock solution is 1-3: 10.
preferably, Ag in the spraying solution B3PO4The mass ratio of the @ HNTs composite particles to the solute in the nanofiber stock solution is 1-3: 10; the solid content of the spraying solution B is 10-30%.
Preferably, the electrostatic spinning process conditions in the step 3) are as follows: the spinning temperature is 30-50 ℃, the positive voltage of the spinning voltage is 10-24 kV, the negative voltage is 1-3 kV, the spinning time is 1-3 h, the propelling speed is 1-3 mL/h, and the receiving distance is 10-18 cm.
Preferably, the spraying method in the step 3) is an air flow spraying method.
Preferably, the spraying process conditions in the step 3) are as follows: the gas flow rate is 400-500 mL/h.
The invention also aims to provide the photocatalytic composite nanofiber membrane prepared by the preparation method of the photocatalytic composite nanofiber membrane.
The invention further aims to provide application of the photocatalytic composite nanofiber membrane in air purification or water body purification.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the photocatalytic composite nanofiber membrane disclosed by the invention is simple in preparation process and convenient for industrial popularization.
(2) The photocatalytic composite nanofiber membrane has good ultraviolet light absorption characteristic and visible light response characteristic, can be excited under the action of sunlight or visible light to generate photogenerated electrons and holes capable of sterilizing, and has good antibacterial performance on escherichia coli and staphylococcus aureus.
(3) The photocatalytic composite nanofiber membrane has good adsorption and photocatalytic degradation effects on formaldehyde in the air under the irradiation of visible light, and can degrade formaldehyde with the initial concentration of 44ppm by about 40% after the irradiation of the visible light for 650 min; in addition, the photocatalytic composite nanofiber membrane prepared by the method disclosed by the invention can degrade gas-phase formaldehyde and can filter and intercept suspended particulate matters such as PM0.3 and PM 2.5.
(4) The photocatalytic composite nanofiber membrane has good adsorption and photocatalytic degradation effects on organic pollutants in wastewater under the irradiation of visible light. And can be directly taken out of the water body, thereby avoiding secondary pollution and being recycled for more than 5 times.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is SEM images of a pure PLA nanofiber membrane prepared in comparative example 1 and a photocatalytic composite nanofiber membrane prepared in example 6; wherein a corresponds to the pure PLA nanofiber membrane prepared in comparative example 1, and b corresponds to the photocatalytic composite nanofiber membrane prepared in example 6;
FIG. 2 shows the purified HNTs nanotubes, Ag prepared in example 13PO4Ag prepared in example 43PO4-XRD patterns of 3@ HNTs composite particles, the pure PLA nanofiber membrane prepared in comparative example 1, and the photocatalytic composite nanofiber membrane prepared in example 6;
FIG. 3 shows Ag obtained in example 13PO4Granules, Ag obtained in example 43PO4-3@ HNTs composite particles and the uv-visible diffuse reflectance absorption spectrum of the photocatalytic composite nanofiber film prepared in example 6;
FIG. 4 shows Ag obtained in example 13PO4Granules, Ag obtained in example 43PO4[ F (R) hv ] of-3 @ HNTs composite particles and photocatalytic composite nanofiber film prepared in example 6]1/2-hv graph;
FIG. 5 shows the purified HNTs nanotubes, Ag prepared in example 13PO4Ag prepared in example 43PO4-3@ HNTs composite particles, the pure PLA nanofiber membrane prepared in comparative example 1, and the photocatalytic composite nanofiber membrane prepared in example 6;
FIG. 6 shows Ag obtained in example 43PO4-thermogravimetric plots of 3@ HNTs composite particles, the pure PLA nanofibrous membrane prepared in comparative example 1, and the photocatalytic composite nanofibrous membrane prepared in example 6;
FIG. 7 is N of the pure PLA nanofiber membrane prepared in comparative example 1 and the photocatalytic composite nanofiber membrane prepared in example 62Adsorption/desorption curves;
FIG. 8 is a graph showing the pore size distribution of a pure PLA nanofiber membrane prepared in comparative example 1 and a photocatalytic composite nanofiber membrane prepared in example 6;
FIG. 9 is a graph showing the degradation performance of the pure PLA nanofiber membrane prepared in comparative example 1 and the sprayed photocatalytic composite nanofiber membranes prepared in examples 4 to 6 with respect to methylene blue;
FIG. 10 is a graph showing the degradation performance of the pure PLA nanofiber membrane prepared in comparative example 1 and the sprayed photocatalytic composite nanofiber membranes prepared in examples 4 to 6 with respect to tetracycline;
FIG. 11 is a graph of the cycle performance of the spray-coated photocatalytic composite nanofiber membrane prepared in example 6 on the degradation of methylene blue;
FIG. 12 is a picture of the inhibition zones of different strains of the pure PLA nanofiber membrane prepared in comparative example 1 and the spray-type photocatalytic composite nanofiber membranes prepared in examples 4-6 under the illumination and dark conditions (a is Escherichia coli under the dark condition, b is Staphylococcus aureus under the dark condition, c is Escherichia coli under the illumination condition, d is Staphylococcus aureus under the illumination condition, 1 is comparative example 1, 2 is example 4, 3 is example 5, and 4 is example 6);
fig. 13 shows the photodegradability of formaldehyde in visible light of the spray-coated photocatalytic composite nanofiber membrane prepared in example 6. Wherein a is a figure of formaldehyde adsorption and photocatalytic degradation, and b is a carbon dioxide yield.
Detailed Description
The invention provides a preparation method of a photocatalytic composite nanofiber membrane, which comprises the following steps:
1) mixing Ag with water3PO4Mixing the @ HNTs composite particles with the nanofiber stock solution to prepare a composite spinning solution A;
2) mixing Ag with water3PO4Mixing the @ HNTs composite particles with the nanofiber stock solution to prepare a spraying solution B;
3) carrying out electrostatic spinning by taking non-woven fabric as a substrate and the composite spinning solution A as a raw material, and spraying by taking the spraying solution B as a raw material to obtain a photocatalytic composite nanofiber membrane;
wherein the electrospinning and spraying are performed simultaneously.
In the invention, the nanofiber stock solution in the step 1) and the nanofiber stock solution in the step 2) are independently polylactic acid solution, polyvinylidene fluoride solution or polyvinylpyrrolidone solution.
In the invention, the mass concentration of the polylactic acid solution is 8-14%, preferably 12%; the solvent is a mixture of N, N-dimethylformamide and dichloromethane, and preferably the mass ratio of the N, N-dimethylformamide to the dichloromethane is 2: 1.
In the invention, the mass concentration of the polyvinylidene fluoride solution is 10-18%, preferably 15%; the solvent is a mixture of N, N-dimethylformamide and acetone, and is preferably a mixture of N, N-dimethylformamide and acetone in a mass ratio of 2: 1.
In the invention, the mass concentration of the polyvinylpyrrolidone solution is 10-16%, preferably 13%; the solvent is deionized water.
In the invention, Ag in the composite spinning solution A3PO4The mass ratio of the @ HNTs composite particles to the solute in the nanofiber stock solution is 1-3: 10, preferably 3: 10.
in the invention, Ag in the spraying solution B3PO4The mass ratio of the @ HNTs composite particles to the solute in the nanofiber stock solution is 1-3: 10, preferably 3: 10; the solid content of the spraying solution B is 10-30%, preferably 15-25%, preferably 30% so as to prevent the spray pipe from being blocked due to overhigh solid content.
In the present invention, Ag3PO4The preparation method of the @ HNTs composite particle comprises the following steps: mixing halloysite nanotubes, sodium dihydrogen phosphate, water, ethylene glycol, dimethyl sulfoxide and sodium citrate (template agent) to obtain solution A, mixing silver nitrate, ethylene glycol and dimethyl sulfoxide to obtain solution B, dropwise adding the solution B into the solution A, stirring, transferring to a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction to carry out loading after stirring uniformly, and obtaining Ag3PO4Composite particles of @ HNTs.
In the invention, the electrostatic spinning process conditions in the step 3) are as follows: the spinning temperature is 30-50 ℃, the positive voltage of the spinning voltage is 10-24 kV, the negative voltage is 1-3 kV, the spinning time is 1-3 h, the propelling speed is 1-3 mL/h, and the receiving distance is 10-18 cm.
When the nanofiber stock solution is a polylactic acid solution, the electrostatic spinning process is preferably as follows: the temperature is 50 ℃, the spinning voltage is 18kV positive, the negative voltage is 2kV, the advancing speed is 3mL/h, and the receiving distance is 15 cm.
When the nanofiber stock solution is a polyvinylidene fluoride solution, the electrostatic spinning process is preferably as follows: the temperature is 35 ℃, the spinning voltage is 16kV positive, the negative voltage is 2kV, the advancing speed is 1mL/L, and the receiving distance is 16 cm.
When the nanofiber stock solution is a polyvinylpyrrolidone solution, the electrospinning process is preferably: the temperature is 30 ℃, the spinning voltage is 10kV positive, the negative voltage is 2kV, the advancing speed is 2mL/L, and the receiving distance is 12 cm.
In the present invention, the spraying method in the step 3) is an air flow spraying method.
In the invention, the spraying process conditions in the step 3) are as follows: the gas flow rate is 400 to 500mL/h, preferably 420 to 480mL/h, and more preferably 460 mL/h.
The invention also provides a photocatalytic composite nanofiber membrane prepared by the preparation method.
The invention also provides application of the photocatalytic composite nanofiber membrane in air purification or water body material purification.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
2g of purified HNTs, 2g of NaH2PO480mL of deionized water, 24mL of ethylene glycol, 12mL of dimethyl sulfoxide and 0.2g of sodium citrate are mixed to obtain a solution A; mixing 3g of silver nitrate, 16mL of ethylene glycol and 8mL of dimethyl sulfoxide to obtain a solution B; dropwise adding the solution B into the solution A by using a peristaltic pumpMixing and stirring for 1h, transferring into a polytetrafluoroethylene reaction kettle, reacting for 4h at 80 ℃, pouring out supernatant after the reaction is finished, and washing, filtering, drying and grinding the obtained solid to obtain 100% Ag3PO4@ HNTs composite particle (namely, the mass ratio of silver phosphate to halloysite nanotube is 1:1, and the silver phosphate is marked as Ag3PO4@HNTs)；
Mixing Ag with water3PO4Mixing the @ HNTs composite particles with polylactic acid solution (Ag)3PO4The mass ratio of the @ HNTs composite particles to the polylactic acid in the polylactic acid solution is 1: 10) to obtain a composite spinning solution A, and mixing Ag3PO4The weight ratio of the @ HNTs composite particles to the polylactic acid in the polylactic acid solution is as follows, 0.2 g: 2g of the mixture was mixed at a mass ratio to obtain a spray solution B. The mass concentration of the polylactic acid solution is 12%, the solvent is N, N-dimethylformamide and dichloromethane in a mass ratio of 2:1, and the solid content of the spraying solution B is 30%.
Carrying out electrostatic spinning (the temperature is 50 ℃, the positive voltage is 18kV, the negative voltage is 2kV, the propelling speed is 2mL/L, the receiving distance is 14cm, and the spinning time is 3h) by taking the PET non-woven fabric as a substrate and taking the composite spinning solution A as a spinning raw material; the spray solution B was applied by air-flow spraying (air flow rate 400 mL/h). The electrostatic spinning and the airflow spraying are carried out simultaneously to obtain the photocatalytic composite nanofiber membrane (marked as PLA-Ag) with the doping amount of 10 percent3PO4@HNTs-10％)。
Example 2
The specific preparation process is referred to example 1, with the only difference that: ag in the spray gun3PO4The mass ratio of the @ HNTs composite particles to the polylactic acid in the polylactic acid solution is 0.4 g: 2g, obtaining the photocatalytic composite nanofiber membrane (marked as PLA-Ag) with the doping amount of 20 percent3PO4@HNTs-20％)。
Example 3
The specific preparation process is referred to example 1, with the only difference that: ag in the spray gun3PO4The mass ratio of the @ HNTs composite particles to the polylactic acid in the polylactic acid solution is 0.6 g: 2g, obtaining the photocatalytic composite nanofiber membrane (marked as PLA-Ag) with the doping amount of 30 percent3PO4@HNTs-30％)。
Example 4
The specific preparation process is as in example 1, except that: 2g of purified HNTs, 6g of NaH2PO4Mixing 240mL of deionized water, 72mL of ethylene glycol and 36mL of dimethyl sulfoxide, and mixing 0.6g of sodium citrate to obtain a solution A; mixing 6g of silver nitrate, 48mL of ethylene glycol and 24mL of dimethyl sulfoxide to obtain a solution B; dropwise adding the solution B into the solution A by using a peristaltic pump, mixing and stirring for 1h, transferring into a polytetrafluoroethylene reaction kettle, reacting for 4h at 80 ℃, pouring out supernatant after the reaction is finished, and washing, filtering, drying and grinding the obtained solid to obtain Ag with the load of 300%3PO4@ HNTs composite particle (namely, the mass ratio of silver phosphate to halloysite nanotube is 3:1, and the mass ratio is marked as Ag3PO4-3@ HNTs). Obtaining the photocatalytic composite nanofiber membrane (marked as PLA-Ag) with the doping amount of 10 percent3PO4-3@HNTs-10％)。
Example 5
The specific preparation process is referred to example 4, with the only difference that: ag in the spray gun3PO4The mass ratio of the @ HNTs composite particles to the polylactic acid in the polylactic acid solution is 0.4 g: 2g, obtaining the photocatalytic composite nanofiber membrane (marked as PLA-Ag) with the doping amount of 20 percent3PO4-3@HNTs-20％)。
Example 6
The specific preparation process is referred to example 4, with the only difference that: ag in the spray gun3PO4The mass ratio of the @ HNTs composite particles to the polylactic acid in the polylactic acid solution is 0.6 g: 2g, obtaining the photocatalytic composite nanofiber membrane (marked as PLA-Ag) with the doping amount of 30 percent3PO4-3@HNTs-30％)。
Example 7
Ag3PO4The preparation method of the @ HNTs composite particles is the same as that of example 1.
Mixing Ag with water3PO4Mixing the @ HNTs composite particles with polyvinylidene fluoride solution (Ag)3PO4The mass ratio of the @ HNTs composite particles to the polyvinylidene fluoride in the polyvinylidene fluoride solution is 2: 10) to obtain a composite spinning solution A, and mixing Ag3PO4The weight ratio of the @ HNTs composite particles to polyvinylidene fluoride in the polyvinylidene fluoride solution is as follows, 0.2 g: 2g of the mixture was mixed at a mass ratio to obtain a spray solution B. The mass concentration of the polyvinylidene fluoride solution is 16%, the solvents are N, N-dimethylformamide and acetone in a mass ratio of 3:1, and the solid content of the spraying solution B is 10%.
Carrying out electrostatic spinning (the temperature is 35 ℃, the positive voltage is 16kV, the negative voltage is 2kV, the propelling speed is 1mL/L, the receiving distance is 16cm, and the spinning time is 1h) by taking the PET non-woven fabric as a substrate and taking the composite spinning solution A as a spinning raw material; the spray solution B was applied by air-flow spraying (air flow rate 500 mL/h). The electrostatic spinning and the airflow type spraying are carried out simultaneously to obtain the photocatalytic composite nanofiber membrane (marked as PVDF-Ag)3PO4@HNTs-10％)。
Example 8
Ag3PO4The preparation method of the @ HNTs composite particles is the same as that of example 1.
Mixing Ag with water3PO4Mixing the composite particles of @ HNTs with polyvinylpyrrolidone solution (Ag)3PO4The mass ratio of the @ HNTs composite particles to the polyvinylpyrrolidone in the polyvinylpyrrolidone solution is 3: 10) to obtain a composite spinning solution A, and mixing Ag3PO4@ HNTs composite particles were mixed with polyvinylpyrrolidone in a polyvinylpyrrolidone solution at a ratio of 0.2 g: 2g of the mixture was mixed at a mass ratio to obtain a spray solution B. The mass concentration of the polyvinylpyrrolidone solution is 15%, the solvent is deionized water, and the solid content of the spraying solution B is 20%.
Carrying out electrostatic spinning (the temperature is 30 ℃, the positive voltage is 10kV, the negative voltage is 2kV, the propelling speed is 2mL/L, the receiving distance is 12cm, and the spinning time is 2h) by taking the PET non-woven fabric as a substrate and taking the composite spinning solution A as a spinning raw material; the spray solution B was applied by air-flow spraying (air flow rate 430 mL/h). The electrostatic spinning and the airflow spraying are carried out simultaneously to obtain the photocatalytic composite nanofiber membrane (marked as PVP-Ag)3PO4@HNTs-10％)。
Comparative example 1
The specific preparation process is as described in example 1, except that Ag is not doped into the composite spinning solution A and the spraying solution B3PO4And (5) @ HNTs are compounded with the particles to obtain the pure PLA nanofiber membrane.
Experimental example 1
The pure PLA nanofiber film obtained in comparative example 1 and the photocatalytic composite nanofiber film obtained in example 6 (PLA-Ag) were separately compared3PO4@ HNTs-10%) were examined by scanning electron microscopy, the results are shown in FIG. 1. FIG. 1a shows that the pure PLA nanofiber membrane fiber has smooth and continuous appearance, the diameter is between 150 nm and 280nm, and the average diameter is about 200 nm; FIG. 1b shows that Ag is attached to Ag3PO4Increasing the doping amount of the-3 @ HNTs composite particles, increasing the fiber diameter, and distributing the diameter of the photocatalytic composite nanofiber membrane prepared in the embodiment 6 to be 150-300 nm. Even when the addition was increased to 30%, the film maintained good nanoclay dispersion and fiber morphology, visible as Ag3PO4Blend spinning of-3 @ HNTs composite particles with PLA was successful and the fiber film was porous.
For purified HNTs nanotubes, Ag prepared in example 13PO4Ag obtained in example 43PO4-3@ HNTs, pure PLA nanofiber membrane prepared in comparative example 1, and photocatalytic composite nanofiber membrane (PLA-Ag) prepared in example 63PO4-3@ HNTs-30%) and the results are shown in FIG. 2, from which FIG. 2 it can be seen that Ag3PO4The diffraction peak positions (respectively 20.88 degrees, 29.69 degrees, 33.27 degrees, 35.58 degrees, 47.78 degrees, 52.69 degrees, 55.08 degrees and 57.27 degrees) of the nano-particles correspond to crystal planes of (110), (200), (210), (211), (310), (222), (320) and (321), and the peak shapes clearly indicate that Ag is3PO4The crystallinity of (3) is good. The major peaks of HNTs are located at 2 θ values of 11.3 °, 19.9 ° and 24.8 °, corresponding to the crystallographic planes of (001), (110) and (003). The Ag is3PO4The characteristic peak of the-3 @ HNTs composite particle is Ag3PO4Superposition of the characteristic peaks of the particles and the halloysite nanotubes indicates that Ag3PO4The particles do not damage respective crystal structure after being loaded on the surface of the halloysite nanotube, and simultaneously show that Ag3PO4-the crystallinity of the 3@ HNTs composite particles is higher; PLA-Ag3PO4-3@ HNTs-30% photocatalytic composite nanoPLA and Ag simultaneously appear in XRD spectrogram of rice fiber film3PO4-diffraction peaks of 3@ HNTs. Description of Ag3PO4-3@ HNTs composite particles are successfully incorporated into nanofiber membranes without damaging Ag during spinning3PO4-3@ HNTs composite particle Crystal Structure, spray-coated PLA-Ag prepared in example 63PO4The-3 @ HNTs-30% photocatalytic composite nanofiber membrane has good crystallinity.
Ag obtained in example 13PO4Granules, Ag obtained in example 43PO4-3@ HNTs composite particles and spray-coated PLA-Ag prepared in example 63PO4Ultraviolet-visible diffuse reflection absorption spectrum detection is carried out on the-3 @ HNTs-30% photocatalytic composite nanofiber membrane, the detection result is shown in figure 3, and figure 3 shows Ag3PO4The maximum absorbance of the particles was 1.2, corresponding to a wavelength around 250nm, and the sample absorption threshold was shown to be 525nm, whereas Ag3PO4The-3 @ HNTs shows red shift to a larger wavelength (540-nm), and the absorption capacity of the pure catalyst to visible light is effectively improved. When PLA nanofiber membrane is doped with Ag3PO4And when the-3 @ HNTs composite particles are adopted, the utilization efficiency of visible light is greatly improved.
FIG. 4 shows Ag obtained in example 13PO4Granules, Ag obtained in example 43PO4-3@ HNTs composite particles and spray-coated PLA-Ag prepared in example 63PO4-3@ HNTs-30% of photocatalytic composite nanofiber film [ F (R) hv]1/2-hv diagram. As can be seen from FIG. 4, Ag3PO4The band gap value of the particles was 2.32 eV. Description of Ag3PO4The particles have good ultraviolet light absorption characteristics and visible light response characteristics, can be excited under the action of sunlight or visible light, and generate photogenerated electrons and holes capable of sterilizing. Ag3PO4The forbidden band value of the-3 @ HNTs composite particle is 2.18eV, which indicates that the addition of HNTs is a key factor for improving the photoresponse range of the catalyst, and is consistent with the result of ultraviolet visible spectrum.
FIG. 5 shows the purified HNTs nanotubes, Ag prepared in example 13PO4And carry outExample 4 Ag obtained3PO4@ HNTs composite particles, pure PLA nanofiber membrane prepared in comparative example 1, and spray-coated PLA-Ag prepared in example 63PO4-3@ HNTs-30% infrared spectrum of the photocatalytic composite nanofiber membrane. As can be seen from FIG. 5, 3693cm-1And 3621cm-1The absorption band at (A) belongs to the-OH stretching vibration peak of HNTs. PLA-Ag3PO4-3@ HNTs-30% of the characteristic peak of the photocatalytic composite nanofiber membrane comprises 1760cm-1(C＝O)、557cm-1And 958cm-1(PO4 3-) Peaks of (A) respectively belong to PLA and Ag3PO4-3@ HNTs composite particles, demonstrating spray-coated PLA-Ag3PO4-3@ HNTs-30% of photocatalytic composite nanofiber membrane.
FIG. 6 shows Ag obtained in example 43PO4-3@ HNTs composite particles, neat PLA nanofiber film prepared in comparative example 1 and spray-coated PLA-Ag prepared in example 63PO4-3@ HNTs-30% thermogravimetric plot of photocatalytic composite nanofiber membrane. As can be seen from FIG. 6, Ag is present at a temperature of 400 to 600 deg.C3PO4The very significant mass loss of the-3 @ HNTs composite particles was primarily attributed to the loss of the second portion of crystal water from the halloysite, which had a weight loss of about 10.2%. At temperatures below 290 ℃ pure PLA and PLA-Ag3PO4The-3 @ HNTs-30% photocatalytic composite nanofiber membrane has a small mass loss, and is caused by the evaporation of water adsorbed and crystallized on the surface of the membrane. Pure PLA nanofiber membrane and PLA-Ag at the temperature of 300-400 DEG C3PO4The-3 @ HNTs-30% photocatalytic composite nanofiber membrane has serious mass loss due to carbonization of the polymer at 400-600 ℃ caused by decomposition of the polymer. PLA-Ag3PO4The TG curve of the-3 @ HNTs-30% photocatalytic composite nanofiber membrane tends to be balanced when the residual mass percentage is about 25%, which is caused by Ag3PO4The presence of 3@ HNTs composite particles indicates a successful incorporation of the composite particles into the PLA nanofibers.
FIG. 7 shows a pure PLA nanofiber membrane prepared in comparative example 1 and a spray prepared in example 6Coating type PLA-Ag3PO4-3@ HNTs-30% N of photocatalytic composite nanofiber membrane2Adsorption/desorption curves. As can be seen from FIG. 7, the pure PLA fiber film and PLA-Ag3PO4The adsorption-desorption curves of the-3 @ HNTs-30% photocatalytic composite nanofiber membrane belong to type IV, and an obvious H4 type hysteresis loop exists between the adsorption curve and the desorption curve, which indicates that PLA-Ag3PO4-3@ HNTs-30% of the photocatalytic composite nanofiber membrane is still porous, and the BET specific surface area is 5.8753m2G and 3.4262m2/g。
FIG. 8 shows a pure PLA nanofiber membrane prepared in comparative example 1 and a spray-coated PLA-Ag prepared in example 63PO4-3@ HNTs-30% of pore size distribution diagram of the photocatalytic composite nanofiber membrane. As can be seen from FIG. 8, the mean pore diameter of the pure PLA nanofiber membrane was 4.1013nm, PLA-Ag3PO4Average pore size of-3 @ HNTs-30% photocatalytic composite nanofiber membrane was 10.7897nm, again demonstrating Ag doping3PO4The nanofiber membrane of the-3 @ HNTs composite particle does not change the original porous structure.
FIG. 9 is a graph of the degradation performance of the pure PLA nanofiber membrane prepared in comparative example 1 and the spray-type photocatalytic composite nanofiber membranes prepared in examples 4 to 6 with respect to methylene blue. As can be seen from fig. 9, the samples, except for the pure PLA nanofiber membrane, all reduced the concentration of the MB solution after 120 minutes of dark stirring. By contrast, the pure PLA nanofiber membrane has almost no adsorption and degradation capability to the MB solution, but the PLA-Ag is exposed to the visible light for 140min3PO4The-3 @ HNTs-30% photocatalytic composite nanofiber membrane shows the best adsorption and photocatalytic degradation capability.
FIG. 10 is a graph showing the degradation performance of the pure PLA nanofiber membrane prepared in comparative example 1 and the sprayed photocatalytic composite nanofiber membranes prepared in examples 4 to 6 on tetracycline. As can also be seen from FIG. 10, Ag3PO4And the degradation rate of the composite nanofiber membrane on TCHC is gradually increased by increasing the doping amount of the-3 @ HNTs composite particles. PLA-Ag3PO4Adsorption degradation effect of-3 @ HNTs-30% photocatalytic composite nanofiber membrane on TCHC within 180min under visible lightThe fruit can reach 94 percent.
Fig. 11 is a graph of the cycle performance of the spray-coated photocatalytic composite nanofiber membrane prepared in example 6 on the degradation of methylene blue. As can be seen from FIG. 11, PLA-Ag3PO4The-3 @ HNTs-30% photocatalytic composite nanofiber membrane is placed in an MB solution with the concentration of 10mg/L and repeatedly degraded for 4 times under visible light. The reaction time of each period is 120min, and the composite nanofiber membrane is cleaned and dried before subsequent operation. The decolorization rate of the first cycle is 95.55 percent, and the decolorization rate is reduced to 45.08 percent after 4 cycles.
FIG. 12 shows the pictures of the inhibition zones of the pure PLA nanofiber membrane prepared in comparative example 1 and the sprayed photocatalytic composite nanofiber membranes prepared in examples 4 to 6 for different strains under the illumination and dark conditions (a is Escherichia coli under the dark condition, b is Staphylococcus aureus under the dark condition, c is Escherichia coli under the illumination condition, d is Staphylococcus aureus under the illumination condition, 1 is comparative example 1, 2 is example 4, 3 is example 5, and 4 is example 6). As can be seen from fig. 12, the pure PLA nanofiber membrane prepared in comparative example 1 had no antibacterial effect against both strains under light conditions, whether under dark conditions or under light conditions. Under the dark condition, the antibacterial effect of the photocatalytic composite nanofiber membrane prepared in the embodiment 4-6 on escherichia coli is superior to that of the photocatalytic composite nanofiber membrane on staphylococcus aureus; under the illumination condition, the photocatalytic composite nanofiber membrane prepared in the embodiments 4-6 has an antibacterial effect on staphylococcus aureus better than that on escherichia coli; as can be seen from fig. 12a, in a dark environment, the average inhibition zone diameters of the photocatalytic composite nanofiber membranes prepared in examples 4 to 6 for escherichia coli are 1.71cm, 2.02cm and 2.24cm in sequence, and the average inhibition zone diameters of the photocatalytic composite nanofiber membranes for staphylococcus aureus are 1.67cm, 1.86cm and 1.91cm in sequence; under the illumination condition, the average inhibition zone diameters of the photocatalytic composite nanofiber membranes prepared in the embodiments 4-6 on escherichia coli are 1.35cm, 1.44cm and 1.45cm in sequence, and the average inhibition zone diameters on staphylococcus aureus are 1.57cm, 1.78cm and 1.80cm in sequence; it can be seen that the antibacterial effect of the composite film increases with the increase of the doping amount.
FIG. 13 shows an example of the present invention6 the photodegradability of formaldehyde in visible light of the prepared spray-type photocatalytic composite nanofiber membrane. As can be seen from FIG. 13a, the concentration of formaldehyde added to the sample before irradiation decreased rapidly within the first 30min, and then gradually reached the adsorption-desorption equilibrium. Meanwhile, no new carbon dioxide gas is generated in the whole process, which indicates that saturated adsorption exists between formaldehyde and the sample. After dark adsorption for 30 minutes, the light irradiation is started, and PLA-Ag is found3PO4After the-3 @ HNTs-30% photocatalytic composite nanofiber membrane is irradiated for 650min by visible light, formaldehyde with the initial concentration of 44ppm can be degraded by about 40%.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of a photocatalytic composite nanofiber membrane is characterized by comprising the following steps:
1) mixing Ag with water3PO4Mixing the @ HNTs composite particles with the nanofiber stock solution to prepare a composite spinning solution A;
2) mixing Ag with water3PO4Mixing the @ HNTs composite particles with the nanofiber stock solution to prepare a spraying solution B;
3) carrying out electrostatic spinning by taking a non-woven fabric as a substrate and the composite spinning solution A as a raw material, and spraying by taking the spraying solution B as a raw material to obtain a photocatalytic composite nanofiber membrane;
wherein the electrospinning and spraying are performed simultaneously.
2. The method for preparing a photocatalytic composite nanofiber membrane as claimed in claim 1, wherein the nanofiber stock solution in step 1) and step 2) is independently polylactic acid solution, polyvinylidene fluoride solution or polyvinylpyrrolidone solution.
3. The preparation method of the photocatalytic composite nanofiber membrane as claimed in claim 2, wherein the mass concentration of the polylactic acid solution is 8% -14%, and the solvent is a mixture of N, N-dimethylformamide and dichloromethane; the mass concentration of the polyvinylidene fluoride solution is 10-18%, and the solvent is a mixture of N, N-dimethylformamide and acetone; the mass concentration of the polyvinylpyrrolidone solution is 10-16%, and the solvent is water.
4. The method for preparing the photocatalytic composite nanofiber membrane as claimed in any one of claims 1 to 3, wherein Ag in the composite spinning solution A3PO4The mass ratio of the @ HNTs composite particles to the solute in the nanofiber stock solution is 1-3: 10.
5. the method for preparing the photocatalytic composite nanofiber membrane as claimed in claim 4, wherein Ag in the spraying solution B3PO4The mass ratio of the @ HNTs composite particles to the solute in the nanofiber stock solution is 1-3: 10; the solid content of the spraying solution B is 10-30%.
6. The method for preparing the photocatalytic composite nanofiber membrane as claimed in any one of claims 1, 2, 3 or 5, wherein the electrospinning process conditions in step 3) are as follows: the spinning temperature is 30-50 ℃, the positive voltage of the spinning voltage is 10-24 kV, the negative voltage is 1-3 kV, the spinning time is 1-3 h, the propelling speed is 1-3 mL/h, and the receiving distance is 10-18 cm.
7. The method for preparing a photocatalytic composite nanofiber membrane as claimed in claim 6, wherein the spraying method in step 3) is an air flow spraying method.
8. The preparation method of the photocatalytic composite nanofiber membrane as claimed in claim 7, wherein the spraying process conditions in the step 3) are as follows: the gas flow rate is 400-500 mL/h.
9. The photocatalytic composite nanofiber membrane prepared by the preparation method of any one of claims 1 to 8.
10. The use of a photocatalytic composite nanofiber membrane as set forth in claim 9 for air purification or water body purification.
CN202210210162.2A 2022-03-03 2022-03-03 Photocatalytic composite nanofiber membrane and preparation method and application thereof Pending CN114471732A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103934008A (en) * 2014-04-17 2014-07-23 常州大学 Preparation method of halloysite loading phosphoric acid Silverlight catalyst
CN110563990A (en) * 2019-09-17 2019-12-13 广西科技大学 Preparation method and application of silver-containing cellulose composite material with photodegradation function
CN110773002A (en) * 2019-11-05 2020-02-11 北京服装学院 Antibacterial composite nanofiber membrane and preparation method and application thereof
CN112781164A (en) * 2021-02-01 2021-05-11 深圳绿蓝技术有限公司 Photocatalytic air purification and sterilization fiber, manufacturing method and application thereof, photocatalytic air purification and sterilization filter and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103934008A (en) * 2014-04-17 2014-07-23 常州大学 Preparation method of halloysite loading phosphoric acid Silverlight catalyst
CN110563990A (en) * 2019-09-17 2019-12-13 广西科技大学 Preparation method and application of silver-containing cellulose composite material with photodegradation function
CN110773002A (en) * 2019-11-05 2020-02-11 北京服装学院 Antibacterial composite nanofiber membrane and preparation method and application thereof
CN112781164A (en) * 2021-02-01 2021-05-11 深圳绿蓝技术有限公司 Photocatalytic air purification and sterilization fiber, manufacturing method and application thereof, photocatalytic air purification and sterilization filter and manufacturing method thereof

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Application publication date: 20220513