A bactericidal and deodorizing mask based on piezocatalytic effect and a preparation method thereof

Abstract

This invention discloses a sterilizing and deodorizing mask based on piezoelectric catalysis and its preparation method, comprising an inner membrane, a middle membrane, and an outer membrane. The middle membrane is made of PVDF membrane, and sterilizing powder is loaded on the PVDF membrane. The sterilizing powder is FeO with a heterostructure. X / ZnO / Zn composite powder. The mask provided by this invention can utilize the vibration generated by breathing to cause the PVDF membrane to form a piezoelectric effect, thereby efficiently trapping pollutants (particulate matter, microorganisms, and volatile organic pollutants (deodorization)) in the air; at the same time, FeO on the membrane... X When the ZnO / Zn composite powder comes into contact with the moisture generated by breathing, it autonomously produces strong oxidizing hydroxyl radicals, thus purifying the trapped pollutants without the need for continuous external energy or chemical agents.

Description

Technical Field

[0001] This invention relates to the field of mask technology, and in particular to a sterilization and deodorization mask based on piezoelectric catalysis and its preparation method. Background Technology

[0002] Face masks, as basic personal protective equipment, are used to reduce the harm to human health caused by pollutants such as particulate matter (PM), bioaerosols, and volatile organic compounds (VOCs) in the air. They play an irreplaceable role, especially in preventing the spread of respiratory infectious diseases, blocking air pollutants, and ensuring public health safety. Most face masks use meltblown microfiber nonwoven fabric as the filter. With its dense mesh structure and sufficient thickness, it achieves efficient capture of air pollutants through physical interception and adsorption, thus meeting air quality standards.

[0003] Currently, traditional masks have significant drawbacks: limited ability to inhibit harmful microorganisms and deodorize (degrade organic matter). Specifically, masks can only trap pathogens and organic pollutants on their surface, but cannot completely inactivate or degrade them. Furthermore, the trapped organic pollutants can become a nutrient source for pathogens, turning the mask into a breeding ground for pathogenic microorganisms and leading to secondary air pollution. Therefore, developing an integrated filter material that can efficiently filter particulate matter, kill microorganisms, and degrade organic matter (deodorize) to block the spread of airborne pathogens has become an urgent need. Summary of the Invention

[0004] To address the aforementioned problems, this invention aims to provide a sterilization and deodorization mask based on piezoelectric catalysis and its preparation method.

[0005] The technical solution of the present invention is as follows: On one hand, a sterilizing and deodorizing mask based on piezoelectric catalysis is provided, comprising an inner membrane, a middle membrane, and an outer membrane. The middle membrane is made of PVDF membrane, and sterilizing powder is loaded on the PVDF membrane. The sterilizing powder is FeO with a heterostructure. X / ZnO / Zn composite powder.

[0006] Preferably, the PVDF film is manufactured using an electrostatic anti-spinning method.

[0007] Preferably, the PVDF membrane is prepared by the following steps: preparing a PVDF precursor solution, injecting the PVDF precursor solution into a syringe, then performing electrospinning, and vacuum drying the obtained fibers to obtain the PVDF membrane.

[0008] Preferably, the PVDF precursor solution is prepared by the following steps: mixing PVDF powder with a solvent, heating for 5 hours under stirring conditions in a water bath at 55°C, and finally allowing it to stand for 5 hours to remove bubbles, thereby obtaining the PVDF precursor solution.

[0009] Preferably, the solvent is a mixture of DMF and acetone in a volume ratio of 3:2.

[0010] Preferably, when performing electrospinning, a 21 G stainless steel needle is used, and spinning is performed at a liquid feed rate of 1.2-4.8 mL / h under conditions of 17 kV voltage and 15 cm receiving distance.

[0011] Preferably, the FeO with a heterostructure X The ZnO / Zn composite powder is prepared by the following steps: Using zinc particles as a carrier, they are immersed in an aqueous solution of zinc nitrate, followed by the addition of an aqueous solution of potassium hydroxide as a precipitant. Through the reaction of zinc nitrate and potassium hydroxide, a ZnO layer is deposited in situ on the surface of the zinc particles to obtain ZnO / Zn composite powder. Prepare an aqueous solution of ferrous chloride, immerse the ZnO / Zn composite powder in the solution, stir at 40°C for 10 min, centrifuge and wash with water to obtain powder loaded with FeOOH precursor; The powder loaded with FeOOH precursor was heat-treated at 300°C for 60 min in a mixed atmosphere of 5% H2 / 95% Ar to obtain the FeO with heterostructure. X / ZnO / Zn composite powder.

[0012] Preferably, the concentration of the zinc nitrate aqueous solution is 0.5 M, the concentration of the potassium hydroxide aqueous solution is 4 M, the volume ratio of the zinc nitrate aqueous solution to the potassium hydroxide aqueous solution is 1:1, and the concentration of the ferrous chloride aqueous solution is 5 mM.

[0013] On the other hand, a method for preparing the sterilizing and deodorizing mask based on the piezoelectric catalytic effect described in any one of the above claims is also provided, comprising the following steps: S1: Prepare PVDF film and FeOX / ZnO / Zn composite powder with heterostructure, respectively; S2: The FeO with the heterostructure... X / ZnO / Zn composite powder is loaded onto the PVDF membrane to obtain a middle layer membrane; S3: Place the middle layer membrane between the inner layer membrane and the outer layer membrane, and fix it to obtain the sterilization and deodorization mask based on the piezoelectric catalytic effect.

[0014] Preferably, in step S2, the FeO with heterostructure is processed through the following sub-steps. X / ZnO / Zn composite powder is loaded onto the PVDF membrane: S21: The FeO with heterostructure... X / ZnO / Zn composite powder was ultrasonically dispersed in water to obtain a dispersion; S22: The dispersion is loaded onto the PVDF membrane by brushing, impregnation or spraying, and then dried and cured to obtain the middle layer membrane.

[0015] The beneficial effects of this invention are: 1. This invention can achieve integrated and long-lasting functions of filtration, sterilization, and deodorization. The self-Fenton (FeO) constructed in this invention X The filter material, combining ZnO / Zn composite powder and piezoelectric effect (PVDF membrane), can continuously generate strong oxidizing hydroxyl radicals (·OH) in situ without external energy input. This effectively kills trapped microorganisms and degrades volatile organic pollutants (deodorization). This fundamentally avoids the problem of pollutant growth and secondary pollution on the filter surface, achieving simultaneous and efficient removal of multiple air pollutants.

[0016] 2. This invention can improve overall purification efficiency and environmental adaptability. Filter materials based on the self-Fenton reaction and piezoelectric effect can effectively capture weak mechanical energy from respiration and vibration in real, complex air environments (where multiple pollutants coexist). Under mechanical force, they spontaneously generate electrical charges, efficiently capturing particulate matter, microorganisms, and volatile organic pollutants through electrostatic adsorption, achieving true self-powered operation. Self-Fenton bactericidal powder utilizes moisture generated by respiration to autonomously and stably produce active species, maintaining highly efficient antibacterial and disinfection performance. This overcomes the limitations of traditional disinfection technologies (such as ultraviolet light and chemical sprays) that rely on external energy or reagents under similar conditions, demonstrating superior adaptability and stability for practical applications.

[0017] 3. This invention can provide a green, safe, and sustainable purification pathway. The sterilization and deodorization mechanism of this invention mainly relies on the inherent properties of the materials themselves. The entire process does not require the addition of traditional chemical disinfectants, thus avoiding the formation of harmful chemical residues and byproducts. It also overcomes the problems of ozone pollution and unsustainable effects associated with ultraviolet light methods, making it an environmentally friendly and sustainable air purification technology solution. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the structure of the antibacterial and deodorizing mask based on the piezoelectric catalytic effect of the present invention; Figure 2 FeO with a heterostructure as described in Example 1 X XRD pattern of ZnO / Zn composite powder; Figure 3 FeO with a heterostructure as described in Example 1 X XPS image of ZnO / Zn composite powder; Figure 4 FeO with a heterostructure as described in Example 1 X Schematic diagram of the antibacterial performance test results of / ZnO / Zn composite powder; Figure 5 FeO with a heterostructure as described in Example 1 X A schematic diagram showing the test results of the electron-deficient and electron-rich pollutant degradation performance of / ZnO / Zn composite powder.

[0020] Labels in the diagram: 1-Inner layer, 2-Middle layer, 3-Outer layer, 4-Zinc core (Zn), 5-Zinc oxide layer (ZnO), 6-Iron oxide layer (FeO) X ). Detailed Implementation

[0021] The present invention will be further described below with reference to the accompanying drawings and embodiments. It should be noted that, unless otherwise specified, the embodiments and technical features described in this application can be combined with each other. It should also be pointed out that, unless otherwise indicated, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. The terms "comprising" or "including" and similar words used in this invention refer to elements or objects preceding the word that encompass the elements or objects listed following the word and their equivalents, without excluding other elements or objects.

[0022] On the one hand, such as Figure 1 As shown, this invention provides a sterilizing and deodorizing mask based on piezoelectric catalytic effect, comprising an inner membrane 1, a middle membrane 2, and an outer membrane 3. The middle membrane 2 is made of PVDF membrane, and sterilizing powder is loaded on the PVDF membrane. The sterilizing powder is FeO with a heterostructure. X / ZnO / Zn composite powder.

[0023] In this invention, FeO with a heterostructure X The ZnO / Zn composite powder is a core-shell structure formed by in-situ growth of a zinc oxide layer 5 and an iron oxide layer 6 on a zinc core 4. When moistened by moisture from human respiration, the Zn core spontaneously donates electrons to the ZnO layer due to the work function difference, generating hydrogen peroxide and FeO. X The hydroxyl radicals generated by the in-situ decomposition of hydrogen peroxide achieve a highly efficient sterilization effect without the need for external energy supply or disinfectant addition.

[0024] PVDF membranes utilize the piezoelectric effect of PVDF material to spontaneously generate an electric charge under the mechanical force of human respiration. Through electrostatic adsorption, they efficiently capture air pollutants such as particulate matter, microorganisms, and volatile organic pollutants (deodorization). Simultaneously, by integrating air pollutant trapping and purification functions into a single material system, they overcome the shortcomings of existing masks that can only trap but not inactivate pathogens or degrade organic pollutants, thus preventing masks from becoming a source of pollution and causing secondary air pollution.

[0025] Through the FeO with heterostructure X The present invention constructs a material system combining a self-Fenton system and a piezoelectric effect using ZnO / Zn composite powder and the PVDF membrane. This system utilizes the vibrations generated by respiration to induce a piezoelectric effect in the PVDF membrane, thereby efficiently trapping airborne pollutants (particulate matter, microorganisms, and volatile organic pollutants (deodorization)). Simultaneously, FeO on the membrane... X When the ZnO / Zn composite powder comes into contact with the moisture generated by breathing, it autonomously produces strong oxidizing hydroxyl radicals, thus purifying the trapped pollutants without the need for continuous external energy or chemical agents.

[0026] In one specific embodiment, the PVDF membrane is manufactured using an electrostatic anti-spinning method. Optionally, the PVDF membrane is manufactured by the following steps: preparing a PVDF precursor solution, injecting the PVDF precursor solution into a syringe, then performing electrospinning, and vacuum drying the obtained fibers to obtain the PVDF membrane.

[0027] In one specific embodiment, the PVDF precursor solution is prepared by the following steps: mixing PVDF powder with a solvent, heating for 5 hours under stirring conditions in a 55°C water bath, and finally allowing it to stand for 5 hours to remove bubbles, thereby obtaining the PVDF precursor solution.

[0028] In one specific embodiment, the solvent is a mixture of DMF and acetone in a volume ratio of 3:2.

[0029] In one specific embodiment, when performing electrospinning, a 21 G stainless steel needle is used, and spinning is performed at a liquid feed rate of 1.2-4.8 mL / h under conditions of 17 kV voltage and a receiving distance of 15 cm.

[0030] It should be noted that the parameters selected in the above embodiments are only preferred experimental parameters of the present invention, and other parameters that can produce the PVDF membrane can also be applied to the present invention.

[0031] In one specific embodiment, the FeO with heterostructure X The ZnO / Zn composite powder is prepared by the following steps: Using zinc particles as a carrier, they are immersed in an aqueous solution of zinc nitrate, followed by the addition of an aqueous solution of potassium hydroxide as a precipitant. Through the reaction of zinc nitrate and potassium hydroxide, a ZnO layer is deposited in situ on the surface of the zinc particles to obtain ZnO / Zn composite powder. Prepare an aqueous solution of ferrous chloride, immerse the ZnO / Zn composite powder in the solution, stir at 40°C for 10 min, centrifuge and wash with water to obtain powder loaded with FeOOH precursor; The powder loaded with FeOOH precursor was heat-treated at 300°C for 60 min in a mixed atmosphere of 5% H2 / 95% Ar to obtain the FeO with heterostructure. X / ZnO / Zn composite powder.

[0032] In the above embodiments, zinc particles serve as the core carrier and substrate, providing an adhesion interface and structural support for the in-situ growth of the ZnO layer, and forming a heterojunction with ZnO. Simultaneously, they can spontaneously supply electrons to the ZnO layer. Zinc nitrate and potassium hydroxide serve as the zinc source and precipitant, respectively, reacting to rapidly and in-situ deposit a ZnO coating on the zinc particle surface. Ferrous chloride serves as the iron source, used to generate the FeOOH precursor on the ZnO / Zn surface, which is then heat-treated and annealed to form FeO. X / ZnO / Zn.

[0033] In one specific embodiment, the concentration of the zinc nitrate aqueous solution is 0.5 M, the concentration of the potassium hydroxide aqueous solution is 4 M, the volume ratio of the zinc nitrate aqueous solution to the potassium hydroxide aqueous solution is 1:1, and the concentration of the ferrous chloride aqueous solution is 5 mM.

[0034] It should be noted that the parameters selected in the above embodiments are only preferred experimental parameters of the present invention. Other parameters that can produce the FeO with the heterostructure may also be used. X The parameters of the / ZnO / Zn composite powder can also be applied to this invention.

[0035] On the other hand, the present invention also provides a method for preparing a bactericidal and deodorizing mask based on piezoelectric catalytic effect as described in any one of the above claims, comprising the following steps: S1: Prepare PVDF film and FeOX / ZnO / Zn composite powder with heterostructure, respectively; S2: The FeO with the heterostructure... X / ZnO / Zn composite powder is loaded onto the PVDF membrane to obtain a middle layer membrane; S3: Place the middle layer membrane between the inner layer membrane and the outer layer membrane, and fix it to obtain the sterilization and deodorization mask based on the piezoelectric catalytic effect.

[0036] In a specific embodiment, in step S2, the FeO with heterostructure is processed through the following sub-steps. X / ZnO / Zn composite powder is loaded onto the PVDF membrane: S21: The FeO with heterostructure... X / ZnO / Zn composite powder was ultrasonically dispersed in water to obtain a dispersion; S22: The dispersion is loaded onto the PVDF membrane by brushing, impregnation or spraying, and then dried and cured to obtain the middle layer membrane.

[0037] Example 1 A bactericidal and deodorizing mask based on piezoelectric catalysis is prepared through the following steps: (1) Preparation of bactericidal powder (FeO with heterostructure) X (ZnO / Zn composite powder) Using zinc particles as a carrier, they were immersed in 5 mL of a 0.5 M zinc nitrate aqueous solution, followed by the addition of 5 mL of a 4 M potassium hydroxide aqueous solution as a precipitant. Through the reaction of zinc nitrate and potassium hydroxide, a ZnO layer was deposited in situ on the surface of the zinc particles, yielding a ZnO / Zn composite powder. A 5 mM ferrous chloride aqueous solution was prepared, and the ZnO / Zn composite powder was immersed in this solution, stirred at 40°C for 10 min, centrifuged, and washed with water to obtain a powder loaded with a FeOOH precursor. The powder loaded with the FeOOH precursor was then heat-treated at 300°C for 60 min in a mixed atmosphere of 5% H₂ / 95% Ar to obtain the FeO with a heterostructure. X / ZnO / Zn composite powder.

[0038] (2) Preparation of PVDF membrane PVDF powder with a mass fraction of 14% and an average molecular weight of 534,000 was added to a mixed solvent of DMF and acetone in a volume ratio of 3:2. The mixture was stirred and heated in a water bath at 55°C for 5 h to ensure complete dissolution. After standing for 5 h to remove bubbles, a PVDF precursor solution was obtained. The PVDF precursor solution was injected into a 15 mL syringe. Using a 21 G stainless steel needle, spinning was performed at a feed rate of 1.2-4.8 mL / h under conditions of 17 kV voltage and a receiving distance of 15 cm. The fibers were deposited on an aluminum foil receiving substrate. The aluminum foil receiving substrate with the deposited fibers was placed in a vacuum drying oven and dried for 12 h to obtain the PVDF film.

[0039] (3) Preparation of sterilization and deodorization masks The FeO with heterostructure X / ZnO / Zn composite powder is ultrasonically dispersed in water to obtain a dispersion; the dispersion is loaded onto the PVDF membrane by brushing, impregnation or spraying, and dried and cured to obtain the middle layer membrane; the middle layer membrane is placed between the inner layer membrane and the outer layer membrane and fixed to obtain the sterilization and deodorization mask based on piezoelectric catalysis.

[0040] Test Example 1 The FeO with heterostructure obtained in step (1) of Example 1 X X-ray photoelectron spectroscopy and X-ray diffraction analysis were performed on the ZnO / Zn composite powder, and the results are as follows: Figure 2 and Figure 3 As shown. From Figure 2 and Figure 3 It can be seen that FeO X Successful loading of FeO on the ZnO / Zn surface, while X The loading does not change the composition structure of ZnO / Zn.

[0041] Test Example 2 The FeO with heterostructure obtained in step (1) of Example 1 X The antibacterial properties of the ZnO / Zn composite powder were tested, and the results are as follows: Figure 4 As shown. From Figure 4 It can be seen that FeO X / ZnO / Zn composite powder has a highly efficient bactericidal ability.

[0042] Test Example 3 The FeO with heterostructure obtained in step (1) of Example 1 X The degradation performance of ZnO / Zn composite powder for electron-deficient and electron-rich pollutants was tested, and the results are as follows: Figure 5 As shown. From Figure 5 It can be seen that FeO X / ZnO / Zn can efficiently degrade a variety of pollutants.

[0043] In summary, this invention selects a Fenton reaction material as the core functional component and integrates it with a PVDF piezoelectric membrane to construct a composite mask that combines highly efficient physical filtration with highly efficient catalytic purification. The piezoelectric properties of the PVDF membrane utilize weak mechanical forces such as breathing and vibration to generate charges, effectively trapping particulate matter, microorganisms, and volatile organic pollutants. Simultaneously, the Fenton material system does not rely on continuous input of external energy or chemical agents; it can autonomously and in-situ generate strong oxidizing hydroxyl radicals (·OH) using only the moisture produced by breathing. The two work synergistically to efficiently purify the air. This synergistic effect ensures that the mask maintains stable and long-lasting antibacterial and disinfection performance even in real and complex usage environments, and fundamentally avoids the growth of microorganisms and volatile organic pollutants and secondary pollution problems.

[0044] The above description is merely a representative embodiment of the present invention and is not intended to limit the present invention in any way. Any embodiment made by those skilled in the art without departing from the scope of the present invention and utilizing the disclosed technical content is an equivalent embodiment of the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A sterilizing and deodorizing mask based on piezoelectric catalytic effect, comprising an inner membrane, a middle membrane, and an outer membrane, characterized in that, The middle layer membrane is made of PVDF membrane, and the PVDF membrane is loaded with bactericidal powder, which is FeO with a heterostructure. X / ZnO / Zn composite powder.

2. The antibacterial and deodorizing mask based on piezoelectric catalytic effect according to claim 1, characterized in that, The PVDF membrane is manufactured using an electrostatic anti-fiber method.

3. The antibacterial and deodorizing mask based on piezoelectric catalytic effect according to claim 2, characterized in that, The PVDF membrane is made by the following steps: preparing a PVDF precursor solution, injecting the PVDF precursor solution into a syringe, then performing electrospinning, and vacuum drying the obtained fibers to obtain the PVDF membrane.

4. The antibacterial and deodorizing mask based on piezoelectric catalytic effect according to claim 3, characterized in that, The PVDF precursor solution is prepared by the following steps: PVDF powder is mixed with a solvent, then heated for 5 hours under stirring conditions in a 55°C water bath, and finally allowed to stand for 5 hours to remove bubbles, thereby obtaining the PVDF precursor solution.

5. The antibacterial and deodorizing mask based on piezoelectric catalytic effect according to claim 4, characterized in that, The solvent used is a mixture of DMF and acetone in a volume ratio of 3:

2.

6. The antibacterial and deodorizing mask based on piezoelectric catalytic effect according to claim 3, characterized in that, When performing electrospinning, a 21 G stainless steel needle is used, and spinning is carried out at a liquid feed rate of 1.2-4.8 mL / h under the conditions of 17 kV voltage and 15 cm receiving distance.

7. The antibacterial and deodorizing mask based on piezoelectric catalytic effect according to claim 1, characterized in that, The FeO with heterostructure X The ZnO / Zn composite powder is prepared by the following steps: Using zinc particles as a carrier, they are immersed in an aqueous solution of zinc nitrate, followed by the addition of an aqueous solution of potassium hydroxide as a precipitant. Through the reaction of zinc nitrate and potassium hydroxide, a ZnO layer is deposited in situ on the surface of the zinc particles to obtain ZnO / Zn composite powder. Prepare an aqueous solution of ferrous chloride, immerse the ZnO / Zn composite powder in the solution, stir at 40°C for 10 min, centrifuge and wash with water to obtain powder loaded with FeOOH precursor; The powder loaded with FeOOH precursor was heat-treated at 300°C for 60 min in a mixed atmosphere of 5% H2 / 95% Ar to obtain the FeO with heterostructure. X / ZnO / Zn composite powder.

8. The antibacterial and deodorizing mask based on piezoelectric catalytic effect according to claim 7, characterized in that, The concentration of the zinc nitrate aqueous solution is 0.5 M, the concentration of the potassium hydroxide aqueous solution is 4 M, and the volume ratio of the zinc nitrate aqueous solution to the potassium hydroxide aqueous solution is 1:1; the concentration of the ferrous chloride aqueous solution is 5 mM.

9. The method for preparing a sterilizing and deodorizing mask based on piezoelectric catalytic effect as described in any one of claims 1-8, characterized in that, Includes the following steps: S1: Prepare PVDF membranes and FeO with heterostructures respectively. X / ZnO / Zn composite powder; S2: The FeO with the heterostructure... X / ZnO / Zn composite powder is loaded onto the PVDF membrane to obtain a middle layer membrane; S3: Place the middle layer membrane between the inner layer membrane and the outer layer membrane, and fix it to obtain the sterilization and deodorization mask based on the piezoelectric catalytic effect.

10. The method for preparing a sterilizing and deodorizing mask based on piezoelectric catalytic effect according to claim 9, characterized in that, In step S2, the FeO with heterostructure is processed through the following sub-steps. X / ZnO / Zn composite powder is loaded onto the PVDF membrane: S21: The FeO with heterostructure... X / ZnO / Zn composite powder was ultrasonically dispersed in water to obtain a dispersion; S22: The dispersion is loaded onto the PVDF membrane by brushing, impregnation or spraying, and then dried and cured to obtain the middle layer membrane.

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