Antibacterial and breathable textile fabric and preparation method thereof

Abstract

The application discloses an antibacterial and breathable textile fabric, characterized in that an antibacterial material of Mn and P double-site doped zinc titanate / oxidized graphene is loaded on a cotton fabric by means of ultrasonic-assisted impregnation and drying, and the preparation method of the Mn and P double-site doped zinc titanate / oxidized graphene is as follows: titanium salt and zinc salt are weighed and added into a deionized water / anhydrous ethanol solvent and stirred; a dopant, an Mn source and a P source are added, stirring is performed, and the mixture is transferred into an autoclave for reaction to obtain Mn and P double-site doped ZnTiO3; oxidized graphene is dissolved in an ethanol solution and uniformly dispersed, the Mn and P double-site doped ZnTiO3 is added into the ethanol solution, and ultrasonic treatment is continuously performed until the mixture is uniform, so that a suspension of oxidized graphene / Mn and P double-site doped ZnTiO3 is obtained; and the suspension is spray dried, so that a composite material of oxidized graphene / Mn and P double-site doped ZnTiO3 is obtained. The antibacterial material has important practical value, and the inhibition rates of the antibacterial material on escherichia coli and staphylococcus aureus are 99.9%, respectively.

Description

Technical Field

[0001] This invention belongs to the field of textiles, and in particular relates to an antibacterial and breathable textile fabric and its preparation method. Background Technology

[0002] With the development of polymer science, various new high-strength and high-performance textile materials have been developed. These new textile materials are being applied in high-tech industries such as communication and information, marine, and aerospace.

[0003] Microorganisms refer to all tiny organisms invisible or barely perceptible to the naked eye, such as bacteria, viruses, fungi, and rickettsiae. They are diverse, microscopic in structure, and closely related to humans; the vast majority are harmless or even beneficial. However, some microorganisms can cause food and medicine spoilage, decomposition of industrial materials and cosmetics, bacterial growth on clothing, and other health hazards. Various textiles used in daily life easily absorb various gases, liquids, and solid impurities. When mixed with metabolic substances such as human skin and sweat, they provide a suitable environment for the proliferation of various pathogenic microorganisms. To meet people's health protection needs, textile companies are continuously increasing their investment in the research and development and production of antibacterial and antiviral textiles, helping consumers build a safe barrier of healthy textiles. Antibacterial textiles are textiles that primarily target bacteria and fungi, possessing bactericidal and bacteriostatic functions. Antiviral textiles act as a barrier against viral invasion, inhibiting viral growth and reproduction, and suppressing viral activity.

[0004] In long-term research on sterilization and bacteriostasis, many methods have been developed, such as controlling temperature, pressure, and pH to alter the environment, using high-energy rays and electromagnetic waves to disrupt physiological structures, and blocking essential nutrients and moisture. Most of these methods can achieve rapid sterilization, but the conditions for their application are quite demanding, limiting their practical use. In nature, there exists a class of materials with inherent bactericidal and bacteriostatic functions; these materials are called antibacterial materials. Similarly, organic compounds, inorganic metals and their compounds, and some natural substances with certain specific functional groups possess antibacterial properties. Currently, most antibacterial materials are prepared by artificially adding antibacterial agents. For example, antibacterial textiles such as antibacterial plastics, antibacterial fibers, and antibacterial ceramics acquire their antibacterial function through antibacterial fiber weaving or antibacterial finishing. Antibacterial fibers or antibacterial agents can act on the biofilm system and cell wall of bacteria and fungi, or on their internal proteins, genetic material or other bioactive substances. These effects are interdependent and do not exist independently. They can destroy the structure of bacteria and fungi and various biochemical reactions in their bodies, disrupt their normal material and energy metabolism, and hinder their development and reproduction, thereby playing a bactericidal and bacteriostatic role.

[0005] Graphene oxide, formed by the oxidation of graphene, possesses potent antibacterial properties. Its antibacterial mechanism primarily involves interaction with bacterial cell membranes, leading to membrane disruption, leakage of intracellular substances, and ultimately cell death. The antibacterial activity of graphene oxide is mainly attributed to its high specific surface area, excellent electrical conductivity, electrochemical properties, and nanoscale size. Due to its superior antibacterial properties and biocompatibility, graphene oxide is widely used in antibacterial materials and medical devices. For example, it can be used to produce antibacterial fibers, plastics, and coatings, and to manufacture antibacterial face masks, goggles, gloves, and other medical protective equipment. Furthermore, graphene oxide can also be used to develop novel antibacterial drugs and medical materials.

[0006] However, in practical applications, graphene oxide has a large specific surface area and is prone to aggregation, which directly affects its antibacterial properties. Moreover, how to combine graphene oxide with other antibacterial materials to further enhance its antibacterial properties has always been a key research focus and challenge for researchers.

[0007] The purpose of this application is to provide a graphene oxide / Mn,P dual-site doped zinc titanate antibacterial material for use in textiles, in order to overcome the above problems. Summary of the Invention

[0008] The application of a graphene oxide / Mn,P dual-site doped zinc titanate antibacterial material in antibacterial textiles is characterized by the following preparation method:

[0009] Weigh out the titanium salt and zinc salt, add them to a solvent of deionized water / anhydrous ethanol with a volume ratio of 1:1, and control the molar ratio of zinc salt to titanium salt to be 1:1. Stir for 10-20 minutes.

[0010] Next, add the dopant, Mn source and P source, stir for 10-20 min, transfer to a hydrothermal reactor, react at 160-180℃ for 5-10 h, and wash the obtained product with deionized water and ethanol 2-3 times to obtain Mn and P dual-site doped ZnTiO3.

[0011] Graphene oxide was dissolved in an ethanol solution and ultrasonically dispersed until uniform. Mn and P doped ZnTiO3 was added to the solution and ultrasonication was continued until uniformity was achieved, resulting in a suspension of graphene oxide / Mn and P doped ZnTiO3. The suspension was then spray-dried to obtain a composite material of graphene oxide / Mn and P doped ZnTiO3.

[0012] Preferably, the zinc source is one of zinc chloride, zinc nitrate, or zinc acetate;

[0013] Preferably, the drying temperature range for spray drying is 100℃~200℃.

[0014] Preferably, the titanium salt is titanium tetrachloride or tetrabutyl titanate;

[0015] Preferably, the manganese source is manganese nitrate, manganese sulfate, or manganese chloride;

[0016] Preferably, the phosphorus source is phosphoric acid, ammonium phosphate, or ammonium dihydrogen phosphate;

[0017] Preferably, the doping amounts of P and Mn are (0.02-0.08) of the molar ratio of the Zn source;

[0018] Preferably, an ultrasonic-assisted impregnation and drying method is used to load the cotton fabric, and the number of impregnation-cycles is continuously increased to increase the load on the cotton fabric.

[0019] Technical Effects: Using graphene oxide / Mn, P dual-site doped ZnTiO3 as an antibacterial agent, the Mn, P dual-site doped ZnTiO3 forms a flower-like structure, which is sandwiched between graphene oxide sheets, improving the aggregation of the two-dimensional graphene oxide sheets; the flower-like structure has a larger specific surface area and better antibacterial effect; through doping, the oxygen atoms of zinc titanate are replaced by P, thereby narrowing the band gap and improving antibacterial properties; through Mn doping, the band structure of ZnTiO3 is changed, reducing the recombination rate of electrons and holes. The visible light range was broadened. Through experiments, we also found that if P and Mn doping were removed, ZnTiO3 eventually formed spherical shapes, indicating that P and Mn also have a crucial influence on the morphology of ZnTiO3. Spray drying easily forms a porous structure, which is conducive to charge transfer between zinc titanate and graphene oxide, thereby generating more ROS and improving antibacterial activity. Tests show that the antibacterial material of this application has an inhibition rate of 99.9% against Escherichia coli and Staphylococcus aureus, respectively, and has important practical value. Attached Figure Description

[0020] Figure 1 This is a SEM image of the graphene oxide / Mn, P dual-site doped ZnTiO3 of this application. Detailed Implementation

[0021] Example 1

[0022] The preparation method of graphene oxide / Mn,P dual-site doped zinc titanate antibacterial material includes the following steps:

[0023] Weigh 0.1 mol of titanium tetrachloride and 0.1 mol of zinc nitrate, add them to 85 ml of a solvent with a volume ratio of 1:1 of deionized water and anhydrous ethanol, and stir for 12 min.

[0024] Next, dopants 0.01 mol manganese nitrate and 0.01 mol phosphoric acid were added, stirred for 10 min, transferred to a hydrothermal reactor, and reacted at 160 °C for 5 h. The resulting product was washed twice with deionized water and ethanol; filtered to obtain Mn and P doped ZnTiO3.

[0025] 35 mg of graphene oxide was dissolved in 20 ml of ethanol solution and ultrasonically dispersed evenly. The resulting Mn, P dual-site doped ZnTiO3 was added to the solution and ultrasonically dispersed until homogeneous, resulting in a graphene oxide / Mn, P dual-site doped ZnTiO3 suspension. The suspension was then spray-dried at 100 °C to obtain a graphene oxide / Mn, P dual-site doped ZnTiO3 composite material.

[0026] Example 2

[0027] The preparation method of graphene oxide / Mn,P dual-site doped zinc titanate antibacterial material includes the following steps:

[0028] Weigh 0.1 mol of titanium tetrachloride and 0.1 mol of zinc nitrate, add them to 85 ml of a solvent with a volume ratio of 1:1 of deionized water and anhydrous ethanol, and stir for 12 min.

[0029] Next, dopants 0.01 mol manganese nitrate and 0.01 mol phosphoric acid were added, stirred for 10 min, transferred to a hydrothermal reactor, and reacted at 160 °C for 5 h. The resulting product was washed twice with deionized water and ethanol; filtered to obtain Mn and P doped ZnTiO3.

[0030] 45 mg of graphene oxide was dissolved in 20 ml of ethanol solution and ultrasonically dispersed evenly. The resulting Mn, P dual-site doped ZnTiO3 was added to the solution and ultrasonically dispersed until homogeneous, resulting in a graphene oxide / Mn, P dual-site doped ZnTiO3 suspension. The suspension was then spray-dried at 100 °C to obtain a graphene oxide / Mn, P dual-site doped ZnTiO3 composite material.

[0031] Example 3

[0032] The preparation method of graphene oxide / Mn,P dual-site doped zinc titanate antibacterial material includes the following steps:

[0033] Weigh 0.1 mol of titanium tetrachloride and 0.1 mol of zinc nitrate, add them to 85 ml of a solvent with a volume ratio of 1:1 of deionized water and anhydrous ethanol, and stir for 12 min.

[0034] Next, dopants 0.01 mol manganese nitrate and 0.008 mol phosphoric acid were added, stirred for 10 min, transferred to a hydrothermal reactor, and reacted at 180 °C for 5 h. The resulting product was washed twice with deionized water and ethanol; filtered to obtain Mn and P doped ZnTiO3.

[0035] 35 mg of graphene oxide was dissolved in 10 ml of ethanol solution and ultrasonically dispersed evenly. The resulting Mn, P dual-site doped ZnTiO3 was added to the solution and ultrasonically dispersed until homogeneous, resulting in a suspension of graphene oxide / Mn, P dual-site doped ZnTiO3. The suspension was then spray-dried at 100 °C to obtain a composite material of graphene oxide / Mn, P dual-site doped ZnTiO3.

[0036] Example 4

[0037] The preparation method of graphene oxide / Mn-zinc titanate antibacterial material includes the following steps:

[0038] Weigh 0.1 mol of titanium tetrachloride and 0.1 mol of zinc nitrate, add them to 85 ml of a solvent with a volume ratio of 1:1 of deionized water and anhydrous ethanol, and stir for 12 min.

[0039] Next, dopants 0.01 mol manganese nitrate and 0.01 mol phosphoric acid were added, stirred for 10 min, transferred to a hydrothermal reactor, and reacted at 180 °C for 5 h. The resulting product was washed twice with deionized water and ethanol; filtered to obtain Mn and P doped ZnTiO3.

[0040] 60 mg of graphene oxide was dissolved in 20 ml of ethanol solution and ultrasonically dispersed evenly. The Mn and P doped ZnTiO3 obtained in step 2 was added to the solution and ultrasonically dispersed until homogeneous, resulting in a graphene oxide / Mn and P doped ZnTiO3 suspension. The suspension was then spray-dried at 100 °C to obtain a graphene oxide / Mn and P doped ZnTiO3 composite material.

[0041] Comparative Example 1

[0042] The difference between this and Example 1 is that the Mn, P double-site doped ZnTiO3 prepared in Example 1 is used directly as the antibacterial agent.

[0043] Comparative Example 2

[0044] The difference between this and Example 1 is that only the graphene oxide from Example 1 is used as the antibacterial agent;

[0045] Comparative Example 3

[0046] The difference between this and Example 1 is that spray drying is replaced with conventional drying;

[0047] Comparative Example 4

[0048] The difference between this and Example 1 is that Mn doping is removed;

[0049] Comparative Example 5

[0050] The difference between this and Example 1 is that P doping is removed.

[0051] According to the national standard GB / T 23763-2009 "Photocatalytic Antibacterial Materials and Products, Evaluation of Antibacterial Properties", the inhibition rates of Examples 1-4 and Comparative Examples 1-5 against Escherichia coli and Staphylococcus aureus were tested. The results demonstrate that ZnTiO3 doped with graphene oxide / Mn,P dual sites possesses excellent antibacterial capabilities.

[0052] Table 1

[0053]

[0054] Those skilled in the art will understand that the above-described embodiments are specific examples of implementing this application, and in practical applications, various changes in form and detail may be made without departing from the spirit and scope of this application. Any person skilled in the art can make their own modifications and alterations without departing from the spirit and scope of this application; therefore, the scope of protection of this application should be determined by the scope defined in the claims.

Claims

1. A graphene oxide / Mn, P dual-site doped zinc titanate antibacterial material, characterized in that, The preparation method includes the following steps: Step 1: Weigh out the titanium salt and zinc salt, and add them to a solvent with a volume ratio of 1:1 of deionized water / anhydrous ethanol. The molar ratio of zinc salt to titanium salt should be controlled at 1:

1. Stir for 10-20 minutes. Step 2: Next, add the dopant, Mn source and P source, stir for 10-20 min, transfer to a hydrothermal reactor, react at 160-180℃ for 5-10 h, wash the obtained product with deionized water and ethanol 2-3 times to obtain Mn and P dual-site doped ZnTiO3. Step 3: Dissolve graphene oxide in an ethanol solution, disperse it evenly by ultrasonication, and then add the obtained Mn, P dual-site doped ZnTiO3 into it. Continue sonication until homogeneous to obtain a suspension of graphene oxide / Mn, P dual-site doped ZnTiO3. Spray dry the suspension to obtain a composite material of graphene oxide / Mn, P dual-site doped ZnTiO3. The manganese source is manganese nitrate, manganese sulfate, or manganese chloride; The phosphorus source is phosphoric acid, ammonium phosphate, or ammonium dihydrogen phosphate; The molar ratios of doped P, Mn, and Zn salts are 0.1:0.1:

1.

2. The graphene oxide / Mn, P dual-site doped zinc titanate antibacterial material according to claim 1, wherein the zinc salt is one of zinc chloride, zinc nitrate or zinc acetate.

3. The graphene oxide / Mn, P dual-site doped zinc titanate antibacterial material according to claim 1, wherein the spray drying temperature range is 100℃~200℃.

4. The graphene oxide / Mn, P dual-site doped zinc titanate antibacterial material according to claim 1, wherein the titanium salt is titanium tetrachloride or tetrabutyl titanate.

5. An antibacterial and breathable textile fabric, characterized in that, An ultrasonic-assisted impregnation and drying method is used to load the graphene oxide / Mn,P dual-site doped zinc titanate antibacterial material according to any one of claims 1-4 onto cotton fabric, and the number of impregnation cycles is continuously increased to improve the loading amount on the cotton fabric.

6. The antibacterial and breathable textile fabric according to claim 5 is impregnated 2-8 times.

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