Novel efficient antibacterial material as well as preparation method and application thereof

Abstract

The invention provides a preparation method of a novel efficient antibacterial material. A molecular sieve with abundant acid sites and abundant pore channels is used as a basic carrier material. The method comprises the following steps: firstly, carrying out ammonium exchange treatment on a basic carrier at 80 DEG C for 2 hours, washing, drying and roasting for 2 hours to obtain a hydrogen type molecular sieve carrier; and then, carrying out metal ion exchange under the condition of room temperature to 80 DEG C, repeating twice, washing and drying to obtain metal exchange molecular sieve powder. Then, silver species are loaded on the zinc exchange molecular sieve through an impregnation method, and silver-loaded molecular sieve composite powder is formed after drying. And finally, molding the silver-loaded molecular sieve composite powder by adopting a rolling ball method, an extrusion method or other molding methods, and roasting to obtain the efficient nano-composite structure bactericide. The material has excellent adsorption performance and long-acting antibacterial effect, and is suitable for various application fields.

Description

Technical Field

[0001] The present invention relates to a new high - efficiency antibacterial material and a preparation method thereof, and particularly relates to the technical field of silver - loaded sterilization materials prepared by modifying porous molecular sieves. Background Art

[0002] With the increasingly serious problems of environmental pollution and microbial infections, the development of high - efficiency antibacterial materials has become a current research hotspot. Traditional antibacterial materials such as silver ions and copper ions, although having certain bactericidal effects, often have problems such as poor stability and easy inactivation in practical applications. In recent years, the development of nanotechnology has provided new ideas for the research of antibacterial materials. By combining metal nanoparticles with porous materials, not only can the specific surface area and adsorption performance of the materials be improved, but also their antibacterial effects and long - term effectiveness can be significantly enhanced. However, existing preparation methods still have many deficiencies in terms of process complexity, cost control, and product performance, which limit their large - scale application.

[0003] At present, porous molecular sieves, as an important type of porous material, have been widely used in fields such as catalysis and adsorption due to their high specific surface area, abundant acidic sites, and good thermal stability. However, how to effectively utilize these characteristics to improve the performance of antibacterial materials remains a challenge. Existing technologies usually use simple impregnation or co - precipitation methods to introduce metal ions into molecular sieves, but this method often leads to uneven metal dispersion, affecting the antibacterial effect of the final product. In addition, existing processes do not control key parameters such as temperature and time finely enough, resulting in unstable product quality and difficulty in meeting the requirements of industrial production. Therefore, it is particularly important to develop a new material with uniform metal distribution, good stability, and high - efficiency antibacterial performance and its preparation method.

[0004] To overcome the above problems, researchers have continuously explored new preparation processes and technical means. For example, using the abundant acidic sites of porous molecular sieve materials for ion - exchange methods can effectively improve the dispersion of metal ions in molecular sieves, thereby enhancing the antibacterial performance of the materials. At the same time, by optimizing conditions such as calcination temperature and time, the structure and stability of the materials can be further improved. Nevertheless, most existing research focuses on the application of single metal species, and the research on multi - metal composite structures is relatively less, and the emergence of a new generation of technologies is urgently needed. Summary of the Invention

[0005] In the above background, the present invention realizes the uniform distribution of various metal species on the molecular sieve through systematic optimization of the modification treatment of the molecular sieve and the metal loading process, significantly improving the adsorption performance and antibacterial effect of the material. This new type of antibacterial material not only has excellent bactericidal efficiency, but also exhibits good thermal stability and durability, and is applicable to multiple fields such as air purification and water treatment, showing broad application prospects. Through in-depth analysis and innovative improvement of the existing technology, the present invention provides a simple, efficient and stable preparation method of antibacterial material, providing a new solution to solve current environmental and health problems.

[0006] Specifically, the present invention discloses a preparation method of a highly efficient antibacterial new material, comprising the following steps:

[0007] Ammonium exchange treatment

[0008] First, the porous molecular sieve material is subjected to ammonium exchange treatment at a temperature of 50 - 90°C. The concentration of the ammonium chloride solution used is 0.1 - 1.5 mol / L, the solid-liquid ratio is 1:10 - 1:30, and the duration is 1 - 4 hours. After the ammonium exchange is completed, it is filtered and washed thoroughly with water, then dried at 100 - 120°C for 2 - 6 hours, and then calcined at 400 - 650°C for 1 - 3 hours to obtain the hydrogen-type molecular sieve.

[0009] Metal ion exchange Metal ion exchange is carried out at a temperature of 20 - 80°C. The concentration of the metal ion solution used is 0.01 - 1.0 mol / L, the solid-liquid ratio is 1:10 - 1:30, and it is repeated 1 - 3 times. After each treatment, it needs to be washed thoroughly with deionized water until the filtrate is neutral. After the metal ion exchange is completed, it is dried at 100 - 120°C for 2 - 6 hours to obtain the metal ion exchanged molecular sieve.

[0010] Silver species loading

[0011] The silver species is loaded onto the metal ion exchanged molecular sieve by the impregnation method, and the silver solution concentration is between 0.1 - 2.0 mol / L. After the loading is completed, it is dried at 100 - 120°C for 4 - 8 hours to obtain the silver-loaded molecular sieve composite material.

[0012] Shaping and calcination

[0013] The above silver-loaded molecular sieve composite material is shaped into particles, fibers, meshes or paper-like materials by the rolling ball method, extrusion or other shaping methods. Then it is calcined at 300 - 650°C for 0.5 - 3 hours to finally obtain the silver-loaded molecular sieve composite structure bactericide.

[0014] For the above technical solutions, more preferably, the porous molecular sieve material may be selected from one or more combinations of 13X, Y, A, β, ZSM-5, ZSM-35, MOR, SSZ-13, clinoptilolite, and levyne, and materials with an SiO2 / Al2O3 ratio lower than 50. More preferably, the material is one or more combinations of 13X, Y, β, ZSM-5, ZSM-35, MOR, and materials with an SiO2 / Al2O3 ratio lower than 40.

[0015] For the above technical solutions, more preferably, the metal ions may be selected from one or more combinations of zinc, titanium, manganese, tin, magnesium, calcium, nickel, copper, iron, lanthanum, and cerium. The mass percentage of the metal ions is 0.1-15%.

[0016] For the above technical solutions, more preferably, the silver species includes nano silver species with a size smaller than 30 nm, and its mass percentage ranges from 0.01-2.0% (based on the total mass of the silver-loaded metal ion-exchanged molecular sieve).

[0017] For the above technical solutions, more preferably, the concentration of the ammonium chloride solution preferably ranges from 0.5-1.2 mol / L, and the solid-liquid ratio is preferably 1:12-18.

[0018] For the above technical solutions, more preferably, the metal ion exchange is preferably carried out under the condition of 30-50 °C, the solid-liquid ratio is 1:12-20, and a 0.02-0.2 mol / L metal ion solution is used. The metal ion solution may be an aqueous solution of one or more combinations of formates, acetates, oxalates, and nitrates of zinc, titanium, manganese, tin, magnesium, calcium, nickel, copper, iron, lanthanum, and cerium.

[0019] For the above technical solutions, more preferably, the silver solution is preferably one or two combinations of acetate and nitrate.

[0020] Another aspect of the present invention is to protect the high-efficiency antibacterial new material described above; the antibacterial material may be granular materials with a diameter ranging from 0.5-5 mm, fibrous materials with a diameter of 10-500 microns and the reticular materials composed thereof, and paper-like materials with a thickness of 50-500 microns.

[0021] For the above technical solutions, more preferably, the silver-loaded molecular sieve composite structure has a bacteria killing rate of 99.99% and a virus killing rate of 98% after 30 seconds of contact. This material is suitable for killing bacteria and viruses in the air in indoor, passenger cars, and ship cabins, etc., and is particularly suitable for air purification in combination with air conditioners.

[0022] For the above technical solution, further preferably, the high-efficiency antibacterial new material is composed of porous molecular sieve, metal ions and silver species, and the specific surface area is greater than 150 m 2 / g. Among them, the mass percentage of silver species is 0.001-15%, the mass percentage of metal ions is 0.1-20%, and the mass percentage of porous molecular sieve material is 65-99.9%. The silver species include one or more combinations of silver ions, silver atoms, silver atom clusters and silver nanoparticles; the metal ions include one or more combinations of zinc, titanium, manganese, tin, magnesium, calcium, nickel, copper, iron, lanthanum and cerium.

[0023] For the above technical solution, further preferably, the specific surface area of the material is between 150 and 750 m 2 / g, and the temperature resistance is 400 °C. After contacting for 30 seconds, the killing rates against Escherichia coli and Staphylococcus aureus reach 99.99%, and the killing rate against influenza virus reaches 98%. The test conditions are room temperature, relative humidity of 50%, initial bacterial concentration of 10^5 CFU / mL, and initial virus concentration of 10^4 PFU / mL.

[0024] Compared with the prior art, the beneficial effects of this patent are:

[0025] The present invention provides a preparation method of a high-efficiency antibacterial new material. By using a specific macroporous molecular sieve as the substrate and undergoing a series of finely tuned chemical treatment steps, including ion exchange, hydrogen form conversion, transition metal zinc exchange, metal oxide loading and silver loading treatment, a nanocomposite with excellent adsorption performance and long-term antibacterial effect is finally obtained. Experimental results show that the materials prepared in Examples 1-4 are excellent in terms of specific surface area, pore volume, average pore diameter, metal content, bactericidal efficiency and thermal stability. In particular, the bactericidal efficiency reaches more than 99.7%, far higher than the materials in the comparative examples. In addition, by optimizing and adjusting different parameters (such as raw material types, solid-liquid ratio, metal solution concentration, etc.), the technology of this patent not only ensures the high efficiency of the material, but also significantly improves its stability and scope of application. In contrast, in Comparative Example 1 and Comparative Example 2, due to the change of key process parameters, the material performance decreased significantly, which further proves the uniqueness and irreplaceability of the technology of the present invention. Brief Description of the Drawings

[0026] Figure 1 It is a schematic diagram of the microstructure of the molecular sieve used in the present invention (Ar adsorption isotherm at 87K). Among them, A) Example 1, B) Example 2, C) Example 3, D) Example 4.

[0027] Figure 2 It is the crystal structure pattern at different treatment stages obtained by X-ray diffraction (XRD).

[0028] Figure 3 These are surface morphology images of the material obtained by scanning electron microscopy (SEM). Among them, A) Example 1, B) Example 2, C) Example 3, D) Example 4. Detailed implementation manners

[0029] To more clearly illustrate the technical solution of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are only for illustrative purposes and do not limit the application scope of the present invention. Unless otherwise specified, all reagents and process steps used in the present invention are conventional selections well-known to those skilled in the art, aiming to show how to prepare a nano-composite structure bactericide with excellent performance.

[0030] It should be understood that these specific embodiments are exemplary descriptions provided for the convenience of understanding and demonstrating the core technical idea of the present invention. In actual applications, those skilled in the art can make appropriate adjustments or optimizations to process parameters, raw material selection, and other details according to specific circumstances without departing from the basic principles and technical concepts of the present invention.

[0031] All reagents (such as ammonium chloride, zinc chloride, silver nitrate solution) and process steps (such as ion exchange, shaping and calcination) involved in the embodiments of the present invention are conventional selections in the industry and are widely used in the preparation of molecular sieve materials unless otherwise specified. These selections ensure the high efficiency and stability of the materials.

[0032] In the specific implementation manner of the present invention, the porous molecular sieve materials used can be selected from 13X type molecular sieves (NaX type molecular sieves, chemical formula: Na2O·Al2O3·2.45SiO2·6.0H2O), Y type molecular sieves (including NaY, HY, USY, etc., chemical formula: Na2O·Al2O3·4.8SiO2·xH2O), A type molecular sieves (including 3A, 4A, 5A, etc., chemical formula: Na2O·Al2O3·2SiO2·4.5H2O), β type molecular sieves (BEA structure, chemical formula: Na2O·Al2O3·xSiO2·yH2O), ZSM-5 type molecular sieves (MFI structure, chemical formula: Na2O·Al2O3·xSiO2·yH2O), ZSM-35 type molecular sieves (FER structure, chemical formula: Na2O·Al2O3·xSiO2·yH2O), MOR type molecular sieves (mordenite structure, chemical formula: Na2O·Al2O3·10SiO2·6.7H2O), SSZ-13 type molecular sieves (CHA structure, chemical formula: Na2O·Al2O3·xSiO2·yH2O), clinoptilolite (chemical formula: (Na,K,Ca) 2-3 Al3(Al,Si)2Si13 O 36 ·12H2O) and phillipsite (chemical formula: (K,Na,Ca) 1-2 Al2Si3O 10 ·4.5H2O), or a combination of one or more thereof, and having an SiO2 / Al2O3 molar ratio of less than 50; more preferably, the porous molecular sieve material is a combination of one or more of type 13X molecular sieve, type Y molecular sieve, type β molecular sieve, type ZSM-5 molecular sieve, type ZSM-35 molecular sieve, and type MOR molecular sieve, and having an SiO2 / Al2O3 molar ratio of less than 40. These porous molecular sieve materials have a high specific surface area and a regular pore structure, and can provide a good carrier basis for subsequent metal ion exchange and silver species loading.

[0033] The type 13X molecular sieve involved in the embodiments of the present invention is as follows:

[0034] For the type 13X macroporous molecular sieve with rich acidic sites, CBV100 of Zeolyst International or Type13X of UOP can be selected. Both of these products have a pore diameter of about 10 Å and a high specific surface area, and are widely used in the fields of air drying and gas purification. Their high adsorption capacity and thermal stability make them ideal starting materials in the present invention and are conventional choices in the industry.

[0035] The type Y molecular sieve involved in the embodiments of the present invention is as follows:

[0036] When selecting the type Y macroporous molecular sieve, CBV720 of Zeolyst International or Zeolum Y-85 of Grace Davison can be used. These two molecular sieves have a pore diameter of about 7.4 Å, excellent thermal stability, and rich acidic sites, and are suitable for high-temperature catalytic cracking reactions. They perform well as catalyst carriers and are common substrate options in the present invention, in line with the standard practices in the industry.

[0037] Example 1: Silver-loaded antibacterial material based on type 13X molecular sieve and zinc ions

[0038] Ammonium exchange treatment

[0039] Raw materials: type 13X molecular sieve (SiO2 / Al2O3 molar ratio is 3).

[0040] Process parameters: The type 13X molecular sieve is subjected to ammonium exchange treatment at 70 °C, using 0.8 mol / L ammonium chloride solution, with a solid-liquid ratio of 1:15, for 2 hours. After the exchange, it is filtered and washed with deionized water until neutral, dried at 110 °C for 4 hours, and then calcined at 500 °C for 2 hours to obtain hydrogen-type 13X molecular sieve.

[0041] Metal ion exchange

[0042] Raw material: zinc nitrate solution (0.1 mol / L).

[0043] Process parameters: The hydrogen form 13X molecular sieve is subjected to ion exchange with the zinc nitrate solution at 40 °C, the solid-liquid ratio is 1:15, repeated 2 times, 2 hours each time. After each exchange, it is washed with deionized water until the filtrate is neutral, dried at 110 °C for 4 hours to obtain the zinc ion-exchanged 13X molecular sieve.

[0044] Silver species loading

[0045] Raw material: silver nitrate solution (1.0 mol / L).

[0046] Process parameters: The silver nitrate solution is loaded onto the zinc ion-exchanged 13X molecular sieve by the impregnation method, and the impregnation time is 2 hours. After loading, it is dried at 110 °C for 6 hours to obtain the silver-loaded 13X molecular sieve composite material.

[0047] Shaping and calcination

[0048] Process parameters: The silver-loaded 13X molecular sieve composite material is shaped into 2 mm diameter particles by the rolling ball method and calcined at 450 °C for 1.5 hours to obtain the final product.

[0049] Performance test

[0050] Antibacterial performance: After 30 seconds of contact, the killing rates against Escherichia coli and Staphylococcus aureus reach 99.99%, and the killing rate against influenza virus reaches 98%.

[0051] Specific surface area: 320 m 2 / g, heat-resistant up to 400 °C.

[0052] Example 2: Silver-loaded antibacterial material based on Y-type molecular sieve and copper ions

[0053] Ammonium exchange treatment

[0054] Raw material: Y-type molecular sieve (SiO2 / Al2O3 molar ratio is 5).

[0055] Process parameters: The Y-type molecular sieve is subjected to ammonium exchange treatment at 60 °C, using 1.0 mol / L ammonium chloride solution, the solid-liquid ratio is 1:20, and it lasts for 3 hours. After the exchange, it is filtered and washed with deionized water until neutral, dried at 120 °C for 3 hours, and then calcined at 550 °C for 2.5 hours to obtain the hydrogen form Y molecular sieve.

[0056] Metal ion exchange

[0057] Raw materials: Copper acetate solution (0.05 mol / L).

[0058] Process parameters: The hydrogen form Y zeolite is ion-exchanged with the copper acetate solution at 50 °C, with a solid-liquid ratio of 1:18, repeated 3 times, 1.5 hours each time. After each exchange, it is washed with deionized water until the filtrate is neutral, and then dried at 120 °C for 3 hours to obtain the copper ion-exchanged Y zeolite.

[0059] Silver species loading

[0060] Raw materials: Silver acetate solution (0.5 mol / L).

[0061] Process parameters: The silver acetate solution is loaded onto the copper ion-exchanged Y zeolite by the impregnation method, and the impregnation time is 3 hours. After loading, it is dried at 120 °C for 5 hours to obtain the silver-loaded Y zeolite composite material.

[0062] Shaping and calcination

[0063] Process parameters: The silver-loaded Y zeolite composite material is shaped into a fibrous material with a diameter of 10 - 500 microns by the extrusion method, and calcined at 500 °C for 2 hours to obtain the final product.

[0064] Performance testing

[0065] Antibacterial performance: After 30 seconds of contact, the killing rates against Escherichia coli and Staphylococcus aureus reach 99.99%, and the killing rate against influenza virus reaches 98%.

[0066] Specific surface area: 450 m 2 / g, heat-resistant up to 400 °C.

[0067] Example 3: Silver-loaded antibacterial material based on β-type zeolite and iron ions

[0068] Ammonium exchange treatment

[0069] Raw materials: β-type zeolite (SiO2 / Al2O3 molar ratio is 40).

[0070] Process parameters: The β-type zeolite is subjected to ammonium exchange treatment at 80 °C, using 0.5 mol / L ammonium chloride solution, with a solid-liquid ratio of 1:12, for 4 hours. After the exchange, it is filtered and washed with deionized water until neutral, dried at 100 °C for 6 hours, and then calcined at 600 °C for 1 hour to obtain the hydrogen form β zeolite.

[0071] Metal ion exchange

[0072] Raw materials: Iron nitrate solution (0.2 mol / L).

[0073] Process parameters: The hydrogen-form β zeolite is ion-exchanged with an iron nitrate solution at 30 °C, with a solid-liquid ratio of 1:20, repeated once for 3 hours. After the exchange, it is washed with deionized water until the filtrate is neutral, and then dried at 100 °C for 6 hours to obtain the iron-ion-exchanged β zeolite.

[0074] Silver species loading

[0075] Raw materials: Silver nitrate solution (1.5 mol / L).

[0076] Process parameters: The silver nitrate solution is loaded onto the iron-ion-exchanged β zeolite by the impregnation method for 1 hour. After the loading is completed, it is dried at 100 °C for 8 hours to obtain the silver-loaded β zeolite composite material.

[0077] Shaping and calcination

[0078] Process parameters: The silver-loaded β zeolite composite material is shaped into a paper-like material with a thickness of 50 - 500 microns by the rolling ball method and calcined at 300 °C for 3 hours to obtain the final product.

[0079] Performance testing

[0080] Antibacterial performance: After 30 seconds of contact, the killing rates against Escherichia coli and Staphylococcus aureus reach 99.99%, and the killing rate against influenza virus reaches 98%.

[0081] Specific surface area: 280 m 2 / g, heat-resistant up to 400 °C.

[0082] Example 4: Silver-loaded antibacterial material based on ZSM-5 zeolite and titanium ions

[0083] Ammonium exchange treatment

[0084] Raw materials: ZSM-5 zeolite (SiO2 / Al2O3 molar ratio is 80).

[0085] Process parameters: The ZSM-5 zeolite is subjected to ammonium exchange treatment at 50 °C using a 1.2 mol / L ammonium chloride solution with a solid-liquid ratio of 1:18 for 1 hour. After the exchange, it is filtered and washed with deionized water until neutral, then dried at 120 °C for 2 hours, and subsequently calcined at 400 °C for 3 hours to obtain the hydrogen-form ZSM-5 zeolite.

[0086] Metal ion exchange

[0087] Raw materials: Titanium oxalate solution (0.02 mol / L).

[0088] Process parameters: The hydrogen-form ZSM-5 molecular sieve is ion-exchanged with a titanyl oxalate solution at 35 °C, with a solid-liquid ratio of 1:12, repeated 2 times, 2 hours each time. After each exchange, it is washed with deionized water until the filtrate is neutral and dried at 120 °C for 2 hours to obtain a titanium-ion-exchanged ZSM-5 molecular sieve.

[0089] Silver species loading

[0090] Raw material: Silver nitrate solution (0.1 mol / L).

[0091] Process parameters: The silver nitrate solution is loaded onto the titanium-ion-exchanged ZSM-5 molecular sieve by the impregnation method, and the impregnation time is 4 hours. After loading, it is dried at 120 °C for 4 hours to obtain a silver-loaded ZSM-5 molecular sieve composite.

[0092] Shaping and calcination

[0093] Process parameters: The silver-loaded ZSM-5 molecular sieve composite is shaped into granular materials with a diameter of 0.5 - 5 mm by the extrusion method and calcined at 650 °C for 0.5 hours to obtain the final product.

[0094] Performance testing

[0095] Antibacterial performance: After 30 seconds of contact, the killing rates against Escherichia coli and Staphylococcus aureus reach 99.99%, and the killing rate against influenza virus reaches 98%.

[0096] Specific surface area: 750 m 2 / g, heat-resistant up to 400 °C.

[0097] Comparative example 1: A silver-loaded antibacterial material based on 13X molecular sieve without metal ion exchange

[0098] Ammonium exchange treatment

[0099] Raw material: 13X molecular sieve (SiO2 / Al2O3 molar ratio is 30).

[0100] Process parameters: The 13X molecular sieve is subjected to ammonium exchange treatment at 70 °C using a 0.8 mol / L ammonium chloride solution, with a solid-liquid ratio of 1:15 for 2 hours. After the exchange, it is filtered and washed with deionized water until neutral, dried at 110 °C for 4 hours, and then calcined at 500 °C for 2 hours to obtain a hydrogen-form 13X molecular sieve.

[0101] Silver species loading

[0102] Raw material: Silver nitrate solution (1.0 mol / L).

[0103] Process parameters: The silver nitrate solution was directly supported on hydrogen-type 13X molecular sieve by the impregnation method (without metal ion exchange), and the impregnation time was 2 hours. After the loading was completed, it was dried at 110 °C for 6 hours to obtain the silver-loaded 13X molecular sieve composite material.

[0104] Forming and calcination

[0105] Process parameters: The silver-loaded 13X molecular sieve composite material was formed into particles with a diameter of 2 mm by the rolling ball method and calcined at 450 °C for 1.5 hours to obtain the final product.

[0106] Performance testing

[0107] Antibacterial performance: After 30 seconds of contact, the killing rates against Escherichia coli and Staphylococcus aureus were only 85%, and the killing rate against influenza virus was 70%.

[0108] Specific surface area: 350 m 2 / g, heat resistance 400 °C.

[0109] Comparative analysis:

[0110] In Comparative Example 1, no metal ion exchange was carried out, resulting in poor dispersion and stability of silver species, and the antibacterial performance was significantly lower than that of Example 1. This indicates that metal ion exchange is a key step to improve antibacterial performance and has creativity.

[0111] Comparative Example 2: Silver-loaded antibacterial material based on Y-type molecular sieve but using too high silver concentration

[0112] Ammonium exchange treatment

[0113] Raw materials: Y-type molecular sieve (SiO2 / Al2O3 molar ratio is 5).

[0114] Process parameters: The Y-type molecular sieve was subjected to ammonium exchange treatment at 60 °C, using 1.0 mol / L ammonium chloride solution, with a solid-liquid ratio of 1:20 for 3 hours. After the exchange was completed, it was filtered and washed with deionized water until neutral, and then dried at 120 °C for 3 hours, and then calcined at 550 °C for 2.5 hours to obtain hydrogen-type Y molecular sieve.

[0115] Metal ion exchange

[0116] Raw materials: Copper acetate solution (0.05 mol / L).

[0117] Process parameters: The hydrogen-type Y molecular sieve was subjected to ion exchange with the copper acetate solution at 50 °C, with a solid-liquid ratio of 1:18, repeated 3 times, each time for 1.5 hours. After each exchange, it was washed with deionized water until the filtrate was neutral, and then dried at 120 °C for 3 hours to obtain the copper ion-exchanged Y molecular sieve.

[0118] Silver species loading

[0119] Raw materials: silver acetate solution (5.0 mol / L, much higher than 0.5 mol / L in Example 2).

[0120] Process parameters: The silver acetate solution was supported on copper ion-exchanged Y zeolite by the impregnation method, and the impregnation time was 3 hours. After the support was completed, it was dried at 120 °C for 5 hours to obtain the silver-loaded Y zeolite composite material.

[0121] Forming and calcination

[0122] Process parameters: The silver-loaded Y zeolite composite material was formed into a fibrous material with a diameter of 10 - 500 microns by the extrusion method and calcined at 500 °C for 2 hours to obtain the final product.

[0123] Performance testing

[0124] Antibacterial performance: After 30 seconds of contact, the killing rates against Escherichia coli and Staphylococcus aureus were 90%, and the killing rate against influenza virus was 75%.

[0125] Specific surface area: 400 m 2 / g, heat resistance 400 °C.

[0126] Effect example - Detection basis

[0127] Specific surface area (BET)

[0128] Test method: The specific surface area of the sample was measured by the nitrogen adsorption method based on the Brunauer-Emmett-Teller (BET) theory.

[0129] Reference standard: ISO 9277:2010 "Determination of the specific surface area of solid materials - Gas adsorption BET method" or ASTM D3663-03(2019) "Standard test method for determining the total specific surface area of porous catalysts and supports by the single-point or multi-point BET method".

[0130] Pore volume and average pore diameter

[0131] Test method: Also based on the nitrogen adsorption isotherm, the pore volume and average pore diameter were calculated by the BJH (Barrett-Joyner-Halenda) model.

[0132] Reference standard: ISO 15901-2:2006 "Determination of pore size distribution and pore volume of microporous and mesoporous materials - Gas adsorption method".

[0133] Metal content

[0134] Test method: The contents of metal elements such as silver, zinc, titanium, and silicon in the sample were determined by inductively coupled plasma optical emission spectrometry (ICP-OES).

[0135] Reference standard: ASTM E1479-18 "Standard Guide for Quantitative Analysis Using Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)".

[0136] Sterilization efficiency

[0137] Test method: According to the standards of GB 21551.1-2008 "General Rules for Antibacterial, Disinfection, and Purification Functions of Household and Similar Electrical Appliances" or ISO 22196:2011 "Measurement of Antibacterial Activity on Plastics and Other Non-Porous Surfaces", the sterilization efficiency was evaluated by calculating the proportion of surviving bacteria after culturing Escherichia coli under specific conditions and contacting with the sample.

[0138] Stability (thermogravimetric analysis)

[0139] Test method: The sample was heated using a thermogravimetric analyzer (TGA) within a set temperature range (such as from room temperature to 500 °C), and the mass change was recorded to evaluate the thermal stability of the material.

[0140] Reference standard: ASTM E1131-19 "Standard Test Method for Determining the Decomposition Temperature of Materials by Thermogravimetry".

[0141] Through Figure 1 As can be seen from the Ar adsorption isotherm of the zeolite of the present invention at 87 K (A-D correspond to Examples 1-4), the zeolites of each example show typical type I isotherm characteristics, indicating that they have a regular microporous structure. The adsorption capacity of Example 4 ( Figure 1 D) is significantly higher than that of other examples, which is consistent with its specific surface area as high as 750 m 2 / g and pore volume data of 0.38 cm 3 / g, which benefits from the high silica-alumina ratio and unique pore system of ZSM-5 zeolite. Figure 2 The crystal structure pattern further confirms that after ammonium exchange, metal ion exchange, and silver loading treatment, the framework structure of the zeolite remains intact (the diffraction peak positions match), ensuring the thermal stability of the material (mass loss ≤ 3% at 500 °C). In addition, Figure 3 The surface morphology images (A-D correspond to Examples 1-4) show that the metal ion exchange process significantly improves the uniformity of the surface active sites of the zeolite (such as the increase in surface roughness after zinc ion modification in Example 1), while silver species are highly dispersed in the form of nanoparticles ( Figure 3 ), which is directly related to the 99.99% sterilization efficiency in the antibacterial performance test.

[0142] Detection indexes of examples and comparative examples:

[0143]

[0144] In summary, this new high-efficiency antibacterial material adopts advanced molecular sieve technology. First, ion exchange treatment is carried out under specific conditions, followed by hydrogen form conversion, transition metal zinc exchange, titanium dioxide and silver loading treatment. Finally, the finished product is obtained by forming with the rolling ball method and calcination. This process significantly improves the dispersion and stability of the supported species due to the large number and uniform distribution of the rich surface active sites of the molecular sieve, ensuring that the material has excellent adsorption performance and long-term antibacterial effect. In addition, since nano-zinc oxide itself has stronger bactericidal ability than TiO2, when it combines with Ag to form a nano-zinc oxide / Ag composite structure, it not only greatly enhances the stability of the material, but also further improves its antibacterial properties. Whether in the form of nano-zinc oxide-Ag or nano-zinc oxide-TiO2 / Ag, etc., all show enhanced antibacterial effects and excellent stability, which makes this material particularly outstanding in air purification and disinfection.

[0145] Therefore, the protection scope of the present invention is not limited to the description in the above specific embodiments, but covers all kinds of improvements and changes based on the core technical idea of the present invention. Any technical solution that follows the basic principles of the present invention and can achieve the same technical effects shall be regarded as falling within the protection scope of the claims of the present invention. This wide applicability and flexibility ensure that the present invention can exert its maximum potential in different application scenarios and provide diverse solutions for solving current environmental and health problems.

Claims

1. A preparation method of a new efficient antibacterial material, characterized in that: It includes the following steps: a) First, subject the porous molecular sieve material to ammonium exchange treatment at a temperature of 50 - 90 °C, using a 0.1 - 1.5 mol / L ammonium chloride solution, with a solid-liquid ratio of 1:10 - 1:30 and a duration of 1 - 4 hours; after the ammonium exchange is completed, filter, wash thoroughly with water, dry at 100 - 120 °C for 2 - 6 hours, and then calcine at 400 - 650 °C for 1 - 3 hours to obtain a hydrogen-type molecular sieve; b) Conduct metal ion exchange at a temperature of 20 - 80 °C, using a 0.01 - 1.0 mol / L metal ion solution, with a solid-liquid ratio of 1:10 - 1:30, repeat 1 - 3 times, and after each treatment, wash thoroughly with deionized water until the filtrate is neutral; after the metal ion exchange is completed, dry at 100 - 120 °C for 2 - 6 hours to obtain a metal ion-exchanged molecular sieve; c) Load silver species onto the metal ion-exchanged molecular sieve by the impregnation method, with the silver solution concentration between 0.1 - 2.0 mol / L. After the loading is completed, dry at 100 - 120 °C for 4 - 8 hours to obtain a silver-loaded molecular sieve composite material; d) Use the rolling ball method, extrusion or other forming methods to form the above silver-loaded molecular sieve composite material into a granular, fibrous, reticular or paper-like material, and then calcine at 300 - 650 °C for 0.5 - 3 hours to finally obtain a silver-loaded molecular sieve composite structure bactericide.

2. The preparation method according to claim 1, characterized in that: The porous molecular sieve material is selected from one or a combination of more than one of 13X, Y, A, β, ZSM-5, ZSM-35, MOR, SSZ-13, clinoptilolite, heulandite, and materials with an SiO2 / Al2O3 ratio lower than 50.

3. The preparation method according to claim 2, characterized in that: The porous molecular sieve material is selected from one or a combination of more than one of 13X, Y, β, ZSM-5, ZSM-35, MOR, and materials with an SiO2 / Al2O3 ratio lower than 40.

4. The preparation method according to claim 1, characterized in that: The metal ions are selected from one or a combination of more than one of zinc, titanium, manganese, tin, magnesium, calcium, nickel, copper, iron, lanthanum, and cerium.

5. The preparation method according to claim 1, characterized in that: The mass percentage of the metal ions is 0.1 - 15%.

6. An efficient antibacterial new material according to claim 1, characterized in that: The silver species include nano-silver species with a size less than 30 nm.

7. For a new high-efficiency antibacterial material according to claim 1, the mass percentage of the silver species is between 0.01 - 2.0%; based on the total mass of the silver-loaded metal ion-exchanged molecular sieve.

8. For a preparation method of a new high-efficiency antibacterial material according to claim 1, the concentration of the ammonium chloride solution in step a) is between 0.5 - 1.2 mol / L, and the solid-liquid ratio is 1:12 - 18.

9. For a preparation method of a new high-efficiency antibacterial material according to claim 1, in step b), the metal ions are exchanged at a temperature of 30 - 50 °C, the solid-liquid ratio is 1:12 - 20, and a 0.02 - 0.2 mol / L metal ion solution is used.

10. For a preparation method of a new high-efficiency antibacterial material according to claim 1, in step b), the metal ion solution is an aqueous solution of one or a combination of more than one of formates, acetates, oxalates, and nitrates of zinc, titanium, manganese, tin, magnesium, calcium, nickel, copper, iron, lanthanum, and cerium.

11. The silver solution in step c) of the method for preparing a new highly efficient antibacterial material according to claim 1 is one or a combination of acetate and nitrate.

12. The antibacterial material in step d) of the method for preparing a new highly efficient antibacterial material according to claim 1 is a granular material with a diameter ranging from 0.5 to 5 mm, a fibrous material with a diameter ranging from 10 to 500 microns, and a network material composed thereof, or a paper-like material with a thickness ranging from 50 to 500 microns.

13. The silver-loaded molecular sieve composite structure in step d) of the method for preparing a new highly efficient antibacterial material according to claim 1 has a bacteria killing rate of 99.99% and a virus killing rate of 98% after 30 seconds of contact.

14. A highly efficient antibacterial new material prepared by the method according to claim 1; characterized in that, The material is composed of porous molecular sieve, metal ions and silver species, and has a specific surface area greater than 150 m 2 / g; Among them, the mass percentage of the silver species is 0.001 - 15%, the mass percentage of the metal ions is 0.1 - 20%, and the mass percentage of the porous molecular sieve material is 65 - 99.9%; among them, the silver species include one or a combination of silver ions, silver atoms, silver atom clusters, and silver nanoparticles; the metal ions include one or a combination of zinc, titanium, manganese, tin, magnesium, calcium, nickel, copper, iron, lanthanum, and cerium.

15. The material according to claim 14; characterized in that, The specific surface area of the said material ranges from 150 to 750 m 2 / g, and it can withstand a temperature of 400 °C.

16. The material according to claim 14, characterized in that, After 30 seconds of contact, the material has a killing rate of 99.99% against Escherichia coli and Staphylococcus aureus and a killing rate of 98% against influenza virus. The test conditions are room temperature, relative humidity of 50%, an initial bacteria concentration of 10^5 CFU / mL, and an initial virus concentration of 10^4 PFU / mL.

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