Zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material as well as preparation method and application thereof

Abstract

The invention discloses a zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material as well as a preparation method and application thereof. The preparation method comprises the following steps: preparing a mixed solution of a template agent and an anchoring agent, loading a metal precursor, adding a silicon source, performing hydrothermal crystallization and performing post-treatment. According to the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material disclosed by the invention, Ag-Cu bimetallic nanoparticles are formed by introducing copper nitrate and silver together, so that the catalytic activity, selectivity and stability of the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material are remarkably enhanced, and the dosage of noble metal silver can be reduced.

Description

Technical Field

[0001] This invention belongs to the field of inorganic nano-antibacterial agent material preparation technology, and in particular relates to a zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material, its preparation method and application. Background Technology

[0002] Currently, inorganic nano-antibacterial agents are widely used due to their excellent stability, biocompatibility, and antibacterial properties. Nano-antibacterial agents, represented by silver and copper ions, are considered the most promising. The antibacterial ability of metal ions is closely related to their release rate and concentration. For example, the optimal concentration of Ag in biological solutions has been determined to be between 100 ppb and 10 ppm, which maintains sufficient toxicity to bacteria while ensuring biocompatibility with the material. Currently, one of the most common methods for controlling the release rate and concentration of metal ions is loading nano-silver onto a support.

[0003] To address this, various types of carrier materials have been adopted and developed, including metal-organic frameworks, rice husks, polymer matrices, titanium substrates, and borosilicates. For example, existing technologies disclose loading silver-zinc antibacterial materials onto SBN glass supports. The porous glass supports provide numerous sites for loading antibacterial metal ions, improving the bactericidal rate of the antibacterial agent. However, the process involves a multi-step purification-calcination method, which is complex and costly. Another existing technology discloses a silver-loaded antibacterial material using nano-silica; however, the nano-silica has a simple pore structure, and the antibacterial particles are prone to detachment, resulting in a short-lasting antibacterial effect. Other carriers, such as coordination polymers and rice husks, suffer from low chemical stability and poor durability. Therefore, developing and exploring efficient and simple strategies to achieve the controlled release of antibacterial particles remains a significant challenge. Summary of the Invention

[0004] In view of this, the main objective of the present invention is to provide a zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material, its preparation method and application. The technical problem to be solved is that by introducing copper nitrate to form Ag-Cu bimetallic nanoparticles with silver, the catalytic activity, selectivity and stability of the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material are significantly enhanced, and the amount of precious metal silver used can be reduced.

[0005] The objective of this invention and the technical problem it solves are achieved through the following technical solution. This invention proposes a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, comprising the following steps: S1, add tetrapropylammonium hydroxide solution and hexadecyltrimethylammonium bromide to deionized water, stir in a water bath until hexadecyltrimethylammonium bromide is completely dissolved and the solution becomes clear; add 3-aminopropyltriethoxysilane to the above clear solution, and continue to stir vigorously at room temperature for 15-20 min to allow 3-aminopropyltriethoxysilane to be fully hydrolyzed, to obtain the first mixture; S2, dissolve copper nitrate trihydrate in deionized water; add the copper nitrate solution dropwise to the first mixture from step S1 while stirring continuously; then add silver nitrate solution and continue stirring for 30-40 minutes to obtain the second mixture; S3, Ludox AS-40 silica sol was added dropwise to the second mixture while stirring at 800~1000 rpm, and then the mixture was continuously stirred at 85~95℃ for 2~2.5 hours to age the mixture and obtain a gel. S4. The gel obtained in step S3 is placed in an environment of 90~95°C to crystallize; after crystallization, it is naturally cooled to room temperature; the obtained product is centrifuged or filtered, washed until neutral, dried, and the dried powder is calcined in static air at 540~550°C to obtain the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material.

[0006] The objectives of this invention and the technical problems solved can be further achieved by the following technical measures.

[0007] Preferably, in the aforementioned method for preparing zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral materials, in step S1, the amount of tetrapropylammonium hydroxide solution is 7.5-8.0 parts by weight, the amount of hexadecyltrimethylammonium bromide is 0.4-0.6 parts by weight, and the amount of 3-aminopropyltriethoxysilane is 0.5-0.6 parts by weight.

[0008] Preferably, in the aforementioned method for preparing zeolite / silver / copper ternary inorganic nanomaterials for antibacterial and antiviral purposes, the temperature of the water bath in step S1 is 40-50°C.

[0009] Preferably, in the aforementioned method for preparing zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral materials, in step S2, the amount of copper nitrate trihydrate is 0.03~0.04 parts by weight, and the amount of silver nitrate is 0.020~0.022 parts by weight.

[0010] Preferably, in the aforementioned method for preparing zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral materials, in step S3, the amount of Ludox AS-40 silica sol used is 10-12 parts by weight.

[0011] Preferably, in the aforementioned method for preparing zeolite / silver / copper ternary inorganic nanomaterials for antibacterial and antiviral purposes, the crystallization time in step S4 is 48-72 hours.

[0012] Preferably, in the aforementioned method for preparing zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral materials, in step S4, the drying temperature is 80~85°C and the time is 24~28h.

[0013] Preferably, in the aforementioned method for preparing zeolite / silver / copper ternary inorganic nanomaterials for antibacterial and antiviral purposes, in step S4, the calcination time is 2-3 hours and the heating rate is 1-2°C / min.

[0014] Preferably, the aforementioned method for preparing zeolite / silver / copper ternary inorganic nanomaterials for antibacterial and antiviral purposes, wherein...

[0015] The objectives of this invention and the technical problems it solves can be further achieved by the following technical measures. This invention proposes a zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material, wherein the molar ratio of silver, copper, and zeolite in the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material is (1.18-1.3):(1.6-2.13):(670-800); the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material is prepared by the above-described method.

[0016] The objectives of this invention and the technical problems it solves can also be achieved by the following technical measures. This invention proposes an antibacterial plastic, wherein the antibacterial plastic uses the aforementioned zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material.

[0017] The objectives of this invention and the solutions to its technical problems can also be achieved using the following technical measures. This invention proposes an antibacterial coating, wherein the antibacterial coating uses the aforementioned zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material.

[0018] The objectives of this invention and the technical problems it solves can also be achieved by the following technical measures. This invention proposes an antibacterial ceramic, wherein the antibacterial ceramic uses the aforementioned zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes.

[0019] Compared with existing technologies, the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes described in this invention, along with its preparation method and applications, has the following beneficial effects: 1. The method for preparing zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral materials proposed in this invention uses CTAB as a mesoporous template agent, which works synergistically with the microporous template agent TPAOH to create a mesoporous system inside the zeolite crystal, which is conducive to the diffusion of reactants and products.

[0020] 2. The method for preparing zeolite / silver / copper ternary inorganic nanomaterials for antibacterial and antiviral purposes proposed in this invention involves introducing copper nitrate to form Ag-Cu bimetallic nanoparticles with silver. The addition of copper can regulate the electronic structure of silver, potentially enhancing catalytic activity, selectivity, and stability, and may reduce the amount of precious metal silver required.

[0021] 3. The method for preparing zeolite / silver / copper ternary inorganic nanomaterials for antibacterial and antiviral purposes proposed in this invention uses low-cost and easily industrialized silica sol as the silicon source; APTES can be used to simultaneously react with Ag. + and Cu 2+ Coordination enables the bimetallic material to be anchored together.

[0022] 4. The zeolite / silver / copper ternary inorganic nanomaterial of the present invention utilizes the synergistic mechanism of zeolite, Ag, and Cu: zeolite is adsorbed and enriched into Ag. + Cu 2+ Provide a "high-concentration reaction environment" to prevent the diffusion and loss of metal ions; Ag + It primarily disrupts cell membranes and enzyme activity, Cu 2+ It focuses on oxidative damage and genetic material disruption, with complementary targets that cover the entire life cycle of bacteria / viruses (adsorption-invasion-proliferation-release); the activity of Ag and Cu is further amplified at the nanoscale, while the sustained release effect of zeolite maintains a long-term concentration, ultimately achieving an antibacterial rate of ≥99% against Escherichia coli and an antiviral rate of ≥95% against MS2 bacteriophage.

[0023] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below. Attached Figure Description

[0024] Figure 1 The XRD patterns are of the zeolite / silver / copper ternary inorganic nanomaterials prepared in Examples 1 and 2 of this invention. Figure 2 This is Embodiment 1 of the present invention (see Figure 2 a) Example 2 (see Figure 2 b) Comparative Example 1 (see Figure 2 c) and Comparative Example 2 (see Figure 2 d) Macroscopic graph of colony count in antibacterial plate test of the prepared antibacterial and antiviral materials in relation to Escherichia coli; Figure 3 The antiviral performance of the antibacterial and antiviral materials prepared in Example 1 and Comparative Example 2 against MS2 is shown in the figure. Figure 4The graph shows the release curves of silver ions in anhydrous ethanol for the antibacterial and antiviral materials prepared in Example 1 and Comparative Example 3 of this invention. Figure 5 The graph shows the comparison of the antibacterial rate of the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral materials prepared in Examples 1-6 of this invention after 2 hours of interaction with Escherichia coli. Figure 6 This is a comparison chart showing the antibacterial rate of the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral materials prepared in Examples 1-6 of this invention after 6 hours of interaction with Escherichia coli. Detailed Implementation

[0025] To further illustrate the technical means and effects adopted by the present invention to achieve its intended purpose, the following detailed description, in conjunction with preferred embodiments, details the specific implementation methods, structures, features, and effects of a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, its preparation method, and its application. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable manner.

[0026] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well-known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art. Where specific experimental steps or conditions are not specified below, they can be performed according to the conventional experimental steps or conditions described in the literature in this field.

[0027] According to some embodiments of the present invention, a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes is provided, comprising the following steps: Step S1, preparing the template agent and anchoring agent mixture: Weigh 7.5-8.0 parts by weight of tetrapropylammonium hydroxide solution (TPAOH) and 0.4-0.6 parts by weight of hexadecyltrimethylammonium bromide (CTAB), add 5-6 parts by weight of deionized water, and stir in a 40-50°C water bath until the hexadecyltrimethylammonium bromide is completely dissolved and the solution becomes clear; TPAOH is the dominant template agent for forming the zeolite microporous structure. CTAB, as a co-templating agent, is crucial for constructing hierarchical channels when its weight ratio of (7.5~8.0):(0.4~0.6) is sufficient to self-assemble into micelles within the crystal, "creating" mesopores during zeolite crystallization without excessively disrupting the integrity of the microporous crystal structure. A ratio lower than (7.5~8.0):(0.4~0.6) prevents the formation of the zeolite phase, while a weight ratio higher than (7.5~8.0):(0.4~0.6) prevents the construction of ordered hierarchical porous zeolites. The weight ratio of TPAOH / CTAB should be controlled within (7.5~8.0):(0.4~0.6). By controlling the template agent ratio, zeolites with different topologies can be synthesized. Hexadecyltrimethylammonium bromide (CTAB) combined with TPAOH synthesizes hierarchical porous zeolites with mesoporous-microporous structures. Tetraethylammonium hydroxide (TEAOH) alone can only synthesize Beta zeolite; CTAB alone cannot synthesize zeolite structures. TPAOH acts as the nucleation driving force for zeolite structures, forming specific "zeolite primary structural units." These units are the core seeds for long-range ordered crystal growth. Without TPAOH, the "blueprint" and "driving force" for forming zeolite-type microporous crystal structures are lost, making zeolite structure formation difficult. The amount of water used determines the concentration, alkalinity, and aging environment of the entire synthesis system. Excessive water will dilute the concentration of TPAOH, thereby lowering the pH of the system. The water bath temperature is set to 40-50℃ to dissolve the template agents CTAB and TPAOH, forming a homogeneous template agent solution. Below 40℃, CTAB is not easily dissolved, and incomplete dissolution will affect the subsequent material structure. Temperatures above 50°C significantly reduce the rate of hydrolysis of APTES. Excessive hydrolysis leads to a large number of APTES molecules undergoing spontaneous condensation reactions in solution, forming oligomers or amorphous siloxane oligomers. APTES oligomers have larger molecular sizes and fixed configurations, making them unable to effectively decoordinate with and anchor Ag⁺ and Cu²⁺ ions via their amino groups. Adding less than 5 parts by weight of deionized water results in incomplete dissolution of the template agent, while adding more than 6 parts by weight increases the hydrolysis rate of subsequent precursors, affecting material properties.Add 0.5–0.6 parts of 3-aminopropyltriethoxysilane (APTES) to the clarified solution and continue vigorous stirring at 380–420 rpm for 15–20 min at room temperature to ensure complete hydrolysis of the 3-aminopropyltriethoxysilane. The key role of APTES here is not only in coordinating Ag⁺ / Cu, but more importantly, its hydrolyzed silanol groups can co-condense with the zeolite precursor, forming a zeolite shell on the silver surface through heterogeneous nucleation. An appropriate amount ensures that each metal ion is sufficiently "embraced" and fixed by amino groups, achieving high metal dispersion. Below 0.5 parts by weight, metal species are easily excluded from the zeolite crystals; above 0.6 parts by weight, it easily leads to wasted production costs. Below 380 rpm, the solution is difficult to dissolve uniformly; above 420 rpm, the solution easily overflows. Less than 15 min results in incomplete dissolution, while more than 20 min easily leads to waste.

[0028] Step S2, Loading the metal precursor: Dissolve 0.03-0.04 parts by weight of copper nitrate trihydrate (Cu(NO3)2•3H2O) in 2-3 parts by weight of deionized water. Copper nitrate trihydrate serves as a copper precursor, added to reduce silver costs and achieve an effective synergistic effect with silver. An appropriate amount of copper acts as a "diluent" for silver, spatially isolating silver atoms and preventing excessive aggregation, thus enhancing the final antibacterial and antiviral properties. If the amount of copper is less than 0.03 parts by weight, the "bimetallic synergy" design becomes ineffective, and the final material performance may only be slightly improved compared to single-metal Ag@zeolite, or even indistinguishable, failing to fully leverage the advantages of the bimetallic system. If the amount of copper is greater than 0.04 parts by weight, it may not be effectively fixed, making it more prone to hydrolysis and migration during hydrothermal processes, ultimately forming large, independently existing copper oxide clusters, and potentially also affecting the crystallinity of the zeolite. The purpose of deionized water is to dissolve the precursor; more than 3 parts by weight of water is too much, increasing the hydrolysis rate of the copper precursor and making it prone to aggregation; less than 2 parts by weight of water is too little, making it difficult for the copper precursor to dissolve completely. Under continuous stirring, copper nitrate solution is slowly added dropwise to the mixture from step S1. Subsequently, 20-22 parts by weight of silver nitrate solution (AgNO3) is slowly added. The mass ratio of copper to silver affects the structural distribution of the two metals in the zeolite. The optimal ratio is conducive to generating a strong electronic synergistic effect. Due to the difference in surface energy and reduction potential between the two metals, a weight ratio lower than or higher than (0.03-0.04):(20-22) will change the catalytic performance of the single metal and affect the antibacterial performance of the ternary material. In this ternary structure, zeolite acts as a carrier. This specific ratio ensures that the metal precursor is adequately isolated and anchored by APTES, enabling the formation of small metal nanoparticles confined within the zeolite channels during subsequent reduction. This exposes more active sites and results in superior performance. If the ratio is below or above (0.03~0.04):(20~22), the precursors agglomerate into large particles on the outside, significantly reducing the material's antibacterial and antiviral properties. Continue stirring for 30~40 min to ensure uniform mixing; mixing less than 30 min results in incomplete mixing, while mixing more than 40 min leads to wasted resources.

[0029] Step S3, Adding the Silicon Source: Measure 10-12 parts by weight of Ludox AS-40 silica sol. Silica sol is a zeolite precursor. Zeolite acts as a carrier for the metal. If the amount of zeolite is less than 10 parts by weight, it will be insufficient to disperse the metal. If the amount of zeolite is greater than 12 parts by weight, the amount of zeolite will be excessive, resulting in a mismatch between the anchoring agent and the template agent, making it difficult to construct a hierarchical porous structure. Under vigorous stirring at 800-1000 rpm, slowly and dropwise add the silica sol to the above mixture. Within this speed range, the silica sol will be uniformly dispersed and dissolved. Below 800 rpm, it will be difficult to dissolve. Above 1000 rpm, the speed is too high, generating a large number of stubborn bubbles / foams. These bubbles will become part of the gel, disrupting the homogeneity of the system and leading to material structural defects. At the same time, excessive shear force will damage or distort these relatively fragile micelle structures, disrupting their orderly arrangement. This process will gradually form a uniform gel. After the addition is complete, the mixture is continuously stirred at 85-95℃ for 2-2.5 hours to allow for aging. This temperature range of 85-95℃ is crucial for gel aging. Temperatures below 85℃ are insufficient for proper aging because the aging process determines the initial state of the precursor, directly impacting the success of subsequent crystallization. Temperatures above 95℃ lead to over-aging, causing uncontrollable pre-nucleation and component deactivation. A aging time of less than 2 hours results in insufficient gel aging, again because the aging process determines the initial state of the precursor, directly affecting the success of subsequent crystallization. A aging time greater than 2.5 hours easily leads to over-aging, causing uncontrollable pre-nucleation and component deactivation.

[0030] Step S4, hydrothermal crystallization: The obtained gel is transferred to a PTFE-lined stainless steel reactor, with a filling degree of approximately 60%–70%. Below 60%, the pressure generated in the reactor is insufficient to influence precursor nucleation; above 70%, the reactor solution is prone to overflow, posing a safety risk. The reactor is placed in a forced-air drying oven at 90–95°C for crystallization for 48–72 hours. This temperature and time are the crystallization temperature and time, which are crucial in determining whether the final product can form a perfect crystal structure. When the temperature / time is below the lower limit, the crystallization driving force is insufficient, leading to incomplete reaction and poor crystallinity. When the temperature / time is above the upper limit, over-crystallization occurs, resulting in the formation of a thermodynamically stable phase and deterioration of crystal properties.

[0031] Step S5, Post-processing: After crystallization, allow to cool naturally to room temperature. Centrifuge or filter the product, wash with plenty of deionized water until neutral, and then dry at 80-85°C for 24-28 hours to remove liquid water. Temperatures above 85°C (especially close to 100°C) may cause partial pre-decomposition or oxidation of TPAOH or CTAB, potentially generating complex intermediates; temperatures below 80°C result in incomplete drying. Calcine the dried powder in a tube furnace at 540-550°C in static air to completely remove the TPAOH and CTAB organic template agents. The chosen temperature range of 540-550°C is crucial for removing the template agents TPAOH and CTAB; below 540°C, incomplete removal results in carbonized residues; above 550°C, the zeolite structure collapses and the metallic species sinter.

[0032] In some optional embodiments, the concentration of the AgNO3 solution in step S1 is 0.014~0.016 mol / L. A suitable concentration is chosen to control the hydrolysis rate of silver nitrate. Above 0.016 mol / L, the hydrolysis rate of silver nitrate in the solution is too fast, making it prone to aggregation; below 0.014 mol / L, the solution volume and water content increase with a certain amount added, thus affecting the dissolution of other components.

[0033] In some optional embodiments, in step S5, the calcination time is 2-3 hours, and the heating rate is 1-2°C / min. The calcination time is crucial; a time greater than 3 hours can easily cause the zeolite structure to collapse, while a time less than 2 hours is too short, resulting in incomplete removal of the template agent. The heating rate is also critical; a heating rate greater than 2°C / min leads to a "bursting" destruction of the zeolite structure, and the large thermal shock from such a high rate accelerates the migration and aggregation of metal atoms, forming large metal particles. A heating rate less than 1°C / min is inefficient and may cause unnecessary metal sintering and structural changes.

[0034] In the above technical solution, this invention employs a synergistic guiding strategy of dual template agents (tetrapropylammonium hydroxide and hexadecyltrimethylammonium bromide) to synthesize a zeolite framework with microporous-mesoporous hierarchical channels in one step via an in-situ hydrothermal method. 3-Aminopropyltriethoxysilane (APTES) is used as a bifunctional coupling agent, whose amino groups simultaneously complex silver and copper metal precursors, ensuring their uniform anchoring during zeolite growth. Using silica sol as the silicon source, highly dispersed Ag and Cu bimetallic nanoparticles are generated in situ within the zeolite channels after gelation, hydrothermal crystallization, calcination, and reduction treatment. Compared to the limitations of existing technologies in terms of limited carrier sites and the ease with which antibacterial particles detach, the hierarchical porous zeolite carrier in this invention not only effectively increases the loading capacity of antibacterial ions but also enhances the fixation of antibacterial components and prevents their easy detachment through the presence of the coupling agent in the preparation method. This design enables the antibacterial material to exhibit highly efficient bactericidal effects, along with strong stability and durability, thereby significantly extending the product's lifespan. The prepared antibacterial and antiviral components are uniformly loaded onto a zeolite framework with microporous and mesoporous hierarchical channels. The construction of the hierarchical channel structure can effectively increase the loading of antibacterial particles. At the same time, the presence of amino groups in the method can complex silver and copper metal ions, making it difficult for the antibacterial components to fall off the carrier. This overcomes the problems of easy agglomeration of metal particles, low carrier loading rate, and single function in existing Ag / zeolite composite materials. The technical route described is simple to operate, low in cost, and high in yield, making it very easy to achieve industrialization.

[0035] Some embodiments of the present invention also provide a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, wherein the molar ratio of silver, copper, and zeolite in the zeolite / silver / copper ternary inorganic nanomaterial is (1.18-1.3):(1.6-2.13):(670-800), and the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes is prepared by the method described above. The ratio of the two metals affects the structural distribution of the two metals in the zeolite. The above-mentioned ratio range is conducive to generating a strong electronic synergistic effect. Due to the difference in surface energy and reduction potential of the two metals, ratios below or above this range will change the catalytic performance of the single metal and affect the antibacterial performance of the ternary material. In this ternary structure, zeolite serves as a carrier. Within the aforementioned ratio range, calculations show that on average, approximately one metal atom pair is loaded for every 280 SiO2 units. This ensures that the metal precursor is fully isolated and anchored by APTES, enabling the formation of small metal nanoparticles confined within the zeolite channels during subsequent reduction. This exposes a richer number of active sites, resulting in superior performance. If the ratio is below or above this range, the nanoparticles tend to agglomerate into large particles on the outside, significantly reducing the antibacterial and antiviral properties of the material.

[0036] Tests have shown that the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material exhibits excellent effects in killing Escherichia coli and bacteriophage MS2, with an antibacterial rate of ≥99% and an antiviral rate of ≥95%.

[0037] The zeolite / silver / copper ternary inorganic nanomaterial exhibits excellent effects in killing Escherichia coli and MS2 bacteriophage, with an antibacterial rate of ≥99% and an antiviral rate of ≥95%. The principle behind this is: 1) The enrichment effect of the zeolite porous structure: The zeolite carrier matches the pore size of the bacterial cell wall and the size of the virus particles. E. coli has a diameter of ~0.5-1 μm, and MS2 bacteriophage particles have a diameter of ~27 nm. Through electrostatic adsorption (the zeolite framework is negatively charged, while the pathogen surface is mostly positively charged), van der Waals forces, and pore retention, pathogens from the environment are rapidly enriched on the material surface and within the pores, increasing the local pathogen concentration and creating a "high-concentration target" environment for the antibacterial components; 2) The zeolite pores can stably load Ag+ and Cu through ion exchange. 2+ This forms a "metal ion reservoir." When pathogens are present in the environment, acidic substances produced by pathogen metabolism (such as lactic acid and acetic acid produced by bacterial fermentation) or extracellular secretions can alter the local pH value, triggering the cation exchange balance in the zeolite channel structure and slowly releasing Ag. + and Cu 2+ ;3)Ag + It can bind to the negatively charged phosphate groups in the phospholipid bilayer of bacterial cell membranes, disrupting the orderly arrangement of phospholipid molecules; at the same time, A⁺ can bind to polar groups such as amino (-NH2) and carboxyl (-COOH) groups in viral capsid proteins, disrupting the secondary structure of proteins, leading to capsid protein denaturation, changes in spatial conformation, and loss of the ability to bind to host bacterial receptors; 4) Cu 2+ Through oxidation (Cu) 2+ It can be reduced to Cu+, and then oxidized to form Cu. 2+ (The cycle generates oxidative stress) attacks unsaturated fatty acids on the cell membrane, triggering lipid peroxidation and generating toxic products such as malondialdehyde, which exacerbates cell membrane damage and ultimately leads to bacterial cell membrane rupture, cell lysis, and death. 5) The activity of Ag and Cu is further amplified at the nanoscale, while the sustained-release effect of zeolite maintains a long-term concentration, ultimately achieving an antibacterial and antiviral rate of ≥99% against Escherichia coli, Staphylococcus aureus, and MS2 bacteriophage.

[0038] Other embodiments of the present invention also provide an antibacterial plastic, which employs the aforementioned zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes. This antibacterial plastic is used in applications such as sewer pipes, where the antibacterial plastic pipes provide antibacterial protection to prevent microbial contamination. Performance is assessed by the antibacterial rate, with an expected antibacterial rate of 99% or higher.

[0039] Other embodiments of the present invention also provide an antibacterial coating, which employs the aforementioned zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material. This antibacterial coating is applied to walls in locations with high hygiene requirements, such as hospitals and schools. Performance is assessed by the antibacterial rate, with an expected antibacterial rate of over 99%.

[0040] Other embodiments of the present invention also provide an antibacterial ceramic, which employs the aforementioned zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes. This antibacterial ceramic is used to manufacture toilets, particularly those for public places, and can achieve an antibacterial effect.

[0041] The present invention will be further described below with reference to specific embodiments, but this should not be construed as a limitation on the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0042] Example 1 This embodiment provides a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.50 g of hexadecyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir in a 40°C water bath until CTAB is completely dissolved and the solution becomes clear; add 0.53 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue to stir vigorously for 20 min at room temperature and 400 rpm to allow APTES to be fully hydrolyzed.

[0043] 2) Dissolve 0.035 g Cu(NO3)2•3H2O in 2.5 ml of deionized water. While stirring at 200 rpm, slowly add copper nitrate solution dropwise to the mixture from step 1) at a rate of 0.3 mL / min; then slowly add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure thorough mixing.

[0044] 3) Measure 11.50 g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a rate of 5 mL / min at a speed of 800 rpm; a uniform gel will gradually form during this process; after the addition is complete, stir continuously at 85°C for 2 hours to age the gel.

[0045] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a forced-air drying oven at 90°C and crystallized for 48 hours.

[0046] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80℃ for 24 h; the dried powder was calcined in a tube furnace at 550℃ in static air for 2 h to obtain the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material, wherein the molar ratio of silver, copper and zeolite in the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material is 1.29:1.87:767.

[0047] Example 2 This embodiment provides a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.50 g of hexadecyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir in a 40°C water bath until CTAB is completely dissolved and the solution becomes clear; add 0.53 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue stirring for 20 min at room temperature and 400 rpm to allow APTES to be fully hydrolyzed.

[0048] 2) Dissolve 0.030 g Cu(NO3)2•3H2O in 2.5 ml of deionized water. While stirring at 200 rpm, slowly add copper nitrate solution dropwise to the mixture from step 1) at a rate of 0.3 mL / min; then add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure thorough mixing.

[0049] 3) Measure 11.50 g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a rate of 5 mL / min at a speed of 800 rpm; a uniform gel will gradually form during this process; after the addition is complete, stir continuously at 85°C for 2 hours to age the gel.

[0050] 4) Transfer the obtained gel to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of approximately 70%. Place the reactor in a 90°C forced-air drying oven and crystallize for 48 hours.

[0051] 5) After crystallization, allow the product to cool naturally to room temperature. Centrifuge the product at 4000 r / min, wash with plenty of deionized water until neutral, and then dry at 80℃ for 24 h. Calcinate the dried powder in a tube furnace at 550℃ in static air for 2 h to obtain the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material. The molar ratio of silver, copper, and zeolite in the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material is 1.29:1.6:767.

[0052] Example 3 This embodiment provides a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.50 g of hexadecyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir in a 40°C water bath until CTAB is completely dissolved and the solution becomes clear; add 0.53 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue stirring for 20 min at room temperature and 400 rpm to allow APTES to be fully hydrolyzed.

[0053] 2) Dissolve 0.04 g Cu(NO3)2•3H2O in 2.5 ml of deionized water. While stirring at 200 rpm, slowly add copper nitrate solution dropwise to the mixture from step 1) at a rate of 0.3 mL / min; then add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure thorough mixing.

[0054] 3) Measure 11.50 g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a rate of 5 mL / min while rotating at 800 rpm; a uniform gel will gradually form during this process. After the addition is complete, stir continuously at 85°C for 2 hours to age the mixture.

[0055] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a forced-air drying oven at 90°C and crystallized for 48 hours.

[0056] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80℃ for 24 h; the dried powder was calcined in a tube furnace at 550℃ in static air for 2 h to obtain the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material, wherein the molar ratio of silver, copper and zeolite in the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material is 1.29:2.13:767.

[0057] Example 4 This embodiment provides a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.50 g of hexadecyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir in a 40°C water bath until CTAB is completely dissolved and the solution becomes clear; add 0.53 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue to stir vigorously for 20 min at room temperature and 400 rpm to allow APTES to be fully hydrolyzed.

[0058] 2) Dissolve 0.035 g Cu(NO3)2•3H2O in 2.5 ml of deionized water and stir at 200 rpm. Slowly add copper nitrate solution dropwise to the mixture in step 1) at 0.3 mL / min. Then, slowly add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure uniform mixing.

[0059] 3) Measure 10 g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a speed of 5 mL / min at 800 rpm; a uniform gel will gradually form during this process; after the addition is complete, stir continuously at 85°C for 2 hours to age the gel.

[0060] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a forced-air drying oven at 90°C and crystallized for 48 hours.

[0061] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80℃ for 24 h; the dried powder was calcined in a tube furnace in static air at 550℃ for 2 h to obtain the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material, wherein the molar ratio of silver, copper and zeolite in the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material is 1.29:1.87:670.

[0062] Example 5 This embodiment provides a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.50 g of hexadecyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir in a 40°C water bath until CTAB is completely dissolved and the solution becomes clear; add 0.53 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue to stir vigorously for 20 min at room temperature and 400 rpm to allow APTES to be fully hydrolyzed.

[0063] 2) Dissolve 0.035 g Cu(NO3)2•3H2O in 2.5 ml of deionized water and stir at 200 rpm. Slowly add copper nitrate solution dropwise to the mixture in step 1) at 0.3 mL / min. Then, slowly add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure uniform mixing.

[0064] 3) Measure 12 g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a speed of 5 mL / min at 800 rpm; a uniform gel will gradually form during this process; after the addition is complete, stir continuously at 85°C for 2 hours to age the gel.

[0065] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a forced-air drying oven at 90°C and crystallized for 48 hours.

[0066] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80℃ for 24 h; the dried powder was calcined in a tube furnace at 550℃ in static air for 2 h to obtain the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material, wherein the molar ratio of silver, copper and zeolite in the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material is 1.29:1.87:800.

[0067] Example 6 This embodiment provides a method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.40 g of hexadecyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir in a 40°C water bath until CTAB is completely dissolved and the solution becomes clear; add 0.5 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue to stir vigorously for 20 min at room temperature and 400 rpm to allow APTES to be fully hydrolyzed.

[0068] 2) Dissolve 0.035 g Cu(NO3)2•3H2O in 2.5 ml of deionized water and stir at 200 rpm. Slowly add copper nitrate solution dropwise to the mixture in step 1) at 0.3 mL / min. Then, slowly add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure uniform mixing.

[0069] 3) Measure 11.5g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a speed of 5 mL / min at 800 rpm; a uniform gel will gradually form during this process; after the addition is complete, stir continuously at 85℃ for 2 hours to age the gel.

[0070] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a forced-air drying oven at 90°C and crystallized for 48 hours.

[0071] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80℃ for 24 h; the dried powder was calcined in a tube furnace at 550℃ in static air for 2 h to obtain the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material, wherein the molar ratio of silver, copper and zeolite in the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material is 1.29:1.87:767.

[0072] Comparative Example 1 This comparative example provides a method for preparing antibacterial and antiviral materials, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH), add 5 ml of deionized water, and stir in a 40°C water bath; add 0.53 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue to stir vigorously at room temperature and a speed of 400 rpm for 20 min to allow APTES to be fully hydrolyzed.

[0073] 2) Dissolve 0.035 g Cu(NO3)2•3H2O in 2.5 ml of deionized water; stir at 200 rpm and slowly add copper nitrate solution dropwise to the mixture in step 1) at 0.3 mL / min; then add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure uniform mixing.

[0074] 3) Measure 11.50 g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a rate of 5 mL / min at a speed of 800 rpm; a uniform gel will gradually form during this process; after the addition is complete, stir continuously at 85°C for 2 hours to age the gel.

[0075] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a forced-air drying oven at 90°C and crystallized for 48 hours.

[0076] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80°C for 24 h; the dried powder was calcined in a tube furnace in static air at 550°C for 2 h to obtain the antibacterial and antiviral material.

[0077] Comparative Example 2 This comparative example provides a method for preparing antibacterial and antiviral materials, including the following steps: 1) Weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.50 g of hexadecyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir in a 40°C water bath until CTAB is completely dissolved and the solution becomes clear; add 0.53 g of 3-aminopropyltriethoxysilane (APTES) to the above clear solution, and continue to stir vigorously for 20 min at room temperature and 400 rpm to allow APTES to be fully hydrolyzed.

[0078] 2) Then, add 9.24 ml of 0.014 M AgNO3 solution to the mixture in step 1), and continue stirring at 200 rpm for 30 min to ensure uniform mixing.

[0079] 3) Measure 11.50 g of Ludox AS-40 silica sol. Add it dropwise to the above mixture at a rate of 5 mL / min while rotating at 800 rpm; a uniform gel will gradually form during this process; after the addition is complete, stir continuously at 85°C for 2 hours to age the gel.

[0080] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a 90°C drying oven and crystallized for 48 hours.

[0081] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80℃ for 24 h; the dried powder was calcined in a tube furnace at 550℃ in static air for 2 h to obtain the antibacterial and antiviral material.

[0082] Comparative Example 3 This comparative example provides a method for preparing a zeolite / silver / copper ternary inorganic material, including the following steps: 1) In a polytetrafluoroethylene beaker or conical flask, weigh 7.5 g of tetrapropylammonium hydroxide solution (TPAOH) and 0.50 g of cetyltrimethylammonium bromide (CTAB), add 5 ml of deionized water, and stir for 20 min in a 40°C water bath at 400 rpm until CTAB is completely dissolved and the solution becomes clear.

[0083] 2) Dissolve 0.035 g Cu(NO3)2•3H2O in 2.5 ml of deionized water; stir at 200 rpm and slowly add copper nitrate solution dropwise to the mixture in step 1) at 0.3 mL / min; then slowly add 9.24 ml of 0.014 M AgNO3 solution and continue stirring for 30 min to ensure uniform mixing.

[0084] 3) Measure 11.50 g of Ludox AS-40 silica sol; add it dropwise to the above mixture at a rate of 5 mL / min while rotating at 800 rpm; a uniform gel will gradually form during this process. After the addition is complete, stir continuously at 85°C for 2 hours to age the mixture.

[0085] 4) The obtained gel was transferred to a stainless steel reactor lined with polytetrafluoroethylene, with a filling degree of about 70%; the reactor was placed in a forced-air drying oven at 90°C and crystallized for 48 hours.

[0086] 5) After crystallization, the product was naturally cooled to room temperature; the product was centrifuged at 4000 r / min, washed with a large amount of deionized water until neutral, and then dried at 80℃ for 24 h; the dried powder was calcined in a tube furnace at 550℃ in static air for 2 h to obtain the antibacterial and antiviral material.

[0087] The antibacterial and antiviral rates in the following tests were obtained using the following formulas: Antibacterial rate = (number of bacterial colonies recovered in control sample - number of bacterial colonies recovered in sample) * 100% / number of bacterial colonies recovered in control sample; where the control sample is the sample with no added materials, only added bacteria; Antiviral rate = (number of viruses recovered in control sample - number of viruses recovered in sample) * 100% / number of viruses recovered in control sample; where the control sample is a sample with no added materials and only added virus.

[0088] Figure 1 The images show the XRD patterns of the zeolite / silver / copper ternary inorganic nanomaterials for antibacterial and antiviral purposes prepared in Examples 1 and 2 of this invention. Figure 1 The spectra show that adding Ag and Cu precursors to the initial zeolite sol-gel system via hydrothermal template method does not interfere with the crystallization process of silicate zeolite. The XRD diffraction peaks of the resulting zeolite / silver / copper ternary composite are similar to those of pure zeolite. Notably, no typical peaks corresponding to Ag / Cu and its oxides were observed, indicating that the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes does not contain large-sized metal particles, and that the diffraction peaks of the metal particles are masked by the diffraction peaks of the zeolite.

[0089] Figure 2 This is Embodiment 1 of the present invention (see Figure 2 a) Example 2 (see Figure 2 b) Comparative Example 1 (see Figure 2 c) and Comparative Example 2 (see Figure 2 d) Macroscopic graph of the antibacterial properties of the prepared material determined by the plate method. The antibacterial test was conducted as follows: 0.5 g of sample was dissolved in 20 ml of sterile water and diluted according to QB / T2738-2012, using a concentration of 5.0 × 10⁻⁶.4 For the CFU / ml Escherichia coli bacterial culture experiment, two time points were taken: 2 h and 6 h to observe the colony growth.

[0090] Depend on Figure 2 It can be seen that in Examples 1 and 2, the antibacterial rate was ≥99.9% after the materials were reacted with the bacterial solution for 6 hours. However, compared to Example 1, the ternary zeolite / silver / copper inorganic nano-antibacterial and antiviral material obtained in Example 2 did not completely kill the bacteria after 2 hours of reaction, with an antibacterial rate of 99%. This indicates that the copper ion content plays an important role in the ternary zeolite / silver / copper inorganic nano-antibacterial and antiviral material, and reducing the copper ion content will reduce its antibacterial effect.

[0091] Depend on Figure 2 It can also be seen that, compared with Comparative Example 1, the template agent CTAB affects the antibacterial effect of the material. In Comparative Example 1, when no CTAB was added, the antibacterial rate of the material was below 90%. This indicates that the change in the type of template agent reduces the antibacterial effect, which may be attributed to the template agent affecting the pore structure and specific surface area of ​​the zeolite carrier, thereby affecting its antibacterial effect.

[0092] Depend on Figure 2 It can also be seen that, compared with Comparative Example 2, copper component is an important factor affecting the antibacterial effect of the material. In Comparative Example 2, no copper precursor was added, and the antibacterial performance of the obtained material was greatly reduced to below 80%. This shows that the synergy between copper and silver ions can achieve a better antibacterial effect.

[0093] Figure 3 This is a comparison of the antiviral performance of the materials prepared in Example 1 and Comparative Example 2 against bacteriophage MS2. The antiviral experiment was conducted as follows: 0.5 g of sample was dissolved in 20 ml of sterile water and diluted according to ISO 18071, using a concentration of 5.0 × 10⁻⁶. 4 In the PFU / ml phage MS2 experiment, two time points were taken: 2 h and 6 h. After incubation, the material was infected with host bacteria, and the antiviral performance of the material was determined by counting the number of phage plaques generated.

[0094] Depend on Figure 3 It can be seen that, compared with Comparative Example 2, the ternary zeolite / silver / copper inorganic nano antibacterial and antiviral material obtained in Example 1 has better antiviral performance, and the antiviral rate increases with the extension of contact time. The antiviral rate of the ternary zeolite / silver / copper inorganic nano antibacterial and antiviral material obtained in Example 1 after 12 hours of contact is 95.9%, while the antiviral rate of the material obtained in Comparative Example 2 after 12 hours of contact is 83.9%. This shows that the copper component in the antibacterial and antiviral material is the key to exerting the antiviral effect, and the lack of this component will significantly reduce the antiviral effect.

[0095] Figure 4The graph shows the release curves of silver ions in anhydrous ethanol for the antibacterial and antiviral materials prepared in Example 1 and Comparative Example 3. Figure 4 It can be seen that the silver ion release rate in the ternary zeolite / silver / copper inorganic nanomaterial for antibacterial and antiviral purposes obtained in Example 1 is lower than that in Comparative Example 3. Nearly 75% of the silver ions were released from the zeolite / silver / copper composite material obtained in Comparative Example 3 within 6 days, while only 10.6% were released from the zeolite / silver / copper composite material obtained in Example 1 within the same time period. This phenomenon can be attributed to the coordination of metal ions with the amino groups of APTES in Example 1, which resulted in the metal ions being firmly and stably loaded into the zeolite structure. Simultaneously, due to the constraint effect of the zeolite itself, the pores and channels of the zeolite can limit the diffusion rates of oxygen, hydrogen ions, and silver ions, ultimately leading to a lower release rate. In contrast, the lack of the anchoring agent APTES in the formulation of Comparative Example 3 resulted in a gradual increase in the metal ion release rate in the obtained zeolite / silver / copper composite material, indicating that the metal ions are easily lost and unstable, thereby reducing the antibacterial lifespan of the material. This verifies the indispensable role of APTES in the synthesis method.

[0096] Figure 5 This study examines the inactivation effect of the ternary zeolite / silver / copper inorganic nanomaterials obtained in Examples 1-6 on *Escherichia coli* over 2 hours. The antibacterial experiment involved dissolving 0.5g of the sample in 20ml of sterile water and diluting it according to QB / T2738-2012, using a concentration of 5.0 × 10⁻⁶. 4 In the experiment with CFU / ml E. coli bacterial suspension, two time points were observed: 2 h and 6 h, to monitor colony growth. Figure 5 A comparison of Examples 1-3 shows that when the material interacts with bacteria for 2 hours, the antibacterial rate increases from 99% to 100% with the increase of copper content (0.03 parts by weight to 0.04 parts by weight), indicating that copper plays a key role in the ternary zeolite / silver / copper inorganic nano-antibacterial and antiviral materials. Figure 5 A comparison of Examples 1, 4, and 5 shows that the silica sol content also affects the final antibacterial effect of the ternary zeolite / silver / copper inorganic nano-antibacterial and antiviral material. With increasing silica sol content (10 parts by weight to 12 parts by weight), the antibacterial rates of the ternary zeolite / silver / copper inorganic nano-antibacterial and antiviral material after 2 hours were 98%, 99.9%, and 100%, respectively. This indicates that the amount of silica sol affects the antibacterial effect. Increasing the amount of silica sol and the proportion of zeolite carrier significantly increases the dispersibility of the metal components and the exposure area of ​​active sites in the material, thereby improving the overall antibacterial effect of the ternary zeolite / silver / copper inorganic nano-antibacterial and antiviral material. Figure 5A comparison of Examples 1 and 6 shows that reducing the amount of coupling agents APTES and CTAB reduces the antibacterial effect of the material (the antibacterial rate decreases from 99.9% to 96%). This is because the reduction of APTES reduces the effective binding of the metal components to the carrier. It is possible that due to the lack of targeted fixation by APTES, some metals agglomerate, reducing the number of active sites. At the same time, the reduction of CTAB affects the pore structure of the final carrier zeolite, thereby affecting the antibacterial performance of the entire ternary zeolite / silver / copper inorganic nano antibacterial and antiviral material.

[0097] Figure 6 This study examines the inactivation effect of the ternary zeolite / silver / copper inorganic nanomaterials obtained in Examples 1-6 on *Escherichia coli* over 6 hours. The antibacterial experiment involved dissolving 0.5g of the sample in 20ml of sterile water and diluting it according to QB / T2738-2012, using a concentration of 5.0 × 10⁻⁶. 4 In the experiment with CFU / ml E. coli bacterial suspension, two time points were observed: 2 h and 6 h, to monitor colony growth. Figure 6 It can be seen that when the molar ratio of silver, copper, and zeolite in the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material is (1.18-1.3):(1.6-2.13):(670-800), the inactivation rate of bacteria by the ternary zeolite / silver / copper inorganic nano-antibacterial and antiviral material can reach over 99% after 6 hours. (Comparison) Figure 5 and Figure 6 It can be seen that the design of the weight ratio of copper nitrate to silver nitrate and the weight ratio of CTAB to TPAOH in the ternary zeolite / silver / copper inorganic nano antibacterial and antiviral materials will affect the antibacterial rate of the final material. The antibacterial rate is basically not different within 6 hours, but there is a significant difference within 2 hours, fluctuating in the range of 96% to 100%.

[0098] Numerous specific details are set forth in this specification. However, it will be understood that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures, and techniques have not been shown in detail so as not to obscure the understanding of this specification.

[0099] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0100] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

[0101] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, characterized in that, Includes the following steps: S1, add tetrapropylammonium hydroxide solution and hexadecyltrimethylammonium bromide to deionized water, stir in a water bath until hexadecyltrimethylammonium bromide is completely dissolved and the solution becomes clear; add 3-aminopropyltriethoxysilane to the above clear solution, and continue to stir vigorously at room temperature for 15-20 min to allow 3-aminopropyltriethoxysilane to be fully hydrolyzed, to obtain the first mixture; S2, dissolve copper nitrate trihydrate in deionized water; add the copper nitrate solution dropwise to the first mixture from step S1 while stirring continuously; then add silver nitrate solution and continue stirring for 30-40 minutes to obtain the second mixture; S3, Ludox AS-40 silica sol was added dropwise to the second mixture while stirring at 800~1000 rpm, and then the mixture was continuously stirred at 85~95℃ for 2~2.5 hours to age the mixture and obtain a gel. S4, crystallize the gel obtained in step S3 in an environment of 90~95°C; After crystallization, the product is naturally cooled to room temperature. The product is then centrifuged or filtered, washed until neutral, dried, and the dried powder is calcined in static air at 540-550°C to obtain the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material.

2. The preparation method of the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes as described in claim 1, characterized in that, In step S1, the amount of tetrapropylammonium hydroxide solution used is 7.5 to 8.0 parts by weight, the amount of hexadecyltrimethylammonium bromide used is 0.4 to 0.6 parts by weight, and the amount of 3-aminopropyltriethoxysilane used is 0.5 to 0.6 parts by weight.

3. The preparation method of the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes as described in claim 1, characterized in that, In step S1, the temperature of the water bath is 40-50°C.

4. The preparation method of the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes as described in claim 1, characterized in that, In step S2, the amount of copper nitrate trihydrate used is 0.03~0.04 parts by weight, and the amount of silver nitrate used is 0.020~0.022 parts by weight.

5. The preparation method of the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes as described in claim 1, characterized in that, In step S3, the amount of Ludox AS-40 silica sol used is 10 to 12 parts by weight.

6. The preparation method of the zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes as described in claim 1, characterized in that, In step S4, the crystallization time is 48-72 h; the drying temperature is 80-85°C and the time is 24-28 h; the calcination time is 2-3 h and the heating rate is 1-2°C / min.

7. A zeolite / silver / copper ternary inorganic nanomaterial for antibacterial and antiviral purposes, characterized in that, The molar ratio of silver, copper, and zeolite in the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material is (1.18-1.3):(1.6-2.13):(670-800); the zeolite / silver / copper ternary inorganic nano-antibacterial and antiviral material is prepared by the method described in any one of claims 1-8.

8. An antibacterial plastic, characterized in that, The antibacterial plastic is the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material described in claim 7.

9. An antibacterial coating, characterized in that, The antibacterial coating uses the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material as described in claim 7.

10. An antibacterial ceramic, characterized in that, The antibacterial ceramic uses the zeolite / silver / copper ternary inorganic nano antibacterial and antiviral material as described in claim 7.

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