Indoor high-efficiency antibacterial odor-removing agent, preparation method and application

Abstract

The present application relates to the field of environmental protection, in particular to an indoor high-efficiency antibacterial odor-removing agent, a preparation method and application, the removing agent comprising a composite antibacterial agent, silver bromide-silver / nano silicon, a hydrogel, a wetting agent, a defoaming agent, and the balance water; the composite antibacterial agent is a wood moldin C4 ester derivative and / or a copper-loaded zinc oxide nano material; the silver bromide-silver / nano silicon is formed by loading silver-silver bromide on nano silicon sheets. The present application has excellent environmental adaptability, and has obvious antibacterial properties under the conditions of natural light, weak light or no light, has broad-spectrum, high-efficiency and rapid sterilization effect, the killing rate of bacteria and viruses is mostly above 99%, and fungi are inhibited and cannot grow; and under visible light, the present application can play an excellent role in decomposing formaldehyde and removing odor molecules, reducing the release of formaldehyde from the substrate itself, purifying and decomposing formaldehyde and odor molecules in the air, and can maintain effectiveness for a long time, continuously purifying indoor air; the raw materials are non-toxic and have no side effects, and are safe and environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of environmental protection technology, specifically to an indoor high-efficiency antibacterial and deodorizing agent, its preparation method, and its application. Background Technology

[0002] In recent years, with the rapid development of my country's economy and the continuous improvement of the modernization level of industry and agriculture, people's living standards have also improved significantly, especially in terms of living conditions. The per capita living space has increased substantially, and interior decoration has become increasingly sophisticated. However, people who spend long periods indoors have experienced various discomforts such as headaches, coughs, and fatigue; in severe cases, they have even developed various diseases. Research has found that this is largely related to indoor air pollution. In many places, the concentration of pollutants in indoor air is 2-5 times higher than outdoors, and urban residents spend approximately 90% of their time indoors each day. Therefore, paying attention to indoor air quality, preventing indoor air pollution, and detecting and controlling indoor air pollution have become a focus of public attention.

[0003] Formaldehyde is one of the main indoor pollutants, primarily originating from paint solvents, plywood adhesives, and some fabric surfaces. Currently, the main methods for treating indoor decoration pollution include physical adsorption, chemical reaction, catalytic oxidation, biological methods, combined methods, and cold plasma methods. Among these, adsorption is the most widely used method due to its low cost and readily available raw materials. However, adsorption methods such as carbon adsorption are only effective for recovering low concentrations of volatile organic gases, carbon dioxide, and sulfur dioxide, and have almost no effect on purifying some chemical releases generated during decoration. In comparison, catalytic oxidation is a promising new method for air purification. "Photocatalyst" is a general term for photocatalytic semiconductor materials, represented by nano-sized titanium dioxide. Coated on a substrate surface, it can effectively degrade toxic and harmful gases in the air under ultraviolet and visible light. However, existing photocatalysts still have limitations, including the ability to degrade only a single type of pollutant, poor catalytic degradation performance under visible light, the ability to limit chemical pollution only for a short period, and the inability to effectively remove formaldehyde hidden inside furniture.

[0004] Antibacterial materials refer to a class of novel functional materials that kill and inhibit the growth and reproduction of microorganisms. Antibacterial materials include natural antibacterial materials, organic antibacterial materials, inorganic antibacterial materials, and organic-inorganic composite antibacterial materials. Natural antibacterial materials are mainly extracts from plants and animals, but currently, they are difficult to meet the market's demand for multi-purpose and large-volume applications. Inorganic antibacterial materials are mainly prepared by supporting metal ions on carriers such as activated carbon, activated alumina, silica gel, or aluminosilicates. Antibacterial materials prepared with different carriers exhibit significantly different antibacterial effects and antibacterial spectra. Furthermore, the carrier materials often have a single composition, making it difficult to leverage the synergistic effect between the carrier and the antibacterial metal ions, thus limiting the full antibacterial activity of the antibacterial metal ions. Organic antibacterial materials include bactericides, fungicides, preservatives, mildew inhibitors, and algaecides. However, conventional organic antibacterial materials also have many fatal weaknesses, such as poor chemical stability, poor heat resistance, easy volatilization when exposed to heat, light or water, making it difficult to achieve long-term effectiveness; under high temperature, high pressure and high shear processing conditions, many polymers are prone to decomposition and failure, and may even produce toxic decomposition products. Summary of the Invention

[0005] To address the problems mentioned in the background art, this invention provides an antibacterial and deodorizing agent that is low in toxicity, has good stability, a broad bactericidal spectrum, and exhibits antibacterial effects while continuously purifying the indoor environment, along with its preparation method and application.

[0006] On the one hand, the present invention provides a highly efficient antibacterial and deodorizing agent for indoor use, the key being that: by weight, it comprises: 8-13 parts silver bromide-silver / nano-silicon, 12-18 parts composite antibacterial agent, 32-38 parts hydrogel, 1-3 parts wetting agent, 0.5-2 parts defoamer, and the balance being water;

[0007] Silver bromide-silver / nanosilicon is formed by attaching silver-silver bromide to nano-silicon wafers;

[0008] The composite antibacterial agent is a C4-position ester derivative of trichoderma and / or copper-loaded zinc oxide nanomaterials. In this scheme, silver bromide-silver / nano-silicon exhibits adsorption and visible-light photocatalytic degradation properties, not only absorbing and decomposing indoor formaldehyde but also purifying and decomposing other gaseous pollutants in indoor air. It has high visible-light degradation performance, and metallic silver, as the antibacterial active center, has a good antibacterial effect against bacteria. The copper-loaded zinc oxide nanomaterials can increase the electrostatic adsorption between the nanomaterials and bacteria, releasing Cu... 2+ Zinc oxide penetrates the cell wall and enters the bacteria, causing internal protein denaturation. On the other hand, zinc oxide generates ·OH and reactive oxygen species through photocatalysis, and dissolves Zn. 2+ Trichodermacin C4-ester derivatives, modified with natural trichodermacin as a lead compound, are effective in killing bacteria and molds. They exhibit low toxicity, broad spectrum, and high efficiency in bactericidal effects.

[0009] Preferably, the intraester derivative of trichoderma at the C4 position has the following general formula:

[0010]

[0011] This scheme uses the natural product trichomycin as a lead compound for modification, and performs derivatization design at the C4 position to improve its biological activity and stability. It exhibits low toxicity, broad-spectrum high efficacy, and a unique mechanism of action in its bactericidal effects. Optimally, the C4 position modification group is [insert C4 position modification group here].

[0012] Preferably, the copper-loaded zinc oxide nanomaterial is prepared by the following method: Modified multi-walled carbon nanotubes are added to a 0.5-0.8 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, then added to a 1.0-1.5 mol / L sodium carbonate solution, ultrasonically dispersed to obtain zinc carbonate colloid, separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes; the zinc oxide / multi-walled carbon nanotubes are added to a 0.5-0.8 mol / L copper sulfate solution, stirred for 12-24 h, separated, washed, dried, and ground to obtain the final product. In this scheme, modified multi-walled carbon nanotubes are enriched with nano-zinc oxide and Cu. 2+ This reduces the negative charge density on its surface, thereby increasing electrostatic adsorption with bacteria, and then releasing Cu. 2+ Zn 2+ Cellular proteins are denatured, and nano-zinc oxide photocatalysis generates ·OH and reactive oxygen species, as well as dissolves Zn. 2+ It kills bacteria and mold.

[0013] Preferably, the modified multi-walled carbon nanotubes are prepared by the following method: multi-walled carbon nanotubes are placed in mixed acid, ultrasonically dispersed for 1-2 hours, then separated, washed, and dried to obtain carboxylated multi-walled carbon nanotubes. Then, the carboxylated multi-walled carbon nanotubes are dispersed in DMF. Under dark conditions, pre-illuminated acrylamide monomer is added, with a mass ratio of acrylamide to carboxylated multi-walled carbon nanotubes of (350-400):1. A composite initiator is added, with the composite initiator being 0.3-0.5% wt of acrylamide. The mixture is stirred and reacted under ultraviolet irradiation for 20-40 minutes, filtered, separated, washed, and dried to obtain the final product. In this scheme, multi-walled carbon nanotubes (MWCNTs) are first subjected to strong oxidation modification to generate carboxyl and hydroxyl groups on their surface and at both ends, and impurities are removed to improve their density. Then, under ultraviolet light, pre-illuminated acrylamide monomers are grafted onto MWCNTs to greatly improve their dispersibility and avoid agglomeration and adhesion when loading metal nanoparticles. In actual operation, the pre-illumination time is preferably 1-3 minutes. After the acrylamide monomers form some active chain growth points, they are then mixed with MWCNTs, and the grafting rate can be as high as 25%.

[0014] Preferably, the composite initiator is camphorquinone and dimethylaminoethyl methacrylate in a mass ratio of 3:1. In this scheme, camphorquinone is used as the main initiator and dimethylaminoethyl methacrylate as the co-initiator to optimize the grafting amount of carbon nanotubes.

[0015] Preferably, the silver bromide-silver / nano-silicon catalyst is prepared by the following method: dispersing nano-silicon in deionized water to form a 1-3% nano-silicon suspension, adding silver bromide solution while stirring, adjusting the pH to 7-9, stirring in the dark for 4-7 hours, centrifuging, and drying to obtain silver bromide / nano-silicon; or dispersing silver bromide / nano-silicon in deionized water to form a 1-3% suspension, stirring under light for 1-1.5 hours, centrifuging, and drying to obtain the catalyst. In this scheme, the preferred molar ratio of silver bromide to nano-silicon is (1-3) mol: 1 g. The catalyst is obtained by photoreduction, and the formed silver bromide-silver heterojunction produces a plasmonic resonance effect, which improves the absorption of visible light and expands the response range to light. At the same time, nano-silicon increases the dispersibility of silver bromide, avoids particle agglomeration, and improves photocatalytic activity.

[0016] Preferably, the nano-silicon is prepared by the following method: using a single-crystal silicon wafer as a substrate, a silicon nanopore array is formed by hydrothermal etching. The pore size on the silicon pillars gradually decreases from 40±5 nm at the top to 15±5 nm at the bottom, with the size of the silicon pillars ranging from 1.9 to 4.5 nm, and the thickness of the pore array region being 2 to 20 μm. The nano-silicon prepared by this method results in a wider band gap in the single-crystal silicon due to the presence of silicon nanopillars, and the regular array structure and special nanoporous structure greatly increase its specific surface area.

[0017] Preferably, the hydrothermal corrosion solution is a mixed aqueous solution of hydrofluoric acid and ferric nitrate, wherein the concentration of hydrofluoric acid is 12-15 mol / L and the concentration of ferric nitrate is 0.04-0.07 mol / L.

[0018] Preferably, the hydrogel is one or a mixture of two or more of sodium lauryl hydrogel, sodium alginate hydrogel, polyvinyl alcohol hydrogel, polyacrylamide hydrogel, agar hydrogel, and polyethylene glycol hydrogel. The gel exhibits thermally reversible phase transition properties, forming a three-dimensional fibrous mesh structure that effectively prevents the aggregation and precipitation of nanoparticles. Furthermore, it can increase the surface hydrophilicity of the substrate, thereby improving its self-cleaning ability.

[0019] On the other hand, the present invention provides a method for preparing an efficient antibacterial and deodorizing agent for indoor use, which mainly includes the following steps: when the hydrogel is heated and dissolved until transparent, a wetting agent and an antifoaming agent are added and dispersed at medium speed for 20-40 minutes; then a composite antibacterial agent and silver bromide-silver / nano-silicon are added and dispersed at high speed for 30-40 minutes; water is added to adjust the viscosity.

[0020] On the other hand, this invention provides an application of an antibacterial and deodorizing agent in indoor air purification. In practical applications, it includes the purification of indoor toxic gases such as formaldehyde, benzene compounds, ammonia, total volatile organic compounds, sulfur dioxide, and carbon monoxide; it also includes the adsorption of odors such as indoor smoke, toilet odor, garbage odor, and animal odor; and it also includes maintaining the stability and continuous sterilization and bacteriostasis of bacteria and mold.

[0021] Preferably, the antibacterial and deodorizing agent is applied to the substrate surface by brushing, rolling, dipping, or spraying.

[0022] Beneficial effects: Compared with existing technologies, this invention has excellent environmental adaptability, exhibiting significant antibacterial properties under natural light, low light, or no light conditions, and possessing a broad-spectrum, highly efficient, and rapid bactericidal effect. The kill rate against bacteria and viruses is mostly above 99%, and fungi are inhibited from growing. Furthermore, under visible light, it effectively decomposes formaldehyde and removes odor molecules, reducing formaldehyde release from the substrate itself, purifying and decomposing formaldehyde and odor molecules in the air, and maintaining effectiveness for a relatively long period, continuously purifying indoor air. The raw materials are non-toxic and have no side effects, making it safe and environmentally friendly. Attached Figure Description

[0023] Figure 1 a and 1b show field emission scanning electron microscopy (FE-SEM) images of nano-silicon and silver-silver bromide / nano-silicon;

[0024] Figure 2 The images shown are TEM images of multi-walled carbon nanotubes before and after modification.

[0025] Figure 3 The image shows the TGA spectra of carbon nanotubes before and after modification. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to specific embodiments. It should also be noted that, to avoid obscuring the invention with unnecessary details, only structures and / or processing steps closely related to the solutions of this invention are shown in the specific embodiments, while other details not closely related to this invention are omitted.

[0027] Additionally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0028] Example 1 Antibacterial and deodorizing agent

[0029] By weight, it comprises: 8 parts silver bromide-silver / nano-silicon, 8 parts trichoderma C4-position intraester derivative, 10 parts copper-loaded zinc oxide nanomaterials, 32 parts sodium lauryl hydrogel, 1 part polyether and dimethylsiloxane graft copolymer, 0.5 parts modified polydimethylsiloxane, and the balance being water.

[0030] The structural formula of the intraester derivative of trichomycin at the C4 position is: The preparation method is as follows: 1.0 g of trichodermacin was dissolved in 20 ml of methanol, and 8% NaOH aqueous solution was added dropwise with stirring. The reaction was carried out for 15 min, and the mixture was concentrated and crystallized to obtain (4R)-4-hydroxytrichodermacin. 0.8 mol of (4R)-4-hydroxytrichodermacin and 0.8 mol of acid were dissolved in 10 ml of dichloromethane, and 0.33 g of dicyclohexylcarbodiimide and 0.195 g of DMAP were added. The mixture was stirred at room temperature for 14-16 h. The reaction solution was washed with dilute hydrochloric acid and distilled water, dried and concentrated, and then separated by column chromatography.

[0031] Copper-loaded zinc oxide nanomaterials were prepared by the following method: Multi-walled carbon nanotubes (MWC nanotubes) were placed in a nitric acid / sulfuric acid solution with a volume ratio of 1:3 and ultrasonically dispersed at 80-90℃ for 1-2 hours. After separation, washing, and drying, carboxylated MMC nanotubes were obtained. 10 mg of carboxylated MMC nanotubes were dispersed in 10 ml of DMF. A 10% solution was prepared in DMF, and 0.3% wt of a composite initiator (3:1 ratio of camphorquinone and dimethylaminoethyl methacrylate) was added. After pre-illumination for 2.5 min, the solution was mixed with the MMC nanotube dispersion under dark conditions. The mass ratio of acrylamide monomer to carboxylated MMC nanotubes was 350:1. After ultrasonic mixing for 5 min, the grafting reaction was carried out under ultraviolet irradiation for 20 min. The product was then filtered and separated, washed with DMF and deionized water, and dried to obtain modified multi-walled carbon nanotubes. The modified multi-walled carbon nanotubes were added to a 0.5 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, and then added to a 1.0 mol / L sodium carbonate solution for ultrasonic dispersion to obtain zinc carbonate colloid. The colloid was separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes. The zinc oxide / multi-walled carbon nanotubes were added to a 0.5 mol / L copper sulfate solution, stirred for 12-24 h, separated, washed, dried, and ground to obtain copper-loaded zinc oxide nanomaterials.

[0032] Silver bromide-silver / nano-silicon was prepared by the following method: A columnar array of silicon nanopores was formed using a hydrothermal etching method on a single-crystal silicon wafer as the substrate. The hydrothermal etching conditions were: hydrofluoric acid concentration of 12 mol / L, ferric nitrate concentration of 0.04 mol / L, etching at 70℃ for 5 min. The pore size of the silicon pillars on the substrate gradually decreased from 40±5 nm at the top to 15±5 nm at the bottom, with a pillar size range of 1.9-2.5 nm. The distance between adjacent pore walls was 3-8 μm, and the thickness of the pore array region was 15-20 μm. The nano-silicon was dispersed in deionized water to form a 1% nano-silicon suspension. Silver bromide solution was added with stirring, the pH was adjusted to 7, and the mixture was stirred in the dark for 4-7 h. After centrifugation and drying, silver bromide / nano-silicon was obtained. Alternatively, silver bromide / nano-silicon was dispersed in deionized water to form a 1% suspension, stirred under light for 1-1.5 h, centrifuged, and dried to obtain the final product.

[0033] Preparation method: The sodium lauryl hydrogel of the formula is heated at 50-60℃ and stirred to dissolve. When the mixture becomes transparent, the polyether-dimethylsiloxane graft copolymer and modified polydimethylsiloxane are added sequentially at a stirring speed of 3500 rpm and stirred for 20-40 min. The stirring speed is increased to 5500 rpm and the trichoderma C4 ester derivative, copper-loaded zinc oxide nanomaterials, and silver bromide-silver / nanosilicon are added sequentially and dispersed for 30-40 min. The aqueous solution is slowly poured along the wall of the container to adjust the viscosity. The mixture is stirred continuously at 2000 rpm and gradually cooled. After stirring for 60 minutes, the mixture is cooled to room temperature to prepare the finished product.

[0034] Example 2 Antibacterial and Deodorizing Agent

[0035] By weight, it includes: 13 parts silver bromide-silver / nano-silicon, 4 parts trichoderma C4-position ester derivative, 8 parts copper-loaded zinc oxide nanomaterials, 38 parts sodium alginate hydrogel, 3 parts polyether and dimethylsiloxane graft copolymer, 2 parts modified polydimethylsiloxane, and the balance being water.

[0036] The structural formula of the intraester derivative of trichomycin at the C4 position is:

[0037] Copper-loaded zinc oxide nanomaterials were prepared by the following method: Multi-walled carbon nanotubes (MWC nanotubes) were placed in a nitric acid / sulfuric acid solution with a volume ratio of 1:3 and ultrasonically dispersed at 80-90℃ for 1-2 hours. After separation, washing, and drying, carboxylated MMC nanotubes were obtained. 10 mg of carboxylated MMC nanotubes were dispersed in 10 ml of DMF. A 10% solution was prepared in DMF, and 0.8% wt of a composite initiator (3:1 ratio of camphorquinone and dimethylaminoethyl methacrylate) was added. After pre-illumination for 1 min, the solution was mixed with the MMC nanotube dispersion under dark conditions. The mass ratio of acrylamide monomer to carboxylated MMC nanotubes was 400:1. After ultrasonic mixing for 5 min, the grafting reaction was carried out under ultraviolet irradiation for 40 min. The product was then filtered and separated, washed with DMF and deionized water, and dried to obtain modified multi-walled carbon nanotubes. The modified multi-walled carbon nanotubes were added to a 0.5 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, and then added to a 1.0 mol / L sodium carbonate solution for ultrasonic dispersion to obtain zinc carbonate colloid. The colloid was separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes. The zinc oxide / multi-walled carbon nanotubes were added to a 0.5 mol / L copper sulfate solution, stirred for 12-24 h, separated, washed, dried, and ground to obtain copper-loaded zinc oxide nanomaterials.

[0038] Silver bromide-silver / nano-silicon was prepared by the following method: A columnar array of silicon nanopores was formed using a hydrothermal etching method on a single-crystal silicon wafer as the substrate. The hydrothermal etching conditions were: hydrofluoric acid concentration of 12 mol / L, ferric nitrate concentration of 0.04 mol / L, etching at 70℃ for 5 min. The pore size of the silicon pillars on the substrate gradually decreased from 40±5 nm at the top to 15±5 nm at the bottom, with a pillar size range of 1.9-2.5 nm. The distance between adjacent pore walls was 3-8 μm, and the thickness of the pore array region was 15-20 μm. The nano-silicon was dispersed in deionized water to form a 1% nano-silicon suspension. Silver bromide solution was added with stirring, the pH was adjusted to 7, and the mixture was stirred in the dark for 4-7 h. After centrifugation and drying, silver bromide / nano-silicon was obtained. Alternatively, silver bromide / nano-silicon was dispersed in deionized water to form a 1% suspension, stirred under light for 1-1.5 h, centrifuged, and dried to obtain the final product.

[0039] The preparation method is the same as in Example 1.

[0040] Example 3 Antibacterial and deodorizing agent

[0041] By weight, it comprises: 10 parts silver bromide-silver / nano-silicon, 6 parts trichoderma C4-position intraester derivative, 8 parts copper-loaded zinc oxide nanomaterials, 35 parts polyvinyl alcohol hydrogel, 1.5 parts polyether and dimethylsiloxane graft copolymer, 1 part modified polydimethylsiloxane, and the balance being water.

[0042] The structural formula of the intraester derivative of trichomycin at the C4 position is:

[0043] Copper-loaded zinc oxide nanomaterials were prepared by the following method: Multi-walled carbon nanotubes (MWC nanotubes) were placed in a nitric acid / sulfuric acid solution with a volume ratio of 1:3 and ultrasonically dispersed at 80-90℃ for 1-2 hours. After separation, washing, and drying, carboxylated MMC nanotubes were obtained. 10 mg of carboxylated MMC nanotubes were dispersed in 10 ml of DMF. A 10% solution was prepared in DMF, and 0.4% wt of a composite initiator (3:1 ratio of camphorquinone and dimethylaminoethyl methacrylate) was added. After pre-illumination for 1.5 min, the solution was mixed with the MMC nanotube dispersion under dark conditions. The mass ratio of acrylamide monomer to carboxylated MMC nanotubes was 380:1. After ultrasonic mixing for 5 min, the grafting reaction was carried out under ultraviolet irradiation for 30 min. The product was then filtered and separated, washed with DMF and deionized water, and dried to obtain modified multi-walled carbon nanotubes. The modified multi-walled carbon nanotubes were added to a 0.5 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, and then added to a 1.0 mol / L sodium carbonate solution for ultrasonic dispersion to obtain zinc carbonate colloid. The colloid was separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes. The zinc oxide / multi-walled carbon nanotubes were added to a 0.5 mol / L copper sulfate solution, stirred for 12-24 h, separated, washed, dried, and ground to obtain copper-loaded zinc oxide nanomaterials.

[0044] Silver bromide-silver / nano-silicon was prepared by the following method: A columnar array of silicon nanopores was formed using a hydrothermal etching method on a single-crystal silicon wafer as the substrate. The hydrothermal etching conditions were: hydrofluoric acid concentration of 12 mol / L, ferric nitrate concentration of 0.04 mol / L, etching at 70℃ for 5 min. The pore size of the silicon pillars on the substrate gradually decreased from 40±5 nm at the top to 15±5 nm at the bottom, with a pillar size range of 1.9-2.5 nm. The distance between adjacent pore walls was 3-8 μm, and the thickness of the pore array region was 15-20 μm. The nano-silicon was dispersed in deionized water to form a 1% nano-silicon suspension. Silver bromide solution was added with stirring, the pH was adjusted to 7, and the mixture was stirred in the dark for 4-7 h. After centrifugation and drying, silver bromide / nano-silicon was obtained. Alternatively, silver bromide / nano-silicon was dispersed in deionized water to form a 1% suspension, stirred under light for 1-1.5 h, centrifuged, and dried to obtain the final product.

[0045] The preparation method is the same as in Example 1.

[0046] Example 4 Antibacterial and Deodorizing Agent

[0047] By weight, it comprises: 12 parts silver bromide-silver / nano-silicon, 8 parts trichoderma C4-position ester derivative, 8 parts copper-loaded zinc oxide nanomaterials, 36 parts polyvinyl alcohol hydrogel, 2 parts polyether and dimethylsiloxane graft copolymer, 1.5 parts modified polydimethylsiloxane, and the balance being water.

[0048] The structural formula of the intraester derivative of trichomycin at the C4 position is:

[0049] Copper-loaded zinc oxide nanomaterials were prepared by the following method: Multi-walled carbon nanotubes (MWC nanotubes) were placed in a nitric acid / sulfuric acid solution with a volume ratio of 1:3 and ultrasonically dispersed at 80-90℃ for 1-2 hours. After separation, washing, and drying, carboxylated MMC nanotubes were obtained. 10 mg of carboxylated MMC nanotubes were dispersed in 10 ml of DMF. A 10% solution was prepared in DMF, and 0.35% wt of a composite initiator (3:1 ratio of camphorquinone and dimethylaminoethyl methacrylate) was added. After pre-illumination for 3 minutes, the solution was mixed with the MMC nanotube dispersion under dark conditions. The mass ratio of acrylamide monomer to carboxylated MMC nanotubes was 370:1. After ultrasonic mixing for 5 min, the grafting reaction was carried out under ultraviolet irradiation for 30 min. The product was then filtered and separated, washed with DMF and deionized water, and dried to obtain modified multi-walled carbon nanotubes. The modified multi-walled carbon nanotubes were added to a 0.5 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, and then added to a 1.0 mol / L sodium carbonate solution for ultrasonic dispersion to obtain zinc carbonate colloid. The colloid was separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes. The zinc oxide / multi-walled carbon nanotubes were added to a 0.5 mol / L copper sulfate solution, stirred for 12-24 h, separated, washed, dried, and ground to obtain copper-loaded zinc oxide nanomaterials.

[0050] Silver bromide-silver / nano-silicon was prepared by the following method: A columnar array of silicon nanopores was formed using a hydrothermal etching method on a single-crystal silicon wafer as the substrate. The hydrothermal etching conditions were: hydrofluoric acid concentration of 15 mol / L, ferric nitrate concentration of 0.07 mol / L, etching at 170℃ for 60 min. The pore size of the silicon pillars on the substrate gradually decreased from 40±5 nm at the top to 15±5 nm at the bottom, with a pillar size range of 4.0-4.5 nm. The distance between adjacent pore walls was 20-25 μm, and the thickness of the pore array region was 2-10 μm. The nano-silicon was dispersed in deionized water to form a 3% nano-silicon suspension. Silver bromide solution was added with stirring, the pH was adjusted to 9, and the mixture was stirred in the dark for 4-7 h. After centrifugation and drying, silver bromide / nano-silicon was obtained. Alternatively, silver bromide / nano-silicon was dispersed in deionized water to form a 3% suspension, stirred under light for 1-1.5 h, centrifuged, and dried.

[0051] The preparation method is the same as in Example 1.

[0052] Example 5 Antibacterial Deodorizing Agent

[0053] By weight, it comprises: 10 parts silver bromide-silver / nano-silicon, 15 parts trichoderma C4-position ester derivative, 35 parts agar hydrogel, 3 parts polyether and dimethylsiloxane graft copolymer, 2 parts modified polydimethylsiloxane, and the balance being water.

[0054] The structural formula of the intraester derivative of trichomycin at the C4 position is:

[0055] Copper-loaded zinc oxide nanomaterials were prepared by the following method: Multi-walled carbon nanotubes (MWC nanotubes) were placed in a nitric acid / sulfuric acid solution with a volume ratio of 1:3 and ultrasonically dispersed at 80-90℃ for 1-2 hours. After separation, washing, and drying, carboxylated MMC nanotubes were obtained. 10 mg of carboxylated MMC nanotubes were dispersed in 10 ml of DMF. A 10% solution was prepared in the DMF, and 0.3% wt of a composite initiator (3:1 ratio of camphorquinone and dimethylaminoethyl methacrylate) was added. After pre-illumination for 2 minutes, the solution was mixed with the MMC nanotube dispersion under dark conditions. The mass ratio of acrylamide monomer to carboxylated MMC nanotubes was 400:1. After ultrasonic mixing for 5 min, the grafting reaction was carried out under ultraviolet irradiation for 30 min. The product was then filtered and separated, washed with DMF and deionized water, and dried to obtain modified multi-walled carbon nanotubes. The modified multi-walled carbon nanotubes were added to a 0.5 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, and then added to a 1.0 mol / L sodium carbonate solution for ultrasonic dispersion to obtain zinc carbonate colloid. The colloid was separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes. The zinc oxide / multi-walled carbon nanotubes were added to a 0.5 mol / L copper sulfate solution, stirred for 12-24 h, separated, washed, dried, and ground to obtain copper-loaded zinc oxide nanomaterials.

[0056] Silver bromide-silver / nano-silicon was prepared by the following method: A columnar array of silicon nanopores was formed using a hydrothermal etching method on a single-crystal silicon wafer as the substrate. The hydrothermal etching conditions were: hydrofluoric acid concentration of 13 mol / L, ferric nitrate concentration of 0.05 mol / L, etching at 100℃ for 60 min. The pore size of the silicon pillars on the substrate gradually decreased from 40±5 nm at the top to 15±5 nm at the bottom, with a pillar size range of 3-3.5 nm. The distance between adjacent pore walls was 10-15 μm, and the thickness of the pore array region was 18-23 μm. The nano-silicon was dispersed in deionized water to form a 1.5% nano-silicon suspension. Silver bromide solution was added with stirring, the pH was adjusted to 8, and the mixture was stirred in the dark for 4-7 h. After centrifugation and drying, silver bromide / nano-silicon was obtained. Alternatively, silver bromide / nano-silicon was dispersed in deionized water to form a 1.5% suspension, stirred under light for 1-1.5 h, centrifuged, and dried.

[0057] The preparation method is the same as in Example 1.

[0058] Example 6 Antibacterial and Deodorizing Agent

[0059] By weight, it comprises: 10 parts silver bromide-silver / nano-silicon, 15 parts copper-loaded zinc oxide nanomaterials, 34 parts polyethylene glycol hydrogel, 2 parts polyether-dimethylsiloxane graft copolymer, 2 parts modified polydimethylsiloxane, and the balance being water.

[0060] The structural formula of the intraester derivative of trichomycin at the C4 position is:

[0061] Copper-loaded zinc oxide nanomaterials were prepared by the following method: Multi-walled carbon nanotubes (MWC nanotubes) were placed in a nitric acid / sulfuric acid solution with a volume ratio of 1:3 and ultrasonically dispersed at 80-90℃ for 1-2 hours. After separation, washing, and drying, carboxylated MMC nanotubes were obtained. 10 mg of carboxylated MMC nanotubes were dispersed in 10 ml of DMF. A 10% solution was prepared in DMF, and 0.45% wt of a composite initiator (3:1 ratio of camphorquinone and dimethylaminoethyl methacrylate) was added. After pre-illumination for 2.5 min, the solution was mixed with the MMC nanotube dispersion under dark conditions. The mass ratio of acrylamide monomer to carboxylated MMC nanotubes was 350:1. After ultrasonic mixing for 5 min, the grafting reaction was carried out under ultraviolet irradiation for 20-40 min. The product was then filtered and separated, washed with DMF and deionized water, and dried to obtain modified multi-walled carbon nanotubes. The modified multi-walled carbon nanotubes were added to a 0.5 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, and then added to a 1.0 mol / L sodium carbonate solution for ultrasonic dispersion to obtain zinc carbonate colloid. The colloid was separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes. The zinc oxide / multi-walled carbon nanotubes were added to a 0.5 mol / L copper sulfate solution, stirred for 12-24 h, separated, washed, dried, and ground to obtain copper-loaded zinc oxide nanomaterials.

[0062] Silver bromide-silver / nano-silicon was prepared by the following method: A columnar array of silicon nanopores was formed using a hydrothermal etching method on a single-crystal silicon wafer as the substrate. The hydrothermal etching conditions were: hydrofluoric acid concentration of 15 mol / L, ferric nitrate concentration of 0.07 mol / L, etching at 150℃ for 40 min. The pore size of the silicon pillars on the substrate gradually decreased from 40±5 nm at the top to 15±5 nm at the bottom, with a pillar size range of 3.8-4.2 nm. The distance between adjacent pore walls was 16-23 μm, and the thickness of the pore array region was 8-15 μm. Nano-silicon was dispersed in deionized water to form a 2.5% nano-silicon suspension. Silver bromide solution was added with stirring, the pH was adjusted to 8, and the mixture was stirred in the dark for 4-7 h. After centrifugation and drying, silver bromide / nano-silicon was obtained. Alternatively, silver bromide / nano-silicon was dispersed in deionized water to form a 2.5% suspension, stirred under light for 1-1.5 h, centrifuged, and dried.

[0063] The preparation method is the same as in Example 1.

[0064] Comparative Example 1

[0065] Based on Example 1, silver bromide-silver / nano silicon was replaced by an equal amount of silver bromide-silver / molecular sieve.

[0066] Comparative Example 2

[0067] Based on Example 2, silver bromide-silver / nano silicon was replaced with an equal amount of natural silicon.

[0068] Comparative Example 3

[0069] Based on Example 3, natural silicon was replaced with an equal amount of nano-silicon.

[0070] Comparative Example 4

[0071] Based on Example 6, the modified multi-walled carbon nanotubes were replaced with an equal amount of multi-walled carbon nanotubes.

[0072] The antibacterial and deodorizing agent prepared according to the present invention was subjected to the following tests:

[0073] (1) Structural and compositional testing (taking Example 1 as an example):

[0074] Figure 1 a is the FESEM image of nano-silicon, which shows that nano-silicon is composed of a large number of regularly arranged, micron-sized silicon pillars; Figure 1 b is a FESEM image of silver-silver bromide / nanosilicon. Observation reveals that a thin film composed of small particles forms at the top of the column, while the intercolumnar region contains a large number of relatively uniform and loosely distributed nanocrystals, indicating that the silver bromide has good particle size and dispersion. The mass percentages of each element obtained from EDS are: O 64.13%, Si 34.64%, Br 0.48%, and Ag 0.75%. The Ag content is slightly greater than Br, indicating that a small amount of Ag+ in AgBr is reduced to Ag under visible light, making its surface Ag content greater than Br.

[0075] Figure 2 The images show TEM images of multi-walled carbon nanotubes before and after modification. 2a shows multi-walled carbon nanotubes before modification, and 2b shows multi-walled carbon nanotubes after modification. It can be observed that the multi-walled carbon nanotubes do not adhere to each other and have a high grafting rate.

[0076] Figure 3 The TGA spectra before and after modification of carbon nanotubes show that the grafting rate reaches 25%.

[0077] (2) Antibacterial activity: *Escherichia coli* ATCC8739 and *Staphylococcus aureus* ATCC6538 were used as test strains. The inhibition zone method was employed to evaluate antibacterial performance; the relevant testing standard was derived from AATCC90-1982, "Determination of Antibacterial Activity of Fibers—Plate Culture Medium Method". The inhibition zone method is a qualitative test method, often used to identify leaching antibacterial materials and products containing leaching antibacterial materials. It utilizes the continuous dissolution of the antibacterial material and its diffusion through agar to create different concentration gradients, thus demonstrating its antibacterial effect.

[0078] (3) Mold resistance: Molds included *Aspergillus brasiliensis* ATCC9642, *Chaetomium globosum* ATCC6205, *Trichoderma viride* ATCC9645, and *Brachystomata buddingii* ATCC15233. According to the national standard GB / T1741-1979 (1989), the anti-mold performance was tested using the petri dish method (suitable for testing the anti-mold performance of coatings using small sample pieces). The prepared sample was coated on sterilized filter paper, irradiated with ultraviolet light for 3 days, and then placed flat on the surface of the culture medium. The bacterial suspension was sprayed evenly and finely onto the sample plate using a sprayer. After slightly drying, the plate was covered. The sample, number, and date were marked on the lid, and the plate was placed in an incubator at 29℃~30℃ for incubation. After 28 days, the mold growth on the sample surface was checked to see if it was normal.

[0079] (4) Virus-killing: Place the coating at 1m 3 Within a confined space, the coating area is controlled to be 1m². 2 The virus was sprayed into the space above the coating, and the virus killing rate in that space was measured after 1 hour; the test results are shown in Table 1:

[0080] Table 1

[0081]

[0082] (5) Durability of air purification:

[0083] Air purification durability: A formaldehyde pollution concentration of 200 μg / L was simulated in a sealed, light-proof climate chamber. The sample was sprayed onto a 0.1m × 0.1m non-woven fabric in the sealed, light-proof climate chamber. The amount of spraying was the same in each chamber. The climate chamber was placed in an indoor visible light environment so that the sample to be tested could receive sufficient visible light. The climate chamber lid was closed and sealed. The bottom air pressure balance port was connected to a water tank to maintain the air pressure and pollutant gas concentration in the climate chamber during sampling. The convection fan was turned on to keep the gas concentration equal in all parts of the climate chamber. After the pollutant gas was introduced to the initial concentration, the air inlet was closed and the test was carried out. The initial formaldehyde concentration in the chamber was recorded. The formaldehyde concentration in the chamber was recorded again after 6h, 24h, 3d, 7d, 15d, and 30d. The formaldehyde removal rate was calculated. The test results are shown in Table 2.

[0084] Table 2

[0085]

[0086] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A highly effective indoor antibacterial and deodorizing agent, characterized in that, By weight, it includes: 8-13 parts silver bromide-silver / nano-silicon, 12-18 parts composite antibacterial agent, 32-38 parts hydrogel, 1-3 parts wetting agent, 0.5-2 parts defoamer, and the balance being water; The silver bromide-silver / nano-silicon catalyst is prepared by the following method: Nano-silicon is dispersed in deionized water to form a 1-3% nano-silicon suspension; silver bromide solution is added with stirring, the molar ratio of silver bromide to nano-silicon is (1-3) mol: 1 g; the pH is adjusted to 7-9; stirring is performed in the dark for 4-7 h; centrifugation is performed; and the solution is dried to obtain silver bromide / nano-silicon. Alternatively, silver bromide / nano-silicon is dispersed in deionized water to form a 1-3% suspension; stirring is performed under light for 1-1.5 h; and centrifugation is performed. The nano-silicon is prepared by separation and drying; wherein the nano-silicon is a columnar silicon nanopore array formed by hydrothermal etching using a single-crystal silicon wafer as the substrate, the pore size on the silicon pillars gradually decreases from 40±5nm at the top to 15±5nm at the bottom, the size range of the silicon pillars is 1.9-4.5nm, and the thickness of the pore array region is 2-20μm; the composite antibacterial agent is a C4-position ester derivative of trichoderma and / or copper-loaded zinc oxide nanomaterials; the C4-position ester derivative of trichoderma has the following general formula:

2. The high-efficiency antibacterial and deodorizing agent for indoor use according to claim 1, characterized in that... The copper-loaded zinc oxide nanomaterial is prepared by the following method: modified multi-walled carbon nanotubes are added to a 0.5-0.8 mol / L zinc sulfate solution, ultrasonically dispersed, separated and washed, then added to a 1.0-1.5 mol / L sodium carbonate solution, ultrasonically dispersed to obtain zinc carbonate colloid, separated, washed, calcined at 280-350℃, and ground to obtain zinc oxide / multi-walled carbon nanotubes; Zinc oxide / carbon nanotubes are added to a 0.5-0.8 mol / L copper sulfate solution, stirred for 12-24 h, and then separated, washed, dried, and ground to obtain the product.

3. The high-efficiency antibacterial and deodorizing agent for indoor use according to claim 2, characterized in that... The modified multi-walled carbon nanotubes (CUVs) are prepared by the following method: CUVs are placed in mixed acid, ultrasonically dispersed for 1-2 hours, then separated, washed, and dried to obtain carboxylated CUVs. The carboxylated CUVs are then dispersed in DMF. Under dark conditions, pre-illuminated acrylamide monomer is added, with a mass ratio of acrylamide to carboxylated CUVs of (350-400):

1. A composite initiator is added, which is 0.3-0.5% wt of acrylamide. The mixture is stirred and reacted under ultraviolet irradiation for 20-40 minutes. After filtration, separation, washing, and drying, the product is obtained.

4. The high-efficiency antibacterial and deodorizing agent for indoor use according to claim 3, characterized in that: The composite initiator is camphorquinone and dimethylaminoethyl methacrylate in a mass ratio of 3:

1.

5. The high-efficiency antibacterial and deodorizing agent for indoor use according to claim 1, characterized in that: The hydrothermal corrosion method uses a mixed aqueous solution of hydrofluoric acid and ferric nitrate as the hydrothermal corrosion solution, wherein the concentration of hydrofluoric acid is 12-15 mol / L and the concentration of ferric nitrate is 0.04-0.07 mol / L.

6. The high-efficiency antibacterial and deodorizing agent for indoor use according to claim 1, characterized in that: The hydrogel is one or a mixture of two or more of the following: sodium lauryl hydrogel, sodium alginate hydrogel, polyvinyl alcohol hydrogel, polyacrylamide hydrogel, agar hydrogel, and polyethylene glycol hydrogel.

7. A method for preparing an indoor high-efficiency antibacterial and deodorizing agent according to any one of claims 1-6, characterized in that... Includes the following steps: When the hydrogel is heated and dissolved until transparent, add wetting agent and defoamer, and disperse at medium speed for 20-40 minutes; then add composite antibacterial agent, silver bromide-silver / nano-silicon, and disperse at high speed for 30-40 minutes; add water to adjust the viscosity.

8. The application of the antibacterial and deodorizing agent according to claims 1-6 in indoor air purification and sterilization.

9. The application according to claim 8, characterized in that: The antibacterial and deodorizing agent is applied to the surface of the substrate by brushing, rolling, dipping, or spraying.

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