Cluster modified chlorine dioxide solid disinfectant, preparation method and disinfection device

Abstract

The invention provides a cluster modified chlorine dioxide solid disinfectant, a preparation method and a disinfection device.The preparation method comprises the steps that a metal group cluster is dissolved in a solvent, and a first dipping solution is prepared; soaking the porous alumina pellets in a first dipping solution; roasting the porous alumina pellets subjected to dipping treatment to obtain cluster modified porous alumina pellets; carrying out vacuum drying on the cluster modified porous alumina pellets; adding a stabilizer into the chlorine dioxide solution to prepare a second dipping solution; soaking the cluster modified porous alumina pellets in a second soaking solution for sealed storage at room temperature; and taking out the soaked cluster-modified porous alumina pellets, washing with deionized water, absorbing moisture on the surfaces of the cluster-modified porous alumina pellets with filter paper, and drying to obtain the porous alumina pellets immobilized with chlorine dioxide. According to the cluster modified chlorine dioxide solid disinfectant prepared by the method disclosed by the invention, the storage period and the validity period are prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of disinfectant preparations, and in particular to a cluster-modified chlorine dioxide solid disinfectant, a preparation method and a disinfection device. Background Art

[0002] Respiratory diseases are among the most serious and high-risk diseases threatening human health, especially those caused by air pollution. Consequently, people are paying increasing attention to air safety and respiratory health. Chlorine dioxide (ClO2) is used as a key disinfectant for sterilizing indoor air and surfaces. Chlorine dioxide is highly effective in killing microorganisms, bacteria, and viruses in the environment, primarily due to its strong adsorption and penetration capabilities through cell walls and its ability to denature intracellular proteins containing -SH enzymes. Chlorine dioxide is known to be highly effective in killing bacterial and viral growth, including bacterial vegetative cells, bacterial spores, fungi, mycobacteria, and viruses. However, chlorine dioxide disinfectants are prone to decomposition when left in the environment, require immediate preparation, and have a strong, pungent odor, raising safety concerns regarding use and storage. Summary of the Invention

[0003] The embodiments of the present invention provide a cluster-modified chlorine dioxide solid disinfectant, a preparation method, and a disinfection device to at least solve some of the above technical problems existing in the prior art.

[0004] In a first aspect, an embodiment of the present invention provides a method for preparing a cluster-modified chlorine dioxide solid disinfectant, comprising:

[0005] dissolving the metal group cluster in a solvent to prepare a first impregnation solution;

[0006] Immersing the porous alumina balls in the first impregnation solution to allow the first impregnation solution to enter the pores of the porous alumina balls;

[0007] calcining the impregnated porous alumina beads to form metal oxides or metal clusters inside the porous alumina beads, thereby obtaining cluster-modified porous alumina beads;

[0008] vacuum drying the cluster-modified porous alumina spheres;

[0009] adding a stabilizer to the chlorine dioxide solution to prepare a second impregnation solution;

[0010] Immersing the cluster-modified porous alumina beads in the second impregnation solution and sealing the solution at room temperature;

[0011] The cluster-modified porous alumina beads after immersion are taken out, washed with deionized water, and the moisture on the surface of the cluster-modified porous alumina beads is absorbed with filter paper, and then dried to obtain porous alumina beads immobilized with chlorine dioxide.

[0012] In an optional embodiment, the metal group cluster includes one or more of TiO2 clusters, ZnO clusters, iron ion clusters, copper nanoclusters, silver nanoclusters, and perovskite clusters; the solvent of the first impregnation solution is one or more of ethylene glycol, water, ethanol, and N,N-dimethylformamide; and the concentration of the first impregnation solution is 0.4-2.0 mol / L.

[0013] In an optional embodiment, the solvent of the first impregnation solution is water, ethanol and N,N-dimethylformamide, and the volume ratio of water, ethanol and N,N-dimethylformamide is 4:2:1.

[0014] In an optional embodiment, the porous alumina balls are immersed in the first impregnation solution at a temperature of 30-70° C. for 6-24 hours;

[0015] The porous alumina balls treated by impregnation are calcined at a temperature of 200-600° C. for a time of 1.0-8.0 h;

[0016] The temperature for vacuum drying the cluster-modified porous alumina beads is 40-120° C., and the time for vacuum drying is 5.0 h-15.0 h.

[0017] In an optional embodiment, the stabilizer is one or more of sodium carboxymethyl cellulose, sodium bicarbonate, sodium chloride, sodium hydroxide, ethylenediamine, polyvinyl alcohol, and sodium bisulfite, and the concentration of the stabilizer in the second impregnation solution is 0.5-5 mol / L;

[0018] The mass of the cluster-modified porous alumina beads is 40-150 g, and the soaking time in the second impregnation solution is 0.5-5.0 h;

[0019] The cluster-modified porous alumina beads after soaking are washed 2-6 times with deionized water;

[0020] The cluster-modified porous alumina beads after immersion are vacuum dried at a temperature of 30-80° C. for a vacuum drying time of 6.0 h to 14.0 h.

[0021] In an optional embodiment, the method of the embodiment of the present invention further includes:

[0022] Solid alumina beads are mixed with a pore-forming agent, pseudo-boehmite and aluminum sol to prepare a sol, and the weak acidity of the system is controlled during the mixing process;

[0023] The sol is dripped into a hot oil column forming device and solidified into a porous alumina wet ball;

[0024] The porous alumina wet balls are heat-treated to obtain the porous alumina small balls;

[0025] Washing the porous alumina balls with ethanol and deionized water in sequence;

[0026] The washed porous alumina beads are vacuum dried.

[0027] In an optional embodiment, the solid alumina balls are 200-300 parts by mass, the pore-forming agent is 50-500 parts by mass, the pore-forming agent is polymethyl methacrylate, the pseudo-boehmite is 20-200 parts by mass, and the aluminum sol is 20-200 parts by mass;

[0028] During the mixing process of the solid alumina balls, the pore-forming agent, the pseudo-boehmite and the aluminum sol, citric acid monohydrate is used to control the weak acidity of the system, the amount of citric acid monohydrate added is 5-20 parts by mass, and the system temperature is 30-120° C.;

[0029] The oil bath temperature of the hot oil column forming device is 80-100°C, and the drip acceleration rate is 10-80d / min;

[0030] The porous alumina wet ball is heat treated at a temperature of 200° C. to 600° C. for a time of 0.5 h to 3.0 h;

[0031] The porous alumina balls are washed 2-3 times with ethanol and deionized water respectively;

[0032] The temperature for vacuum drying the porous alumina balls is 40° C.-120° C., and the vacuum drying time is 5.0 h-15.0 h.

[0033] In an optional embodiment, the mass ratio of the pore-forming agent, the pseudo-boehmite and the aluminum sol is (4-1):1:1.

[0034] In an optional embodiment, the method of the embodiment of the present invention further includes:

[0035] Sodium sulfite and sodium chlorate are added to ultrapure water as a solvent, and stirred in an ice bath until completely dissolved to obtain a first solution, wherein the concentration of the sodium sulfite is 2-6 mol / L, and the concentration of the sodium chlorate is 3-10 mol / L;

[0036] Slowly dissolving an inorganic acid dropwise in the first solution under heating and uniform stirring conditions to prepare chlorine dioxide gas, wherein the inorganic acid is one or more of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, the concentration of the inorganic acid is 2-10 mol / L, and the heating temperature is 30-100° C.;

[0037] Passing the chlorine dioxide gas generated by the reaction into a plurality of gas collecting bottles containing a mixed solution of hydrogen peroxide and sodium hydroxide in an ice bath, wherein the concentration of the hydrogen peroxide is 1-5 mol / L, and the concentration of the sodium hydroxide is 1-5 mol / L;

[0038] After the reaction is completed, the first gas collecting bottle into which chlorine dioxide gas is introduced is collected and refrigerated.

[0039] In a second aspect, an embodiment of the present invention provides a cluster-modified chlorine dioxide solid disinfectant, which is prepared according to the method described in an embodiment of the present invention.

[0040] In a third aspect, an embodiment of the present invention provides a disinfection device, comprising the cluster-modified chlorine dioxide solid disinfectant described in an embodiment of the present invention.

[0041] An embodiment of the present invention has the following advantages or beneficial effects:

[0042] In the preparation method of the cluster chlorine dioxide solid disinfectant of the embodiment of the present invention, the metal group cluster is dissolved in a solvent, and the porous alumina ball is immersed therein for impregnation, so that the first impregnation solution enters the pores of the porous alumina ball; further by roasting, the metal group cluster is formed into a metal oxide or a metal cluster inside the porous alumina ball to obtain a cluster-modified porous alumina ball. The cluster-modified porous alumina ball has richer surface active sites and a larger specific surface area, which can provide more adsorption and binding sites for chlorine dioxide molecules, thereby significantly increasing the loading amount of chlorine dioxide. The chlorine dioxide is fixed to the porous alumina ball through the cluster material, which can effectively retain the high efficiency, strong power, fast and long-lasting, broad-spectrum sterilization, non-toxic and non-irritating and green and safe performance of chlorine dioxide, and can also continuously disinfect the air, thereby achieving the purpose of long-term, safe, green and efficient air purification, and improving the storage period and validity period. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The above and other features and advantages of the present invention will become more apparent by describing in detail example embodiments thereof with reference to the accompanying drawings.

[0044] Figure 1 1 is a schematic flow chart of a method for preparing a cluster-modified chlorine dioxide solid disinfectant according to an exemplary embodiment;

[0045] Figure 2 is an X-ray diffractometer (XRD) structure spectrum of porous alumina spheres obtained in a method for preparing a cluster-modified chlorine dioxide solid disinfectant according to an exemplary embodiment;

[0046] Figure 31 is a comparison chart of the specific surface areas of the porous alumina spheres prepared in Example 1, Example 2, Example 3, and Comparative Examples 1 and 2;

[0047] Figure 4 1 is a comparison chart of the porosity of porous alumina spheres prepared in Example 1, Example 2, Example 3, and Comparative Examples 1 and 2;

[0048] Figure 5 This is a characterization diagram of the characteristic peaks of the ultraviolet absorption spectrum of the chlorine dioxide sample prepared in Example 1 of the present invention;

[0049] Figure 6 This is a characterization diagram of the characteristic peaks of the ultraviolet absorption spectra of the chlorine dioxide samples prepared in Comparative Example 1 and Comparative Example 2;

[0050] Figure 7a This is a graph showing the average killing rate of Escherichia coli against silver cluster-modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Example 1 over time;

[0051] Figure 7b This is a graph showing the change in the average killing rate of Staphylococcus aureus over time by silver cluster modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Example 1;

[0052] Figure 8a This is a graph showing the average killing rate of Escherichia coli against perovskite cluster-modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Example 2 over time;

[0053] Figure 8b This is a graph showing the change in the average killing rate of Staphylococcus aureus over time by using perovskite cluster-modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Example 2;

[0054] Figure 9a This is a graph showing the average killing rate of Escherichia coli against the copper cluster modified porous alumina spheres prepared in Example 3 with different doses of chlorine dioxide immobilized thereon over time;

[0055] Figure 9b This is a graph showing the change in the average killing rate of Staphylococcus aureus over time by copper cluster modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Example 3;

[0056] Figure 10a This is a graph showing the change in the average killing rate of Escherichia coli over time by silver cluster-modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Comparative Example 1;

[0057] Figure 10bThis is a graph showing the change in the average killing rate of Staphylococcus aureus over time by silver cluster-modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Comparative Example 1;

[0058] Figure 11a This is a graph showing the change in the average killing rate of Escherichia coli over time by silver cluster-modified porous alumina spheres immobilized with different doses of chlorine dioxide prepared in Comparative Example 2;

[0059] Figure 11b This is a graph showing the change in the average killing rate of Staphylococcus aureus over time by silver cluster-modified porous alumina spheres loaded with different doses of chlorine dioxide prepared in Comparative Example 2. DETAILED DESCRIPTION

[0060] Example embodiments will now be described more fully with reference to the accompanying drawings. However, example embodiments can be embodied in many forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concepts of the example embodiments to those skilled in the art. Like reference numerals in the figures represent like or similar structures, and thus their detailed description will be omitted.

[0061] The terms "a", "an", "the", and "said" are used to indicate the presence of one or more elements / components / etc.; the terms "including" and "having" are used to express an open-ended inclusive meaning and mean that additional elements / components / etc. may be present in addition to the listed elements / components / etc.

[0062] See also Figure 1 The embodiment of the present invention provides a method for preparing a cluster-modified chlorine dioxide solid disinfectant, comprising:

[0063] dissolving the metal group cluster in a solvent to prepare a first impregnation solution;

[0064] Immersing the porous alumina balls in a first impregnation solution to allow the first impregnation solution to enter the pores of the porous alumina balls;

[0065] The impregnated porous alumina beads are calcined to form metal oxides or metal clusters inside the porous alumina beads, thereby obtaining cluster-modified porous alumina beads;

[0066] The cluster-modified porous alumina spheres were vacuum dried;

[0067] adding a stabilizer to the chlorine dioxide solution to prepare a second impregnation solution;

[0068] The cluster-modified porous alumina beads are immersed in the second impregnation solution and sealed and stored at room temperature;

[0069] The cluster-modified porous alumina beads after immersion are taken out, washed with deionized water, and the moisture on the surface of the cluster-modified porous alumina beads is absorbed with filter paper, followed by drying to obtain porous alumina beads immobilized with chlorine dioxide.

[0070] In the cluster-modified chlorine dioxide solid disinfectant preparation method of the embodiment of the present invention, porous alumina beads are used as carriers for loading chlorine dioxide, with large specific surface area and pore volume, good adsorption performance and mechanical strength, thermal stability, low density and environmentally friendly non-toxic advantages, its porous structure can not only effectively immobilize chlorine dioxide and improve the utilization rate of chlorine dioxide, but also provide more reactive sites, thereby enhancing the disinfection and sterilization effect. By using metal group clusters to cluster-modify porous alumina beads, the surface properties and pore structure of porous alumina beads can be adjusted based on the presence of metal group clusters, chlorine dioxide molecules can be stably fixed on the surface and pores of the beads, reducing direct contact of chlorine dioxide with the external environment, making the diffusion and release of chlorine dioxide in the beads slower and more controllable, thereby significantly improving the stability of chlorine dioxide, and enhancing sustained-release performance. This sustained-release effect enables chlorine dioxide to be continuously released over a long period of time, maintaining an effective sterilization and disinfection concentration, avoiding the problem of too high or too low concentration caused by the rapid release of chlorine dioxide, thereby improving the durability and reliability of its sterilization and disinfection effect, and improving the storage period and validity period. The chlorine dioxide fixed by the cluster-modified porous alumina pellet material helps to reduce the risk of leakage of chlorine dioxide during the sterilization and disinfection process, and ensures the safety of operators. The embodiment of the present invention adopts the cluster-modified porous alumina pellet material to fix the chlorine dioxide disinfection and sterilization material to improve air quality, ensure people's respiratory health and safety, and create a clean space in the air field.

[0071] Adding a stabilizer at an appropriate concentration to the chlorine dioxide solution can effectively immobilize the chlorine dioxide, reduce the volatility of chlorine dioxide, and delay the decomposition of chlorine dioxide, thereby extending the sustained release time of chlorine dioxide and improving its use efficiency.

[0072] In the embodiment of the present invention, the metal group cluster can be prepared by hydrolysis polymerization. The metal group cluster is dissolved in a suitable solvent to prepare the first impregnation solution.

[0073] In some embodiments, the metal group cluster includes one or more of TiO2 clusters, ZnO clusters, iron ion clusters, copper nanoclusters, silver nanoclusters, and perovskite clusters. In an embodiment of the present invention, a metal group cluster is selected to modify the porous alumina spheres, and the cluster material itself also has antibacterial properties, which synergizes with chlorine dioxide to further enhance the killing effect of the porous alumina spheres immobilized with chlorine dioxide on microorganisms, broaden the antibacterial spectrum, and improve the antibacterial efficiency. It can be widely used in antibacterial disinfection in the fields of medical care, food preservation, water treatment, etc. The selection of metal group clusters to modify the porous alumina spheres helps the chlorine dioxide molecules to bind to the active sites on the surface of the porous alumina spheres, thereby improving the immobilization efficiency.

[0074] Water-soluble modified clusters are synthesized by selecting ligands with specific functional groups and structures. These ligands can form stable interactions with chlorine dioxide. The use of ligands containing functional groups such as amino, carboxyl, and hydroxyl groups can not only enhance the solubility of the clusters in water, but also bind to chlorine dioxide through hydrogen bonding and electrostatic interactions, thereby improving loading stability.

[0075] In some embodiments, the solvent of the first impregnation solution is one or more of ethylene glycol, water, ethanol, and N,N-dimethylformamide (DMF). In an exemplary embodiment, the solvent of the first impregnation solution is water, ethanol, and N,N-dimethylformamide, and the volume ratio of water, ethanol, and N,N-dimethylformamide can be (3-5):2:1. In specific implementations, the volume ratio of water, ethanol, and N,N-dimethylformamide can be 5:2:1, 4:2:1, or 3:2:1.

[0076] In some embodiments, the concentration of the first impregnation solution is 0.4-2.0 mol / L. In an exemplary embodiment, the concentration of the first impregnation solution may be 0.6-1.2 mol / L. In a specific implementation, the concentration of the first impregnation solution may be 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, or 1.1 mol / L.

[0077] In some embodiments, the temperature at which the porous alumina spheres are immersed in the first impregnation solution is 30-70°C. In an exemplary embodiment, the temperature at which the porous alumina spheres are immersed in the first impregnation solution may be 40-60°C. In a specific implementation, the temperature at which the porous alumina spheres are immersed in the first impregnation solution may be 42°C, 45°C, 50°C, 55°C, or 58°C. The time for immersing the porous alumina spheres in the first impregnation solution may be 6-24h. In an exemplary embodiment, the time for immersing the porous alumina spheres in the first impregnation solution may be 10-15h. In a specific implementation, the time for immersing the porous alumina spheres in the first impregnation solution may be 11h, 12h, 13h, or 14h. Immersing under certain temperature and time conditions allows the first impregnation solution to fully enter the pores of the spheres.

[0078] In some embodiments, the temperature of the impregnated porous alumina pellets is 200-600°C and the time is 1.0-8.0h. In an exemplary embodiment, the calcination temperature may be 400-500°C. In a specific embodiment, the calcination temperature may be 420°C, 450°C, 460°C, 480°C, or 490°C. In an exemplary embodiment, the calcination time may be 3.0-6.0h. In a specific implementation, the calcination time may be 3.5h, 4h, 4.5h, 5h, or 5.5h. By calcining, the metal group clusters can form metal oxides or metal clusters inside the pellets, thereby obtaining cluster-modified porous alumina pellets.

[0079] In some embodiments, the temperature for vacuum drying of the cluster-modified porous alumina beads is 40-120°C, and the time for vacuum drying is 5.0h-15.0h. In an exemplary embodiment, the temperature for vacuum drying of the cluster-modified porous alumina beads may be 50-80°C. In a specific implementation, the temperature for vacuum drying of the cluster-modified porous alumina beads may be 45°C, 55°C, 60°C, 65°C, 70°C, or 75°C. In an exemplary embodiment, the time for vacuum drying of the cluster-modified porous alumina beads may be 8.0-12.0h. In a specific implementation, the time for vacuum drying of the cluster-modified porous alumina beads may be 8.5h, 9.0h, 9.5h, 10.0h, 10.5h, 11.0h, or 11.5h.

[0080] In some embodiments, after vacuum drying for a certain period of time, the cluster-modified porous alumina beads can be stored at room temperature in the dark. In an exemplary embodiment, the cluster-modified porous alumina beads can be stored in a light-proof glass container.

[0081] The prepared cluster modified porous alumina beads have excellent stability, can effectively immobilize chlorine dioxide and stably release it, extend the storage and shelf life of the sample, and reduce the safety risks that may occur during production and storage. Cluster modified porous alumina beads are used as carriers, which have good environmental protection and regeneration properties, reduce pollution to the environment and consumption of resources, and the chlorine dioxide immobilized on the beads does not produce toxic byproducts after release, is safe and harmless to the environment and human body, and meets the requirements of green environmental protection. Compared with traditional disinfectants, the release of immobilized chlorine dioxide on cluster modified porous alumina beads is extremely stable, reduces the risk of chlorine dioxide directly contacting the human body, and improves the safety of the disinfection process. The embodiment of the present invention immobilizes chlorine dioxide on cluster modified porous alumina beads, and has great application potential in the field of disinfection and sterilization air safety. The preparation method of cluster modified porous alumina beads immobilized chlorine dioxide can flexibly adjust the pore volume of the beads and the immobilized amount of chlorine dioxide, and is suitable for multiple fields such as air purification, medical and health care, and food processing, with broad market prospects and application space.

[0082] In some embodiments, the stabilizer is one or more of sodium carboxymethyl cellulose, sodium bicarbonate, sodium chloride, sodium hydroxide, ethylenediamine, polyvinyl alcohol, and sodium bisulfite. In order to control the release rate and prolong the release time of chlorine dioxide, selecting a suitable stabilizer helps control the release rate of chlorine dioxide, making the chlorine dioxide release process more stable and long-lasting. In the embodiments of the present invention, factors such as the compatibility of the stabilizer with chlorine dioxide, the ability to control the release rate, and the stability of the stabilizer are taken into consideration according to the reaction system.

[0083] In some embodiments, the concentration of the stabilizer in the second impregnation solution is 0.5-5 mol / L. In the embodiment of the present invention, the appropriate type and dosage of the stabilizer are selected according to the adsorption properties of the porous alumina spheres to ensure the effective use and safety of chlorine dioxide. A stabilizer of appropriate concentration is added to the chlorine dioxide solution, such as sodium carboxymethyl cellulose, sodium bicarbonate, sodium chloride, sodium hydroxide, ethylenediamine, polyvinyl alcohol (PVA), sodium bisulfite, etc. to delay its decomposition, control the pH value of the reaction system, and maintain its stability in a neutral or weak acid environment.

[0084] The specific mass of the cluster-modified porous alumina beads immersed in the second impregnation solution is not limited, as long as all the cluster-modified porous alumina beads are immersed in the second impregnation solution. In an exemplary embodiment, the mass of the cluster-modified porous alumina beads immersed in the second impregnation solution can be 500g. In a specific implementation, the mass of the cluster-modified porous alumina beads can be 75g, 80g, 85g, 90g, 95g, 100g, 105g, 110g, or 115g. The cluster-modified porous alumina beads are immersed in the second impregnation solution for 0.5-5.0h. In an exemplary embodiment, the immersion time can be 2.5-3.0h.

[0085] In some embodiments, the cluster-modified porous alumina spheres are immersed and stirred in the second impregnation solution for 2.5-3.0 hours.

[0086] After soaking, the cluster-modified porous alumina beads are washed 2-6 times with deionized water, for example, 3 times, 4 times, 5 times, etc.

[0087] The temperature for vacuum drying the cluster-modified porous alumina beads after immersion is 30-80°C. In an exemplary embodiment, the temperature for vacuum drying can be 40-60°C. In a specific implementation, the temperature for vacuum drying can be 45°C, 50°C, 55°C, etc. The vacuum drying time for the cluster-modified porous alumina beads after immersion can be 6.0h-14.0h. In an exemplary embodiment, the vacuum drying time for the cluster-modified porous alumina beads after immersion can be 8.0-10.0h.

[0088] In the embodiment of the present invention, the porous alumina spheres can be purchased or prepared by using existing technology.

[0089] In some embodiments, the method of the present invention further comprises preparing porous alumina spheres, specifically comprising:

[0090] Solid alumina beads are mixed with a pore-forming agent, pseudo-boehmite and aluminum sol (a(Al2O3·nH2O)·bHx·cH2O, wherein: Al2O3·nH2O is hydrated aluminum oxide, Hx is a peptizer, coefficient: b<a, c, n) to prepare a sol. During the mixing process, the weak acidity of the system is controlled. The pore-forming agent can be polymethyl methacrylate (PMMA, (C5O2H8) n );

[0091] The sol is dripped into a hot oil column forming device and solidified into a porous alumina wet ball;

[0092] The porous alumina wet ball is heat-treated to obtain porous alumina small balls;

[0093] The porous alumina beads were washed with ethanol and deionized water in sequence;

[0094] The washed porous alumina beads were vacuum dried.

[0095] In the embodiment of the present invention, alumina (Al2O3) pellets of suitable particle size are selected as raw materials, and precise pore formation and heat treatment processes are designed to ensure that the alumina pellets have good porous structure, adsorption performance and mechanical strength. Pseudoboehmite can be SB powder.

[0096] In some embodiments, the solid alumina beads are present in an amount of 200-300 parts by mass, the pore-forming agent is present in an amount of 50-500 parts by mass, the pore-forming agent may be polymethyl methacrylate, the pseudo-boehmite is present in an amount of 20-200 parts by mass, and the alumina sol is present in an amount of 20-200 parts by mass. In a specific embodiment, the pore-forming agent may be present in an amount of 100-350 parts by mass, the pseudo-boehmite may be present in an amount of 50-150 parts by mass, and the alumina sol may be present in an amount of 50-150 parts by mass.

[0097] In some embodiments, the mass ratio of the pore former, pseudo-boehmite, and alumina sol is (4-1):1:1. In specific embodiments, the mass ratio of the pore former, pseudo-boehmite, and alumina sol is 4:1:1, 3:1:1, 2:1:1, or 1:1:1.

[0098] During the mixing process of the solid alumina spheres with the pore-forming agent, pseudo-boehmite, and aluminum sol, a pH adjuster is used to control the weak acidity of the system. Citric acid monohydrate can be used as the pH adjuster. Controlling the weak acidity of the system can form an organic film on the surface of the spheres, preventing the spheres from being damaged and settling due to collisions. The pH adjuster can be added in an amount of 5-20 parts by mass. In exemplary embodiments, the pH adjuster can be added in an amount of 10-15 parts by mass. In specific implementations, the pH adjuster can be added in an amount of 11 parts by mass, 12 parts by mass, 13 parts by mass, or 14 parts by mass. The temperature of the system in which the solid alumina spheres are mixed with the pore-forming agent, pseudo-boehmite, and aluminum sol can be 30-120°C. In exemplary embodiments, the temperature of the system in which the solid alumina spheres are mixed with the pore-forming agent, pseudo-boehmite, and aluminum sol can be 50-100°C. In a specific implementation, the system temperature can be 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C.

[0099] In an embodiment of the present invention, porous alumina spheres can be prepared using a hot oil column forming method. A sol obtained by mixing solid alumina spheres with a pore-forming agent, pseudo-boehmite, and aluminum sol is dripped into a hot oil column forming apparatus filled with white oil, and the wet porous alumina spheres are collected at the bottom. The oil bath temperature of the hot oil column forming apparatus is 80-100°C, and the dripping rate is 10-80 d / min. In an exemplary embodiment, the dripping rate can be 30-60 d / min. In specific implementations, the dripping rate can be 35 d / min, 40 d / min, 45 d / min, 50 d / min, or 55 d / min.

[0100] The porous alumina balls are heat-treated to remove pore-forming agents and other intermediate organic substances. The temperature for heat treatment of the porous alumina wet balls can be 200°C-600°C. In exemplary embodiments, the heat treatment temperature can be 220-550°C or 240-480°C. In specific implementations, the heat treatment temperature can be 240°C, 250°C, 300°C, 350°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, or 490°C. The heat treatment time can be 0.5h-3.0h. In exemplary embodiments, the heat treatment time can be 1.0-2.0h.

[0101] The porous alumina beads were washed 2-3 times with ethanol and deionized water respectively.

[0102] The temperature for vacuum drying the porous alumina spheres is 40°C-120°C. In exemplary embodiments, the temperature for vacuum drying may be 45-100°C or 50-80°C. In specific implementations, the temperature for vacuum drying may be 55°C, 60°C, 65°C, 70°C, or 75°C. The vacuum drying time is 5.0 hours-15.0 hours. In exemplary embodiments, the vacuum drying time may be 8.0-12.0 hours. In specific implementations, the vacuum drying time may be 8.5 hours, 9.0 hours, 9.5 hours, 10.0 hours, 10.5 hours, 11.0 hours, or 11.5 hours.

[0103] In the embodiments of the present invention, chlorine dioxide can be purchased from the market or prepared. Chlorine dioxide can be prepared using existing methods.

[0104] In some embodiments, the method of the present invention further comprises preparing chlorine dioxide, specifically comprising:

[0105] Sodium sulfite (Na2SO3) and sodium chlorate (NaClO3) are added to ultrapure water as a solvent, and stirred for a certain period of time under an ice bath until they are completely dissolved to obtain a first solution;

[0106] The inorganic acid is slowly dissolved dropwise in the first solution under heating and uniform stirring conditions until the solution is completely dissolved to prepare ClO2 gas;

[0107] The ClO2 gas generated by the reaction is passed into multiple gas collecting bottles containing a mixed solution of hydrogen peroxide (H2O2) and sodium hydroxide (NaOH) in an ice bath;

[0108] After the reaction is completed, the first gas collection bottle into which ClO2 gas is introduced is collected and can be stored in a refrigerator at a certain temperature.

[0109] In some embodiments, sodium sulfite and sodium chlorate are added to ultrapure water as a solvent and stirred in an ice bath until completely dissolved to obtain a first solution, wherein the concentration of sodium sulfite is 2-6 mol / L and the concentration of sodium chlorate is 3-10 mol / L. In an exemplary embodiment, the concentration of sodium sulfite can be 3-5 mol / L, and the concentration of sodium chlorate can be 5-8 mol / L. The stirring time in the ice bath can be 10-30 minutes. In a specific implementation, the stirring time in the ice bath can be 15-20 minutes.

[0110] In some embodiments, chlorine dioxide gas is prepared by slowly dissolving an inorganic acid dropwise in a first solution under conditions of heating and uniform stirring. The inorganic acid is one or more of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. The concentration of the inorganic acid is 2-10 mol / L, and the heating temperature is 30-100°C. The inorganic acid may be selected from only one of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, or a combination of two or more. For example, the inorganic acid may be selected from sulfuric acid and hydrochloric acid. Sulfuric acid can provide an acidic environment and stabilize the reaction, while hydrochloric acid can participate in the reaction as a reducing agent. The molar ratio of sulfuric acid to hydrochloric acid can be 1:(1-2), and the total concentration of the inorganic acid can be 3-6 mol / L, which can avoid both an overly rapid reaction that is difficult to control and an overly slow reaction rate that affects efficiency. In an exemplary embodiment, the total concentration of the inorganic acid can be 3-6 mol / L. In a specific implementation, the total concentration of the inorganic acid can be 5 mol / L.

[0111] The chlorine dioxide gas generated by the reaction is passed into multiple gas collecting bottles containing a mixture of hydrogen peroxide and sodium hydroxide in an ice bath. The concentration of hydrogen peroxide is 1-5 mol / L, and the concentration of sodium hydroxide is 1-5 mol / L. In an exemplary embodiment, the concentration of hydrogen peroxide can be 2-3 mol / L, and the concentration of sodium hydroxide can be 2-3 mol / L.

[0112] The refrigerated temperature of the collected chlorine dioxide solution is 0-10°C. In a specific implementation, the refrigerated temperature can be 2-5°C.

[0113] The embodiments of the present invention are described below in conjunction with specific embodiments and related tests.

[0114] Example 1

[0115] 1. The synthesis steps of porous alumina (Al2O3) spheres are as follows:

[0116] Step S11: 250 g of solid alumina beads, 300 g of polymethyl methacrylate (PMMA), 100 g of SB powder, and 100 g of aluminum sol are mixed to prepare a sol. During the mixing process, 10-15 g of citric acid monohydrate is used to control the weak acidity of the system. The temperature during the mixing process is controlled within the range of 70° C. to 80° C.

[0117] Step S12: dripping the mixed sol prepared in step S11 into a hot oil column forming device at a dripping rate of 40-50 d / min, wherein the oil bath temperature of the hot oil column forming device is controlled within the range of 85° C. to 95° C., dripping the sol into the high-temperature oil column and solidifying it into porous alumina balls, and collecting the porous alumina wet balls at the lower end of the hot oil column forming device;

[0118] Step S13: heat-treating the porous alumina wet balls obtained in step S12 at 450° C. for 1.5 hours. The heat treatment is performed to remove residual organic matter and enhance the mechanical strength of the porous alumina balls.

[0119] Step S14: Wash the porous alumina balls after the heat treatment in step S13 with ethanol and deionized water twice in sequence to remove oil stains and other impurities on the surface;

[0120] Step S15: vacuum-dry the porous alumina beads treated in step S14 at a temperature of 65-70° C. for 10.0 h, and store the dried porous alumina beads in a glass container at room temperature.

[0121] 2. The synthesis steps of cluster-modified porous alumina spheres are as follows:

[0122] Step S21, preparing silver nanoclusters by hydrolysis polymerization reaction, dissolving the silver nanoclusters in a solvent prepared by water, ethanol and N,N-dimethylformamide (DMF) in a volume ratio of 4:2:1 to obtain a first impregnation solution, wherein the concentration of the first impregnation solution is 1.0 mol / L;

[0123] Step S22: soaking the porous alumina balls in the first impregnation solution obtained in step S21 at a temperature of 50° C. for 13 hours, so that the first impregnation solution fully enters the pores of the balls;

[0124] Step S23, calcining the porous alumina beads after the immersion treatment in step S22 at a temperature of 450° C. for 4.5 hours to allow the silver nanoclusters to be adsorbed inside the porous alumina beads, thereby obtaining cluster-modified porous alumina beads;

[0125] Step S24: vacuum-dry the cluster-modified alumina beads at 70° C. for 9.0 h, and store the dried cluster-modified alumina beads in a light-proof glass container at room temperature.

[0126] 3. The synthesis steps of chlorine dioxide are as follows:

[0127] S31, adding sodium sulfite (Na2SO3) and sodium chlorate (NaClO3) to ultrapure water as a solvent, stirring for 15-20 minutes in an ice bath until completely dissolved, to obtain a first solution, wherein the concentration of sodium sulfite is 4 mol / L; the concentration of sodium chlorate is 7 mol / L;

[0128] Step S32: slowly dissolving a mixture of sulfuric acid and hydrochloric acid with a total concentration of 5 mol / L in the first solution dropwise under heating and uniform stirring until the solution is completely dissolved to prepare ClO2 gas. The reaction heating temperature is 70°C, and the molar ratio of sulfuric acid to hydrochloric acid is 1:1.

[0129] Step S33, the ClO2 gas generated by the reaction is sequentially introduced into four gas collecting bottles containing a mixed solution of hydrogen peroxide (H2O2) and sodium hydroxide (NaOH) in an ice bath, wherein the concentration of hydrogen peroxide is 2.5 mol / L and the concentration of sodium hydroxide is 2.5 mol / L;

[0130] Step S34: After the reaction is completed, the first gas collecting bottle into which the ClO2 gas is introduced is collected. The gas collecting bottle contains a chlorine dioxide solution, and the gas collecting bottle containing the chlorine dioxide solution is placed in a refrigerator and refrigerated at a temperature of 2-5°C.

[0131] 4. The synthesis steps of cluster-modified porous alumina spheres immobilized with chlorine dioxide are as follows:

[0132] Step S41: adding sodium carboxymethyl cellulose to the prepared chlorine dioxide solution and stirring at room temperature to dissolve the sodium carboxymethyl cellulose to a final concentration of 2.5 mol / L;

[0133] Step S42: taking 100 g of cluster-modified porous alumina beads and soaking them in the solution obtained in step S41, sealing the solution and storing it under stirring at room temperature for 3.0 h;

[0134] Step S43: Take out the soaked cluster-modified porous alumina balls through a filter, wash them four times with deionized water, and dry the surface of the balls with filter paper;

[0135] Step S44: Place the cluster-modified porous alumina beads treated in step S43 in a vacuum drying oven at 50° C. for 9.0 h, take them out and place them in a brown light-proof bottle for storage.

[0136] Example 2

[0137] 1. The synthesis steps of porous alumina (Al2O3) spheres are as follows:

[0138] Step S11: 220 g of solid alumina beads, 200 g of polymethyl methacrylate (PMMA), 100 g of SB powder, and 100 g of aluminum sol are mixed to prepare a sol. During the mixing process, 10-15 g of citric acid monohydrate is used to control the weak acidity of the system. The temperature during the mixing process is controlled within the range of 70° C. to 80° C.

[0139] Step S12: dripping the mixed sol prepared in step S11 into a hot oil column forming device at a dripping rate of 40-50 d / min, wherein the oil bath temperature of the hot oil column forming device is controlled within the range of 85° C. to 95° C., dripping the sol into the high-temperature oil column and solidifying it into porous alumina balls, and collecting the porous alumina wet balls at the lower end of the hot oil column forming device;

[0140] Step S13: heat-treating the porous alumina wet balls obtained in step S12 at 450° C. for 2 hours. The heat treatment is performed to remove residual organic matter and enhance the mechanical strength of the porous alumina balls.

[0141] Step S14: Wash the porous alumina balls after the heat treatment in step S13 with ethanol and deionized water twice in sequence to remove oil stains and other impurities on the surface;

[0142] Step S15: vacuum-dry the porous alumina beads treated in step S14 at a temperature of 65-70° C. for 10.0 h, and store the dried porous alumina beads in a glass container at room temperature.

[0143] 2. The synthesis steps of cluster-modified porous alumina spheres are as follows:

[0144] Step S21, preparing Cs2AgBiBr6 perovskite nanoclusters by a ligand-assisted reprecipitation method, dissolving the Cs2AgBiBr6 perovskite nanoclusters in a solvent prepared by water, ethanol, and N,N-dimethylformamide (DMF) in a volume ratio of 4:2:1 to obtain a first impregnation solution, wherein the concentration of the first impregnation solution is 1.0 mol / L;

[0145] Step S22: soaking the porous alumina balls in the first impregnation solution obtained in step S21 at a temperature of 50° C. for 13 hours, so that the first impregnation solution fully enters the pores of the balls;

[0146] Step S23, calcining the porous alumina beads after the immersion treatment in step S22 at a temperature of 240° C. for 4.5 hours to allow the perovskite clusters to be adsorbed inside the porous alumina beads, thereby obtaining cluster-modified porous alumina beads;

[0147] Step S24: vacuum-dry the cluster-modified alumina beads at 70° C. for 9.0 h, and store the dried cluster-modified alumina beads in a light-proof glass container at room temperature.

[0148] 3. The synthesis steps of chlorine dioxide are as follows:

[0149] S31, adding sodium sulfite and sodium chlorate to ultrapure water as a solvent, stirring for 15-20 minutes under an ice bath until completely dissolved, to obtain a first solution, wherein the concentration of sodium sulfite is 5 mol / L; the concentration of sodium chlorate is 7 mol / L;

[0150] Step S32: slowly dissolving a mixture of sulfuric acid and hydrochloric acid having a total concentration of 4 mol / L obtained by mixing in a 1:1 molar ratio in the first solution dropwise under heating and uniform stirring until the mixture is completely dissolved to prepare ClO2 gas, with the reaction heating temperature being 70°C;

[0151] Step S33, the ClO2 gas generated by the reaction is sequentially introduced into four gas collecting bottles containing a mixed solution of hydrogen peroxide and sodium hydroxide in an ice bath, wherein the concentration of hydrogen peroxide is 2 mol / L and the concentration of sodium hydroxide is 2 mol / L;

[0152] Step S34: After the reaction is completed, the first gas collecting bottle into which the ClO2 gas is introduced is collected. The gas collecting bottle contains a chlorine dioxide solution, and the gas collecting bottle containing the chlorine dioxide solution is placed in a refrigerator and refrigerated at a temperature of 2-5°C.

[0153] 4. The synthesis steps of cluster-modified porous alumina spheres immobilized with chlorine dioxide are as follows:

[0154] Step S41: adding sodium carboxymethyl cellulose to the prepared chlorine dioxide solution and stirring at room temperature to dissolve the sodium carboxymethyl cellulose to a final concentration of 2.5 mol / L;

[0155] Step S42: taking 100 g of cluster-modified porous alumina beads and soaking them in the solution obtained in step S41, sealing the solution and storing it under stirring at room temperature for 3.0 h;

[0156] Step S43: Take out the soaked cluster-modified porous alumina balls through a filter, wash them four times with deionized water, and dry the surface of the balls with filter paper;

[0157] Step S44: Place the cluster-modified porous alumina beads treated in step S43 in a vacuum drying oven at 50° C. for 9.0 h, take them out and place them in a brown light-proof bottle for storage.

[0158] Example 3

[0159] 1. The synthesis steps of porous alumina (Al2O3) spheres are as follows:

[0160] Step S11: 280 g of solid alumina beads, 400 g of polymethyl methacrylate (PMMA), 100 g of SB powder, and 100 g of aluminum sol are mixed to prepare a sol. During the mixing process, 12-14 g of citric acid monohydrate is used to control the weak acidity of the system. The temperature of the mixing process is controlled within the range of 70° C. to 80° C.

[0161] Step S12: dripping the mixed sol prepared in step S11 into a hot oil column forming device at a dripping rate of 40-50 d / min, wherein the oil bath temperature of the hot oil column forming device is controlled within the range of 85° C. to 95° C., dripping the sol into the high-temperature oil column and solidifying it into porous alumina balls, and collecting the porous alumina wet balls at the lower end of the hot oil column forming device;

[0162] Step S13: heat-treating the porous alumina wet balls obtained in step S12 at 460° C. for 2 hours. The heat treatment is performed to remove residual organic matter and enhance the mechanical strength of the porous alumina balls.

[0163] Step S14: Wash the porous alumina balls after the heat treatment in step S13 with ethanol and deionized water twice in sequence to remove oil stains and other impurities on the surface;

[0164] Step S15: vacuum-dry the porous alumina beads treated in step S14 at a temperature of 65-70° C. for 10.0 h, and store the dried porous alumina beads in a glass container at room temperature.

[0165] 2. The synthesis steps of cluster-modified porous alumina spheres are as follows:

[0166] Step S21, preparing copper nanoclusters by hydrolysis polymerization reaction, dissolving the copper nanoclusters in a solvent prepared by water, ethanol and N,N-dimethylformamide (DMF) in a volume ratio of 4:2:1 to obtain a first impregnation solution, wherein the concentration of the first impregnation solution is 1.0 mol / L;

[0167] Step S22: soaking the porous alumina balls in the first impregnation solution obtained in step S21 at a temperature of 50° C. for 13 hours, so that the first impregnation solution fully enters the pores of the balls;

[0168] Step S23, calcining the porous alumina pellets after the immersion treatment in step S22 at a temperature of 350° C. for 4.5 hours, so that the copper nanoclusters form copper oxide clusters inside the pellets, thereby obtaining cluster-modified porous alumina pellets;

[0169] Step S24: vacuum-dry the cluster-modified alumina beads at 70° C. for 9.0 h, and store the dried cluster-modified alumina beads in a light-proof glass container at room temperature.

[0170] 3. The synthesis steps of chlorine dioxide are as follows:

[0171] S31, adding sodium sulfite and sodium chlorate to ultrapure water as a solvent, stirring for 15-20 minutes under an ice bath until completely dissolved, to obtain a first solution, wherein the concentration of sodium sulfite is 5 mol / L; the concentration of sodium chlorate is 8 mol / L;

[0172] Step S32: slowly dissolving a mixture of sulfuric acid and hydrochloric acid with a total concentration of 6 mol / L in a molar ratio of 1:1.5 in the first solution dropwise under heating and uniform stirring until the mixture is completely dissolved to prepare ClO2 gas, with the reaction heating temperature being 70°C;

[0173] Step S33, the ClO2 gas generated by the reaction is sequentially introduced into four gas collecting bottles containing a mixed solution of hydrogen peroxide and sodium hydroxide in an ice bath, wherein the concentration of hydrogen peroxide is 3 mol / L and the concentration of sodium hydroxide is 3 mol / L;

[0174] Step S34: After the reaction is completed, the first gas collecting bottle into which the ClO2 gas is introduced is collected. The gas collecting bottle contains a chlorine dioxide solution, and the gas collecting bottle containing the chlorine dioxide solution is placed in a refrigerator and refrigerated at a temperature of 2-5°C.

[0175] 4. The synthesis steps of cluster-modified porous alumina spheres immobilized with chlorine dioxide are as follows:

[0176] Step S41: adding sodium carboxymethyl cellulose to the prepared chlorine dioxide solution and stirring at room temperature to dissolve the sodium carboxymethyl cellulose to a final concentration of 2.5 mol / L;

[0177] Step S42: taking 100 g of cluster-modified porous alumina beads and soaking them in the solution obtained in step S41, sealing the solution and storing it under stirring at room temperature for 3.0 h;

[0178] Step S43: Take out the soaked cluster-modified porous alumina balls through a filter, wash them four times with deionized water, and dry the surface of the balls with filter paper;

[0179] Step S44: Place the cluster-modified porous alumina beads treated in step S43 in a vacuum drying oven at 50° C. for 9.0 h, take them out and place them in a brown light-proof bottle for storage.

[0180] Comparative Example 1

[0181] 1. The synthesis steps of porous alumina (Al2O3) spheres are as follows:

[0182] Step S11: 220 g of solid alumina beads, 100 g of polymethyl methacrylate (PMMA), 100 g of SB powder, and 100 g of aluminum sol are mixed to prepare a sol. During the mixing process, 10-12 g of citric acid monohydrate is used to control the weak acidity of the system. The temperature during the mixing process is 70-80° C.

[0183] Step S12: dripping the mixed sol prepared in step S11 into a hot oil column forming device at a dripping rate of 40-50 d / min, wherein the oil bath temperature of the hot oil column forming device is 85-95° C., dripping into the high-temperature oil column to solidify into porous alumina balls, and collecting the porous alumina wet balls at the lower end of the hot oil column forming device;

[0184] Step S13: heat-treating the porous alumina wet balls obtained in step S12 at 450° C. for 1.5 hours. The heat treatment is performed to remove residual organic matter and enhance the mechanical strength of the porous alumina balls.

[0185] Step S14: Wash the porous alumina balls after the heat treatment in step S13 with ethanol and deionized water twice in sequence to remove oil stains and other impurities on the surface;

[0186] Step S15: vacuum-dry the porous alumina beads treated in step S14 at a temperature of 65-70° C. for 10.0 h, and store the dried porous alumina beads in a glass container at room temperature.

[0187] 2. The synthesis steps of cluster-modified porous alumina spheres are as follows:

[0188] Step S21, preparing silver nanoclusters by hydrolysis polymerization reaction, dissolving the silver nanoclusters in a solvent prepared by water, ethanol and N,N-dimethylformamide (DMF) in a volume ratio of 4:2:1 to obtain a first impregnation solution, wherein the concentration of the first impregnation solution is 1.0 mol / L;

[0189] Step S22: soaking the porous alumina balls in the first impregnation solution obtained in step S21 at a temperature of 50° C. for 13 hours, so that the first impregnation solution fully enters the pores of the balls;

[0190] Step S23, calcining the porous alumina beads after the immersion treatment in step S22 at a temperature of 450° C. for 4.5 hours, so that the metal group clusters form silver metal clusters inside the beads, thereby obtaining cluster-modified porous alumina beads;

[0191] Step S24: vacuum-dry the cluster-modified alumina beads at 70° C. for 9.0 h, and store the dried cluster-modified alumina beads in a light-proof glass container at room temperature.

[0192] 3. The synthesis steps of chlorine dioxide are as follows:

[0193] S31, adding sodium sulfite and sodium chlorate to ultrapure water as a solvent, stirring for 15-20 minutes under an ice bath until completely dissolved, to obtain a first solution, wherein the concentration of sodium sulfite is 2 mol / L; the concentration of sodium chlorate is 4 mol / L;

[0194] Step S32: slowly dissolving a mixture of 5 mol / L sulfuric acid and hydrochloric acid in the first solution dropwise under heating and uniform stirring until the mixture is completely dissolved, with the reaction heating temperature being 70° C.;

[0195] Step S33, the ClO2 gas generated by the reaction is sequentially introduced into four gas collecting bottles containing a mixed solution of hydrogen peroxide and sodium hydroxide in an ice bath, wherein the concentration of hydrogen peroxide is 2 mol / L and the concentration of sodium hydroxide is 2 mol / L;

[0196] Step S34: After the reaction is completed, the first gas collecting bottle into which the ClO2 gas is introduced is collected. The gas collecting bottle contains a chlorine dioxide solution, and the gas collecting bottle containing the chlorine dioxide solution is placed in a refrigerator and refrigerated at a temperature of 2-5°C.

[0197] 4. The synthesis steps of cluster-modified porous alumina spheres immobilized with chlorine dioxide are as follows:

[0198] Step S41: adding sodium carboxymethyl cellulose to the prepared chlorine dioxide solution and stirring at room temperature to dissolve the sodium carboxymethyl cellulose to a final concentration of 2.5 mol / L;

[0199] Step S42: taking 100 g of cluster-modified porous alumina beads and soaking them in the solution obtained in step S41, sealing the solution and storing it under stirring at room temperature for 3.0 h;

[0200] Step S43: Take out the soaked cluster-modified porous alumina balls through a filter, wash them four times with deionized water, and dry the surface of the balls with filter paper;

[0201] Step S44: Place the cluster-modified porous alumina beads treated in step S43 in a vacuum drying oven at 50° C. for 9.0 h, take them out and place them in a brown light-proof bottle for storage.

[0202] Comparative Example 2

[0203] 1. The synthesis steps of porous alumina (Al2O3) spheres are as follows:

[0204] Step S11: 220 g of solid alumina beads, 80 g of polymethyl methacrylate (PMMA), 100 g of SB powder, and 100 g of aluminum sol are mixed to prepare a sol. During the mixing process, 10-15 g of citric acid monohydrate is used to control the weak acidity of the system. The temperature during the mixing process is 70-80° C.

[0205] Step S12: dripping the mixed sol prepared in step S11 into a hot oil column forming device at a dripping rate of 40-50 d / min, wherein the oil bath temperature of the hot oil column forming device is 85-95° C., dripping into the high-temperature oil column to solidify into porous alumina balls, and collecting the porous alumina wet balls at the lower end of the hot oil column forming device;

[0206] Step S13: heat-treating the porous alumina wet balls obtained in step S12 at 450° C. for 1.5 hours. The heat treatment is performed to remove residual organic matter and enhance the mechanical strength of the porous alumina balls.

[0207] Step S14: Wash the porous alumina balls after the heat treatment in step S13 with ethanol and deionized water twice in sequence to remove oil stains and other impurities on the surface;

[0208] Step S15: vacuum-dry the porous alumina beads treated in step S14 at a temperature of 65-70° C. for 10.0 h, and store the dried porous alumina beads in a glass container at room temperature.

[0209] 2. The synthesis steps of cluster-modified porous alumina spheres are as follows:

[0210] Step S21, preparing silver nanoclusters by hydrolysis polymerization reaction, dissolving the silver nanoclusters in a solvent prepared by water, ethanol and N,N-dimethylformamide (DMF) in a volume ratio of 4:2:1 to obtain a first impregnation solution, wherein the concentration of the first impregnation solution is 1.0 mol / L;

[0211] Step S22: soaking the porous alumina balls in the first impregnation solution obtained in step S21 at a temperature of 50° C. for 13 hours, so that the first impregnation solution fully enters the pores of the balls;

[0212] Step S23, calcining the porous alumina beads after the immersion treatment in step S22 at 300° C. for 4.5 hours to allow the silver nanoclusters to be adsorbed inside the porous alumina beads, thereby obtaining cluster-modified porous alumina beads;

[0213] Step S24: vacuum-dry the cluster-modified alumina beads at 70° C. for 9.0 h, and store the dried cluster-modified alumina beads in a light-proof glass container at room temperature.

[0214] 3. The synthesis steps of chlorine dioxide are as follows:

[0215] S31, adding sodium sulfite and sodium chlorate to ultrapure water as a solvent, stirring for 15-20 minutes under an ice bath until completely dissolved, to obtain a first solution, wherein the concentration of sodium sulfite is 4 mol / L; the concentration of sodium chlorate is 7 mol / L;

[0216] Step S32: slowly dissolving a mixture of sulfuric acid and hydrochloric acid having a concentration of 5 mol / L in the first solution dropwise under heating and uniform stirring until the mixture is completely dissolved to prepare ClO2 gas, with the reaction heating temperature being 70°C;

[0217] Step S33, the ClO2 gas generated by the reaction is sequentially introduced into four gas collecting bottles containing a mixed solution of hydrogen peroxide and sodium hydroxide in an ice bath, wherein the concentration of hydrogen peroxide is 1.0 mol / L and the concentration of sodium hydroxide is 2.0 mol / L;

[0218] Step S34: After the reaction is completed, the first gas collecting bottle into which the ClO2 gas is introduced is collected. The gas collecting bottle contains a chlorine dioxide solution, and the gas collecting bottle containing the chlorine dioxide solution is placed in a refrigerator and refrigerated at a temperature of 2-5°C.

[0219] 4. The synthesis steps of cluster-modified porous alumina spheres immobilized with chlorine dioxide are as follows:

[0220] Step S41: adding sodium carboxymethyl cellulose to the prepared chlorine dioxide solution and stirring at room temperature to dissolve the sodium carboxymethyl cellulose to a final concentration of 2.5 mol / L;

[0221] Step S42: taking 100 g of cluster-modified porous alumina beads and soaking them in the solution obtained in step S41, sealing the solution and storing it under stirring at room temperature for 3.0 h;

[0222] Step S43: Take out the soaked cluster-modified porous alumina balls through a filter, wash them four times with deionized water, and dry the surface of the balls with filter paper;

[0223] Step S44: Place the cluster-modified porous alumina beads treated in step S43 in a vacuum drying oven at 50° C. for 9.0 h, take them out and place them in a brown light-proof bottle for storage.

[0224] The porous alumina spheres prepared in Example 1 were subjected to X-ray diffraction (XRD) to obtain a structural diagram. Figure 2 , XRD crystal structure analysis shows that the porous alumina spheres are γ-Al2O3.

[0225] Specific surface area and porosity are key parameters for evaluating the performance of porous alumina spheres. The specific surface area test adopts the BET method based on the multi-molecular layer adsorption theory, and measures the adsorption amount of nitrogen and the adsorption isotherm of the sample at low temperature to obtain the specific surface area of ​​the sample. Porous alumina spheres with a larger specific surface area can provide more active sites, thereby improving the adsorption efficiency of clusters and chlorine dioxide. Porosity is an important parameter for the ratio of the internal pore volume of the material to its total volume. Porous alumina spheres with higher porosity are conducive to the passage of gas or liquid, thereby improving its effect in sterilization and disinfection applications. In order to fully understand the performance of porous alumina spheres, the specific surface area and porosity of the porous alumina spheres prepared in Example 1, Example 2, Example 3 and Comparative Examples 1 and 2 were analyzed, and the specific surface area and porosity comparison diagrams of different examples and comparative examples are shown as follows. Figure 3 and Figure 4 As shown. The research results show that the porous alumina spheres prepared in Example 1, Example 2 and Example 3, as well as Comparative Example 1, all exhibit relatively excellent pore structure performance in terms of specific surface area and porosity. However, in Comparative Example 2, due to the insufficient amount of polymethyl methacrylate (PMMA) pore-forming agent added (only 50wt% of Example 1), the specific surface area and porosity of the prepared porous alumina spheres are not good. This lower specific surface area and porosity limits the adsorption capacity of chlorine dioxide, thereby significantly weakening its effect in sterilization and disinfection applications. This comparative example emphasizes the key role of the amount of pore-forming agent added on the performance of porous alumina spheres, as well as the importance of optimizing the preparation process in practical applications.

[0226] The characteristic peaks of the ultraviolet absorption spectrum of the chlorine dioxide sample prepared in Example 1 were characterized by a UV-visible spectrophotometer test instrument. The test results are as follows: Figure 5 As shown, the characteristic peak of the ultraviolet absorption peak corresponding to the aqueous solution of the chlorine dioxide sample is 359nm, indicating the successful synthesis of chlorine dioxide. The characteristic peaks of the ultraviolet absorption spectra of the chlorine dioxide samples prepared in Comparative Example 1 and Comparative Example 2 were characterized by a UV-visible spectrophotometer test instrument. The test results are shown in FIG. Figure 6 As shown, the characteristic peak of the ultraviolet absorption peak corresponding to the aqueous solution of the chlorine dioxide sample in Comparative Example 1 is not obvious at 359 nm, and a miscellaneous peak appears at 478 nm, indicating that chlorine dioxide is not successfully synthesized; the characteristic peak of the ultraviolet absorption peak corresponding to the aqueous solution of the chlorine dioxide sample in Comparative Example 2 is 359 nm, but miscellaneous peaks appear at 491 nm and 412 nm, indicating that the synthesis effect of chlorine dioxide is poor.

[0227] The silver cluster modified porous alumina beads with different weights of 1g, 2g, 5g and 10g of chlorine dioxide immobilized prepared in Example 1 were sterilized for 10s, 30s, 60s, 120s, 180s, 240s and 300s respectively. 6 The average killing rate of Staphylococcus aureus (5.0×10 6 The average killing rates of 100 cfu / mL are shown in Table 2. Figure 7a and Figure 7b The antibacterial kinetic behavior of silver cluster modified porous alumina spheres immobilized with different doses of chlorine dioxide (1g, 2g, 5g, 10g) was demonstrated. Figure 7a Based on the data in Table 1 , the temporal trend of the average killing rate against E. coli is presented; Figure 7b The data in Table 2 reflects the dynamic changes in the bactericidal efficiency against Staphylococcus aureus. Studies have shown that higher-quality chlorine dioxide-loaded silver nanocluster-modified porous alumina spheres exhibit greater killing rates against Escherichia coli and Staphylococcus aureus. Specifically, 1g, 2g, 5g, and 10g of chlorine dioxide-loaded silver nanocluster-modified porous alumina spheres achieved 100% kill rates against E. coli and 100% kill rates against Staphylococcus aureus within 300 seconds.

[0228] Table 1

[0229]

[0230] Table 2

[0231]

[0232]

[0233] The porous alumina beads modified with chlorine dioxide-loaded perovskite clusters of different weights (1 g, 2 g, 5 g, and 10 g) prepared in Example 2 were sterilized with E. coli for 10 s, 30 s, 60 s, 120 s, 180 s, 240 s, and 300 s, respectively. 6 The average killing rate of Staphylococcus aureus (5.0×10 6 cfu / mL) are shown in Table 4. Figure 8a and Figure 8b The antibacterial kinetic behavior of perovskite cluster modified porous alumina spheres immobilized with different doses of chlorine dioxide (1g, 2g, 5g, 10g) was demonstrated. Figure 8a Based on the data in Table 3 , the temporal trend of the average killing rate against E. coli is presented; Figure 8b The data in Table 4 shows the dynamic changes in the bactericidal efficiency against Staphylococcus aureus. Specifically, 1g, 2g, 5g, and 10g of chlorine dioxide-loaded perovskite nanocluster-modified porous alumina spheres achieved a 100% kill rate against Escherichia coli within 300s and a 100% kill rate against Staphylococcus aureus within 420s.

[0234] Table 3

[0235]

[0236] Table 4

[0237]

[0238]

[0239] The experimental conditions were the same as those in Example 2. The copper cluster modified porous alumina spheres with different weights of 1g, 2g, 5g, and 10g of chlorine dioxide immobilized prepared in Example 3 were sterilized at different times. 6 The average killing rate of Staphylococcus aureus (5.0×10 6 cfu / mL) are shown in Table 6. Figure 9a and Figure 9b The antibacterial kinetic behavior of copper cluster modified porous alumina spheres immobilized with different doses of chlorine dioxide (1g, 2g, 5g, 10g) was demonstrated. Figure 9a Based on the data in Table 5 , the temporal trend of the average killing rate against E. coli is presented; Figure 9b The data in Table 6 shows the dynamic changes in the bactericidal efficiency against Staphylococcus aureus. Specifically, 1g, 2g, 5g, and 10g of chlorine dioxide-immobilized copper nanocluster-modified porous alumina spheres achieved a 100% kill rate against Escherichia coli within 300s and a 100% kill rate against Staphylococcus aureus within 420s.

[0240] Table 5

[0241]

[0242] Table 6

[0243]

[0244]

[0245] The experimental conditions were the same as those in Example 2. The silver cluster modified porous alumina beads with different weights of 1g, 2g, 5g, and 10g, prepared in Comparative Example 1, were sterilized at different times. 6 The average killing rate of Staphylococcus aureus (5.0×10 6 cfu / mL) are shown in Table 8. Figure 10a and Figure 10b The antibacterial kinetic behavior of silver cluster modified porous alumina spheres immobilized with different doses of chlorine dioxide (1g, 2g, 5g, 10g) was demonstrated. Figure 10a Based on the data in Table 7, the trend of the average killing rate against E. coli over time is presented; Figure 10b According to the data in Table 8, the dynamic changes in the sterilization efficiency of Staphylococcus aureus are reflected. Among them, 1g, 2g, 5g, and 10g of silver nanocluster modified porous alumina beads loaded with chlorine dioxide can achieve a 100% killing rate for Escherichia coli within 300s and a 100% killing rate for Staphylococcus aureus within 420s. Compared with Examples 1, 2, and 3, the sterilization timeliness of this embodiment is reduced. This is mainly attributed to the fact that the amount of polymethyl methacrylate (PMMA) pore-forming agent was reduced by 10wt%, resulting in the prepared porous alumina beads having a specific surface area (284m 2 / g) and porosity (33%) decreased, resulting in reduced immobilization capacity of silver clusters and chlorine dioxide, and ultimately reduced bactericidal efficiency against Escherichia coli and Staphylococcus aureus.

[0246] Table 7

[0247]

[0248] Table 8

[0249]

[0250] The experimental conditions were the same as those in Example 2. The silver cluster modified porous alumina beads with different masses of 1g, 2g, 5g and 10g of chlorine dioxide immobilized prepared in Comparative Example 2 were sterilized at different times. 6 The average killing rate of Staphylococcus aureus (5.0×10 6 cfu / mL) are shown in Table 10. Figure 11a and Figure 11b The antibacterial kinetic behavior of silver cluster modified porous alumina spheres immobilized with different doses of chlorine dioxide (1g, 2g, 5g, 10g) was demonstrated. Figure 11a Based on the data in Table 9, the trend of the average killing rate against E. coli over time is presented; Figure 11b According to the data in Table 10, the dynamic changes in the sterilization efficiency of Staphylococcus aureus are reflected. Among them, 10g of silver nanoclusters modified porous alumina beads loaded with chlorine dioxide achieved a killing rate of 28.31% against Escherichia coli within 300s and a killing rate of 42.69% against Staphylococcus aureus within 420s, and the sterilization effect was not good. Compared with Examples 1, 2 and 3, the sterilization timeliness and sterilization rate of this embodiment showed a significant downward trend. This is mainly attributed to the fact that the amount of polymethyl methacrylate (PMMA) pore-forming agent was reduced by 50wt%, resulting in the prepared porous alumina beads having a specific surface area (86m 2 The significant reduction in the silver clusters' and chlorine dioxide's immobilization capacity was due to a significant decrease in the porous alumina spheres' mass (g / g) and porosity (9%). Furthermore, the concentration of the hydrogen peroxide solution used to generate and collect ClO2 gas decreased by 50%, resulting in a 50% decrease in the collected ClO2 concentration, which compromised the ClO2 immobilization efficiency of the porous alumina spheres and ultimately significantly reduced their sterilization efficiency against Escherichia coli and Staphylococcus aureus.

[0251] Table 9

[0252]

[0253] Table 10

[0254]

[0255] An embodiment of the present invention provides a chlorine dioxide disinfectant, which is prepared by the method of an embodiment of the present invention.

[0256] An embodiment of the present invention provides a disinfection device, comprising the chlorine dioxide disinfectant of the embodiment of the present invention.

[0257] In the embodiments of the present invention, the term "plurality" refers to two or more, unless otherwise specified. Terms such as "installed," "connected," and "fixed" should be interpreted broadly. For example, "connected" can refer to a fixed connection, a detachable connection, or an integral connection. Those skilled in the art will understand the specific meanings of these terms in the embodiments of the present invention based on specific circumstances.

[0258] In the description of the embodiments of the present invention, it should be understood that the terms "upper" and "lower" and the like indicate directions or positional relationships based on the directions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the embodiments of the present invention and simplifying the description, rather than indicating or implying that the device or unit referred to must have a specific direction, be constructed and operated in a specific direction. Therefore, they cannot be understood as limitations on the embodiments of the present invention.

[0259] Throughout this specification, terms such as "one embodiment" and "a preferred embodiment" mean that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0260] The above is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations are possible in the present invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a cluster-modified chlorine dioxide solid disinfectant, characterized in that: include: dissolving the metal group cluster in a solvent to prepare a first impregnation solution; Immersing the porous alumina balls in the first impregnation solution to allow the first impregnation solution to enter the pores of the porous alumina balls; calcining the impregnated porous alumina beads to form metal oxides or metal clusters inside the porous alumina beads, thereby obtaining cluster-modified porous alumina beads; vacuum drying the cluster-modified porous alumina spheres; adding a stabilizer to the chlorine dioxide solution to prepare a second impregnation solution; Immersing the cluster-modified porous alumina beads in the second impregnation solution and sealing the solution at room temperature; The cluster-modified porous alumina beads after immersion are taken out, washed with deionized water, and the moisture on the surface of the cluster-modified porous alumina beads is absorbed with filter paper, and then dried to obtain porous alumina beads immobilized with chlorine dioxide.

2. The preparation method according to claim 1, characterized in that The metal group cluster includes one or more of TiO2 clusters, ZnO clusters, iron ion clusters, copper nanoclusters, silver nanoclusters, and perovskite clusters; the solvent of the first impregnation solution is one or more of ethylene glycol, water, ethanol, and N,N-dimethylformamide; the concentration of the first impregnation solution is 0.4-2.0 mol / L.

3. The preparation method according to claim 2, characterized in that The solvents of the first impregnation solution are water, ethanol and N,N-dimethylformamide, and the volume ratio of water, ethanol and N,N-dimethylformamide is 4:2:

1.

4. The preparation method according to claim 1, characterized in that The porous alumina balls are immersed in the first impregnation solution at a temperature of 30-70° C. for 6-24 hours; The porous alumina balls treated by impregnation are calcined at a temperature of 200-600° C. for a time of 1.0-8.0 h; The temperature for vacuum drying the cluster-modified porous alumina beads is 40-120° C., and the time for vacuum drying is 5.0 h-15.0 h.

5. The preparation method according to claim 1, characterized in that The stabilizer is one or more of sodium carboxymethyl cellulose, sodium bicarbonate, sodium chloride, sodium hydroxide, ethylenediamine, polyvinyl alcohol, and sodium bisulfite, and the concentration of the stabilizer in the second impregnation solution is 0.5-5 mol / L; The mass of the cluster-modified porous alumina beads is 40-150 g, and the soaking time in the second impregnation solution is 0.5-5.0 h; The cluster-modified porous alumina beads after immersion are washed 2-6 times with deionized water; The cluster-modified porous alumina beads after immersion are vacuum dried at a temperature of 30-80° C. for a vacuum drying time of 6.0 h to 14.0 h.

6. The preparation method according to claim 1, characterized in that Also includes: Solid alumina beads are mixed with a pore-forming agent, pseudo-boehmite and aluminum sol to prepare a sol, and the weak acidity of the system is controlled during the mixing process; The sol is dripped into a hot oil column forming device and solidified into a porous alumina wet ball; The porous alumina wet balls are heat-treated to obtain the porous alumina small balls; Washing the porous alumina balls with ethanol and deionized water in sequence; The washed porous alumina beads are vacuum dried.

7. The preparation method according to claim 6, characterized in that 200-300 parts by mass of the solid alumina beads, 50-500 parts by mass of the pore-forming agent, wherein the pore-forming agent is polymethyl methacrylate, 20-200 parts by mass of the pseudo-boehmite, and 20-200 parts by mass of the aluminum sol; During the mixing process of the solid alumina balls, the pore-forming agent, the pseudo-boehmite and the aluminum sol, citric acid monohydrate is used to control the weak acidity of the system, the amount of citric acid monohydrate added is 5-20 parts by mass, and the system temperature is 30-120° C.; The oil bath temperature of the hot oil column forming device is 80-100°C, and the drip acceleration rate is 10-80d / min; The porous alumina wet ball is heat treated at a temperature of 200° C. to 600° C. for a time of 0.5 h to 3.0 h; The porous alumina balls are washed 2-3 times with ethanol and deionized water respectively; The temperature for vacuum drying the porous alumina balls is 40° C.-120° C., and the vacuum drying time is 5.0 h-15.0 h.

8. The preparation method according to claim 7, characterized in that The mass ratio of the pore-forming agent, the pseudo-boehmite and the aluminum sol is (4-1):1:

1.

9. The preparation method according to claim 1, characterized in that Also includes: Sodium sulfite and sodium chlorate are added to ultrapure water as a solvent, and stirred in an ice bath until completely dissolved to obtain a first solution, wherein the concentration of the sodium sulfite is 2-6 mol / L, and the concentration of the sodium chlorate is 3-10 mol / L; Slowly dissolving an inorganic acid dropwise in the first solution under heating and uniform stirring conditions to prepare chlorine dioxide gas, wherein the inorganic acid is one or more of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, the concentration of the inorganic acid is 2-10 mol / L, and the heating temperature is 30-100° C.; Passing the chlorine dioxide gas generated by the reaction into a plurality of gas collecting bottles containing a mixed solution of hydrogen peroxide and sodium hydroxide in an ice bath, wherein the concentration of the hydrogen peroxide is 1-5 mol / L, and the concentration of the sodium hydroxide is 1-5 mol / L; After the reaction is completed, the first gas collecting bottle into which chlorine dioxide gas is introduced is collected and refrigerated.

10. A cluster-modified chlorine dioxide solid disinfectant, characterized in that: Prepared according to the method of claim 1.

11. A disinfection device comprising the cluster-modified chlorine dioxide solid disinfectant according to claim 10.

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