Cage-shaped nickel cobaltate material, preparation method thereof, slow-release sterilization type chlorine dioxide air freshener based on cage-shaped nickel cobaltate material and application of slow-release sterilization type chlorine dioxide air freshener

Abstract

According to the cage-shaped nickel cobaltate material, the preparation method thereof, the slow-release sterilization type chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material and the application of the slow-release sterilization type chlorine dioxide air freshener, the cage-shaped nickel cobaltate is obtained from the nickel-containing substance, the cobalt-containing substance and the potassium acetate through a high-temperature hydrothermal method, and the slow-release chlorine dioxide is obtained on the basis that the cage-shaped nickel cobaltate is loaded with the chlorine dioxide; the slow-release sterilization type chlorine dioxide air freshener is prepared from the chlorine dioxide powder, a light stabilizer, gel, modified negative oxygen ion powder, plant essential oil, auxiliaries and deionized water. The slow-release chlorine dioxide gas is mainly used for achieving the efficient broad-spectrum sterilization and bacteriostasis functions, chlorine dioxide makes contact with microorganisms and viruses in air, protein, DNA and RNA of the microorganisms and the viruses are damaged, the sterilization and disinfection functions are achieved for limited spaces such as rooms, automobiles and trains, and the continuous sterilization effect is achieved within 180 days. Meanwhile, the added modified negative oxygen ion powder has negative oxygen ion inducing performance and can synergistically sterilize and resist bacteria, so that the air quality is improved.

Description

Technical Field

[0001] The present invention belongs to the technical fields of material preparation, health and epidemic prevention, and disinfection technology, and relates to a cage-shaped nickel cobaltate material and a preparation method thereof, a slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material, and applications thereof. Background Art

[0002] Tourmaline is a complex silicate mineral with a ring structure characterized by boron, belonging to the trigonal crystal system, and having obvious pyroelectricity, piezoelectricity, and negative oxygen ion induction functions. The smaller the particle size of tourmaline, the larger the specific surface area, the higher the specific surface energy, and the more negative oxygen ions are induced. However, during the preparation and processing, agglomeration is very likely to occur, making the dispersion of tourmaline in the composite material uneven, thus affecting the comprehensive performance of the composite material. Therefore, chemical modification of tourmaline is required to inhibit its agglomeration without changing its intrinsic property of inducing negative oxygen ions.

[0003] Aerosol transmission is an important way for viruses to spread in the air. An aerosol refers to a dispersion system formed by solid or liquid particles stably suspended in a gas medium. Healthy uninfected people may be infected by inhaling aerosols containing viruses suspended in the air without direct contact with infected people. If the air in a limited indoor space does not flow, the virus can survive for a long time in such an environment. Therefore, ensuring good indoor ventilation, regularly disinfecting the indoor environment, and wearing masks to protect family members when suspected patients or mild patients are quarantined at home will help block the air transmission route of the virus.

[0004] Traditional air fresheners are mainly characterized by leaving a fragrance and freshening the air. With the rapid spread of viruses, it is particularly important to develop a new type of antibacterial and bactericidal solid air freshener that can not only improve the surrounding air environment, relieve people's fatigue, relieve drowsiness, and bring a sense of coolness, but also have a long-term bactericidal and bacteriostatic effect. How to develop a bactericidal and antibacterial air freshener while extending the bactericidal and antibacterial time is of great significance for inhibiting the spread of viruses in a limited indoor space and improving air quality.

[0005] A patent with the publication number CN 113854286 A, which was published on December 31, 2021, discloses a chlorine dioxide sustained-release agent and its preparation method and application, including a porous organic polymer material and a chlorite solution; the porous organic polymer material includes acidic sites. In the chlorine dioxide sustained-release agent provided by the present invention, the carrier is a porous organic polymer material, and the pore structure thereon can improve the loading amount of the chlorine dioxide precursor (aluminum chlorite); chlorite will release chlorine dioxide gas under acidic conditions, and the stronger the acidity, the faster the release. Therefore, increasing the acidic sites will increase the release rate. The porous organic polymer material has acidic sites, so it can activate chlorite to produce chlorine dioxide gas; the pore structure in the porous organic polymer material can regulate the diffusion rate of chlorine dioxide, that is, it can make the generated chlorine dioxide gas slowly release, extend the release period of chlorine dioxide, and the released strongly oxidizing chlorine dioxide gas can purify the air. However, the disclosed preparation raw materials of the porous organic polymer material include benzene-based acidic derivatives, and the preparation method is complex and the cost is high. Summary of the Invention

[0006] The purpose of the present invention is to provide a cage-shaped nickel cobaltate material and a preparation method, and use a simple method to prepare a cage-shaped nickel cobaltate, and the preparation method is simple and the cost is low.

[0007] Another purpose of the present invention is to provide a sustained-release bactericidal chlorine dioxide air freshener and application based on the cage-shaped nickel cobaltate material. By loading chlorine dioxide gas into the cage-shaped nickel cobaltate, the chlorine dioxide gas can reach a sustained-release effect through the adsorption-desorption equilibrium in the cage-shaped nickel cobaltate, and then achieve the effects of long-term, safe, non-toxic, and highly efficient sterilization and air purification. At the same time, chlorine dioxide has a certain function of oxidizing and decomposing formaldehyde.

[0008] The specific technical solution of the present invention is as follows:

[0009] The preparation method of the cage-shaped nickel cobaltate material provided by the present invention includes the following steps:

[0010] Mix a nickel source, a cobalt source and potassium acetate in polyethylene glycol, stir and mix to obtain a mixed solution, heat and react, dry after cooling, and calcine to obtain a cage-shaped nickel cobaltate material;

[0011] The mass ratio of the nickel source, the cobalt source and potassium acetate is 25-35:55-65:45-50, and the pH value of the mixed solution is controlled to be 8.0-9.5;

[0012] The nickel source is selected from nickel sulfate;

[0013] The cobalt source is selected from cobalt sulfate;

[0014] The polyethylene glycol is selected from polyethylene glycol-800;

[0015] The dosage ratio of the nickel source to polyethylene glycol is 0.25 - 0.45 g / m;

[0016] For the heating reaction, in an autoclave, maintain the reaction at 220 - 300 °C for 12 - 18 h;

[0017] After the heating reaction ends, cool it in air, wash it with deionized water 3 - 5 times, and dry it to a constant weight;

[0018] The calcination means calcining in a muffle furnace in an air atmosphere at 380 - 450 °C for 2 - 5 h; after calcination, cool it with the furnace, and finally obtain cage-shaped nickel cobaltate;

[0019] A cage-shaped nickel cobaltate material provided by the present invention is prepared by the above method. The cage-shaped nickel cobaltate material has a hollow structure inside, with undulating surfaces, showing interlaced textures. The overall hollow cage-shaped cuboid has a length of 10 - 20 μm, a width of 3 - 7 μm, and a height of 3 - 7 μm.

[0020] The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material provided by the present invention is prepared using the cage-shaped nickel cobaltate material.

[0021] The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material comprises the following raw materials in parts by mass: 10 - 15 parts of slow-release chlorine dioxide, 0.1 - 0.3 part of light stabilizer, 2 - 3 parts of gelling agent, 3 - 9 parts of negative oxygen ion powder, 0.1 - 1.5 parts of auxiliary agent, 0.5 - 1.0 part of alkaline regulator, 0.5 - 1.0 part of plant essential oil, and 10 - 82 parts of deionized water.

[0022] The preparation method of the slow-release chlorine dioxide is as follows: Mix the cage-shaped nickel cobaltate material with a saturated aqueous solution of chlorine dioxide, continuously stir at 15 - 20 °C for 15 - 24 h, continue to add the same amount of saturated aqueous solution of chlorine dioxide after vacuum filtration, cycle 3 - 5 times according to the same method, and finally centrifuge to obtain slow-release chlorine dioxide;

[0023] Among them, the mass ratio of the cage-shaped nickel cobaltate to the saturated aqueous solution of chlorine dioxide is 18 - 25:40 - 60.

[0024] The slow-release chlorine dioxide is obtained by obtaining cage-shaped nickel cobaltate from a nickel-containing substance, a cobalt-containing substance, and potassium acetate through a high-temperature hydrothermal method; then mixing and adsorbing the cage-shaped nickel cobaltate with a saturated aqueous solution of chlorine dioxide to obtain slow-release chlorine dioxide. The present invention uses an impregnation method to load the saturated chlorine dioxide solution into the cage-shaped nickel cobaltate, and through the adsorption-desorption equilibrium, the chlorine dioxide gas can achieve a slow-release effect.

[0025] The light stabilizer is composed of an antioxidant and a light absorber in a mass ratio of 1:1 to 1:5. Among them, the antioxidant is 2,6-tert-butyl-4-methylphenol and / or bis(3,5-tert-butyl-4-hydroxyphenyl)sulfide, and the light absorber is dihydroartemisinin, erythromycin or kanamycin.

[0026] The gelling agent is one or more of carbomer, sodium carboxymethyl cellulose and xanthan gum;

[0027] The preparation method of the modified negative oxygen ion powder is as follows: solid-phase reaction of mica powder and tourmaline powder in a B2O3 atmosphere at a high temperature of 600 °C to 900 °C for 5 to 10 h; among them, the mass ratio of mica powder to tourmaline powder is 1:5 to 1:10, the mica powder has a flaky structure with a diameter of 0.1 to 0.5 μm, and the particle size of the tourmaline powder is 1 to 20 μm. High-temperature compounding is carried out through the Si-O-Si bonds in mica powder and tourmaline powder.

[0028] The auxiliary agent is one or a combination of several of disodium ethylenediaminetetraacetate, glycerol or polyethylene glycol;

[0029] The alkaline regulator is one or a combination of several of sodium hydroxide, triethanolamine, potassium hydroxide;

[0030] The plant essential oil is one or more of rose essential oil, peppermint essential oil and lavender essential oil.

[0031] The preparation method of the slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material is as follows:

[0032] 1) Add the formulated amount of gelling agent to deionized water and soak at room temperature for 12 to 24 h, add the auxiliary agent, and after ultrasonic dispersion, obtain mixture A;

[0033] 2) Add the light stabilizer to mixture A and stir evenly, then add slow-release chlorine dioxide and stir evenly to obtain mixture B;

[0034] 3) Mix and stir mixture B with plant essential oil and negative oxygen ion powder, then add the alkaline regulator to adjust the pH value of the gel to 7 to 8 to obtain mixture C, that is, the slow-release bactericidal chlorine dioxide air freshener.

[0035] The application of the slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material provided by the present invention is used for indoor sterilization and disinfection, and has a continuous bactericidal effect within 210 days.

[0036] The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material provided by the present invention can be used as a slow-volatile air freshener to play the functions of bactericidal and bacteriostatic and air freshening in the air. This product has a bactericidal and disinfection function for limited spaces such as rooms, cars and trains, and has a continuous bactericidal effect within 180 days.

[0037] Compared with the prior art, the present invention has the following effects:

[0038] 1. In the present invention, chlorine dioxide gas is loaded into cage-shaped nickel cobaltate, so that the chlorine dioxide gas reaches a slow release effect through the adsorption-desorption equilibrium in the cage-shaped nickel cobaltate, and further achieves the effects of long-acting, safe, non-toxic and efficient sterilization and air purification. At the same time, chlorine dioxide has a certain function of oxidizing and decomposing formaldehyde. The added plant essential oil has the function of purifying the air and improving the surrounding air environment.

[0039] 2. The modified negative oxygen ion powder added in the present invention is formed by the high-temperature solid-phase reaction of mica and tourmaline powder. Through the high-temperature compounding of the Si-O-Si bonds in mica powder and tourmaline powder, the flaky mica can reduce the agglomeration of tourmaline powder and improve the dispersion performance of the modified negative oxygen ion powder in the gel. The negative oxygen ions induced by the modified negative oxygen ion powder can form a negative ion protection layer in the air, reduce high-voltage static electricity, have a certain sterilization and virus inhibition effect, and improve the air quality.

[0040] 3. Nickel cobaltate belongs to double metal oxides with high morphology controllability, and its morphology is related to the acidity and alkalinity in the preparation process. The present invention reports a preparation method of cage-shaped nickel cobaltate. Specifically, potassium acetate is used to form a weak alkaline environment (pH 8.0-9.5) to adjust the acidity and alkalinity of nickel source and cobalt source in the hydrothermal reaction of polyethylene glycol. Through calcination, a cage-shaped structure is finally formed, providing space for loading chlorine dioxide, which can slow down the release rate of chlorine dioxide in the gel and achieve the slow release effect.

[0041] 4. The present invention mainly uses the slowly released chlorine dioxide gas to achieve the functions of high-efficiency broad-spectrum sterilization and antibacterial. Chlorine dioxide contacts with microorganisms and viruses in the air, destroys their proteins, DNA and RNA, has the function of sterilization and disinfection in limited spaces such as rooms, cars and trains, and has a continuous sterilization effect within 180 days. At the same time, the added modified negative oxygen ion powder has the performance of inducing negative oxygen ions, which can cooperate with sterilization and antibacterial and improve the air quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of the operation steps for preparing slow-release chlorine dioxide in Example 1 of the present invention;

[0043] Figure 2 Scanning electron microscope (SEM) photograph of the cage-shaped nickel cobaltate prepared in Example 1 of the present invention;

[0044] Figure 3 Simulated structure diagram of cobaltate nickel coated with chlorine dioxide prepared in Example 1 of the present invention;

[0045] Figure 4 X-ray diffraction spectrum (XRD) of the cobaltate nickel prepared in Example 1 provided by the embodiment of the present invention;

[0046] Figure 5 This is the infrared absorption spectrum (FT-IR) of nickel cobaltate prepared in Example 1 of the present invention;

[0047] Figure 6 This is the X-ray photoelectron spectroscopy (XPS) spectrum of cage-shaped nickel cobaltate prepared in Example 1 provided by the embodiments of the present invention;

[0048] Figure 7 Schematic diagram of the modified negative oxygen ion powder prepared in Example 1 of the present invention. Detailed implementation manners

[0049] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0050] The test materials and reagents used in the following embodiments, unless otherwise specified, can all be obtained through commercial channels.

[0051] For those embodiments where specific technologies or conditions are not indicated, they can all be carried out according to the technologies or conditions described in the literature in this field or according to the product specifications.

[0052] Example 1

[0053] Preparation method of a slow-release bactericidal chlorine dioxide air freshener based on cage-shaped nickel cobaltate material:

[0054] 1) Preparation of slow-release chlorine dioxide:

[0055] 1-1) Dissolve 30.2 g of nickel sulfate, 61.3 g of cobalt sulfate and 49.5 g of potassium acetate in 100 mL of polyethylene glycol (PEG-800). After stirring evenly, the pH value of the mixed solution is 8.8. Then put the mixture into a stainless steel autoclave with a polytetrafluoroethylene liner, keep it at 280 °C for 15 h, cool it in air, wash it 5 times with deionized water, and dry it; calcine it in a muffle furnace at 380 °C for 3 h, and cool it with the furnace. Finally, nickel cobaltate powder, that is, cage-shaped nickel cobaltate material, is obtained. The microscopic morphology photo is shown in Figure 2 ; The inside of the nickel cobaltate powder is a hollow structure, with undulating surfaces and interlaced textures, presenting an overall cage-like shape similar to a cuboid. This structure provides sufficient access channels and internal space for the loading and adsorption-desorption balance of chlorine dioxide.

[0056] (1-2) Take 20 g of nickel cobaltate powder (cage-shaped nickel cobaltate material) and mix it with 50 mL of saturated aqueous chlorine dioxide solution. Continuously stir slowly at 20 °C for 20 h. After vacuum filtration, continue to add the same amount of saturated aqueous chlorine dioxide solution. After 4 cycles, perform centrifugal separation to obtain slow-release chlorine dioxide. The simulated structure of nickel cobaltate-coated chlorine dioxide is shown in Figure 3 . The external cuboid cage structure is the nickel cobaltate skeleton prepared by the hydrothermal method, and the internal red spheres are chlorine dioxide loaded into the skeleton using the vacuum impregnation method (see Figures 4 - 6 ).

[0057] From Figure 4 , obvious diffraction peaks are observed at 31.3°, 36.7°, 44.4°, 55.7°, 59.1°, and 64.9°, corresponding to the five crystal planes of (220), (311), (400), (422), (511), and (440). This is in complete agreement with the corresponding situation of the nickel cobaltate standard card (JCPDS No. 02-1074), and there are no impurity peaks between the diffraction peaks, indicating that the prepared nickel cobaltate has a high purity. At the same time, the infrared spectrum of the prepared nickel cobaltate is shown in Figure 5 , and the stretching vibrations of Ni-O and Co-O bonds at 555 cm -1 and 652 cm -1 prove the existence of chemical bonds in the self-made nickel cobaltate. XPS ( Figure 6 ) is used to further characterize the more detailed elemental composition information and elemental oxidation state information of the prepared nickel cobaltate. For the Ni element, there are two spin-orbit doublets with Ni 2+ and Ni 3+ characteristics, and two oscillating satellite peaks on its 2p orbital, as shown in Figure 6 b. For the Co element, as shown in its 2p emission spectrum, two spin-orbit doublets with Co 2+ and Co 3+ characteristics and a recombined satellite peak can be fitted, as shown in Figure 6 c. For the O element, its emission spectrum can be well fitted with three sub-peaks. Among them, the peak at 529.2 eV is a typical metal-oxygen bond, and the peaks at 532.6 eV and 530.8 eV correspond to low oxygen defects and adsorbed water defects on the surface or nearby, respectively. See Figure 6 d for details.

[0058] (2) Preparation of modified negative oxygen ion powder

[0059] It is to carry out high-temperature solid-phase reaction in a tubular furnace with 100 g of mica powder and 500 g of tourmaline powder in a B2O3 atmosphere at 700 °C (5 g of B2O3 is added in the tubular furnace to form a B2O3 atmosphere at high temperature). Through the high-temperature composite of the Si-O-Si bonds in the mica powder and tourmaline powder, the mica powder has a flaky structure with a diameter of 0.1 - 0.5 μm, and the particle size of the tourmaline powder is 1 - 20 μm. After 8 h of high-temperature solid-phase reaction, it is cooled with the furnace, and finally, the modified negative oxygen ion powder is obtained. The microscopic morphology photos are shown in Figure 7 , Figure 7 It can be observed that through the high-temperature solid-phase reaction, the mica powder can inhibit the agglomeration of the tourmaline powder, and subsequently improve the dispersion performance of the modified negative oxygen ion powder in the gel.

[0060] 3) Preparation of slow-release bactericidal chlorine dioxide air freshener:

[0061] 3-1) Soak 2 g of xanthan gum and 1 g of carbomer in 73 g of deionized water, add 0.2 g of disodium ethylenediaminetetraacetate, and after ultrasonic dispersion for 5 h, obtain mixture A;

[0062] 3-2) After adding 0.3 g of light stabilizer to mixture A and stirring evenly, then add 15 g of self-made slow-release chlorine dioxide and stir evenly to obtain mixture B; The 0.3 g of light stabilizer used consists of 0.1 g of 2,6-tert-butyl-4-methylphenol and 0.2 g of erythromycin;

[0063] 3-3) Mix mixture B with 0.5 g of rose essential oil and 8 g of modified negative oxygen ion powder, and then adjust the pH value to pH 7.5 with sodium hydroxide to obtain mixture C, that is, the slow-release bactericidal chlorine dioxide air freshener.

[0064] 3-4) Fill the slow-release bactericidal chlorine dioxide air freshener into a plastic box with holes, package it, and obtain a commercially available air freshener. The obtained slow-release bactericidal chlorine dioxide air freshener has a bactericidal and disinfection function for limited spaces such as rooms, cars, and trains, and has a continuous bactericidal effect within 180 days.

[0065] Application and evaluation of the above-prepared slow-release bactericidal chlorine dioxide air freshener:

[0066] In 30 m 3Indoor room, windows closed, door closed after each sampling, environmental temperature 15 - 20°C, humidity 55 - 75%, no forced ventilation (air conditioner, electric fan, etc. are turned off). Place them diagonally. Place 2 fragrance bottles containing 100 mL of the air freshener prepared in Example 1 above at an equal distance on a shelf 1 meter above the ground along the AC diagonal, and open the bottle caps. During the antibacterial experiment, place three petri dishes with a diameter of 9 cm at an equal distance on a shelf 1 meter above the ground along the BD diagonal, and conduct the experiment according to the disinfection and antibacterial test specifications (2002 edition standard). After cultivation, measure the number of colonies in the three petri dishes, calculate the average, and then calculate the antibacterial rate. The specific results are shown in Table 1.

[0067] Table 1 Antibacterial rate of the air freshener in Example 1 at different times

[0068] Time / day 1 14 28 49 100 150 180 210 Bacteriostatic rate % 99.9 99.9 99.9 99.9 95.6 94.5 93.8 89.1

[0069] As can be seen from Table 1, after 210 days, the antibacterial rate is still as high as 89.1%.

[0070] Example 2

[0071] Preparation method of a slow-release bactericidal chlorine dioxide air freshener based on a cage-like nickel cobaltate material: The same as Example 1, except that the calcination temperature of nickel cobaltate in the muffle furnace is 420°C and the calcination time is 3 h. To determine the successful preparation of nickel cobaltate (NiCo2O4), the component test of the calcined product was carried out using an X-ray diffractometer (XRD), and the results are consistent with those recorded in Example 1. The application process is the same as that in Example 1, and the specific bactericidal effects after 180 days and 210 days are shown in Table 2 for details.

[0072] Example 3

[0073] Preparation method of a slow-release bactericidal chlorine dioxide air freshener based on a cage-like nickel cobaltate material: The same as Example 1, except that during the preparation of the air freshener, all 3 g of xanthan gum is used as the gelling agent, and carbomer is not added. Their application process is the same as that in Example 1, and the specific bactericidal effects after 180 days and 210 days are shown in Table 2 for details.

[0074] Comparative Example 1

[0075] Preparation method of a slow-release bactericidal chlorine dioxide air freshener based on a cage-like nickel cobaltate material: The same as Example 1, except that during the preparation of the air freshener, add 8 g of modified negative oxygen ion powder is changed to 8 g of deionized water, Their application process is the same as that in Example 1, and the specific bactericidal effects after 180 days and 210 days are shown in Table 2 for details.

[0076] Comparative Example 2

[0077] Preparation method of slow-release bactericidal chlorine dioxide air freshener based on cage-shaped nickel cobaltate material: The same as Example 1, except that in the preparation process of the air freshener, the addition of 15 g of slow-release chlorine dioxide is changed to add 15 g of deionized water , and the application process is the same as that of Example 1. The specific bactericidal effects after 180 days and 210 days are shown in Table 2.

[0078] Comparative Example 3

[0079] Preparation method of slow-release bactericidal chlorine dioxide air freshener based on cage-shaped nickel cobaltate material: The same as Example 1, except that in the preparation process of the air freshener, the addition of 15 g of slow-release chlorine dioxide is changed to add 15 g of saturated chlorine dioxide solution , and their application processes are the same as that of Example 1. The specific bactericidal effects after 180 days and 210 days are shown in Table 2.

[0080] Comparative Example 4

[0081] Preparation method of slow-release bactericidal chlorine dioxide air freshener based on cage-shaped nickel cobaltate material: The same as Example 1, except that in the preparation process of the air freshener, the addition of 15 g of slow-release chlorine dioxide and 8 g of modified negative oxygen ion powder are changed to add 23 g of deionized water, Their application processes are the same as that of Example 1. The specific bactericidal effects after 180 days and 210 days are shown in Table 2.

[0082] Table 2 Bacteriostatic rates of air fresheners in each example and comparative example

[0083]

[0084]

[0085] By comprehensively comparing the bactericidal effects of the air fresheners prepared in different examples and comparative examples after 180 days and 210 days, it can be found that the modified negative oxygen ion powder has a synergistic effect on the bactericidal efficiency of slow-release chlorine dioxide. When only slow-release chlorine dioxide is added without adding the modified negative oxygen ion powder, the antibacterial and bactericidal rates of the product are significantly lower than those of the examples after 180 days; if only negative oxygen ion powder is added to the air freshener, the antibacterial and bactericidal rates of the product are extremely low after 180 days; at the same time, when neither slow-release chlorine dioxide nor modified negative oxygen ion powder is added, the product has no bactericidal effect after 180 days; if the cage-shaped nickel cobaltate loaded saturated chlorine dioxide solution prepared according to the examples of the present invention is not used, the volatilization rate of chlorine dioxide in the air freshener is fast, and the antibacterial effect becomes significantly worse after long-term placement.

[0086] The slow-release bactericidal chlorine dioxide air freshener of the present invention realizes the slow-release function mainly through loading a saturated chlorine dioxide solution on cage-shaped nickel cobaltate; it uses the vacuum impregnation method to load the chlorine dioxide saturated solution into the self-made cage-shaped nickel cobaltate, and then achieves the slow-release effect through the adsorption-desorption equilibrium; the air freshener of the present invention has a bactericidal and disinfection function for limited spaces such as rooms, cars and trains, and has a continuous bactericidal effect within 210 days; and it achieves high-efficiency and broad-spectrum sterilization. At the same time, adding negative ion powder in the components has the performance of inducing negative ions, which can synergistically sterilize and antibacterial, and improve the air quality.

[0087] Those underlined above do not meet the requirements of the present invention.

[0088] The description of the above embodiments is for the convenience of those of ordinary skill in the art to understand and use the invention. It is obvious that those who are familiar with the technology in this field can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art without departing from the scope of the present invention according to the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. Preparation method of cage-shaped nickel cobaltate material, characterized in that, The preparation method includes the following steps: Mix a nickel source, a cobalt source and potassium acetate in polyethylene glycol, stir and mix to obtain a mixed solution, heat and react, dry after cooling, and calcine to obtain a cage-shaped nickel cobaltate material.

2. The preparation method according to claim 1, wherein The mass ratio of the nickel source, the cobalt source and potassium acetate is 25-35:55-65:45-50, and the pH value of the mixed solution is controlled to be 8.0-9.

5.

3. The preparation method according to claim 1 or 2, characterized in that, For the heating reaction, in an autoclave, keep the temperature at 220-300 °C for 12-18 h.

4. The preparation method according to claim 1 or 2, characterized in that, The calcination means calcining in a muffle furnace at 380-450 °C for 2-5 h.

5. A cage-shaped nickel cobaltate material prepared by the preparation method according to any one of claims 1-4, characterized in that, The cage-shaped nickel cobaltate material has a hollow structure inside, with undulating surfaces and interlaced textures. The overall hollow cage-shaped cuboid has a length of 10-20 μm, a width of 3-7 μm, and a height of 3-7 μm.

6. The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material is characterized in that, It is prepared by using the cage-shaped nickel cobaltate material described in claim 5.

7. The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material according to claim 6, characterized in that, The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material includes the following raw materials in parts by mass: 10-15 parts of slow-release chlorine dioxide, 0.1-0.3 part of a light stabilizer, 2-3 parts of a gelling agent, 3-9 parts of negative oxygen ion powder, 0.1-1.5 parts of an auxiliary agent, 0.5-1.0 part of an alkaline regulator, 0.5-1.0 part of plant essential oil, and 10-82 parts of deionized water; the preparation method of the slow-release chlorine dioxide is: mix the cage-shaped nickel cobaltate with a saturated aqueous solution of chlorine dioxide, continuously stir at 15-20 °C for 15-24 h, continue to add the same amount of saturated aqueous solution of chlorine dioxide after vacuum filtration, cycle 3-5 times according to the same method, and finally perform centrifugal separation to obtain slow-release chlorine dioxide; wherein, the mass ratio between the cage-shaped nickel cobaltate and the saturated aqueous solution of chlorine dioxide is 18-25:40-60.

8. The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material according to claim 7, characterized in that, The preparation method of the modified negative oxygen ion powder is: carry out a solid-phase reaction on mica powder and tourmaline powder in a B2O3 atmosphere at a high temperature of 600 °C-900 °C for 5-10 h. The alkaline regulator is one or a combination of sodium hydroxide, triethanolamine, and potassium hydroxide.

9. The slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material according to claim 7, characterized in that, The preparation method of the slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material is as follows: 1) Add the formulated amount of gelling agent to deionized water and soak for 12-24 h, add the auxiliary agent, and perform ultrasonic dispersion to obtain mixture A; 2) Add the light stabilizer to mixture A and stir evenly, then add the slow-release chlorine dioxide and stir evenly to obtain mixture B; 3) Mix and stir mixture B with plant essential oil and negative oxygen ion powder, then add the alkaline regulator to adjust the pH value of the gel to 7-8 to obtain mixture C, that is, obtain the slow-release bactericidal chlorine dioxide air freshener.

10. Use of the slow-release bactericidal chlorine dioxide air freshener based on the cage-shaped nickel cobaltate material according to any one of claims 6-9, characterized in that, It is used for indoor sterilization and disinfection.

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