Material capable of releasing negative oxygen ions and preparation method thereof

Abstract

The invention relates to the technical field of functional materials, and discloses a material capable of releasing negative oxygen ions and a preparation method thereof.The preparation method comprises the following steps that kieselguhr, nanometer titania and modified graphene oxide are added into deionized water, ultrasonic dispersion is conducted for 30-35 min, and composite slurry is prepared; the preparation method comprises the following steps: firstly preparing a slurry, then activating modified tourmaline by a planetary ball mill until the particle size D50 is 1-2 microns, adding the activated modified tourmaline into the slurry, stirring for 30-40 minutes at the high speed of 700-800 rpm at the temperature of 50-60 DEG C, then adding citric acid and gamma-aminopropyltriethoxysilane, reducing the speed to 300-400 rpm, continuously mixing for 25-35 minutes, and drying for 1-2 hours at the temperature of 50-70 DEG C to obtain the material capable of releasing negative oxygen ions. The material capable of releasing the negative oxygen ions not only can efficiently release the negative oxygen ions, but also has a good antibacterial effect.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, specifically to a material that can release negative oxygen ions and its preparation method. Background Technology

[0002] With increasing health awareness, people are demanding higher air quality in their living environments. Negative oxygen ions, known as "air vitamins," have bactericidal, dust-reducing, deodorizing, and cardiopulmonary-improving effects, and are widely used in environmental protection, medical, and health products. However, existing negative oxygen ion releasing materials suffer from low release efficiency, poor stability, and insufficient environmental friendliness. Therefore, avoiding these problems is key to solving the issue. Developing a highly efficient, stable, low-cost, and environmentally friendly material that can release negative oxygen ions has significant market value and social significance. For example, patent CN119424711A discloses a bio-composite liquid material that can release negative oxygen ions, its preparation method, and its application. This invention's bio-composite liquid material has the characteristic of highly efficient negative oxygen ion release, effectively improving air quality. It also exhibits good stability, ease of use, and safety, but its antibacterial properties need improvement. Summary of the Invention

[0003] (a) Technical problems to be solved

[0004] To address the shortcomings of existing technologies, this invention provides a material capable of releasing negative oxygen ions and its preparation method. The material prepared by this invention not only releases negative oxygen ions efficiently but also has good antibacterial effects.

[0005] (II) Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a material capable of releasing negative oxygen ions, comprising the following weight components: 5-8 parts by weight of modified tourmaline, 12-15 parts by weight of diatomaceous earth, 4-6 parts by weight of nano-titanium dioxide, 2-4 parts by weight of modified graphene oxide, 0.8-1 parts by weight of citric acid, 1-1.5 parts by weight of γ-aminopropyltriethoxysilane, and 3-5 parts by weight of deionized water.

[0007] Furthermore, the preparation method of the modified tourmaline is as follows:

[0008] Step 1: Add distilled water and anhydrous ethanol to the reactor to prepare a solution. Add tourmaline powder to the solution, sonicate for 10-15 min, heat to 60-65℃ and stir for 10-12 min. Then slowly add vinyltrimethoxysilane dropwise and stir the reaction for 2-3 h. After the reaction is complete, wash the reaction product with ethanol, filter and dry to obtain alkenylated tourmaline.

[0009] Step 2: Place cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone in a reactor, stir and mix, heat to 90-100℃, then add acrylic acid dropwise, and react at 95-100℃ for 5-8 hours. After the reaction is complete, cool, filter and dry to obtain intermediate 1.

[0010] Step 3: Add alkenylated tourmaline to deionized water and sonicate for 8-12 minutes. Add intermediate 1 and methacryloyl ethyl sulfobetaine, stir and mix, and purge with nitrogen for 20-30 minutes to remove oxygen. Then add azobisisobutyronitrile and react at 80-100℃ for 6-8 hours. After the reaction is complete, filter, wash and dry to obtain modified tourmaline.

[0011] Furthermore, in step one, the ratio of distilled water, anhydrous ethanol, tourmaline, and vinyltrimethoxysilane is 48-52 mL: 8-10 mL: 10-10.5 g: 2-2.06 mL.

[0012] Furthermore, in step two, the ratio of cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid is 30.4-30.8g: 0.53-0.57g: 0.01-0.03g: 5.22-5.26g.

[0013] Furthermore, in step three, the ratio of deionized water, alkenylated tourmaline, intermediate 1, methacryloyl ethyl sulfobetaine, and azobisisobutyronitrile is 20-25 mL: 2.54-2.58 g: 4.02-4.06 g: 3.65-3.68 g: 0.16-0.2 g.

[0014] Furthermore, the method for preparing the modified graphene oxide is as follows:

[0015] S1: Gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1-hydroxybenzotriazole were added to an N,N-dimethylformamide solution and stirred in an ice-water bath at 0-5°C for 1-2 hours. Taurine and triethylamine were then added, and the reaction was continued with stirring for 30-40 minutes. The mixture was then brought to room temperature and reacted for 20-24 hours. After the reaction was completed, the mixture was precipitated and washed with anhydrous ethanol and purified to obtain intermediate 2.

[0016] S2: Dissolve graphene oxide in deionized water and sonicate in an ice bath for 1-1.5 hours using an ultrasonic probe. Adjust the pH to 4-5 with 0.1 mol / L dilute hydrochloric acid solution. Then add intermediate 2 and stir magnetically for 22-26 hours. After the reaction is complete, dialyze using an 800-1000 Da dialysis bag for 45-50 hours. Wash and dry to obtain modified graphene oxide.

[0017] Further, the ratio of N,N-dimethylformamide, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole, taurine, and triethylamine in S1 is 15-20 mL: 1.71-1.75 g: 2.49-2.53 g: 1.54-1.58 g: 1.62-1.66 g: 3.30-3.07 g.

[0018] Furthermore, the ratio of graphene oxide, deionized water, dilute hydrochloric acid, and intermediate 2 in S2 is 25-30 mg: 100-120 mL: 0.02-0.03 mL: 125-128 mg.

[0019] Furthermore, the preparation method of the material that can release negative oxygen ions is as follows: First, diatomaceous earth, nano-titanium dioxide, and modified graphene oxide are added to deionized water and ultrasonically dispersed for 30-35 minutes to prepare a composite slurry; then, modified tourmaline is activated by a planetary ball mill to a particle size D50 of 1-2 μm and added to the slurry. The mixture is stirred at 700-800 rpm at 50-60℃ for 30-40 minutes. Then, citric acid and γ-aminopropyltriethoxysilane are added, and the mixing speed is reduced to 300-400 rpm and mixed for 25-35 minutes. The mixture is then dried at 50-70℃ for 1-2 hours to obtain the material that can release negative oxygen ions.

[0020] (III) Beneficial Technical Effects

[0021] This invention involves reacting vinyltrimethoxysilane with tourmaline. Vinyltrimethoxysilane hydrolyzes upon contact with water, and the resulting silanol reacts with the hydroxyl groups on the surface of tourmaline under certain conditions, thereby introducing carbon-carbon double bonds that can react with polymers onto the tourmaline surface. This produces an alkenylated tourmaline with polymerization capabilities. Cashew phenol glycidyl ether and acrylic acid are reacted to generate intermediate 1, which imbues cashew phenol with an alkenyl group. Subsequently, it is polymerized with methacryloyl ethyl sulfobetaine and the alkenylated tourmaline to obtain modified tourmaline. The long carbon chain on the cashew phenol is hydrophobic, preventing tourmaline agglomeration and allowing for better adhesion to diatomaceous earth. The sulfonic acid groups in methacryloyl ethyl sulfobetaine can absorb... Water molecules are attached to promote the ionization of the tourmaline surface, improving the material's negative ion release efficiency. The reaction of gallic acid and taurine to generate intermediate 2 imbues the gallic acid with sulfonic acid groups, which are then grafted onto graphene oxide for modification. The phenolic hydroxyl groups of gallic acid can disrupt bacterial cell membranes, causing leakage of contents and enhancing the material's antibacterial effect. Tourmaline is a source of negative oxygen ions, continuously releasing them. These negative oxygen ions can disrupt bacterial cell membranes, leading to cell structure damage. The synergistic effect of graphene oxide and nano-titanium dioxide enhances the generation of reactive oxygen species, improving the material's antibacterial effect. Furthermore, graphene oxide possesses excellent conductivity, a large specific surface area, and surface functionality, which can further enhance the negative oxygen ion release capacity of tourmaline. Attached Figure Description

[0022] Figure 1 This is the synthesis reaction formula for intermediate 1.

[0023] Figure 2 It is the synthesis reaction formula for intermediate 2. Detailed Implementation

[0024] 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 are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific embodiments.

[0026] Example 1

[0027] (1) Add 48 mL of distilled water and 8 mL of anhydrous ethanol to the reactor to prepare a solution. Add 10 g of tourmaline powder to the solution, sonicate for 10 min, heat to 60 °C and stir for 10 min. Then slowly add 2 mL of vinyltrimethoxysilane and stir for 2 h. After the reaction is completed, wash the reaction product with ethanol, filter and dry to obtain alkenylated tourmaline.

[0028] (2) Place 30.4g of cashew phenol glycidyl ether, 0.53g of triphenylphosphine and 0.01g of hydroquinone in a reactor, stir and mix, heat to 90℃, then add 5.22g of acrylic acid dropwise, react at 95℃ for 5h, after the reaction is completed, cool, filter and dry to obtain intermediate 1;

[0029] (3) Add 2.54 g of alkenyl tourmaline to 20 mL of deionized water, sonicate for 8 min, add 4.02 g of intermediate 1 and 3.65 g of methacryloyl ethyl sulfobetaine, stir and mix, purge with nitrogen for 20 min to remove oxygen, then add 0.16 g of azobisisobutyronitrile, react at 80 °C for 6 h, after the reaction is complete, filter, wash and dry to obtain modified tourmaline;

[0030] (4) Add 1.71 g of gallic acid, 2.49 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1.54 g of 1-hydroxybenzotriazole to 15 mL of N,N-dimethylformamide solution. Stir for 1 h in an ice-water bath at 0 °C. Add 1.62 g of taurine and 3.30 g of triethylamine. Continue stirring for 30 min. Then restore to room temperature and react for 20 h. After the reaction is complete, precipitate and wash with anhydrous ethanol to purify and obtain intermediate 2.

[0031] (5) Dissolve 25 mg of graphene oxide in 100 mL of deionized water, sonicate in an ice bath for 1 h using an ultrasonic probe, add 0.02 mL of 0.1 mol / L dilute hydrochloric acid solution to adjust the pH to 4, then add 125 mg of intermediate 2, stir magnetically for 22 h, after the reaction is complete, dialyze using an 800 Da dialysis bag for 45 h, wash and dry to obtain modified graphene oxide.

[0032] (6) First, add 12 parts by weight of diatomaceous earth, 4 parts by weight of nano titanium dioxide and 2 parts by weight of modified graphene oxide to 3 parts by weight of deionized water and ultrasonically disperse for 30 min to prepare a composite slurry; then, activate 5 parts by weight of modified tourmaline to a particle size D50 of 1 μm using a planetary ball mill and add it to the slurry. Stir at 700 rpm for 30 min at 50 °C. Then, add 0.8 parts by weight of citric acid and 1 part by weight of γ-aminopropyltriethoxysilane, reduce the speed to 300 rpm and continue mixing for 25 min. Dry at 50 °C for 1 h to obtain a material that can release negative oxygen ions.

[0033] Example 2

[0034] (1) Add 52 mL of distilled water and 10 mL of anhydrous ethanol to the reactor to prepare a solution. Add 10.5 g of tourmaline powder to the solution, sonicate for 15 min, heat to 65 °C and stir for 12 min. Then slowly add 2.06 mL of vinyltrimethoxysilane and stir for 3 h. After the reaction is complete, wash the reaction product with ethanol, filter and dry to obtain alkenylated tourmaline.

[0035] (2) Place 30.8g of cashew phenol glycidyl ether, 0.57g of triphenylphosphine and 0.03g of hydroquinone in a reactor, stir and mix, heat to 100℃, then add 5.26g of acrylic acid dropwise, and react at 100℃ for 8h. After the reaction is completed, cool, filter and dry to obtain intermediate 1.

[0036] (3) Add 2.58g of alkenylated tourmaline to 25mL of deionized water, sonicate for 12min, add 4.06g of intermediate 1 and 3.68g of methacryloyl ethyl sulfobetaine, stir and mix, purge with nitrogen for 30min to remove oxygen, then add 0.2g of azobisisobutyronitrile, react at 100℃ for 8h, after the reaction is completed, filter, wash and dry to obtain modified tourmaline;

[0037] (4) Add 1.75 g of gallic acid, 2.53 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1.58 g of 1-hydroxybenzotriazole to 20 mL of N,N-dimethylformamide solution. Stir for 2 h in an ice-water bath at 5 °C. Add 1.66 g of taurine and 3.07 g of triethylamine. Continue stirring for 40 min. Then restore to room temperature and react for 24 h. After the reaction is complete, precipitate and wash with anhydrous ethanol to purify and obtain intermediate 2.

[0038] (5) Dissolve 30 mg of graphene oxide in 120 mL of deionized water, sonicate in an ice bath for 1.5 h using an ultrasonic probe, add 0.03 mL of 0.1 mol / L dilute hydrochloric acid solution to adjust the pH to 5, then add 128 mg of intermediate 2, stir magnetically for 26 h, after the reaction is complete, dialyze using a 1000 Da dialysis bag for 50 h, wash and dry to obtain modified graphene oxide;

[0039] (6) First, add 15 parts by weight of diatomaceous earth, 6 parts by weight of nano titanium dioxide and 4 parts by weight of modified graphene oxide to 5 parts by weight of deionized water and ultrasonically disperse for 35 min to prepare a composite slurry; then, activate 8 parts by weight of modified tourmaline to a particle size D50 of 2 μm using a planetary ball mill and add it to the slurry. Stir at 800 rpm at 60°C for 40 min. Then, add 1 part by weight of citric acid and 1.5 parts by weight of γ-aminopropyltriethoxysilane, reduce the speed to 400 rpm and continue mixing for 35 min. Dry at 70°C for 2 h to obtain a material that can release negative oxygen ions.

[0040] Example 3

[0041] (1) Add 50 mL of distilled water and 9 mL of anhydrous ethanol to the reactor to prepare a solution. Add 10.2 g of tourmaline powder to the solution, sonicate for 12 min, heat to 62 °C and stir for 11 min. Then slowly add 2.03 mL of vinyltrimethoxysilane and stir the reaction for 2.5 h. After the reaction is completed, wash the reaction product with ethanol, filter and dry to obtain alkenylated tourmaline.

[0042] (2) Place 30.6g of cashew phenol glycidyl ether, 0.55g of triphenylphosphine and 0.02g of hydroquinone in a reactor, stir and mix, heat to 95°C, then add 5.24g of acrylic acid dropwise, and react at 98°C for 6 hours. After the reaction is completed, cool, filter and dry to obtain intermediate 1.

[0043] (3) Add 2.56g of alkenylated tourmaline to 22mL of deionized water, sonicate for 10min, add 4.04g of intermediate 1 and 3.66g of methacryloyl ethyl sulfobetaine, stir and mix, purge with nitrogen for 25min to remove oxygen, then add 0.18g of azobisisobutyronitrile, react at 90℃ for 7h, after the reaction is completed, filter, wash and dry to obtain modified tourmaline;

[0044] (4) Add 1.73 g of gallic acid, 2.51 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1.56 g of 1-hydroxybenzotriazole to 18 mL of N,N-dimethylformamide solution. Stir for 1.5 h in an ice-water bath at 2 °C. Add 1.64 g of taurine and 3.34 g of triethylamine. Continue stirring for 35 min. Then restore to room temperature and react for 22 h. After the reaction is complete, precipitate and wash with anhydrous ethanol to purify and obtain intermediate 2.

[0045] (5) Dissolve 28 mg of graphene oxide in 110 mL of deionized water, sonicate in an ice bath for 1.2 h using an ultrasonic probe, add 0.02 mL of 0.1 mol / L dilute hydrochloric acid solution to adjust the pH to 4, then add 126 mg of intermediate 2, stir magnetically for 24 h, after the reaction is complete, dialyze using a 900 Da dialysis bag for 48 h, wash and dry to obtain modified graphene oxide;

[0046] (6) First, add 13 parts by weight of diatomaceous earth, 5 parts by weight of nano titanium dioxide and 3 parts by weight of modified graphene oxide to 4 parts by weight of deionized water and ultrasonically disperse for 33 min to prepare a composite slurry; then, activate 6 parts by weight of modified tourmaline to a particle size D50 of 1 μm using a planetary ball mill and add it to the slurry. Stir at 750 rpm at 55°C for 35 min. Then, add 0.9 parts by weight of citric acid and 1.2 parts by weight of γ-aminopropyltriethoxysilane, reduce the speed to 350 rpm and continue mixing for 30 min. Dry at 60°C for 1.5 h to obtain a material that can release negative oxygen ions.

[0047] Example 4

[0048] (1) Add 49 mL of distilled water and 8 mL of anhydrous ethanol to the reactor to prepare a solution. Add 10.1 g of tourmaline powder to the solution, sonicate for 11 min, heat to 61 °C and stir for 10 min. Then slowly add 2.02 mL of vinyltrimethoxysilane and stir for 2 h. After the reaction is completed, wash the reaction product with ethanol, filter and dry to obtain alkenylated tourmaline.

[0049] (2) Place 30.5g of cashew phenol glycidyl ether, 0.54g of triphenylphosphine and 0.01g of hydroquinone in a reactor, stir and mix, heat to 92°C, then add 5.23g of acrylic acid dropwise, and react at 96°C for 6 hours. After the reaction is completed, cool, filter and dry to obtain intermediate 1.

[0050] (3) Add 2.55g of alkenylated tourmaline to 21mL of deionized water, sonicate for 9min, add 4.03g of intermediate 1 and 3.66g of methacryloyl ethyl sulfobetaine, stir and mix, purge with nitrogen for 22min to remove oxygen, then add 0.17g of azobisisobutyronitrile, react at 85℃ for 6h, after the reaction is completed, filter, wash and dry to obtain modified tourmaline;

[0051] (4) Add 1.72 g of gallic acid, 2.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1.55 g of 1-hydroxybenzotriazole to 16 mL of N,N-dimethylformamide solution. Stir for 1 h in an ice-water bath at 1 °C. Add 1.63 g of taurine and 3.32 g of triethylamine. Continue stirring for 32 min. Then restore to room temperature and react for 21 h. After the reaction is complete, precipitate and wash with anhydrous ethanol to purify and obtain intermediate 2.

[0052] (5) Dissolve 26 mg of graphene oxide in 105 mL of deionized water, sonicate in an ice bath for 1 h using an ultrasonic probe, add 0.02 mL of 0.1 mol / L dilute hydrochloric acid solution to adjust the pH to 4, then add 126 mg of intermediate 2, stir magnetically for 23 h, after the reaction is complete, dialyze using an 800 Da dialysis bag for 46 h, wash and dry to obtain modified graphene oxide;

[0053] (6) First, add 13 parts by weight of diatomaceous earth, 5 parts by weight of nano titanium dioxide and 3 parts by weight of modified graphene oxide to 3 parts by weight of deionized water and ultrasonically disperse for 32 min to prepare a composite slurry; then, activate 6 parts by weight of modified tourmaline to a particle size D50 of 1 μm using a planetary ball mill and add it to the slurry. Stir at 725 rpm at 52 °C for 32 min. Then, add 0.8 parts by weight of citric acid and 1 part by weight of γ-aminopropyltriethoxysilane, reduce the speed to 300 rpm and continue mixing for 28 min. Dry at 55 °C for 1 h to obtain a material that can release negative oxygen ions.

[0054] Example 5

[0055] (1) Add 51 mL of distilled water and 10 mL of anhydrous ethanol to the reactor to prepare a solution. Add 10.4 g of tourmaline powder to the solution, sonicate for 14 min, heat to 64 °C and stir for 12 min. Then slowly add 2.05 mL of vinyltrimethoxysilane and stir for 3 h. After the reaction is complete, wash the reaction product with ethanol, filter and dry to obtain alkenylated tourmaline.

[0056] (2) 30.7g of cashew phenol glycidyl ether, 0.56g of triphenylphosphine and 0.03g of hydroquinone were placed in a reactor, stirred and mixed, heated to 98°C, and then 5.25g of acrylic acid was added dropwise. The reaction was carried out at 98°C for 7 hours. After the reaction was completed, the mixture was cooled, filtered and dried to obtain intermediate 1.

[0057] (3) Add 2.57g of alkenylated tourmaline to 24mL of deionized water, sonicate for 11min, add 4.05g of intermediate 1 and 3.67g of methacryloyl ethyl sulfobetaine, stir and mix, purge with nitrogen for 28min to remove oxygen, then add 0.19g of azobisisobutyronitrile, react at 95℃ for 8h, after the reaction is completed, filter, wash and dry to obtain modified tourmaline;

[0058] (4) Add 1.74 g of gallic acid, 2.52 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1.57 g of 1-hydroxybenzotriazole to 19 mL of N,N-dimethylformamide solution. Stir for 2 h in an ice-water bath at 4 °C. Add 1.65 g of taurine and 3.36 g of triethylamine. Continue stirring for 38 min. Then restore to room temperature and react for 23 h. After the reaction is complete, precipitate and wash with anhydrous ethanol to purify and obtain intermediate 2.

[0059] (5) Dissolve 29 mg of graphene oxide in 115 mL of deionized water, sonicate in an ice bath for 1.5 h using an ultrasonic probe, add 0.03 mL of 0.1 mol / L dilute hydrochloric acid solution to adjust the pH to 5, then add 127 mg of intermediate 2, stir magnetically for 25 h, after the reaction is complete, dialyze using a 1000 Da dialysis bag for 48 h, wash and dry to obtain modified graphene oxide;

[0060] (6) First, 14 parts by weight of diatomaceous earth, 6 parts by weight of nano titanium dioxide and 4 parts by weight of modified graphene oxide were added to 4 parts by weight of deionized water and ultrasonically dispersed for 33 min to prepare a composite slurry. Then, 7 parts by weight of modified tourmaline were activated by a planetary ball mill until the particle size D50 was 2 μm and added to the slurry. The mixture was stirred at 775 rpm at 58 °C for 38 min. Then, 1 part by weight of citric acid and 1.5 parts by weight of γ-aminopropyltriethoxysilane were added and the speed was reduced to 400 rpm and mixed for 32 min. The mixture was then dried at 65 °C for 2 h to obtain a material that can release negative oxygen ions.

[0061] Comparative Example 1

[0062] The difference between this comparative example and Example 5 is that tourmaline was used instead of modified tourmaline.

[0063] Comparative Example 2

[0064] The difference between this comparative example and Example 5 is that graphene oxide was used instead of modified graphene oxide.

[0065] Performance testing:

[0066] (1) Negative oxygen ion release capacity test: In accordance with standard JC / T2110-2012 "Negative Ion Functional Coatings", the test chamber was cleaned and pre-ventilated to ensure the initial negative ion background value was stable. The temperature and humidity inside the chamber were controlled to simulate a normal indoor environment. Then, the materials that can release negative oxygen ions prepared in Examples 1-5 and Comparative Examples 1-2 were ground into powder and evenly spread in a tray with a thickness controlled at 0.5-0.7 cm. They were placed in the test chamber respectively, and the negative ion concentration values ​​under stable conditions at 10 min, 20 min and 30 min were continuously monitored and recorded using an air ion counter. The results are shown in Table 1.

[0067] Table 1: Test of negative oxygen ion release capacity.

[0068]

[0069] As can be seen from Table 1, the materials that can release negative oxygen ions prepared in Examples 1-5 have better negative oxygen ion release capabilities.

[0070] (2) Stability Test: In accordance with standard JC / T2110-2012 "Negative Ion Functional Coatings", the test chamber was cleaned and pre-ventilated to ensure the initial negative ion background value was stable. Different temperatures and humidity levels were set inside the chamber. Then, the materials that release negative oxygen ions prepared in Examples 1-5 and Comparative Examples 1-2 were ground into powder and evenly spread in trays with a thickness controlled at 0.5-0.7 cm. They were placed in the test chambers respectively, and the negative ion concentration value under stable conditions was continuously monitored and recorded using an air ion counter after 30 minutes. The results are shown in Table 2.

[0071] Table 2: Stability Tests.

[0072]

[0073] As can be seen from Table 2, the materials that can release negative oxygen ions prepared in Examples 1-5 have better stability in terms of negative oxygen ion release capacity.

[0074] (3) Antibacterial performance test: The materials that release negative oxygen ions obtained in Examples 1-5 and Comparative Examples 1-2 were ground into powder, and 0.5g of each was weighed and placed in a sterile test tube. Escherichia coli ATCC25922 was cultured and a concentration of 1×10⁻⁶ was prepared. 7A bacterial suspension of 1 / mL was added to each group of sterile test tubes under aseptic conditions. An appropriate amount of physiological saline was then added to bring the total volume of liquid in the test tubes to 10mL. The sterile test tubes were then placed in a constant temperature shaking incubator and incubated at 100 rpm for 20 hours at room temperature. After incubation, the sterile test tubes were removed, and viable bacteria were counted using the dilution plate method. The number of viable bacteria in each group of samples was counted, and the inhibition rate was calculated. The results are shown in Table 3.

[0075] Table 3: Antibacterial performance test.

[0076] project Antibacterial rate / % Example 1 97.4 Example 2 98.4 Example 3 97.9 Example 4 97.7 Example 5 98.1 Comparative Example 1 94.3 Comparative Example 2 91.4

[0077] As can be seen from Table 3, the materials that release negative oxygen ions prepared in Examples 1-5 have better antibacterial properties.

[0078] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0079] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0080] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A material capable of releasing negative oxygen ions, characterized in that, It comprises the following components by weight: 5-8 parts by weight of modified tourmaline, 12-15 parts by weight of diatomaceous earth, 4-6 parts by weight of nano-titanium dioxide, 2-4 parts by weight of modified graphene oxide, 0.8-1 parts by weight of citric acid, 1-1.5 parts by weight of γ-aminopropyltriethoxysilane, and 3-5 parts by weight of deionized water.

2. The material capable of releasing negative oxygen ions according to claim 1, characterized in that, The method for preparing the modified tourmaline is as follows: Step 1: Add distilled water and anhydrous ethanol to the reactor to prepare a solution. Add tourmaline powder to the solution, sonicate for 10-15 min, heat to 60-65℃ and stir for 10-12 min. Then slowly add vinyltrimethoxysilane dropwise and stir the reaction for 2-3 h. After the reaction is complete, wash the reaction product with ethanol, filter and dry to obtain alkenylated tourmaline. Step 2: Place cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone in a reactor, stir and mix, heat to 90-100℃, then add acrylic acid dropwise, and react at 95-100℃ for 5-8 hours. After the reaction is complete, cool, filter and dry to obtain intermediate 1. Step 3: Add alkenylated tourmaline to deionized water and sonicate for 8-12 minutes. Add intermediate 1 and methacryloyl ethyl sulfobetaine, stir and mix, and purge with nitrogen for 20-30 minutes to remove oxygen. Then add azobisisobutyronitrile and react at 80-100℃ for 6-8 hours. After the reaction is complete, filter, wash and dry to obtain modified tourmaline.

3. The material capable of releasing negative oxygen ions according to claim 2, characterized in that, In step one, the ratio of distilled water, anhydrous ethanol, tourmaline, and vinyltrimethoxysilane is 48-52 mL: 8-10 mL: 10-10.5 g: 2-2.06 mL.

4. The material capable of releasing negative oxygen ions according to claim 2, characterized in that, In step two, the ratio of cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid is 30.4-30.8g: 0.53-0.57g: 0.01-0.03g: 5.22-5.26g.

5. The material capable of releasing negative oxygen ions according to claim 2, characterized in that, In step three, the ratio of deionized water, alkenylated tourmaline, intermediate 1, methacryloyl ethyl sulfobetaine, and azobisisobutyronitrile is 20-25 mL: 2.54-2.58 g: 4.02-4.06 g: 3.65-3.68 g: 0.16-0.2 g.

6. The material capable of releasing negative oxygen ions according to claim 1, characterized in that, The method for preparing the modified graphene oxide is as follows: S1: Gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1-hydroxybenzotriazole were added to an N,N-dimethylformamide solution and stirred in an ice-water bath at 0-5°C for 1-2 hours. Taurine and triethylamine were then added, and the reaction was continued with stirring for 30-40 minutes. The mixture was then brought to room temperature and reacted for 20-24 hours. After the reaction was completed, the mixture was precipitated and washed with anhydrous ethanol and purified to obtain intermediate 2. S2: Dissolve graphene oxide in deionized water and sonicate in an ice bath for 1-1.5 hours using an ultrasonic probe. Adjust the pH to 4-5 with 0.1 mol / L dilute hydrochloric acid solution. Then add intermediate 2 and stir magnetically for 22-26 hours. After the reaction is complete, dialyze using an 800-1000 Da dialysis bag for 45-50 hours. Wash and dry to obtain modified graphene oxide.

7. The material capable of releasing negative oxygen ions according to claim 6, characterized in that, The ratio of N,N-dimethylformamide, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole, taurine, and triethylamine in S1 is 15-20 mL. 1.71-1.75g:2.49-2.53g:1.54-1.58g:1.62-1.66g:3.30-3.07g.

8. The material capable of releasing negative oxygen ions according to claim 6, characterized in that, The ratio of graphene oxide, deionized water, dilute hydrochloric acid, and intermediate 2 in S2 is 25-30 mg: 100-120 mL: 0.02-0.03 mL: 125-128 mg.

9. A method for preparing a material capable of releasing negative oxygen ions as described in any one of claims 1-8, characterized in that, The preparation method of the material that can release negative oxygen ions is as follows: First, diatomaceous earth, nano titanium dioxide, and modified graphene oxide are added to deionized water and ultrasonically dispersed for 30-35 minutes to prepare a composite slurry; then, modified tourmaline is activated by a planetary ball mill to a particle size D50 of 1-2 μm and added to the slurry. The mixture is stirred at 700-800 rpm at 50-60℃ for 30-40 minutes. Then, citric acid and γ-aminopropyltriethoxysilane are added, and the mixing speed is reduced to 300-400 rpm and mixed for 25-35 minutes. The mixture is then dried at 50-70℃ for 1-2 hours to obtain the material that can release negative oxygen ions.

Images