An antibacterial material, its preparation method and application

Abstract

This invention provides an antibacterial material, its preparation method, and its application. The preparation method includes: calcining boehmite to prepare an Al2O3 support; impregnating the Al2O3 support in a soluble salt solution of an antibacterial active component, and drying to obtain an antibacterial material precursor; and heat-treating the antibacterial material precursor to prepare the antibacterial material. The antibacterial active component includes Ag and / or Cu. This invention uses boehmite as the raw material for the Al2O3 support and Ag and / or Cu as the antibacterial active component, resulting in an antibacterial material that achieves high antibacterial activity at a relatively low loading.

Description

Technical Field

[0001] This invention relates to the field of sterilization technology, specifically to the field of sterilization materials, and particularly to an antibacterial material, its preparation method, and its application. Background Technology

[0002] Pathogenic microorganisms, including bacteria, fungi, and viruses, can induce various diseases and endanger human health. Currently, commonly used antibacterial materials involve Ag2O, CuO, Cu2O, ZnO, TiO2, CaO, MgO, and their composite materials. Existing technologies often load antibacterial active components onto the surface of materials with high specific surface area to improve the dispersion and antibacterial performance of the antibacterial active components.

[0003] CN115254139A discloses a transition metal-modified Ag / Al2O3 catalyst, its preparation method, and its uses. The transition metal-modified Ag / Al2O3 catalyst consists of a transition metal component with a mass content of 1%–15%, an active component Ag with a mass content of 1%–15%, and a γ-crystalline phase nano-Al2O3 support. The Fe-modified Ag / Al2O3 catalyst prepared by this patent achieves a 100% inactivation rate against Escherichia coli, but its Ag loading is as high as 8 wt%.

[0004] CN103524118A discloses a silver-based η-Al2O3 mesoporous fiber antibacterial powder and antibacterial ceramics, which uses H-Al2O3(PEG) mesoporous fibers as antibacterial agent carriers. The silver-based H-Al2O3(PEG) antibacterial powder effectively utilizes the good adsorption properties of H-Al2O3(PEG) mesoporous fibers, and the silver-loaded H-Al2O3(PEG) antibacterial powder has obvious antibacterial effects against Escherichia coli and Staphylococcus aureus.

[0005] CN103918711A discloses a method for preparing halloysite-loaded silver nanoparticle antibacterial material. The method involves mixing acid-treated halloysite with a silver nitrate ethanol solution under vacuum, then connecting the mixture to atmospheric pressure to allow silver nitrate to fully enter the halloysite tube, thereby obtaining a halloysite-loaded silver nanoparticle antibacterial material. The advantage of this invention is that it allows silver nitrate to enter the tube, and then uses high temperature under vacuum to decompose the silver nitrate into elemental silver nanoparticles, resulting in a halloysite-loaded silver nanoparticle antibacterial material with better antibacterial effects.

[0006] In existing technologies, silver is typically chosen as the antibacterial active component to obtain high antibacterial activity, but silver is expensive. Therefore, providing a supported, high-efficiency, and low-cost antibacterial material is of great significance. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide an antibacterial material, its preparation method, and its application. This invention uses boehmite as a raw material for an Al2O3 carrier and Ag and / or Cu as the antibacterial active components. The resulting antibacterial material achieves high antibacterial activity even with a relatively low loading.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing an antibacterial material, the method comprising:

[0010] Al2O3 support was prepared by calcining boehmite; the Al2O3 support was impregnated in a soluble salt solution of antibacterial active components and dried to obtain an antibacterial material precursor; the antibacterial material precursor was heat-treated to prepare the antibacterial material.

[0011] The antibacterial active components include Ag and / or Cu.

[0012] This invention uses boehmite as the raw material for an Al2O3 support. The Al2O3 support prepared from boehmite has a high surface area and different hydroxyl functional groups (Al-OH), which is beneficial for the anchoring and dispersion of active sites. Ag and / or Cu are used as antibacterial active components. When both Ag and Cu are included as antibacterial active components, electron transfer occurs between Ag and Cu, affecting their valence state, redox properties, and the generation of reactive oxygen species. The antibacterial material prepared by this invention achieves high antibacterial activity at a relatively low loading.

[0013] In this invention, the calcination temperature of pseudoboehmite affects the specific surface area, type and number of hydroxyl functional groups of Al2O3 support. If the temperature is too high, the specific surface area and the number of hydroxyl functional groups will decrease, which is not conducive to the anchoring and dispersion of active components. If the temperature is too low, pseudoboehmite cannot be converted into Al2O3, which is not conducive to improving antibacterial activity.

[0014] Preferably, the temperature for calcining the pseudoboehmite is 250℃-900℃, for example, it can be 250℃, 300℃, 400℃, 500℃, 600℃, 700℃, 800℃ or 900℃, including but not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0015] Preferably, the calcination time of the pseudoboehmite is 2h-6h, for example, it can be 2h, 3h, 4h, 5h or 6h, including but not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0016] Preferably, the Al2O3 support has a particle size of 20nm-10μm, for example, it can be 20nm, 40nm, 60nm, 80nm, 100nm, 200nm, 400nm, 600nm, 800nm, 1μm, 2μm, 4μm, 6μm, 8μm, or 10μm, and a specific surface area of ​​150m². 2 / g-350m 2 / g, for example, could be 150m 2 / g、170m 2 / g、190m 2 / g、210m 2 / g、230m 2 / g、250m 2 / g、300m 2 / g or 350m 2 / g, with a pore size of 6nm-18nm, for example, it can be 6nm, 8nm, 10nm, 12nm, 14nm, 16nm or 18nm. The particle size, specific surface area or pore size of the above Al2O3 support includes but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0017] Preferably, in the soluble salt solution of the antibacterial active component, the mass ratio of the antibacterial active component to the Al2O3 carrier is (0.01-0.2):1, for example, it can be 0.01:1, 0.03:1, 0.05:1, 0.07:1, 0.09:1, 0.11:1, 0.13:1, 0.15:1, 0.17:1, 0.19:1 or 0.2:1, including but not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0018] In this invention, the temperature of heat treatment of the antibacterial material precursor affects the occurrence state of the active components. If the heat treatment temperature is too high, the particle size of the active components will become larger; if the heat treatment temperature is too low, the antibacterial material will have poor stability.

[0019] Preferably, the heat treatment temperature is 300℃-600℃, for example, it can be 300℃, 350℃, 400℃, 450℃, 500℃, 550℃ or 600℃, including but not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0020] Preferably, the heat treatment time is 2h-6h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, including but not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0021] Preferably, the heat treatment includes a first heat treatment and a second heat treatment. The temperature of the first heat treatment is 300℃-400℃, for example, it can be 300℃, 320℃, 340℃, 360℃, 380℃, or 400℃, including but not limited to the listed values. Other unlisted values ​​within the range are also applicable. The time is 2h-6h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, or 6h, including but not limited to the listed values. Other values ​​not listed within the range also apply. The temperature of the second heat treatment is 400℃-600℃, for example, it can be 400℃, 450℃, 500℃, 550℃ or 600℃, including but not limited to the listed values. Other values ​​not listed within the range also apply. The time is 2h-6h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 6h, including but not limited to the listed values. Other values ​​not listed within the range also apply.

[0022] In the preparation method provided by the present invention, the two-stage heat treatment process of the first heat treatment and the second heat treatment is more conducive to the uniform dispersion of active components compared with the single heat treatment process.

[0023] Preferably, the soluble salt solution of the antibacterial active component includes any one or a combination of at least two of silver nitrate, silver acetate, copper nitrate, copper sulfate, copper chloride, or copper acetate. Typical but non-limiting combinations include combinations of silver nitrate and silver acetate, silver nitrate and copper nitrate, copper sulfate and copper chloride, or copper acetate and silver acetate.

[0024] In a second aspect, the present invention provides an antibacterial material, which is prepared by the preparation method described in the first aspect.

[0025] Preferably, the antibacterial material comprises an Al2O3 carrier and an antibacterial active component; the loading of the antibacterial active component in the antibacterial material is 1wt%-20wt%; the antibacterial active component comprises Ag and / or Cu.

[0026] In the antibacterial materials provided in this invention, the loading of the antibacterial active component is 1wt%-20wt%, for example, it can be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, or 20wt%, including but not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0027] Thirdly, the present invention provides an application of the antibacterial material as described in the second aspect, wherein the antibacterial material is applied in the field of catalytic sterilization.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] This invention uses boehmite as the raw material for Al2O3 support and Ag and / or Cu as the antibacterial active components. The resulting antibacterial material can achieve high antibacterial activity at a low loading. Attached Figure Description

[0030] Figure 1 These are the antibacterial performance test results of the antibacterial materials prepared in Examples 1, 4, 7 and 11. Detailed Implementation

[0031] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0032] Example 1

[0033] This embodiment provides a method for preparing an antibacterial material, the method comprising:

[0034] Boehmite was calcined at 900℃ for 4 hours to obtain an Al2O3 support. The prepared Al2O3 support was impregnated in an aqueous silver nitrate solution, wherein the mass ratio of silver to Al2O3 support in the aqueous silver nitrate solution was 0.02:1. After the Al2O3 support and the aqueous silver nitrate solution were stirred evenly, the mixture was rotary evaporated to obtain a mixed powder, which was then dried at 100℃ to obtain an antibacterial material precursor. The antibacterial material precursor was subjected to a first heat treatment at 400℃ for 3 hours, followed by a second heat treatment for 3 hours to prepare an antibacterial material with a loading of 2wt% Ag.

[0035] Example 2

[0036] This embodiment provides a method for preparing an antibacterial material. Except for directly heat-treating the antibacterial material precursor at 500°C for 3 hours, the preparation method is the same as in Example 1, and an antibacterial material with a loading of 2 wt% Ag is prepared.

[0037] Example 3

[0038] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as in Example 1, except that the mass ratio of silver to Al2O3 carrier in the silver nitrate aqueous solution is 0.01:1. An antibacterial material with a loading of 1 wt% Ag is prepared.

[0039] Example 4

[0040] This embodiment provides a method for preparing an antibacterial material, the method comprising:

[0041] Boehmite was calcined at 250℃ for 6 hours to obtain an Al2O3 support. The prepared Al2O3 support was impregnated in an aqueous silver nitrate solution, wherein the mass ratio of silver to Al2O3 support in the aqueous silver nitrate solution was 0.02:1. After the Al2O3 support and the aqueous silver nitrate solution were stirred evenly, the mixture was rotary evaporated to obtain a mixed powder, which was then dried at 100℃ to obtain an antibacterial material precursor. The antibacterial material precursor was heat-treated at 300℃ for 5 hours to prepare an antibacterial material with a loading of 2wt% Ag.

[0042] Example 5

[0043] This embodiment provides a method for preparing an antibacterial material. Except for calcining boehmite at 500°C for 2 hours to obtain an Al2O3 carrier, the preparation method is the same as in Example 2, and an antibacterial material with a loading of 2wt% Ag is prepared.

[0044] Example 6

[0045] This embodiment provides a method for preparing an antibacterial material, the method comprising:

[0046] Boehmite was calcined at 500℃ for 4 hours to obtain an Al2O3 support. The prepared Al2O3 support was impregnated in an aqueous copper nitrate solution, wherein the mass ratio of copper to Al2O3 support in the aqueous copper nitrate solution was 0.06:1. After the Al2O3 support and the aqueous copper nitrate solution were stirred evenly, the mixture was rotary evaporated to obtain a mixed powder, which was then dried at 100℃ to obtain an antibacterial material precursor. The antibacterial material precursor was heat-treated at 600℃ for 2 hours to prepare an antibacterial material with a Cu loading of 6 wt%.

[0047] Example 7

[0048] This embodiment provides a method for preparing an antibacterial material, the method comprising:

[0049] Boehmite was calcined at 900℃ for 4 hours to obtain an Al2O3 support. The prepared Al2O3 support was impregnated in an aqueous copper nitrate solution, wherein the mass ratio of copper to Al2O3 support in the aqueous copper nitrate solution was 0.06:1. After the Al2O3 support and the aqueous copper nitrate solution were stirred evenly, the mixture was rotary evaporated to obtain a mixed powder, which was then dried at 100℃ to obtain an antibacterial material precursor. The antibacterial material precursor was heat-treated at 500℃ for 3 hours to prepare an antibacterial material with a Cu loading of 6 wt%.

[0050] Example 8

[0051] This embodiment provides a method for preparing an antibacterial material, the method comprising:

[0052] Boehmite was calcined at 900℃ for 4 hours to obtain an Al2O3 support. The prepared Al2O3 support was impregnated in an aqueous copper nitrate solution, wherein the mass ratio of copper to Al2O3 support in the copper nitrate solution was 0.05:1. After the Al2O3 support and the copper nitrate solution were stirred evenly, the mixture was rotary evaporated to obtain a mixed powder, which was then dried at 100℃ to obtain an antibacterial material precursor. The antibacterial material precursor was subjected to a first heat treatment at 400℃ for 3 hours, followed by a second heat treatment for 3 hours to prepare an antibacterial material with a Cu loading of 5 wt%.

[0053] Example 9

[0054] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as in Example 8, except that the mass ratio of copper to Al2O3 carrier in the copper nitrate aqueous solution is 0.06:1. An antibacterial material with a loading of 6 wt% Cu is prepared.

[0055] Example 10

[0056] This embodiment provides a method for preparing an antibacterial material. The method is the same as in Example 8, except that the Al2O3 support is impregnated in a mixed aqueous solution of silver nitrate and copper nitrate, wherein the mass ratio of copper and silver in the mixed aqueous solution to the mass of Al2O3 support is 0.04:0.01:1. An antibacterial material with a loading of 1 wt% Ag + 4 wt% Cu is prepared.

[0057] Example 11

[0058] This embodiment provides a method for preparing an antibacterial material. The method is the same as in Example 8, except that the Al2O3 support is impregnated in a mixed aqueous solution of silver nitrate and copper nitrate, wherein the mass ratio of copper and silver in the mixed aqueous solution to the mass of Al2O3 support is 0.06:0.02:1. An antibacterial material with a loading of 2wt% Ag + 6wt% Cu is prepared.

[0059] Example 12

[0060] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as in Example 8, except that the mass ratio of copper to Al2O3 carrier in the copper nitrate aqueous solution is 0.16:1. An antibacterial material with a loading of 16 wt% Cu is prepared.

[0061] Example 13

[0062] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as in Example 8, except that the mass ratio of copper to Al2O3 carrier in the copper nitrate aqueous solution is 0.2:1. An antibacterial material with a loading of 20 wt% Cu is prepared.

[0063] Example 14

[0064] This embodiment provides a method for preparing an antibacterial material. Except for the sintering temperature of boehmite being 1000℃, the preparation method is the same as in Example 1, and an antibacterial material with a loading of 2wt% Ag is obtained.

[0065] Example 15

[0066] This embodiment provides a method for preparing an antibacterial material. Except for the sintering temperature of boehmite being 150°C, the preparation method is the same as in Example 1, and an antibacterial material with a loading of 2 wt% Ag is obtained.

[0067] Example 16

[0068] This embodiment provides a method for preparing an antibacterial material. Except for the sintering temperature of the antibacterial material precursor being 250°C, the preparation method is the same as in Example 2 to obtain an antibacterial material with a loading of 2wt% Ag.

[0069] Example 17

[0070] This embodiment provides a method for preparing an antibacterial material. Except for the sintering temperature of the antibacterial material precursor being 700°C, the preparation method is the same as in Example 2, and an antibacterial material with a loading of 2wt%Ag is obtained.

[0071] Comparative Example 1

[0072] This comparative example provides a method for preparing an antibacterial material. Except for the use of commercial Al2O3 as a carrier, the preparation method is the same as in Example 1, and an antibacterial material with a loading of 2wt% Ag is prepared.

[0073] Comparative Example 2

[0074] This comparative example provides an Al2O3 support, and the preparation method of the Al2O3 support is the same as that of the Al2O3 support in Example 2.

[0075] Comparative Example 3

[0076] This comparative example provides an Al2O3 support, and the preparation method of the Al2O3 support is the same as that of the Al2O3 support in Example 4.

[0077] Comparative Example 4

[0078] This comparative example provides an Al2O3 support, and the preparation method of the Al2O3 support is the same as that of the Al2O3 support in Example 5.

[0079] Performance testing:

[0080] The antibacterial properties of the antibacterial materials prepared in all the above examples and Comparative Example 1, as well as the Al2O3 carriers prepared in Comparative Examples 2 to 4, were tested. The antibacterial properties of the antibacterial materials prepared in Examples 1, 4, 7, and 11 were also tested.

[0081] The test conditions for the bactericidal performance test are as follows:

[0082] The initial concentration of E. coli was 10. 7 ~10 8 The concentration of the antibacterial material was 50 μg / mL. After adding the antibacterial material to the E. coli solution and reacting for 30 min, 0.5 mL of the solution was taken out, diluted multiple times using the 10-fold dilution method, and then incubated at 37℃ for 24 h. The decrease in the concentration of E. coli was then measured by the lg value.

[0083] The antibacterial performance was tested using the inhibition zone experiment. 500 μg of material was applied to a filter paper with a diameter of 5 mm, and then the side of the filter paper with the antibacterial material was attached to a petri dish coated with Escherichia coli. The mixture was then incubated at 37°C for 24 h.

[0084] The test results for bactericidal performance are shown in Table 1, and the test results for antibacterial performance are shown in Table 2. Figure 1 .

[0085] Table 1

[0086]

[0087]

[0088] Based on the data from Examples 1 to 17, the present invention, by selecting boehmite as the raw material for the Al2O3 carrier and using Ag and / or Cu as the antibacterial active components, produces an antibacterial material that achieves high antibacterial activity at a relatively low loading. In Example 1, the antibacterial material containing only 2 wt% Ag achieved a 6 log reduction in Escherichia coli concentration.

[0089] Based on the data results of Examples 8 and 10, after replacing 1% Cu by mass in Example 8 with an equal amount of Ag, the synergistic effect of Ag and Cu on the valence state, redox properties and reactive oxygen species of Ag and Cu, depending on the electron transfer between them, increased the lg value of Escherichia coli concentration from 1.0 to 3.7.

[0090] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing an antibacterial material, characterized in that, The preparation method includes: Al2O3 support was prepared by calcining boehmite; the Al2O3 support was impregnated in a soluble salt solution of antibacterial active components and dried to obtain an antibacterial material precursor; the antibacterial material precursor was heat-treated to prepare the antibacterial material. The antibacterial active components include Ag and Cu; The temperature for calcining the pseudoboehmite is 250℃-900℃, and the time is 2h-6h. In the soluble salt solution of the antibacterial active component, the mass ratio of the antibacterial active component to the Al2O3 carrier is (0.01-0.2):1; The heat treatment includes a first heat treatment and a second heat treatment; the temperature of the first heat treatment is 300℃-400℃ and the time is 2h-5h; the temperature of the second heat treatment is 400℃-600℃ and the time is 2h-5h. The antibacterial material has an antibacterial active component loading of 1wt%-20wt%.

2. The preparation method according to claim 1, characterized in that, The Al2O3 support has a particle size of 20nm-10μm and a specific surface area of ​​150m². 2 / g-350m 2 / g, with a pore size of 6nm-18nm.

3. The preparation method according to claim 1, characterized in that, The heat treatment temperature is 300℃-600℃.

4. The preparation method according to claim 1, characterized in that, The heat treatment time is 2h-5h.

5. The preparation method according to claim 1, characterized in that, The soluble salt solution of the antibacterial active component includes any one or a combination of at least two of silver nitrate, silver acetate, copper nitrate, copper sulfate, copper chloride, or copper acetate.

6. An antibacterial material, characterized in that, The antibacterial material is prepared by the preparation method according to any one of claims 1-5.

7. The antibacterial material as described in claim 6, characterized in that, The antibacterial material includes an Al2O3 carrier and antibacterial active components; In the antibacterial material, the loading of the antibacterial active component is 1wt%-20wt%; The antibacterial active components include Ag and Cu.

8. The application of the antibacterial material as described in claim 7, characterized in that, The antibacterial material is used in the field of catalytic sterilization.

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