Antibacterial material as well as preparation method and application thereof

Abstract

The invention provides an antibacterial material as well as a preparation method and application thereof, and the preparation method comprises the following steps: roasting pseudo-boehmite to prepare an Al2O3 carrier; dipping the Al2O3 carrier in a soluble salt solution of an antibacterial active component, and drying to obtain an antibacterial material precursor; the antibacterial material precursor is subjected to heat treatment, and the antibacterial material is prepared; the antibacterial active component comprises Ag and / or Cu. Pseudo-boehmite is selected as a raw material of an Al2O3 carrier, Ag and / or Cu are / is used as antibacterial active components, and the prepared antibacterial material can achieve high antibacterial activity under the condition of low loading capacity.

Description

Technical Field

[0001] The present invention relates to the field of sterilization technology, specifically to the field of sterilization materials, and in particular to an antibacterial material and a preparation method and application thereof. Background Art

[0002] Pathogenic microorganisms include bacteria, fungi, viruses, etc., which can induce a variety of diseases and endanger human health. At present, commonly used antibacterial materials include Ag2O, CuO, Cu2O, ZnO, TiO2, CaO, MgO, etc. and their composite materials. In the prior art, components with antibacterial activity are often loaded onto the surface of materials with high specific surface area to improve the dispersion and antibacterial performance of antibacterial active components.

[0003] CN115254139A discloses a transition metal modified Ag / Al2O3 catalyst and its preparation method and use, wherein the transition metal modified Ag / Al2O3 catalyst is composed of a transition metal component with a mass content of 1% to 15%, an active component Ag with a mass content of 1% to 15%, and a γ-crystalline nano-Al2O3 carrier. The Fe-modified Ag / Al2O3 catalyst prepared in the patent can achieve a 100% inactivation rate for Escherichia coli, but its Ag loading is as high as 8wt%.

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

[0005] CN103918711A discloses a preparation method of a halloysite-loaded nano-silver antibacterial material, comprising mixing an acid-treated halloysite with a silver nitrate ethanol solution under vacuum, then connecting to the atmosphere, and allowing the silver nitrate to fully enter the halloysite tube under atmospheric pressure to obtain a halloysite-loaded nano-silver antibacterial material. The advantage of the invention is that the silver nitrate can enter the pipeline, and then the silver nitrate is decomposed under high temperature under vacuum to obtain elemental nano-silver particles, and the prepared halloysite-loaded nano-silver antibacterial material has a better antibacterial effect.

[0006] In the prior art, in order to obtain higher antibacterial activity, silver materials are usually selected as antibacterial active components, but the cost of silver materials is relatively high. Therefore, it is of great significance to provide a loaded, efficient, and low-cost antibacterial material. Summary of the invention

[0007] In view of the shortcomings of the prior art, the present invention aims to provide an antibacterial material and its preparation method and application. The present invention uses pseudo-boehmite as the raw material of the Al2O3 carrier and Ag and / or Cu as the antibacterial active components to prepare an antibacterial material that can achieve high antibacterial activity at a relatively low loading amount.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

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

[0010] The Al2O3 carrier is prepared by calcining pseudo-boehmite; the Al2O3 carrier is impregnated in a soluble salt solution of an antibacterial active component, and dried to obtain an antibacterial material precursor; and the antibacterial material precursor is heat-treated to obtain the antibacterial material;

[0011] The antimicrobial active component includes Ag and / or Cu.

[0012] The present invention uses pseudo-boehmite as the raw material of the Al2O3 carrier. The Al2O3 carrier prepared from the pseudo-boehmite has a high surface area and different hydroxyl functional groups (Al-OH), which is conducive to the anchoring and dispersion of active sites. Ag and / or Cu are used as antibacterial active components. When the antibacterial active components include Ag and Cu at the same time, there is electron transfer between Ag and Cu, which affects the valence state, redox performance and active oxygen species generation of Ag and Cu. The antibacterial material prepared by the present invention can achieve high antibacterial activity at a relatively low loading amount.

[0013] In the present invention, the calcination temperature of pseudo-boehmite affects the specific surface area, type and quantity of hydroxyl functional groups of the Al2O3 carrier. If the temperature is too high, the specific surface area and the quantity of hydroxyl functional groups are reduced, which is not conducive to the anchoring and dispersion of the active components. If the temperature is too low, the pseudo-boehmite cannot be converted into Al2O3, which is not conducive to improving the antibacterial activity.

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

[0015] Preferably, the calcining time of the pseudo-boehmite is 2 h-6 h, for example, 2 h, 3 h, 4 h, 5 h or 6 h, including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0016] Preferably, the particle size of the Al2O3 carrier is 20nm-10μm, for example, it can be 20nm, 40nm, 60nm, 80nm, 100nm, 200nm, 400nm, 600nm, 800nm, 1μm, 2μm, 4μm, 6μm, 8μm or 10μm, and the specific surface area is 150m 2 / g-350m 2 / g, for example, it can 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, and a pore size of 6nm-18nm, for example, 6nm, 8nm, 10nm, 12nm, 14nm, 16nm or 18nm. The particle size, specific surface area or pore size of the above-mentioned Al2O3 carrier include but are not limited to the listed values, and other values ​​not listed in the numerical 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 numerical range are also applicable.

[0018] In the present invention, the temperature of heat treatment of the antibacterial material precursor affects the existence state of the active component. If the heat treatment temperature is too high, the particle size of the active component becomes larger. If the heat treatment temperature is too low, the stability of the antibacterial material is poor.

[0019] Preferably, the heat treatment temperature is 300°C-600°C, for example, it can be 300°C, 350°C, 400°C, 450°C, 500°C, 550°C or 600°C, including but not limited to the listed values, and other unlisted values ​​within the numerical 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 numerical 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°C-400°C, for example, it can be 300°C, 320°C, 340°C, 360°C, 380°C or 400°C, including but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable, and 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, the numerical range is Other unlisted values ​​within the range are also applicable. The temperature of the second heat treatment is 400°C-600°C, for example, it can be 400°C, 450°C, 500°C, 550°C or 600°C, including but not limited to the listed values, and other unlisted values ​​within the numerical 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, and other unlisted values ​​within the numerical range are also applicable.

[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 uniform dispersion of the active components than the one-stage heat treatment process.

[0023] Preferably, in the soluble salt solution of the antimicrobial active component, the soluble salt of the antimicrobial active component includes any one of silver nitrate, silver acetate, copper nitrate, copper sulfate, copper chloride or copper acetate, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of silver nitrate and silver acetate, a combination of silver nitrate and copper nitrate, a combination of copper sulfate and copper chloride, or a combination of 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; in the antibacterial material, the loading amount of the antibacterial active component is 1wt%-20wt%; and the antibacterial active component comprises Ag and / or Cu.

[0026] In the antibacterial material provided in the present invention, the loading amount 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 values ​​not listed within the numerical range are also applicable.

[0027] In a third aspect, 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] The present invention uses pseudo-boehmite as the raw material of the Al2O3 carrier and Ag and / or Cu as the antibacterial active components. The prepared antibacterial material can achieve high antibacterial activity at a relatively low loading amount. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 These are the antibacterial performance test results of the antibacterial materials prepared in Example 1, Example 4, Example 7 and Example 11. DETAILED DESCRIPTION

[0031] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0032] Example 1

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

[0034] Pseudo-boehmite is calcined at 900°C for 4 hours to obtain an Al2O3 carrier; the prepared Al2O3 carrier is immersed in a silver nitrate aqueous solution, wherein the mass ratio of silver in the silver nitrate aqueous solution to the Al2O3 carrier is 0.02:1, the Al2O3 carrier and the silver nitrate aqueous solution are stirred evenly, and then a mixed powder is obtained by rotary evaporation and dried at 100°C to obtain an antibacterial material precursor. The antibacterial material precursor is subjected to a first heat treatment at 400°C for 3 hours, and then the antibacterial material precursor is subjected to 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. The preparation method is the same as that of Example 1, except that the antibacterial material precursor is directly heat-treated at 500° C. for 3 hours, to prepare an antibacterial material with a loading of 2 wt % Ag.

[0037] Example 3

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

[0039] Example 4

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

[0041] Pseudo-boehmite was calcined at 250°C for 6 hours to obtain an Al2O3 carrier; the prepared Al2O3 carrier was immersed in a silver nitrate aqueous solution, wherein the mass ratio of silver in the silver nitrate aqueous solution to the Al2O3 carrier was 0.02:1, the Al2O3 carrier and the silver nitrate aqueous solution were stirred evenly, and then a mixed powder was obtained by rotary evaporation and dried at 100°C to obtain an antibacterial material precursor. The antibacterial material precursor was heat treated at 300°C 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, which is the same as that of Example 2 except that pseudo-boehmite is calcined at 500°C for 2h to obtain an Al2O3 carrier, 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 preparation method comprising:

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

[0047] Example 7

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

[0049] The pseudo-boehmite was calcined at 900°C for 4 hours to obtain an Al2O3 carrier; the prepared Al2O3 carrier was immersed in a copper nitrate aqueous solution, wherein the mass ratio of copper in the copper nitrate aqueous solution to the Al2O3 carrier was 0.06:1, the Al2O3 carrier and the copper nitrate aqueous solution were stirred evenly, and then the mixed powder was obtained by rotary evaporation and dried at 100°C to obtain an antibacterial material precursor. The antibacterial material precursor was heat treated at 500°C for 3 hours to prepare an antibacterial material with a loading of 6wt% Cu.

[0050] Example 8

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

[0052] Pseudo-boehmite is calcined at 900°C for 4 hours to obtain an Al2O3 carrier; the prepared Al2O3 carrier is impregnated in a copper nitrate aqueous solution, wherein the mass ratio of copper in the copper nitrate aqueous solution to the Al2O3 carrier is 0.05:1, the Al2O3 carrier and the copper nitrate aqueous solution are stirred evenly, and then a mixed powder is obtained by rotary evaporation and dried at 100°C to obtain an antibacterial material precursor. The antibacterial material precursor is subjected to a first heat treatment at 400°C for 3 hours, and then the antibacterial material precursor is subjected to a second heat treatment for 3 hours to prepare an antibacterial material with a loading of 5wt% Cu.

[0053] Example 9

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

[0055] Example 10

[0056] The present embodiment provides a method for preparing an antibacterial material, which is the same as that in Example 8, except that the prepared Al2O3 carrier 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 Al2O3 carrier is 0.04:0.01:1, to prepare an antibacterial material with a loading of 1wt% Ag+4wt% Cu.

[0057] Embodiment 11

[0058] The present embodiment provides a method for preparing an antibacterial material, which is the same as that in Example 8, except that the prepared Al2O3 carrier 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 Al2O3 carrier is 0.06:0.02:1, to obtain an antibacterial material with a loading of 2wt% Ag+6wt% Cu.

[0059] Example 12

[0060] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as that of Example 8, except that the mass ratio of copper in the copper nitrate aqueous solution to the Al2O3 carrier is 0.16:1, and 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 that of Example 8, except that the mass ratio of copper in the copper nitrate aqueous solution to the Al2O3 carrier is 0.2:1, and an antibacterial material with a Cu loading of 20 wt% is prepared.

[0063] Embodiment 14

[0064] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as that of Example 1 except that the sintering temperature of pseudo-boehmite is 1000° C., and an antibacterial material with a loading amount of 2 wt % Ag is prepared.

[0065] Embodiment 15

[0066] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as that of Example 1 except that the sintering temperature of pseudo-boehmite is 150° C., and an antibacterial material with a loading amount of 2 wt % Ag is prepared.

[0067] Example 16

[0068] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as that of Embodiment 2 except that the sintering temperature of the antibacterial material precursor is 250° C. to prepare an antibacterial material with a loading of 2 wt % Ag.

[0069] Embodiment 17

[0070] This embodiment provides a method for preparing an antibacterial material. The preparation method is the same as that of Embodiment 2 except that the sintering temperature of the antibacterial material precursor is 700° C., and an antibacterial material with a loading of 2 wt % Ag is prepared.

[0071] Comparative Example 1

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

[0073] Comparative Example 2

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

[0075] Comparative Example 3

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

[0077] Comparative Example 4

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

[0079] Performance Testing:

[0080] The bactericidal performance of the antibacterial materials prepared in all the above examples and comparative example 1 and the Al2O3 carriers prepared in comparative examples 2 to 4 was tested, and the antibacterial performance of the antibacterial materials prepared in example 1, example 4, example 7 and example 11 was tested.

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

[0082] The initial concentration of E. coli was 10 7 ~10 8 cfu / mL, the concentration of antibacterial material is 50μg / mL. After adding the antibacterial material to the E. coli solution for 30 minutes, 0.5mL of the solution was taken out, diluted multiple times by 10-fold dilution method, and cultured in a 37℃ incubator for 24 hours to test the concentration of E. coli to reduce the lg value.

[0083] The antibacterial performance test used an antibacterial ring experiment. 500 μg of the material was coated on a filter paper with a diameter of 5 mm. The side of the filter paper with the antibacterial material was then attached to a culture dish coated with Escherichia coli and cultured in a 37°C incubator for 24 hours.

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

[0085] Table 1

[0086]

[0087]

[0088] According to the data results of Examples 1 to 17, the present invention uses pseudo-boehmite as the raw material of the Al2O3 carrier and uses Ag and / or Cu as the antibacterial active components to prepare an antibacterial material that can achieve high antibacterial activity at a relatively low loading amount. In Example 1, the antibacterial material with only 2wt% Ag can achieve a 6-log reduction in the concentration of Escherichia coli.

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

[0090] The applicant declares that the above is only a specific implementation mode 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 thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing an antibacterial material, characterized in that: The preparation method comprises: The Al2O3 carrier is prepared by calcining pseudo-boehmite; the Al2O3 carrier is impregnated in a soluble salt solution of an antibacterial active component, and dried to obtain an antibacterial material precursor; and the antibacterial material precursor is heat-treated to obtain the antibacterial material; The antimicrobial active component includes Ag and / or Cu.

2. The preparation method according to claim 1, characterized in that The temperature of calcining the pseudo-boehmite is 250°C-900°C; Preferably, the time for roasting the pseudo-boehmite is 2h-6h.

3. The preparation method according to claim 1, characterized in that: The particle size of the Al2O3 carrier is 20nm-10μm, and the specific surface area is 150m 2 / g-350m 2 / g, pore size is 6nm-18nm.

4. The preparation method according to claim 1, characterized in that: 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.

5. The preparation method according to claim 1, characterized in that: The temperature of the heat treatment is 300°C-600°C; Preferably, the heat treatment time is 2h-5h.

6. The preparation method according to claim 1, characterized in that: The heat treatment includes a first heat treatment and a second heat treatment; Preferably, the temperature of the first heat treatment is 300°C-400°C, and the time is 2h-5h; Preferably, the temperature of the second heat treatment is 400° C.-600° C., and the time is 2 h-5 h.

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

8. An antibacterial material, characterized in that: The antibacterial material is prepared by the preparation method according to any one of claims 1 to 7.

9. The antibacterial material according to claim 8, characterized in that: The antibacterial material comprises an Al2O3 carrier and an antibacterial active component; In the antibacterial material, the loading amount of the antibacterial active component is 1wt%-20wt%; The antimicrobial active component includes Ag and / or Cu.

10. A use of the antibacterial material according to claim 9, characterized in that: The antibacterial material is applied in the field of catalytic sterilization.

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