Two-component inorganic antibacterial filler based on ZIF-8 silver loading and preparation method of two-component inorganic antibacterial filler
By loading silver components onto ZIF-8, a two-component inorganic antibacterial filler in which AgNPs and ZnO coexist was prepared, which solved the problems of poor antibacterial broad spectrum of inorganic antibacterial agents and easy aggregation of AgNPs, and achieved a highly efficient and broad-spectrum antibacterial effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-03
- Publication Date
- 2026-03-24
AI Technical Summary
Existing inorganic antibacterial agents have poor broad-spectrum antibacterial activity due to their single composition and insufficient specific surface area. AgNPs are prone to aggregation and are highly dependent on stabilizers, which limits their practical application.
Using ZIF-8 as a carrier, ZIF-8 powder was generated by reacting zinc nitrate hexahydrate with 2-methylimidazole. After impregnation with a methanol solution of AgNO3, the powder was heat-treated to prepare Ag+/ZIF-8 powder. The powder was then subjected to high-temperature oxidation-reduction under air conditions to obtain a two-component inorganic antibacterial filler in which AgNPs and ZnO coexist.
It achieves high dispersion and uniform particle size of AgNPs, with synergistic antibacterial effect, making it a highly efficient and broad-spectrum antibacterial agent. It solves the problems of single component and insufficient specific surface area, and avoids the aggregation of AgNPs and dependence on stabilizers.
Smart Images
Figure CN121718072A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of antibacterial filler technology, and in particular to a two-component inorganic antibacterial filler based on ZIF-8 silver loading and its preparation method. Background Technology
[0002] With the continuous expansion of the application fields of functional materials, inorganic fillers with antibacterial properties have received widespread attention in functional composite materials such as textiles and packaging. Inorganic antibacterial agents are often used in high-temperature processing systems due to their high temperature resistance and ease of processing. Silver-based antibacterial agents have been widely used in the field of high-efficiency antibacterial materials due to their broad antibacterial spectrum, high antibacterial activity, and good inhibitory effect on various drug-resistant bacteria. However, traditional silver-based antibacterial agents are limited by the excessively rapid release rate of silver ions and the problem of antibacterial persistence. AgNPs, due to their high specific surface area and multiple antibacterial mechanisms, exhibit excellent antibacterial activity even at low doses.
[0003] However, inorganic antibacterial agents suffer from poor broad-spectrum antibacterial activity due to their simple composition and insufficient specific surface area. AgNPs, on the other hand, are limited in practical application because of their tendency to aggregate during preparation and their strong dependence on stabilizers.
[0004] Therefore, it is of great significance to provide a highly efficient broad-spectrum antibacterial agent based on ZIF-8 silver-loaded two-component inorganic antibacterial filler. Summary of the Invention
[0005] The purpose of this invention is to provide a two-component inorganic antibacterial filler based on ZIF-8 silver loading and its preparation method, addressing the shortcomings of existing technologies.
[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing a two-component inorganic antibacterial filler based on ZIF-8 silver loading, comprising the following steps: 1) A mixture of zinc nitrate hexahydrate solution and 2-methylimidazole solution was dried to obtain ZIF-8 powder; 2) ZIF-8 powder was impregnated in a methanol solution of AgNO3 and then dried to obtain Ag. + / ZIF-8 powder; 3) Ag + / ZIF-8 powder was heat-treated to obtain a two-component inorganic antibacterial filler based on ZIF-8 silver loading.
[0007] Preferably, the solvent for the zinc nitrate hexahydrate solution in step 1) is methanol, and the concentration of the zinc nitrate hexahydrate solution is 14.875~89.250 g / L; the solvent for the 2-methylimidazole solution is methanol, and the concentration of the 2-methylimidazole solution is 16.42~82.10 g / L.
[0008] Preferably, the molar ratio of zinc nitrate hexahydrate in the zinc nitrate hexahydrate solution to 2-methylimidazole in the 2-methylimidazole solution is 1:2~10.
[0009] Preferably, the mixing time in step 1) is 20-28 hours, and stirring is performed during the mixing process; the impregnation time in step 2) is 4-6 hours, and stirring is performed during the impregnation process.
[0010] Preferably, after mixing in step 1), the mixture is washed and centrifuged; after soaking in step 2), the mixture is washed and centrifuged. The washing reagent is methanol, and the number of centrifugations is 2 to 4 times at a speed of 8000 to 12000 rpm. The drying temperature is 55 to 65°C, and the drying time is 8 to 14 hours.
[0011] Preferably, in step 2), the mass-to-volume ratio of ZIF-8 powder to AgNO3 methanol solution is 0.1~0.3g:20mL, and the concentration of AgNO3 in the AgNO3 methanol solution is 0.010~0.075mol / L.
[0012] Preferably, the heat treatment temperature in step 3) is 300~500℃, the heat treatment time is 1~6h, and the heating rate to the heat treatment temperature is 15~25℃ / min.
[0013] The present invention also provides a two-component inorganic antibacterial filler based on ZIF-8 silver loading prepared by the aforementioned preparation method.
[0014] The beneficial effects of this invention are: 1) In this invention, ZIF-8 powder is prepared from zinc nitrate hexahydrate and 2-methylimidazole, and then impregnated in a methanol solution of silver nitrate to obtain Ag. + / ZIF-8 powder. Finally, a two-component inorganic antibacterial filler Ag / ZnO was obtained through high-temperature oxidation-reduction treatment under air conditions, achieving broad-spectrum antibacterial activity from both AgNPs and ZnO components.
[0015] 2) The synthesis conditions of the ZIF-8 silver-loaded two-component inorganic antibacterial filler of the present invention are mild, the process is simple, and the economic feasibility is strong.
[0016] 3) In the silver-loaded two-component inorganic antibacterial filler based on ZIF-8 of the present invention, AgNPs are highly dispersed and the Ag / ZnO two-component antibacterial filler has a uniform particle size with a diameter of about 30~50nm.
[0017] 4) The highly dispersed AgNPs and ZnO in the ZIF-8 silver-loaded two-component inorganic antibacterial filler of this invention have a synergistic antibacterial effect and belong to a highly efficient broad-spectrum antibacterial agent.
[0018] 5) This invention solves the problem of poor broad-spectrum antibacterial activity of inorganic antibacterial agents due to their single component and insufficient specific surface area, and avoids the limitations of AgNPs' easy aggregation and strong dependence on stabilizers. Attached Figure Description
[0019] Figure 1 This is a flowchart illustrating the preparation process of the ZIF-8 silver-loaded two-component inorganic antibacterial filler of the present invention. Figure 2 ZIF-8 and Ag prepared in Example 1 + SEM images of ZIF-8 and Ag / ZnO, where A represents ZIF-8 and B represents Ag. + / ZIF-8, C is Ag / ZnO; Figure 3 ZIF-8 and Ag prepared in Example 1 + XRD patterns of / ZIF-8 and Ag / ZnO; Figure 4 The image shows the antibacterial effect of Ag / ZnO prepared in Example 1, where a is a graph of colony growth and b is the antibacterial rate of Ag / ZnO against Escherichia coli and Staphylococcus aureus. Detailed Implementation
[0020] This invention provides a method for preparing a two-component inorganic antibacterial filler based on ZIF-8 silver loading, comprising the following steps: 1) A mixture of zinc nitrate hexahydrate solution and 2-methylimidazole solution was dried to obtain ZIF-8 powder; 2) ZIF-8 powder was impregnated in a methanol solution of AgNO3 and then dried to obtain Ag. + / ZIF-8 powder; 3) Ag + / ZIF-8 powder was heat-treated to obtain a two-component inorganic antibacterial filler based on ZIF-8 silver loading.
[0021] In this invention, the solvent for the zinc nitrate hexahydrate solution in step 1) is preferably methanol, and the concentration of the zinc nitrate hexahydrate solution is preferably 14.875~89.250 g / L, more preferably 20~60 g / L, and even more preferably 29.75~30.00 g / L; the solvent for the 2-methylimidazole solution is preferably methanol, and the concentration of the 2-methylimidazole solution is preferably 16.42~82.10 g / L, more preferably 40~70 g / L, and even more preferably 65.68~66.00 g / L.
[0022] In this invention, the molar ratio of zinc nitrate hexahydrate in the zinc nitrate hexahydrate solution to 2-methylimidazole in the 2-methylimidazole solution is preferably 1:2 to 10, more preferably 1:4 to 9, and even more preferably 1:6 to 8.
[0023] In this invention, the mixing time in step 1) is preferably 20-28h, more preferably 22-26h, and even more preferably 24h, and stirring is preferably performed during the mixing process. The impregnation time in step 2) is preferably 4-6h, more preferably 4.5-5.5h, and even more preferably 5h, and stirring is preferably performed during the impregnation process.
[0024] In this invention, the stirring rate in steps 1) and 2) is preferably 100-300 rpm, more preferably 150-250 rpm, and even more preferably 200 rpm.
[0025] In this invention, after mixing in step 1), the mixture is washed and centrifuged; after soaking in step 2), the mixture is washed and centrifuged. The washing reagent is preferably methanol. The number of centrifugations is preferably 2 to 4 times, more preferably 3 times. The centrifugation speed is preferably 8000 to 12000 rpm, more preferably 9000 to 11000 rpm, and more preferably 10000 rpm. The drying temperature is preferably 55 to 65°C, more preferably 57 to 62°C, and more preferably 60°C. The drying time is preferably 8 to 14 hours, more preferably 10 to 12 hours, and more preferably 10 hours.
[0026] In this invention, the mass-to-volume ratio of ZIF-8 powder and AgNO3 methanol solution in step 2) is preferably 0.1~0.3g:20mL, more preferably 0.15~0.25g:20mL, and even more preferably 0.2g:20mL. The concentration of AgNO3 in the AgNO3 methanol solution is preferably 0.010~0.075mol / L, more preferably 0.015~0.050mol / L, and even more preferably 0.025~0.050mol / L.
[0027] In this invention, the heat treatment temperature in step 3) is preferably 300~500℃, more preferably 350~450℃, and even more preferably 400℃. The heat treatment time is preferably 1~6h, more preferably 2~4h, and even more preferably 3h. The heating rate to the heat treatment temperature is preferably 15~25℃ / min, more preferably 17~22℃ / min, and even more preferably 20℃ / min.
[0028] The present invention also provides a two-component inorganic antibacterial filler based on ZIF-8 silver loading prepared by the aforementioned preparation method.
[0029] The ZIF-8 silver-loaded two-component inorganic antibacterial filler of the present invention can be used in polymer, coating or composite matrix.
[0030] This invention uses the metal-organic framework material ZIF-8 as a carrier, utilizing its porous framework structure to load silver components, which is beneficial for the uniform dispersion and stable existence of silver components in the material. The confinement effect of the porous structure of ZIF-8 can suppress the aggregation behavior of AgNPs. This invention involves thermal oxidation-reduction treatment of Ag under air conditions. + / ZIF-8 ensures that AgNPs and ZnO coexist in the prepared antibacterial filler.
[0031] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0032] Example 1
[0033] 2.975 g of zinc nitrate hexahydrate solid and 6.568 g of 2-methylimidazole solid were dissolved in 100 mL of methanol to obtain zinc nitrate hexahydrate solution and 2-methylimidazole solution, respectively. Then, the zinc nitrate hexahydrate solution was slowly added to the 2-methylimidazole solution through a constant pressure dropping funnel at a rate of 5 drops / s. The mixture was stirred at 200 rpm for 24 h at room temperature to obtain a white suspension. The suspension was washed with methanol and centrifuged three times at 10000 rpm. Then, it was vacuum dried at 60 °C for 10 h to obtain a white powder, which was designated as ZIF-8 powder.
[0034] 0.2 g of ZIF-8 was immersed in 20 mL of a methanol solution of AgNO3 (0.025 mol / L) at room temperature, with stirring at 200 rpm for 5 h during the immersion process. After immersion, the sample was washed with methanol and centrifuged three times at 10,000 rpm. Then, it was vacuum dried at 60 °C for 10 h to obtain a white powder, denoted as Ag. + / ZIF-8 powder.
[0035] Ag + / ZIF-8 powder was spread evenly at the bottom of the crucible (the thickness of the spread should not exceed 0.5 cm), and then sent to the middle of the muffle furnace. The temperature was increased to 400 °C at a rate of 20 °C / min. The crucible was then heat-treated at 400 °C for 2 h to obtain a dark purple solid, which was denoted as Ag / ZnO.
[0036] Example 2
[0037] 5.950 g of zinc nitrate hexahydrate solid and 6.568 g of 2-methylimidazole solid were dissolved in 100 mL of methanol to obtain zinc nitrate hexahydrate solution and 2-methylimidazole solution, respectively. Then, the zinc nitrate hexahydrate solution was slowly added to the 2-methylimidazole solution through a constant pressure dropping funnel at a rate of 5 drops / s. The mixture was stirred at 200 rpm for 24 h at room temperature to obtain a white suspension. The suspension was washed with methanol and centrifuged three times at 10,000 rpm. Then, it was vacuum dried at 55 °C for 12 h to obtain a white powder, which was designated as ZIF-8 powder.
[0038] 0.2 g of ZIF-8 was immersed in 20 mL of a methanol solution of AgNO3 (0.02 mol / L) at room temperature, with stirring at 200 rpm for 5 h during the immersion process. After immersion, the sample was washed with methanol and centrifuged three times at 9000 rpm. Then, it was vacuum dried at 60 °C for 12 h to obtain a white powder, denoted as Ag. + / ZIF-8 powder.
[0039] Ag + / ZIF-8 powder was spread evenly at the bottom of the crucible (the thickness of the spread should not exceed 0.5 cm), and then sent to the middle of the muffle furnace. The temperature was increased to 300 °C at a rate of 20 °C / min, and the crucible was heat-treated at 300 °C for 2.5 h to obtain a dark purple solid, which was denoted as Ag / ZnO.
[0040] Example 3
[0041] 2.975 g of zinc nitrate hexahydrate solid and 8.210 g of 2-methylimidazole solid were dissolved in 100 mL of methanol to obtain zinc nitrate hexahydrate solution and 2-methylimidazole solution, respectively. Then, the zinc nitrate hexahydrate solution was slowly added to the 2-methylimidazole solution through a constant pressure dropping funnel at a rate of 5 drops / s. The mixture was stirred at 200 rpm for 24 h at room temperature to obtain a white suspension. The suspension was washed with methanol and centrifuged three times at 11000 rpm. Then, it was vacuum dried at 65 °C for 10 h to obtain a white powder, which was designated as ZIF-8 powder.
[0042] 0.2 g of ZIF-8 was immersed in 20 mL of a methanol solution of AgNO3 (0.075 mol / L) at room temperature with stirring at 200 rpm for 5 h during the immersion process. After immersion, the sample was washed with methanol and centrifuged three times at 11,000 rpm. The sample was then vacuum dried at 65 °C for 10 h to obtain a white powder, denoted as Ag. + / ZIF-8 powder.
[0043] Ag + / ZIF-8 powder was spread evenly at the bottom of the crucible (the thickness of the spread should not exceed 0.5 cm), and then sent to the middle of the muffle furnace. The temperature was increased to 350 °C at a rate of 20 °C / min, and the crucible was heat-treated at 350 °C for 1.5 h to obtain a dark purple solid, which was denoted as Ag / ZnO.
[0044] Example 4
[0045] 2.975 g of zinc nitrate hexahydrate solid and 3.284 g of 2-methylimidazole solid were dissolved in 100 mL of methanol to obtain zinc nitrate hexahydrate solution and 2-methylimidazole solution, respectively. Then, the zinc nitrate hexahydrate solution was slowly added to the 2-methylimidazole solution through a constant pressure dropping funnel at a rate of 5 drops / s. The mixture was stirred at 200 rpm for 24 h at room temperature to obtain a white suspension. The suspension was washed with methanol and centrifuged three times at 10000 rpm. Then, it was vacuum dried at 60 °C for 10 h to obtain a white powder, which was designated as ZIF-8 powder.
[0046] 0.2 g of ZIF-8 was immersed in 20 mL of a methanol solution of AgNO3 (0.01 mol / L) at room temperature, with stirring at 200 rpm for 5 h during the immersion process. After immersion, the sample was washed with methanol and centrifuged three times at 10,000 rpm. Then, it was vacuum dried at 60 °C for 10 h to obtain a white powder, denoted as Ag. + / ZIF-8 powder.
[0047] Ag + / ZIF-8 powder was spread evenly at the bottom of the crucible (the thickness of the spread should not exceed 0.5 cm), and then sent to the middle of the muffle furnace. The temperature was increased to 450 °C at a rate of 20 °C / min. The crucible was then heat-treated at 450 °C for 2 h to obtain a dark purple solid, which was denoted as Ag / ZnO.
[0048] Example 5
[0049] 2.975 g of zinc nitrate hexahydrate solid and 1.642 g of 2-methylimidazole solid were dissolved in 100 mL of methanol to obtain zinc nitrate hexahydrate solution and 2-methylimidazole solution, respectively. Then, the zinc nitrate hexahydrate solution was slowly added to the 2-methylimidazole solution through a constant pressure dropping funnel at a rate of 5 drops / s. The mixture was stirred at 200 rpm for 24 h at room temperature to obtain a white suspension. The suspension was washed with methanol and centrifuged three times at 10000 rpm. Then, it was vacuum dried at 60 °C for 10 h to obtain a white powder, which was designated as ZIF-8 powder.
[0050] 0.2 g of ZIF-8 was immersed in 20 mL of a methanol solution of AgNO3 (0.03 mol / L) at room temperature with stirring at 200 rpm for 5 h during the immersion process. After immersion, the sample was washed with methanol and centrifuged three times at 10,000 rpm. The sample was then vacuum dried at 60 °C for 10 h to obtain a white powder, denoted as Ag. + / ZIF-8 powder.
[0051] Ag + / ZIF-8 powder was spread evenly at the bottom of the crucible (the thickness of the spread should not exceed 0.5 cm), and then sent to the middle of the muffle furnace. The temperature was increased to 500 °C at a rate of 20 °C / min, and the crucible was heat-treated at 500 °C for 2 h to obtain a dark purple solid, which was denoted as Ag / ZnO.
[0052] ZIF-8 and Ag prepared in Example 1 + The morphology, composition, and structure of / ZIF-8 and Ag / ZnO were detected and characterized.
[0053] ZIF-8 and Ag were studied using a scanning electron microscope. + Morphological analysis was performed on ZIF-8 and Ag / ZnO prepared in Example 1. + SEM images of / ZIF-8 and Ag / ZnO are shown below. Figure 2 As shown, A is ZIF-8 and B is Ag. + / ZIF-8, C is Ag / ZnO. (From...) Figure 2 It can be seen that ZIF-8 has a dodecahedral structure, and the Ag after impregnation treatment + The / ZIF-8 structure exhibits a certain irregular morphology; the heat-treated Ag / ZnO morphology consists of irregular nanoparticles with a particle size of 30~50nm.
[0054] XRD diffraction was used to analyze ZIF-8 and Ag. + Compositional analysis was performed on ZIF-8 and Ag / ZnO prepared in Example 1. + The XRD patterns of / ZIF-8 and Ag / ZnO are as follows: Figure 3 As shown. By Figure 3 It can be seen that Ag +The ZIF-8 spectrum shows a good crystal structure with diffraction peaks at 7.352°, 10.404°, and 12.752°, corresponding to the (011), (002), and (112) crystal plane diffraction of ZIF-8, consistent with the ZIF-8 spectrum. Furthermore, Ag / ZnO has diffraction peaks at 31.769°, 34.421°, 36.252° and 38.116°, 44.277°, and 64.426°, corresponding to the (100), (002), and (101) crystal plane diffraction of ZnO and the (111), (200), and (220) crystal plane diffraction of Ag, indicating successful silver recombination.
[0055] The antibacterial properties of Ag / ZnO against Escherichia coli and Staphylococcus aureus were evaluated. The antibacterial effect of Ag / ZnO prepared in Example 1 was as follows: Figure 4 As shown, a represents the colony growth, and b represents the antibacterial rate of Ag / ZnO against Escherichia coli and Staphylococcus aureus. Figure 4 It can be seen that Ag / ZnO at a concentration of 200 μg / mL for 30 min has a bactericidal rate of 96.6% against Escherichia coli and 90% against Staphylococcus aureus, respectively, indicating that the two-component inorganic antibacterial filler of the present invention has a highly efficient and spectral bactericidal effect under trace presence conditions.
[0056] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a two-component inorganic antibacterial filler based on ZIF-8 silver loading, characterized in that, It includes the following steps: 1) A mixture of zinc nitrate hexahydrate solution and 2-methylimidazole solution was dried to obtain ZIF-8 powder; 2) ZIF-8 powder was impregnated in a methanol solution of AgNO3 and then dried to obtain Ag. + / ZIF-8 powder; 3) Ag + / ZIF-8 powder was heat-treated to obtain a two-component inorganic antibacterial filler based on ZIF-8 silver loading.
2. The preparation method according to claim 1, characterized in that, In step 1), the solvent for the zinc nitrate hexahydrate solution is methanol, and the concentration of the zinc nitrate hexahydrate solution is 14.875~89.250 g / L; the solvent for the 2-methylimidazole solution is methanol, and the concentration of the 2-methylimidazole solution is 16.42~82.10 g / L.
3. The preparation method according to claim 1 or 2, characterized in that, The molar ratio of zinc nitrate hexahydrate in zinc nitrate hexahydrate solution to 2-methylimidazole in 2-methylimidazole solution is 1:2~10.
4. The preparation method according to claim 3, characterized in that, Step 1) The mixing time is 20~28h, and stirring is carried out during the mixing process. Step 2) The soaking time is 4~6h, and stirring is carried out during the soaking process.
5. The preparation method according to claim 3, characterized in that, After mixing in step 1), the mixture is washed and centrifuged. After soaking in step 2), the mixture is washed and centrifuged. The washing reagent is methanol. The number of centrifugations is 2 to 4, and the centrifugation speed is 8000 to 12000 rpm. The drying temperature is 55 to 65℃, and the drying time is 8 to 14 hours.
6. The preparation method according to claim 4 or 5, characterized in that, In step 2), the mass-to-volume ratio of ZIF-8 powder to AgNO3 methanol solution is 0.1~0.3g:20mL, and the concentration of AgNO3 in the AgNO3 methanol solution is 0.010~0.075mol / L.
7. The preparation method according to claim 6, characterized in that, Step 3) The heat treatment temperature is 300~500℃, the heat treatment time is 1~6h, and the heating rate to the heat treatment temperature is 15~25℃ / min.
8. The two-component inorganic antibacterial filler based on ZIF-8 silver loading prepared by the preparation method according to any one of claims 1 to 7.