Preparation method and application of high-activity CoFePBA material
By controlling the synthesis process and combining it with Ag nanoparticles, highly active CoFePBA materials and CoFePBA@Ag composite materials were prepared, solving the problem of low reactivity of CoFePBA crystals and achieving effective inhibition of Staphylococcus aureus.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGSU UNIV OF SCI & TECH
- Filing Date
- 2024-03-29
- Publication Date
- 2026-06-02
AI Technical Summary
The lowest energy stable crystal plane (220) of the existing CoFePBA crystal results in low reactivity, making it difficult to effectively inhibit the growth of Staphylococcus aureus.
CoFePBA material was synthesized at high temperature by controlling the dropping rate and stirring rate of surfactant and Fe(CN)6 salt to ensure the exposure of the (220) crystal plane, and the reaction activity was improved by forming CoFePBA@Ag material by combining with Ag nanoparticles.
The prepared CoFePBA material and CoFePBA@Ag composite material significantly improved the antibacterial activity against Staphylococcus aureus, achieving effective bacterial growth inhibition.
Smart Images
Figure CN118270808B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing a highly active CoFePBA material, and also to the application of the above-mentioned CoFePBA material as an antibacterial material in the fight against Staphylococcus aureus. Background Technology
[0002] Staphylococcus aureus is a common bacterium widely found in the natural environment, on animal skin, and on human skin. It can cause a variety of infections, from minor skin infections to serious bloodstream infections and pneumonia. With the increasing prevalence of drug-resistant Staphylococcus aureus, the development of novel antimicrobial materials can serve as a supplement to antibiotic therapy and slow the progression of resistance.
[0003] Prussian blue analogs (PBAs) have the chemical formula M1[M2(CN)6] (where M1 / M2 are transition metals such as Fe, Co, Ni, Zn, and Mn). Their abundant metal sites and redox properties make them widely used and studied in environmental remediation (degradation of organic matter), gas adsorption, drug delivery, electrocatalysis, and electrode materials. However, existing CoFePBA crystals typically expose the lowest-energy stable crystal plane (220), resulting in low reactivity. Modification methods, including doping, etching, or compositing with other materials, are usually required to improve their reactivity. Summary of the Invention
[0004] Purpose of the invention: The purpose of this invention is to provide a method for preparing a highly active CoFePBA material; another purpose of this invention is to provide the application of the above-mentioned highly active CoFePBA material in the fight against Staphylococcus aureus. The CoFePBA material prepared by this invention is preferably oriented to the (220) crystal plane, and the (220) crystal plane is a highly reactive crystal plane, which makes it have good antibacterial activity when applied to the fight against Staphylococcus aureus.
[0005] Technical solution: The preparation method of the highly active CoFePBA material of the present invention includes the following steps:
[0006] (1) At room temperature, the surfactant and CoCl2·6H2O are dissolved in deionized water to form solution A; the pH of solution A is adjusted to 7.0-8.0;
[0007] (2) Dissolve K3[Fe(CN)6] in deionized water to form solution B. Adjust the pH of solution B to 7.0–8.0;
[0008] (3) Under magnetic stirring, solution B is slowly added dropwise to solution A to obtain a mixed solution; wherein, the dropping rate is 4-8 mL / min; the control of the dropping rate is crucial for the formation of uniform CoFePBA crystals, and the dropping rate is uniform, 40 mL is added every 5-10 minutes.
[0009] (4) The mixed solution was reacted under high temperature and stirring. The solid product after the reaction was washed and dried to obtain the highly active CoFePBA material.
[0010] In step (1), the surfactant is polyvinylpyrrolidone or sodium citrate dihydrate.
[0011] In step (1), the molar ratio of the surfactant to CoCl2·6H2O is 1 to 2:1.
[0012] In step (2), the molar ratio of K3[Fe(CN)6] to CoCl2·6H2O is 0.125 to 0.5:1.
[0013] In step (3), during the dropwise addition process, the stirring rate is 200 rpm to 600 rpm to ensure that the solution is mixed evenly.
[0014] In step (4), the mixed solution is stirred at 55-80°C for at least 24 hours.
[0015] In step (4), the obtained dark purple precipitate is washed with deionized water and ethanol to remove unreacted precursors and byproducts, and dried overnight at 60°C to obtain pure CoFePBA. During the washing process, the precipitate is washed three times with deionized water and once with ethanol after each wash to ensure the purity of the material.
[0016] The CoFePBA@Ag composite material based on the above CoFePBA material is composed of CoFePBA and silver nanoparticles adsorbed on the crystal surface of CoFePBA(200).
[0017] The preparation method of the above composite material includes the following steps:
[0018] (1) Disperse CoFePBA in deionized water to form a uniform suspension; add AgNO3 to the suspension to achieve the composite of CoFePBA and Ag; the amount of AgNO3 added is 1% to 5% of the mass of CoFePBA.
[0019] (2) Irradiate the mixture with a xenon lamp to promote Ag +The reduction and formation of Ag nanoparticles were used to prepare CoFePBA@Ag composite materials; during the irradiation process, the mixture was kept in a stirring state to ensure uniform light irradiation.
[0020] (3) The sample was thoroughly washed with deionized water to remove unreacted AgNO3; the washing was repeated 5 times during the washing process; the washed sample was dried at 60°C to obtain CoFePBA@Ag composite material.
[0021] In step (1), the stirring rate is 200-500 rpm during the dispersion process to ensure uniform dispersion of CoFePBA particles.
[0022] In step (2), the xenon lamp irradiation intensity is 300W and the wavelength is greater than 420nm; the irradiation time is 1 to 3 hours.
[0023] The above-mentioned CoFePBA material is used as an antibacterial material in the treatment of Staphylococcus aureus.
[0024] The above-mentioned CoFePBA@Ag composite material is used as an antibacterial material in the treatment of Staphylococcus aureus.
[0025] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The CoFePBA material prepared by the present invention is preferably oriented to the (220) crystal plane. The (220) crystal plane is a highly reactive crystal plane, which makes it have good antibacterial activity when applied to Staphylococcus aureus; (2) The CoFePBA@Ag composite material obtained by the present invention based on highly reactive CoFePBA can further improve the antibacterial activity of the material against Staphylococcus aureus and effectively inhibit the growth of Staphylococcus aureus. Attached Figure Description
[0026] Figure 1 XRD patterns of pure CoFePBA (in the prior art) and CoFePBA with exposed (220) active crystal planes prepared in Example 1;
[0027] Figure 2 This is a scanning electron microscope image of the CoFePBA@Ag composite material prepared in Example 2.
[0028] Figure 3 This is a distribution map of the total number of points;
[0029] Figure 4 The UV-Vis absorption spectrum of the CoFePBA@Ag composite material prepared in Example 2 is shown below.
[0030] Figure 5The results show the inhibition of Staphylococcus aureus by (a) the blank control group, (b) the CoFePBA material prepared in Comparative Example 1, (c) the CoFePBA@Ag composite material prepared in Example 2, and (d) the CoFePBA material prepared in Example 1. Detailed Implementation
[0031] Example 1
[0032] The preparation method of the CoFePBA material with exposed crystal planes of the present invention (220) includes the following steps:
[0033] (1) At room temperature, 2 mmol sodium citrate dihydrate (C6H5Na3O7·2H2O) and 1 mmol CoCl2·6H2O were dissolved in 40 mL of deionized water to form solution A; the pH of solution A was adjusted to 7.0.
[0034] (2) Dissolve 0.5 mmol K3[Fe(CN)6] in 40 mL of deionized water to form solution B; adjust the pH of solution B to 7.0;
[0035] (3) Under magnetic stirring, solution B is slowly added dropwise to solution A to obtain a mixed solution; the dropping speed is uniform, and the dropping speed is 4 mL / min (40 mL is added in 10 minutes); during the dropping process, the stirring speed is 300 rpm to ensure that the solution is mixed evenly.
[0036] (4) Stir the mixed solution at 55°C for 24 h; then wash the resulting dark purple precipitate with deionized water and ethanol, and then dry it at 60°C overnight to obtain CoFePBA material with (220) crystal plane exposed.
[0037] pass Figure 1 It can be seen that the CoFePBA material prepared in Example 1 exposes more (220) active crystal faces.
[0038] The CoFePBA material prepared in Example 1 was applied to inhibit Staphylococcus aureus. Specifically, Staphylococcus aureus bacterial suspension was evenly spread on an agar plate to form a uniform colony layer. 0.1 mL of the CoFePBA material prepared in Example 1 was evenly added dropwise to the center of the agar plate. The treated agar plate was placed in a constant temperature incubator at 37°C and incubated for 24 hours to ensure bacterial growth and the manifestation of the antibacterial effect. After incubation, the presence of a clear zone, i.e., an inhibition zone, was observed on the agar plate. The results showed that the antibacterial effect was as follows: Figure 5 As shown in (d), there is a clear inhibition zone on the agar plate.
[0039] pass Figure 5It can be seen that Staphylococcus aureus grew well in the blank control group (a), while obvious clear zones appeared in groups (c) and (d), indicating that the growth of Staphylococcus aureus was completely inhibited by the CoFePBA material and the CoFePBA@Ag composite material.
[0040] Example 2
[0041] The preparation of CoFePBA@Ag composite materials based on the CoFePBA material obtained in Example 1 includes the following steps:
[0042] (1) 50 mg of CoFePBA with exposed (220) crystal faces was dispersed in 50 mL of deionized water to form a uniform suspension. During the dispersion process, the stirring speed was 500 rpm to ensure the uniform dispersion of CoFePBA particles. AgNO3 was added to the suspension to achieve the composite of CoFePBA and Ag. The amount of AgNO3 added was 5% of the mass of CoFePBA.
[0043] (2) Irradiate the mixture with a xenon lamp (300W, wavelength greater than 420nm) for 2 hours to promote Ag + The reduction and formation of Ag nanoparticles are achieved to prepare CoFePBA@Ag composite material; during the irradiation process, the mixture is kept in a stirring state to ensure uniform light irradiation;
[0044] (3) The solid product generated after irradiation was thoroughly washed with deionized water to remove unreacted AgNO3 and possible impurities; the washing process was repeated 5 times to ensure the purity of the material; the washed sample was dried at 60°C to obtain CoFePBA@Ag composite material.
[0045] pass Figure 2 It can be seen that the structure of the composite material is that Ag nanoparticles were successfully deposited on the (200) crystal plane of CoFePBA, indicating the successful preparation of the CoFePBA@Ag composite material with exposed (220) active crystal planes in this invention. Figure 3 Elemental analysis showed that Co, Fe, C, N and Ag were all present in the CoFePBA@Ag composite material, which further illustrates the successful preparation of the CoFePBA@Ag composite material of this invention.
[0046] pass Figure 4 It can be seen that the CoFePBA@Ag composite material prepared in Example 2 has obvious visible light absorption properties, indicating that this antibacterial material also has application prospects under visible light.
[0047] The CoFePBA@Ag composite material prepared in Example 2 was applied to inhibit Staphylococcus aureus. Specifically, Staphylococcus aureus bacterial suspension was evenly spread on an agar plate to form a uniform colony layer. 0.1 mL of the CoFePBA@Ag composite material prepared in Example 2 was evenly added dropwise to the center of the agar plate. The treated agar plate was placed in a constant temperature incubator at 37°C and incubated for 24 hours to ensure bacterial growth and the manifestation of the antibacterial effect. After incubation, the presence of a clear zone, i.e., an inhibition zone, was observed on the agar plate. The results showed that the antibacterial effect was as follows: Figure 5 As shown in (c), there is a clear inhibition zone on the agar plate.
[0048] Example 3
[0049] The preparation method of the CoFePBA material with exposed crystal planes of the present invention (220) includes the following steps:
[0050] (1) At room temperature, 2 mmol sodium citrate dihydrate (C6H5Na3O7·2H2O) and 2 mmol CoCl2·6H2O were dissolved in 40 mL of deionized water to form solution A; the pH of solution A was adjusted to 7.0.
[0051] (2) Dissolve 0.25 mmol K3[Fe(CN)6] in 40 mL of deionized water to form solution B; adjust the pH of solution B to 8.0;
[0052] (3) Under magnetic stirring, solution B is slowly added dropwise to solution A to obtain a mixed solution; the dropping speed is uniform, and the dropping speed is 8 mL / min (40 mL is added in 5 minutes); during the dropping process, the stirring speed is 600 rpm to ensure that the solution is mixed evenly.
[0053] (4) Stir the mixed solution at 80°C for 24 h; then wash the resulting dark purple precipitate with deionized water and ethanol, and then dry it at 60°C overnight to obtain CoFePBA material with (220) crystal plane exposed.
[0054] Example 4
[0055] The preparation of CoFePBA@Ag composite materials based on the CoFePBA material obtained in Example 3 includes the following steps:
[0056] (1) 50 mg of CoFePBA with exposed (220) crystal faces was dispersed in 50 mL of deionized water to form a uniform suspension. During the dispersion process, the stirring speed was 500 rpm to ensure uniform dispersion of CoFePBA particles. AgNO3 was added to the suspension to achieve the composite of CoFePBA and Ag. The amount of AgNO3 added was 1% of the mass of CoFePBA.
[0057] (2) Irradiate the mixture with a xenon lamp (300W, wavelength greater than 420nm) for 1 hour to promote Ag + The reduction and formation of Ag nanoparticles are achieved to prepare CoFePBA@Ag composite material; during the irradiation process, the mixture is kept in a stirring state to ensure uniform light irradiation;
[0058] (3) The solid product generated after irradiation was thoroughly washed with deionized water to remove unreacted AgNO3 and possible impurities; the washing process was repeated 5 times to ensure the purity of the material; the washed sample was dried at 60°C to obtain CoFePBA@Ag composite material.
[0059] The CoFePBA@Ag composite material prepared in Example 4 was applied to inhibit Staphylococcus aureus. Specifically, Staphylococcus aureus bacterial suspension was evenly spread on an agar plate to form a uniform colony layer. 0.1 mL of the CoFePBA@Ag composite material prepared in Example 4 was evenly added to the center of the agar plate. The treated agar plate was placed in a constant temperature incubator and incubated at 37°C for 48 hours to ensure bacterial growth and the manifestation of antibacterial effect. After incubation, the presence of a clear zone, i.e., an inhibition zone, was observed on the agar plate. The results showed that the material had a good antibacterial effect, and a clear inhibition zone was observed on the agar plate.
[0060] Comparative Example 1
[0061] At room temperature, 2 mmol of sodium citrate dihydrate and 1 mmol of CoCl2·6H2O were dissolved in 40 mL of deionized water to form solution A; the pH of solution A was adjusted to 7.0. 0.5 mmol of K3[Fe(CN)6] was dissolved in 40 mL of deionized water to form solution B; the pH of solution B was adjusted to 7.0. Under magnetic stirring, solution B was slowly added dropwise to solution A to obtain a mixed solution. The dropping rate was uniform at 4 mL / min (40 mL added every 10 minutes). During the dropping process, the stirring rate was 300 rpm to ensure uniform mixing. The mixed solution was stirred at 25 °C for 24 h. Then, the obtained precipitate was washed with deionized water and ethanol, and then dried overnight at 60 °C to obtain CoFePBA material with no active crystal faces exposed.
[0062] The CoFePBA material prepared in Comparative Example 1 was applied to inhibit Staphylococcus aureus. Specifically, Staphylococcus aureus bacterial suspension was evenly spread on an agar plate to form a uniform colony layer. 0.1 mL of the CoFePBA material prepared in Comparative Example 1 was then evenly added dropwise to the center of the agar plate. The treated agar plate was placed in a constant temperature incubator at 37℃ and incubated for 48 hours to ensure bacterial growth and the manifestation of the antibacterial effect. After incubation, the appearance of a clear zone, i.e., an inhibition zone, was observed on the agar plate. The results showed that the antibacterial effect was as follows: Figure 5 As shown in (b), there is no obvious inhibition zone on the agar plate.
[0063] Comparative Example 2
[0064] At room temperature, 2 mmol of sodium citrate dihydrate and 1 mmol of CoCl2·6H2O were dissolved in 40 mL of deionized water to form solution A; the pH of solution A was adjusted to 7.0. 0.5 mmol of K3[Fe(CN)6] was dissolved in 40 mL of deionized water to form solution B; the pH of solution B was adjusted to 7.0. Under magnetic stirring, solution B was slowly added dropwise to solution A to obtain a mixed solution. The dropping rate was uniform at 20 mL / min (40 mL added every 2 minutes). During the dropping process, the stirring rate was 300 rpm to ensure uniform mixing. The mixed solution was stirred at 55 °C for 24 h. Then, the obtained precipitate was washed with deionized water and ethanol, and then dried overnight at 60 °C to obtain CoFePBA material with no active crystal faces exposed.
[0065] Comparative Example 3
[0066] At room temperature, 2 mmol of sodium citrate dihydrate and 1 mmol of CoCl2·6H2O were dissolved in 40 mL of deionized water to form solution A; the pH of solution A was adjusted to 6.0. 0.5 mmol of K3[Fe(CN)6] was dissolved in 40 mL of deionized water to form solution B; the pH of solution B was adjusted to 6.0. Under magnetic stirring, solution B was slowly added dropwise to solution A to obtain a mixed solution. The dropping rate was uniform at 4 mL / min (40 mL added every 10 minutes). During the dropping process, the stirring rate was 300 rpm to ensure uniform mixing. The mixed solution was stirred at 55 °C for 24 h. Then, the obtained precipitate was washed with deionized water and ethanol, and then dried overnight at 60 °C to obtain CoFePBA material with no active crystal faces exposed.
Claims
1. A method for preparing a highly active CoFePBA material, characterized in that, Includes the following steps: (1) At room temperature, the surfactant and CoCl2·6H2O are dissolved in deionized water to form solution A; the pH of solution A is adjusted to 7.0~8.0; (2) Dissolve K3[Fe(CN)6] in deionized water to form solution B; adjust the pH of solution B to 7.0~8.0; (3) Under magnetic stirring, solution B is slowly added dropwise to solution A to obtain a mixed solution; wherein, the dropping rate is 4~8 mL / min; the control of the dropping rate is crucial for the formation of uniform CoFePBA crystals, and the dropping rate is uniform, 40 mL is added every 5~10 minutes. (4) Stir the mixed solution at 55~80℃ for no less than 24h. After the reaction, the solid product is washed and dried to obtain the highly active CoFePBA material.
2. The method for preparing the highly active CoFePBA material according to claim 1, characterized in that: In step (1), the surfactant is polyvinylpyrrolidone or sodium citrate dihydrate; the molar ratio of the surfactant to CoCl2·6H2O is 1~2:
1.
3. The method for preparing the highly active CoFePBA material according to claim 1, characterized in that: In step (2), the molar ratio of K3[Fe(CN)6] to CoCl2·6H2O is 0.125~0.5:
1.
4. The method for preparing the highly active CoFePBA material according to claim 1, characterized in that: In step (3), the stirring rate is 200 rpm to 600 rpm during the dripping process.
5. A CoFePBA@Ag composite material prepared based on the CoFePBA material according to claim 1, characterized in that: It consists of CoFePBA and silver nanoparticles adsorbed on the crystal surface of CoFePBA (200).
6. The method for preparing the CoFePBA@Ag composite material according to claim 5, characterized in that, Includes the following steps: (1) Disperse CoFePBA in deionized water to form a uniform suspension; add AgNO3 to the suspension; the amount of AgNO3 added is 1%~5% of the mass of CoFePBA; (2) Irradiate the mixture with a xenon lamp. The xenon lamp irradiation intensity is 300 W and the wavelength is greater than 420 nm. The irradiation time is 1~3 h. (3) The solid product generated after irradiation is washed and dried to obtain CoFePBA@Ag composite material.
7. The method for preparing the CoFePBA@Ag composite material according to claim 6, characterized in that: In step (1), the stirring rate is 200~500 rpm during the dispersion process.
8. The application of the CoFePBA material according to claim 1 as an antibacterial material in the treatment of Staphylococcus aureus.
9. The application of the CoFePBA@Ag composite material according to claim 5 as an antibacterial material in the fight against Staphylococcus aureus.