Phosphorus-iron oxyhydroxide composite material, preparation method and application
By preparing a composite material of β-hydroxy iron oxide and black and red phosphorus, the heterogeneous Fenton technology has solved the problems of narrow pH range, low generation rate and high H2O2 consumption in degrading antibiotics, and achieved efficient and broad-spectrum antibiotic degradation effect.
Patent Information
- Application Number
- CN202411851677.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-16
- Publication Date
- 2025-03-07
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The existing heterogeneous Fenton technology has problems such as narrow optimal reaction pH range, low divalent iron ion generation rate, and high H2O2 consumption in degrading antibiotics, which limits its application in large-scale environmental restoration.
By preparing a composite material of β-hydroxy iron oxide and black-red phosphorus (β-FeOOH@BRP), black-red phosphorus is used to promote the conversion of trivalent iron ions into divalent iron, activate H2O2, and generate hydroxyl radicals, thereby building a heterogeneous Fenton system with anti-interference ability.
The composite material exhibits high catalytic activity and application range in degrading antibiotics, can effectively degrade antibiotics within a wide pH range, and has good anti-interference performance and cycling stability.
Smart Images
Figure CN119565646A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a preparation method of a phosphorus-iron oxyhydroxide composite material and application of the composite material in heterogeneous Fenton degradation of antibiotics, belonging to the technical field of Fenton. Background Art
[0002] In the context of increasingly severe environmental problems today, the residue of antibiotics in water bodies has become a major challenge. Traditional water treatment methods have certain limitations in removing antibiotics. In addition, their migration and transformation pathways in the environment are complex. Their persistence and bioaccumulation may pose a threat to ecological stability and human health.
[0003] Advanced oxidation processes (AOPs) have shown remarkable effects in degrading refractory organic pollutants, mainly by producing free radicals and non-radical active species with high redox potentials. Among AOPs, the Fenton process has attracted extensive attention from researchers as a cost-effective treatment method. However, the traditional Fenton process also has certain defects. For example, during the reaction, a large amount of hydrogen peroxide (H2O2) is required, the pH application range is narrow, a large amount of iron sludge is produced, and it is easy to cause secondary pollution. In addition, the difficulty in separating active catalytic components from the reaction mixture further complicates the process and increases the cost of post-treatment.
[0004] Heterogeneous Fenton effectively solves several of the problems mentioned above. However, the process still faces significant practical challenges, such as the narrow pH range for the optimal reaction, which makes it difficult to operate under neutral or alkaline conditions. In addition, the generation rate of divalent iron ions is still low, while the consumption of H2O2 is relatively high. These limitations remain the main obstacles that hinder the widespread application of heterogeneous Fenton reactions in large-scale environmental remediation.
[0005] β-Iron oxyhydroxide (β-FeOOH) nanomaterials have relatively stable physical and chemical properties, characterized by a tunnel-like structure in which iron atoms are tightly bound to the skeleton. The shape and size of these nanomaterials are well controlled, making them ideal for catalytic applications due to their high specific surface area, strong hydrophilicity, abundant surface hydroxyl groups, and excellent electron transmittance, which promotes the rapid surface migration of small molecular species.
[0006] Black red phosphorus (BRP) is an intermediate form between red phosphorus and black phosphorus with strong reducibility. This high reduction potential can efficiently convert ferric iron to ferrous iron, thereby promoting the redox cycle of iron ions and accelerating the Fenton reaction. BRP also combines some of the advantages of red phosphorus and black phosphorus. Like red phosphorus, it is relatively stable and cost-effective, while it also has the excellent conductivity and high electron mobility of black phosphorus, which makes it very effective in enhancing electron transfer processes. These combined properties make BRP an ideal material for catalytic applications. Summary of the invention
[0007] In view of the problems existing in the existing heterogeneous Fenton technology, the present invention aims to provide a phosphorus-iron oxyhydroxide composite material, a preparation method and its application. The present invention prepares a composite material of β-iron oxyhydroxide and black-red phosphorus for the first time. The introduction of black-red phosphorus makes it easy for trivalent iron ions to transform into divalent iron ions, thereby activating H2O2 and promoting the generation of hydroxyl radicals. The heterogeneous Fenton-like system constructed by the composite material and H2O2 has strong anti-interference ability and shows high catalytic activity and application range in the degradation of antibiotics.
[0008] The specific preparation process of the phosphorus-iron oxyhydroxide composite material includes the following steps:
[0009] A certain amount of β-FeOOH and BRP were added to ethanol for magnetic stirring and then transferred into a polytetrafluoroethylene high-pressure reactor for closed solvent thermal reaction. The black-red phosphorus-containing iron oxyhydroxide composite material was obtained by filtration, washing and drying, which was recorded as β-FeOOH@BRP.
[0010] Furthermore, the molar ratio of β-FeOOH to black red phosphorus is 1:2.15.
[0011] Furthermore, the molar ratio of β-FeOOH to ethanol is 1.28:1.
[0012] Furthermore, the magnetic stirring time is 30 min.
[0013] Furthermore, the solvothermal temperature was 180 °C and the hydrothermal time was 12 h.
[0014] The present invention seeks to protect the use of the above-mentioned phosphorus-iron oxyhydroxide composite material (β-FeOOH@BRP) in the degradation of antibiotics.
[0015] Furthermore, antibiotics include levofloxacin (LVX) and the like.
[0016] Compared with the prior art, the present invention has the following beneficial effects:
[0017] The present invention prepares a phosphorus-iron oxyhydroxide composite material based on a solvothermal method, which has the advantages of strong anti-interference ability, wide pH application range, high catalytic degradation activity and good economy in the advanced oxidation catalytic degradation of organic pollutants, and therefore has good application prospects in the field of antibiotic degradation. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 (a) is the XRD pattern of the products of Example 1, Comparative Example 1 and Comparative Example 2; Figure 1 (b) is the Raman spectra of Example 1, Comparative Example 1, and the comparative example product;
[0019] Figure 2 TEM images of Example 1, Comparative Example 1, and the comparative example product;
[0020] Figure 3 The activity diagram of heterogeneous Fenton degradation of levofloxacin in Example 1, Comparative Example 1 and the comparative example product;
[0021] Figure 4 is the EPR of the product of Example 1;
[0022] Figure 5 This is the activity diagram of the product of Example 1 in degrading LVX at different pH values.
[0023] Figure 6 This is the activity diagram of the product of Example 1 in Fenton degradation of LVX under the influence of 5 mM different ions.
[0024] Figure 7 This is a cycle test diagram of heterogeneous Fenton degradation of LVX by the product of Example 1;
[0025] Figure 8 This is the activity diagram of the product of Example 1 in degrading LVX under different water environments. DETAILED DESCRIPTION
[0026] The following will be described in more detail through specific embodiments to better illustrate the purpose, technical solutions and advantages of the present invention. It should be understood by those skilled in the art that the specific embodiments described herein are only used to explain the present invention, and the protection scope of the invention is not limited to these embodiments.
[0027] Example 1
[0028] This embodiment provides a method for preparing a phosphorus-iron oxyhydroxide composite material, comprising the following steps:
[0029] 0.90 mmol β-FeOOH and 1.94 mmol BRP were added to 70 mL ethanol and magnetically stirred for 30 min. The mixture was then transferred to a polytetrafluoroethylene-lined high-pressure reactor and heated at 180 °C for 12 h. After cooling to room temperature, the product was collected by centrifugation, washed with deionized water and ethanol several times, and vacuum dried at 60 °C for 12 h to obtain β-FeOOH@BRP material.
[0030] Comparative Example 1
[0031] Disperse 0.27g of ferric chloride hexahydrate and 0.25g of urea in 50mL of deionized water and stir magnetically until completely dissolved. Then transfer the solution to a 150ml round-bottom flask and heat it in an 80℃ oil bath for 24h. After cooling naturally to room temperature, collect the product by centrifugation and wash it with deionized water and anhydrous ethanol several times. Dry it under vacuum at 60℃ for 12h to obtain β-FeOOH.
[0032] Comparative Example 2
[0033] 1.5 g of red phosphorus was added to 60 mL of deionized water, stirred for 30 min, transferred to a 100 ml polytetrafluoroethylene autoclave liner, heated at 200 ° C for 12 h, cooled to room temperature, centrifuged to collect the product, washed with deionized water and anhydrous ethanol for multiple times, and dried at 70 ° C for 12 h to collect. Next, 1.0 g of the collected product was added to 60 mL of EDA and transferred to a 100 ml polytetrafluoroethylene autoclave liner, heated at 180 ° C for 12 h, cooled to room temperature, centrifuged to collect the product, washed with deionized water and anhydrous ethanol for multiple times, and vacuum dried at 60 ° C for 12 h to collect BRP.
[0034] The XRD patterns of the products obtained in Example 1, Comparative Example 1 and Comparative Example 2 are as follows: Figure 1 As shown in (a), Figure 1 (a) It can be seen that both comparative examples 1 and 2 correspond to the peaks of the standard card, which shows the success of the synthesis product. Example 1 does not have a peak of BRP, but Figure 1 (b) The peak of BRP can be seen in the Raman spectrum, indicating the successful synthesis of the product.
[0035] The TEM images of the product of Example 1, Comparative Example 1 and Comparative Example 2 are as follows: Figure 2 As shown by Figure 2 It can be seen that the shuttle-shaped β-FeOOH is loaded on the layered BRP. The method for investigating the degradation performance of the products of Example 1, Comparative Example 1 and Comparative Example 2 provided by the present invention on antibiotics is as follows:
[0036] Weigh 10 mg of each product of Example 1, Comparative Example 1, and Comparative Example 2, add them to a 50 mg / L levofloxacin (LVX) solution, stir the suspension with a magnetic stirrer, stir for 15 min in the dark to reach adsorption equilibrium, add 5 mM H2O2, take out 1 mL of the solution at a specified time, filter with a syringe with a 0.45 μm filter, and immediately add an equal amount of Na2S2O3 to terminate the reaction. Then, high performance liquid chromatography (HPLC, Shimadzu 2030C) was used to analyze the concentration of the remaining LVX. After the reaction was completed, the catalyst was centrifuged and washed, and then a cyclic stability test was performed.
[0037] The degradation efficiency of the products of Example 1, Comparative Example 1 and Comparative Example 2 on LVX is as follows: Figure 3 As shown by Figure 3 It can be seen that Example 1 exhibits a higher catalytic degradation efficiency for LVX; while Comparative Examples 1 and 2 have little removal effect on LVX.
[0038] Example 1 The EPR pattern of product activated H2O2 is as follows Figure 4 As shown, it can be seen that in the β-FeOOH@BRP / H2O2 system, there are a large number of hydroxyl radicals, some superoxide radicals and singlet oxygen generated, thereby oxidatively removing LVX.
[0039] The activity of β-FeOOH@BRP for Fenton degradation of LVX at different pH values in Example 1 is shown in Figure 1. Figure 5 As shown in the results, the degradation effects were almost the same at pH values between 3 and 9, and LVX could be treated in a wider pH range.
[0040] In Example 1, β-FeOOH@BRP was exposed to 5 mM of different ions such as Cl - 、SO4 2- 、HPO4 2- 、CO3 2- Mg 2+ , Ca 2+ and the activity of Fenton degradation of LVX under the influence of humic acid (HA), e.g. Figure 6 As shown, β-FeOOH@BRP in CO3 2- 、HPO4 2- It is slightly affected in cationic environment, but generally has strong anti-interference performance.
[0041] The results of the cycle test of β-FeOOH@BRP Fenton degradation of LVX in Example 1 are as follows: Figure 7 As shown, it can be seen that β-FeOOH@BRP has good reusability and cycle stability.
[0042] The effect of heterogeneous Fenton degradation of LVX by β-FeOOH@BRP in different water bodies in Example 1 is as follows Figure 8 As shown in Figure 2, the catalyst basically maintains a high degradation activity in different water bodies, except for tap water, because the type and concentration of cations in tap water have an effect on the degradation of β-FeOOH@BRP ( Figure 6 The results show its good potential and environmental application value in the remediation of organic pollutants in most water environments.
Claims
1. A method for preparing a phosphorus-iron oxyhydroxide composite material, characterized in that The specific preparation steps are as follows: The first step: adding a certain amount of β-iron oxyhydroxide (β-FeOOH) and black red phosphorus (BRP) into ethanol and stirring magnetically; Step 2: The mixture is transferred into a polytetrafluoroethylene high-pressure reactor for closed solvent thermal reaction, and filtered, washed and dried to obtain a black red phosphorus-containing iron oxyhydroxide composite material, which is recorded as β-FeOOH@BRP.
2. The preparation method according to claim 1, characterized in that: In the first step, the molar ratio of β-FeOOH to black red phosphorus was 1:
1.
3. The preparation method according to claim 1, characterized in that: In the first step, the molar ratio of β-FeOOH to ethanol was 1.28:
1.
4. The preparation method according to claim 1, characterized in that: In the first step, the magnetic stirring time was 30 min.
5. The preparation method according to claim 1, characterized in that: In the second step, the solvothermal temperature was 180 °C and the hydrothermal time was 12 h.
6. The preparation method according to claim 1, characterized in that: In the second step, the filtering method is centrifugation, and after filtering, water and ethanol are used for centrifugal washing and drying to obtain the phosphorus-iron hydroxide composite material.
7. The use of the phosphorus-iron oxyhydroxide composite as claimed in claim 7 in the degradation of antibiotics, comprising constructing a heterogeneous Fenton system with H2O2 to degrade antibiotic pollutants.
8. The use according to claim 8, characterized in that: The antibiotics include levofloxacin and the like.