Ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst as well as preparation method and application thereof
By preparing a ternary cobalt-manganese-iron Prussian blue analog calcination derivative catalyst, the problems of secondary pollution and high cost of cobalt-based materials were solved, achieving efficient and stable degradation of organic pollutants, which is suitable for advanced oxidation technology in water treatment.
Patent Information
- Application Number
- CN202511645259.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-11
- Publication Date
- 2026-02-03
AI Technical Summary
Existing cobalt-based materials used as persulfate-activated catalysts suffer from problems such as secondary pollution caused by cobalt ion dissolution and high cost. Further research is needed on the catalytic activity enhancement of ternary metal Prussian blue derivatives and the mechanism of action of internal defects in the materials.
A method for preparing ternary cobalt-manganese-iron Prussian blue analogue calcination derivative catalysts was adopted. Through co-precipitation and high-temperature calcination processes, a catalyst with a porous structure and high specific surface area was prepared. The synergistic effect of ternary metals was utilized to optimize the electronic structure and form oxygen vacancies, thereby promoting electron transfer and the formation of high-valence metal species.
The catalyst achieves high activity and stability over a wide pH range, and can efficiently degrade organic pollutants in water through multiple pathways, including free radicals and non-free radicals. It is environmentally friendly, easy to operate, and has the potential for large-scale production.
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Figure CN121446531A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of advanced oxidation technology for water treatment, and relates to a ternary cobalt-manganese-iron Prussian blue analogue calcination derivative catalyst as well as a preparation method and application thereof. BACKGROUND
[0002] With the rapid development of industrialization, the residue and accumulation of various types of refractory organic pollutants in water bodies have become a serious environmental problem. In particular, persistent organic pollutants such as antibiotics, dyes, and endocrine disruptors, traditional water treatment technologies are difficult to effectively remove, and pose a potential threat to the ecosystem and human health. The advanced oxidation technology based on sulfate radicals is an effective method for treating such persistent organic pollutants. Among them, the activation of persulfate by catalyst is the main way to generate sulfate radicals and other active oxygen species.
[0003] At present, cobalt-based materials are considered to be efficient persulfate activation catalysts, but there are problems such as secondary pollution caused by cobalt ion leaching and high cost. Prussian blue analogues, as a kind of metal-organic framework material, have become an ideal precursor for preparing efficient catalysts due to their adjustable structure, simple synthesis and low cost. By calcining Prussian blue analogue precursors at high temperature, metal oxides or metal / carbon composites with porous structure and high specific surface area can be obtained. However, the related researches on utilizing the synergistic effect of ternary metals (such as cobalt, manganese and iron) to improve the catalytic activity of Prussian blue derivatives, and in-depth study on the mechanism of internal defects of the material in the process of persulfate activation, still need to be further studied. Therefore, it is of great practical significance to develop a ternary metal Prussian blue derivative catalyst with simple preparation, high activity and good stability. SUMMARY
[0004] The purpose of the present application is to overcome the shortcomings of the prior art, and to provide a ternary metal synergistic cobalt-manganese-iron Prussian blue analogue calcination derivative catalyst as well as a preparation method and application thereof.
[0005] To solve the above technical problems, the following technical solutions are adopted in the present application:
[0006] A preparation method of a ternary cobalt-manganese-iron Prussian blue analogue calcination derivative catalyst, characterized in that the method comprises the following steps:
[0007] S1, preparation of a ternary cobalt-manganese-iron Prussian blue analogue precursor: under strong magnetic stirring, a mixed solution of potassium ferricyanide and polyvinylpyrrolidone is added to a solution obtained by mixing cobalt chloride and manganese chloride, and stirring is continued at a temperature of 70-80 DEG C for 60 min, and then aging in an oven at a temperature of 35-40 DEG C for 24 h. Subsequently, the ternary cobalt-manganese-iron Prussian blue analogue precursor is obtained by washing, centrifuging, drying and grinding.
[0008] S2, calcining the precursor obtained in step S1 to obtain a ternary cobalt-manganese-iron Prussian blue analogue calcined derivative.
[0009] The preparation method of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst, further improved, the mass ratio of potassium ferricyanide and polyvinylpyrrolidone is 1.6:1; the molar ratio of the potassium ferricyanide, cobalt chloride and manganese chloride is 1:0.75:0.75; the ratio of the potassium ferricyanide and the solvent is 33g:1000mL; the solvent is water. The washing solvent is ethanol and deionized water. The centrifugal speed is 8000-10000r / min; the centrifugal time is 3-5min. The drying is carried out in a vacuum drying oven; the drying temperature is 60-70℃; the drying time is 12h.
[0010] The preparation method of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst, further improved, the calcination is carried out in a tube furnace; the heating rate during the calcination process is 3-3.5℃ / min, the calcination temperature is 700-750℃; the calcination time is 1h. The calcination process is carried out under the protection of 98.5%-99.99% nitrogen.
[0011] The application also provides a ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst, which is used for activating persulfate and efficiently degrading organic pollutants in water, so as to realize the rapid removal of organic pollutants in water.
[0012] The application, further improved, comprises the following steps:
[0013] The ratio of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst to the water sample containing organic pollutants is 2.5-10mg:1L; the initial concentration of the organic pollutants in the organic pollutant wastewater is 0.25-10mg / L; the persulfate is peroxymonosulfate; the ratio of the persulfate to the water sample containing organic pollutants is 0.325-1.3mmol:1L; the oxidation reaction time is 0-20min, and the initial pH value of the water sample containing organic pollutants is 3-11.
[0014] Compared with the prior art, the application has the following advantages:
[0015] 1. Synergy, high activity. The coexistence of cobalt, manganese and iron effectively regulates the electronic structure of the material and optimizes the properties of the active site. And the high-temperature calcination process creates a large number of oxygen vacancies on the surface and inside the material. Oxygen vacancies not only serve as the main adsorption and activation sites for persulfate, but also promote electron transfer and the formation of high-valent metal species. This special structure makes the catalyst of the present application exhibit ultra-high catalytic activity, and can efficiently degrade pollutants through multiple pathways of free radicals and non-free radicals.
[0016] 2. The two-step method of "co-precipitation + high-temperature calcination" adopted by the present application is a mature and widely used technology in industry. The raw materials used are common inorganic salts, which are low in price and have low requirements for equipment and conditions. The entire preparation process is green, environmentally friendly and easy to operate, and has the potential for large-scale production, laying a solid foundation for the industrial application of this technology.
[0017] 3. The catalyst provided by the present application can maintain high activity in a wide pH range. More importantly, the removal effect of organic pollutants in various real water samples is still significant, showing good stability and tolerance to complex water environments, and has practical application value. BRIEF DESCRIPTION OF DRAWINGS
[0018] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the drawings in the embodiments of the present application.
[0019] Figure 1 SEM image of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative prepared in Example 1.
[0020] Figure 2 XRD image of the ternary cobalt-manganese-iron Prussian blue analogue, binary cobalt-iron Prussian blue analogue prepared in Example 1.
[0021] Figure 3 XRD image of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative, binary cobalt-iron Prussian blue analogue calcined derivative prepared in Example 1.
[0022] Figure 4 Degradation effect diagram of sulfamethoxazole in water sample by ternary cobalt-manganese-iron Prussian blue analogue calcined derivative, ternary cobalt-manganese-iron Prussian blue analogue, binary cobalt-iron Prussian blue analogue calcined derivative, binary cobalt-iron Prussian blue analogue activated persulfate prepared in Example 2.
[0023] Figure 5 Degradation effect diagram of sulfamethoxazole degraded by ternary cobalt-manganese-iron Prussian blue analogue calcined derivative activated persulfate under different catalyst addition amounts in Example 3 of the present application.
[0024] Figure 6 Figure for degradation effect of ternary cobalt-manganese-iron Prussian blue analogue calcined derivative activated persulfate on degradation of sulfamethoxazole under different persulfate addition amounts in embodiment 4 of the present application.
[0025] Figure 7 Figure for degradation effect of ternary cobalt-manganese-iron Prussian blue analogue calcined derivative activated persulfate on degradation of sulfamethoxazole under different pH values in embodiment 5 of the present application.
[0026] Figure 8 XPS spectra of Co2p, Mn2p, Fe2p and O1s of ternary cobalt-manganese-iron Prussian blue analogue calcined derivative before and after reaction in embodiment 6 of the present application.
[0027] Figure 9 Figure for degradation effect of ternary cobalt-manganese-iron Prussian blue analogue calcined derivative activated persulfate on degradation of sulfamethoxazole under different actual background water quality conditions in embodiment 7 of the present application. DETAILED DESCRIPTION
[0028] The present application will be further described in conjunction with the accompanying drawings and specific preferred embodiments of the present application, but the protection scope of the present application is not limited thereby.
[0029] In the following comparative examples and embodiments, if no special description is given, the raw materials and instruments used are commercially available, the processes used are conventional processes, the equipment used is conventional equipment, and the data obtained are the average values of more than three repeated experiments.
[0030] Example 1
[0031] In the present example, the preparation method of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst used includes the following specific steps:
[0032] Dissolve 3.2 g of potassium ferricyanide and 2 g of polyvinylpyrrolidone (PVP) in 100 mL of deionized water to obtain a yellow transparent solution A. Then, dissolve 1 g of cobalt (II) chloride and 1.5 g of manganese (II) chloride in 100 mL of deionized water to form solution B. Add the A solution dropwise to the B solution at 80°C while stirring vigorously. After the A solution is completely added, continue to stir the obtained suspension at 80°C for 1 h. Then, place it in a 40°C oven for 24 h. Centrifuge the above precipitate, and wash it with deionized water and ethanol for 3 times. After vacuum drying at 60°C for 12 h, grind the ternary cobalt-manganese-iron Prussian blue analogue in a corundum mortar, and name it as CoMnFe-PBAs.
[0033] Subsequently, the obtained material was placed into a porcelain boat, covered with a lid and moved into a tube furnace, calcined at 700℃ for 1 h with a heating rate of 3℃ / min under nitrogen atmosphere to obtain a ternary cobalt-manganese-iron Prussian blue analog calcined derivative, named CoMnFe-NC.
[0034] In this example, a binary cobalt-iron Prussian blue analog and a binary cobalt-iron Prussian blue analog calcined derivative were also prepared. The preparation method was basically the same as that of the ternary cobalt-manganese-iron Prussian blue analog (CoMnFe-PBAs), except that the B solution was 2 g of cobalt (II) chloride dissolved in 100 mL of deionized water. The obtained binary cobalt-iron Prussian blue analog was named CoFe-PBAs, and the catalyst obtained after calcination was a binary cobalt-iron Prussian blue analog calcined derivative, named CoFe-NC.
[0035] Figure 1 SEM image of the ternary cobalt-manganese-iron Prussian blue analog calcined derivative (CoMnFe-NC) prepared in Example 1 of the present application. As can be seen from the figure, the obtained catalyst is composed of cubes with uneven surfaces and regular shapes. This special microstructure will form more reaction sites on the surface of the catalyst and provide more opportunities for contact with chemical oxidants and pollutant molecules during the reaction process.
[0036] Figure 2 XRD pattern of the ternary cobalt-manganese-iron Prussian blue analog (CoMnFe-PBAs) and the binary cobalt-iron Prussian blue analog (CoFe-PBAs) prepared in Example 1 of the present application. The diffraction peak positions are 2θ = 17.2°, 24.4°, 34.8° and 39.1°, corresponding to the (200), (220), (400) and (420) crystal planes of Prussian blue analogs with face-centered cubic structure (Co(Fe(CN)6) 0.667 (H2O) 3.333 (PDF #01-086-0502), indicating that Prussian blue analogs were successfully prepared in this study.
[0037] Figure 3 XRD pattern of the ternary cobalt-manganese-iron Prussian blue analog calcined derivative (CoMnFe-NC) and the binary cobalt-iron Prussian blue analog calcined derivative (CoFe-NC) prepared in Example 1 of the present application. Through phase analysis, it was proved that a heterojunction was formed, and there were two phases of Mn-Fe-O and Co-Fe-O, which formed a large number of contact interfaces between them. At the interface, an internal electric field was formed because of the different electronic band structures of different materials. This electric field can promote the transmission of ions and electrons, reduce the activation energy of the reaction and increase the reaction kinetics. Because of the different valence bands between each component of the heterojunction composite, an internal electric field is generated at the heterojunction interface.
[0038] Example 2
[0039] The application of a ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst, specifically the application of a ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst to activate persulfate and efficiently degrade sulfamethoxazole in a water sample, comprises the following steps:
[0040] 0.5 mg of ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC), ternary cobalt-manganese-iron Prussian blue analogue (CoMnFe-PBAs), binary cobalt-iron Prussian blue analogue calcined derivative (CoFe-NC), and binary cobalt-iron Prussian blue analogue (CoFe-PBAs) were weighed and added to 100 mL of a 5 mg / L sulfamethoxazole solution, respectively. 0.1 mol / L hydrochloric acid and 0.1 mol / L sodium hydroxide solution were used to adjust the initial pH of the reaction to 7. Then, solid peroxymonosulfate (chemical formula, KHSO5, PMS) was added to make the PMS concentration in the system 0.325 mM, and the catalytic degradation reaction was carried out for 20 min to complete the degradation of sulfamethoxazole in the water sample.
[0041] During the catalytic degradation reaction, 1 mL of reaction solution was taken at 0 min, 0.5 min, 1 min, 2.5 min, 5 min, 7.5 min, 10 min, 12.5 min, 15 min, and 20 min, 0.22 μm water filter head was used, and 20 μL of 1 M sodium thiosulfate solution was added to a liquid phase vial, and the concentration of sulfamethoxazole in the solution was detected by high performance liquid chromatography.
[0042] Control experiment:
[0043] PMS group: no catalyst was added, and other conditions were the same.
[0044] CoMnFe-NC group: only CoMnFe-NC was added, no PMS was added, and other conditions were the same.
[0045] Figure 4The figure shows the degradation effect of sulfamethoxazole in water samples by activating persulfate with the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC), ternary cobalt-manganese-iron Prussian blue analogue (CoMnFe-PBAs), binary cobalt-iron Prussian blue analogue calcined derivative (CoFe-NC), and binary cobalt-iron Prussian blue analogue (CoFe-PBAs) prepared in Example 2. Compared with the ternary cobalt-manganese-iron Prussian blue analogue (CoMnFe-PBAs), binary cobalt-iron Prussian blue analogue calcined derivative (CoFe-NC), and binary cobalt-iron Prussian blue analogue (CoFe-PBAs), the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst can effectively activate per-sulfate, thereby effectively degrading sulfamethoxazole in water samples, and degrading 100% of sulfamethoxazole within 15 minutes. This indicates that the synergistic effect between the ternary metals cobalt, manganese, and iron promotes the occurrence of the catalytic reaction. This ternary metal catalyst is a high-performance heterogeneous Fenton-like catalyst, has good ability to activate persulfate, and can effectively remove organic pollutants in water bodies.
[0046] Example 3
[0047] The effect of different catalyst addition amounts on antibiotic degradation was investigated. Specifically, the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst was used to activate persulfate to degrade sulfamethoxazole-containing water samples, including the following steps:
[0048] 0 mg, 2.5 mg, 5 mg, 7.5 mg, and 10 mg of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) prepared in Example 1 were respectively added to 100 mL of a 5 mg / L sulfamethoxazole solution, and the initial pH of the reaction was 7. Then, solid persulfate (chemical formula: KHSO5, PMS) was added to make the concentration of PMS in the system 0.325 mM, and the catalytic degradation reaction was carried out for 20 min to complete the degradation of sulfamethoxazole in the water sample. During the catalytic degradation reaction, 1 mL of reaction solution was taken at 0 min, 0.5 min, 1 min, 2.5 min, 5 min, 7.5 min, 10 min, 12.5 min, 15 min, and 20 min, a 0.22 μm water filter was used, and 20 μL of 1 M sodium thiosulfate solution was added to a liquid phase vial, and the concentration of sulfamethoxazole in the solution was detected by high performance liquid chromatography.
[0049] Figure 5 The figure shows the degradation effect of sulfamethoxazole by activating persulfate with the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst under different catalyst addition amounts in Example 3. The results are as follows Figure 5As shown, the dosage of CoMnFe-NC catalyst has a significant positive effect on the degradation of sulfamethoxazole.
[0050] Example 4
[0051] The effect of different amounts of persulfate on antibiotic degradation was investigated. Specifically, the degradation of sulfamethoxazole in water samples was treated by activating persulfate with ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst, including the following steps:
[0052] Five portions of 0.5 mg of ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) were weighed and added to 100 mL of 5 mg / L sulfamethoxazole solution, and the initial pH of the reaction was 7. Then, solid sodium persulfate (chemical formula: KHSO5, PMS) was added to make the concentration of PMS in the system 0 mM, 0.325 mM, 0.65 mM, 0.975 mM, and 1.3 mM, respectively, and the catalytic degradation reaction was carried out for 20 min to complete the degradation of sulfamethoxazole in the water sample.
[0053] During the catalytic degradation reaction, 1 mL of reaction solution was taken at 0 min, 0.5 min, 1 min, 2.5 min, 5 min, 7.5 min, 10 min, 12.5 min, 15 min, and 20 min, and a 0.22 μm water filter was used and added to a liquid phase vial pre-added with 20 μL of 1 M sodium thiosulfate solution, and the concentration of sulfamethoxazole in the solution was detected by high performance liquid chromatography.
[0054] Figure 6 The degradation effect of ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst activated persulfate on sulfamethoxazole degradation at different amounts of persulfate in Example 4 of the present application is shown in the figure. The results are as follows Figure 6 As shown, when the amount of persulfate increased from 0 mM to 1.3 mM, the degradation efficiency of sulfamethoxazole first increased and then decreased, which may be due to the saturation of the active sites of CoMnFe-NC, which cannot participate in more persulfate activation.
[0055] Example 5
[0056] The effect of different pH values on antibiotic degradation was investigated. Specifically, the degradation of sulfamethoxazole in water samples was treated by activating persulfate with ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst, including the following steps:
[0057] Take 5 parts of 0.5 mg of ternary cobalt manganese iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst, add 100 mL, 5 mg / L of sulfamethoxazole solution, and adjust the initial pH of the reaction to 3, 4, 5, 7, 9, 10, and 11 using 0.1 mol / L hydrochloric acid and 0.1 mol / L sodium hydroxide solution. Then, add solid sodium persulfate (chemical formula: KHSO5, PMS) to make the concentration of PMS in the system 0.325 mM, and carry out catalytic degradation reaction for 20 min to complete the degradation of sulfamethoxazole in the water sample.
[0058] During the catalytic degradation reaction, 1 mL of reaction solution was taken at 0 min, 0.5 min, 1 min, 2.5 min, 5 min, 7.5 min, 10 min, 12.5 min, 15 min, and 20 min, 0.22 μm water filter was used, and 20 μL of 1 M sodium thiosulfate solution was added to the liquid phase vial, and the concentration of sulfamethoxazole in the solution was detected by high performance liquid chromatography.
[0059] Figure 7 The degradation effect diagram of ternary cobalt manganese iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst activated persulfate degradation of sulfamethoxazole at different pH values in Example 5 of the present application. As shown in Figure 7 , the removal rate of sulfamethoxazole is 100% at various initial pH values of 4 to 10. The degradation efficiency of sulfamethoxazole is inhibited to a certain extent at pH values of 3 and 11. This phenomenon is due to the fact that when the acidity is too strong, a large number of hydrogen ions combine with the hydroxyl groups on the surface of the catalyst, occupying the active sites used to activate persulfate; when the alkalinity is too strong, HSO5 - is converted to SO5 2- , and the oxidation-reduction potential of SO5 2- is low and the activity is poor, so that fewer active free radicals are generated. However, overall, the ternary cobalt manganese iron Prussian blue analogue calcined derivative (CoMnFe-NC) activated persulfate degradation of antibiotics in water has a wide pH range.
[0060] Example 6
[0061] The valence state changes of metal cobalt, metal iron, and metal manganese before and after the reaction of the ternary cobalt manganese iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst in the present application were investigated,
[0062] including the following steps:
[0063] Take 0.5 mg ternary cobalt manganese iron Prussian blue analogue calcined derivative (CoMnFe-NC) into 100 mL, 5 mg / L sulfamethoxazole solution, and adjust the initial pH of the reaction to 7 using 0.1 mol / L hydrochloric acid and 0.1 mol / L sodium hydroxide solution. Then add solid peroxymonosulfate (chemical formula: KHSO5, PMS) to make the PMS concentration in the system 0.325 mM, and carry out the catalytic degradation reaction for 20 min to complete the degradation of sulfamethoxazole in the water sample.
[0064] Figure 8 The XPS spectra of Co2p, Fe2p, Mn2p and O1s of the ternary cobalt manganese iron Prussian blue analogue calcined derivative (CoMnFe-NC) before and after reaction in Example 6 of the present application are shown in the figure. As shown in the figure, after reaction, the peak area ratio of Co 2+ decreases, and the peak area ratio of Co 3+ increases; after reaction, the peak area ratio of Fe 2+ decreases, and the peak area ratio of Fe 3+ increases, indicating that in the process of activating persulfate, cobalt and iron are the main catalytic active centers, which trigger the reaction by losing electrons. Manganese participates in an internal redox cycle, greatly enhancing the stability and sustained combat capability of the catalyst.
[0065] Example 7
[0066] Take 5 portions of 0.5 mg ternary cobalt manganese iron Prussian blue analogue calcined derivative (CoMnFe-NC) into 100 mL, 5 mg / L sulfamethoxazole actual water sample, and adjust the initial pH of the reaction to 7 using 0.1 mol / L hydrochloric acid and 0.1 mol / L sodium hydroxide solution. Then add solid peroxymonosulfate (chemical formula: KHSO5, PMS) to make the PMS concentration in the system 0.325 mM, and carry out the catalytic degradation reaction for 20 min to complete the degradation of sulfamethoxazole in the actual water sample. The above-mentioned actual water samples are tap water pipeline water sample, Xiangjiang River water sample, Taoshu Lake water sample and Houhu Lake water sample, and deionized water containing the same concentration of sulfamethoxazole is used as a control.
[0067] During the catalytic degradation reaction process, 1 mL of reaction solution was taken at 0 min, 0.5 min, 1 min, 2.5 min, 5 min, 7.5 min, 10 min, 12.5 min, 15 min and 20 min, 0.22 μm water filter head was used, and 20 μL of 1 M sodium thiosulfate solution was added to a liquid phase vial, and the concentration of sulfamethoxazole in the solution was detected by high performance liquid chromatography.
[0068] Figure 9The degradation effect diagram of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative (CoMnFe-NC) catalyst activated persulfate for degrading sulfamethoxazole under different actual background water quality conditions in embodiment 7 of the present application is shown in the results. Figure 9 As shown in the results, in Xiangjiang water sample, Taosihu water sample and Houhu water sample, the degradation rate of sulfamethoxazole is slightly lower than that in ultrapure water system, which is due to the existence of a large amount of free organic matter, free ions and part of organic matter in the actual water body, which leads to the reduction of the degradation rate of the active substances generated in the reaction, but the removal effect of sulfamethoxazole can still reach more than 85% within 20 min, which shows that the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative activated persulfate for degrading organic pollutants in water body in the present application has broad practical application prospect and application value.
[0069] In summary, the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst has the advantages of simple process, convenient operation, high treatment efficiency, less oxidant addition, strong anti-interference ability and the like.
[0070] The ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst can realize efficient removal of organic pollutants in water body, has high use value and good application prospect.
[0071] The above is only a preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with a preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make many possible changes and modifications to the technical solutions of the present application, or modify equivalent embodiments, without departing from the spirit and technical solutions of the present application. Therefore, any simple modification, equivalent replacement, equivalent change and modification of the above embodiments according to the technical essence of the present application, all still belong to the protection scope of the technical solutions of the present application.
Claims
1. A method for preparing a ternary cobalt-manganese-iron Prussian blue analog calcination derivative catalyst, characterized in that, The method includes the following steps: S1. Preparation of a ternary cobalt-manganese-iron Prussian blue analog precursor, characterized in that: a mixture of potassium ferricyanide and polyvinylpyrrolidone is added to a solution obtained by mixing cobalt chloride and manganese chloride under strong magnetic stirring, and stirring is continued at 70-80°C for 60 min, followed by aging in an oven at 35-40°C for 24 h; then, the ternary cobalt-manganese-iron Prussian blue analog precursor is obtained by washing, centrifugation, drying, and grinding. S2. The precursor obtained in step S1 is calcined to obtain a calcined derivative of a ternary cobalt manganese iron Prussian blue analog. According to the preparation method of claim 1, in step S1, the mass ratio of potassium ferricyanide to polyvinylpyrrolidone is 1.6:1; the molar ratio of potassium ferricyanide, cobalt chloride, and manganese chloride is 1:0.75:0.75; the ratio of potassium ferricyanide to solvent is 33-34 g:1000 mL; the solvent is deionized water; the washing solvent is ethanol and water; the centrifugation speed is 8000-10000 r / min; the centrifugation time is 3-5 min; the drying is carried out in a vacuum drying oven; the drying temperature is 60-70℃; and the drying time is 12 h. According to the preparation method of claim 1, the calcination in step S2 is carried out in a tube furnace; the heating rate during the calcination process is 3-3.5℃ / min, the calcination temperature is 700-750℃, the calcination time is 1h, and the calcination process is carried out under nitrogen protection of 98.5%-99.99%.
2. The application of the ternary cobalt-manganese-iron Prussian blue analog calcination derivative catalyst as described in claim 1, characterized in that, It is used to activate persulfate and efficiently degrade organic pollutants in water, thereby achieving rapid removal of organic pollutants from water bodies.
3. The application according to claim 2, characterized in that, Includes the following steps: By adding the calcined derivative of the ternary cobalt-manganese-iron Prussian blue analogue to a water sample containing organic pollutants, and then adding persulfate for oxidation, the organic pollutants in the water can be efficiently removed.
4. The application according to claim 3, characterized in that, The ratio of the ternary cobalt-manganese-iron Prussian blue analogue calcined derivative catalyst to the water sample containing organic pollutants is 2.5–10 mg:1 L; the initial concentration of organic pollutants in the organic pollutant wastewater is 0.25–10 mg / L; the persulfate is permonosulfate; the organic pollutant wastewater is sulfonamide antibiotic wastewater; the sulfonamide antibiotic is sulfamethoxazole; the ratio of persulfate to the water sample containing organic pollutants is 0.325–1.3 mmol:1 L; the oxidation reaction time is 0–20 min; and the initial pH value of the water sample containing organic pollutants is 3–11.