Efficient Fenton-like catalyst of phenanthroline modified monatomic iron loaded carbon nitride as well as preparation method and application of efficient Fenton-like catalyst
By modifying single-atom iron-supported carbon nitride catalyst by orthophenolone, the iron sludge, pH limit and insufficient stability of the traditional Fenton reaction was solved, and efficient and easy-to-production catalyst applications were achieved, especially the degradation of organic pollutants in a wide pH range.
Patent Information
- Application Number
- CN202510516121.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-23
- Publication Date
- 2025-07-11
AI Technical Summary
The traditional homogeneous Fenton reaction has problems such as iron sludge generation, narrow pH application range, many by-products and insufficient stability. In addition, single-atom iron-supported carbon nitride catalysts are complex in preparation and limited load, making it difficult to apply on a large scale.
The single-atom iron-supported carbon nitride catalyst was modified by orthophenylon-modified single-atom iron-supported carbon nitride catalyst, and the metal atoms were fixed on the support using orthophenylon-modified single-atom iron-supported carbon nitride was prepared.
It realizes the high-efficiency tetracycline hydrochloride degradation performance of the catalyst, has strong anti-pH interference ability, high degradation efficiency, wide application range, simple operation, and meets green chemistry requirements.
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Figure CN120286072A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of catalysts, and in particular to a highly efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride, and a preparation method and application thereof. Background Art
[0002] With the increasingly severe environmental problems, the development of efficient and environmentally friendly catalysts for environmental remediation and energy conversion has become a research hotspot. The traditional homogeneous Fenton reaction plays an important role in the field of water treatment. Its principle is that ferrous ions (Fe 2+ ) react with hydrogen peroxide (H2O2) to generate highly oxidizing hydroxyl radicals (·OH), thereby degrading organic pollutants in water. This reaction system is simple, easy to operate, and can effectively treat some refractory organic pollutants. However, the traditional homogeneous Fenton reaction also has some deficiencies. First, a large amount of iron sludge is generated during the reaction process, increasing the difficulty and cost of subsequent treatment. Second, its pH application range is relatively narrow and usually needs to be carried out under acidic conditions, which limits its application under different water quality conditions. In addition, the traditional homogeneous Fenton reaction also produces more by-products, such as iron ions, which may cause secondary pollution to the environment. At present, the research focus is mainly on the improvement of the homogeneous Fenton process, such as by adding chelating ligands, using carbon dots to prepare new catalysts, etc., to solve problems such as iron sludge and pH limitation, and to improve the efficiency and environmental friendliness of the Fenton reaction. Nowadays, researchers have proposed a single-atom iron supported on carbon nitride catalyst (Fe-SACs), which shows great application potential in the fields of advanced oxidation processes (AOPs), oxygen reduction reaction (ORR), and photocatalysis. Its structural formula is as follows in formula (II):
[0003]
[0004] Single-atom iron catalysts have attracted considerable attention in environmental remediation due to their unique properties, including the highest atomic utilization efficiency, adjustable electronic structure, and excellent catalytic efficacy. However, the preparation process of Fe-SACs is complex, requiring precise control of synthesis conditions, with a high technical threshold and being difficult to produce on a large scale; and its loading amount is limited, and the metal loading amount is usually low, which may limit its application in high-concentration reaction systems; in addition, this substance is sensitive to reaction conditions. In some applications, the performance of the catalyst may be limited by reaction conditions (such as temperature, pH value, etc.), resulting in insufficient stability. Especially under long-term operation or extreme conditions, metal atoms may migrate or agglomerate.
[0005] Therefore, it is very urgent to develop a stable, efficient, and easy-to-produce highly efficient Fenton-like catalyst. Summary of the Invention
[0006] The first object of the present invention is to solve the deficiencies of the above-mentioned traditional technologies and provide a highly efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride. As a metal chelating agent, phenanthroline can immobilize metal atoms on the carrier, thereby increasing the active sites. The Fenton-like catalyst of single-atom iron supported on carbon nitride modified with phenanthroline not only exhibits highly efficient degradation performance of tetracycline hydrochloride at room temperature but also has excellent anti-pH interference ability.
[0007] To achieve the above object, the present invention adopts the following technical solutions:
[0008] A highly efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride has the following chemical structural formula:
[0009]
[0010] The second object of the present invention is to provide a preparation method of a highly efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride, specifically:
[0011] Mix 1,10-phenanthroline and an iron source and dissolve them in a solvent. After complete dissolution, pour in melamine and grind. After drying, raise the temperature for calcination to obtain the highly efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride, denoted as phen-Fe-CN; wherein, the iron element in the iron source accounts for 0.5%-5% of the mass of phen-Fe-CN.
[0012] Further, the iron source is a soluble salt of divalent or trivalent iron, and its anion is selected from at least one of chloride ion, nitrate ion, and sulfate ion.
[0013] Further, the mass ratio of 1,10-phenanthroline to melamine is 1:20-22, more preferably 1:20.
[0014] Further, the solvent is a mixed solvent of ethanol and water.
[0015] Further, the drying temperature is 60-65°C, more preferably 60°C.
[0016] Further, the calcination is specifically: raise the temperature from room temperature to 700°C and then calcine at 700°C for 2-2.5 h, and the heating rate is 5°C / min.
[0017] Further, the iron source is ferrous sulfate.
[0018] Further, the iron element accounts for 3% of the mass of the highly efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride, phen-Fe-CN.
[0019] The third object of the present invention is to provide an application of the above-mentioned efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride in the degradation of pollutants by Fenton-like reaction.
[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0021] 1. The present invention synthesizes phen-Fe-CN by a one-pot method. The synthesis steps are simple, the operation is convenient, and the raw materials are inexpensive and easy to purchase. It does not involve complex chemical treatments and the generation of toxic and harmful substances, meeting the development requirements of green chemistry.
[0022] 2. Based on the introduction of phenanthroline, the present invention endows phen-Fe-CN with more reactive sites and more excellent Fenton-like performance than Fe-CN.
[0023] 3. Compared with the existing heterogeneous Fenton catalyst water treatment technology, the heterogeneous phenanthroline-modified single-atom iron supported on carbon nitride in the present invention for activating peroxymonosulfate to degrade pollutants is not limited by pH and has broad application prospects.
[0024] 4. The heterogeneous phenanthroline-modified single-atom iron supported on carbon nitride Fenton-like catalyst of the present invention can efficiently degrade tetracycline hydrochloride at room temperature, and the reaction conditions are mild and easy to achieve.
[0025] 5. The catalyst of the present invention can catalyze and degrade a variety of organic pollutants within 10 minutes at room temperature, and has a high catalytic efficiency. Description of the Drawings
[0026] Figure 1 It is the X-ray diffraction pattern (XRD) of Example 1 and the comparative example.
[0027] Figure 2 It is the X-ray photoelectron spectroscopy (XPS) of Example 1 and the comparative example.
[0028] Figure 3 It is the comparison diagram of the degradation activity of phen-Fe-CN loaded with single-atom iron in different ratios for tetracycline hydrochloride.
[0029] Figure 4 It is the comparison diagram of the degradation activity of Example 1 for tetracycline hydrochloride at different pH values.
[0030] Figure 5 It is the comparison diagram of the degradation activity of Example 1 and the comparative example for tetracycline hydrochloride. Detailed Embodiments
[0031] The present invention will be described more comprehensively and clearly below in conjunction with the accompanying drawings and embodiments, but the present invention is not limited to the scope of the described embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the protection scope of the present invention.
[0032] As described above, the present invention provides a method for preparing phenanthroline-modified single-atom iron supported on carbon nitride, comprising the following steps:
[0033] 1 g of 1,10-phenanthroline and 0.1 - 0.5 g of an iron source are mixed and dissolved in a solvent. After complete dissolution, 20 - 22 g of melamine is added, ground, dried in an oven at 60 - 65 °C, and then calcined in a muffle furnace at 700 °C for 2 - 2.5 h with a heating rate of 5 °C / min to produce the phenanthroline-modified single-atom iron supported on carbon nitride catalyst phen-Fe-CN. Among them, the iron element accounts for 0.5% - 5% of the mass of the phenanthroline-modified single-atom iron supported on carbon nitride catalyst phen-Fe-CN; the iron source can be selected according to actual needs. For example, it can be a soluble salt of divalent or trivalent iron, and its anion is selected from at least one of chloride ion, nitrate ion, and sulfate ion. For example, it can be one or more of ferrous sulfate, ferrous chloride, ferrous nitrate, ferric sulfate, ferric chloride, and ferric nitrate, and can be selected according to actual needs.
[0034] Furthermore, in the embodiments of the present invention, the iron source is preferably ferrous sulfate, which is easily soluble in water, facilitating uniform doping, and has a low cost and is easy to obtain; the meaning of the mass fraction is that the iron element in the iron source accounts for 0.5% - 5% of the mass of phen-Fe-CN.
[0035] In some embodiments, the mass of the iron source can specifically be selected from 0.1 g, 0.2 g, 0.3 g, 0.4 g, or 0.5 g, and the iron element in the iron source accounts for 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of the mass of phen-Fe-CN, or other values within the range, which can be selected according to actual needs and are not limited herein.
[0036] The following further describes the present invention; unless otherwise specified, the raw materials used in the examples are all commercially available or can be prepared by conventional methods.
[0037] Example 1: Preparation of phenanthroline-modified single-atom iron supported on carbon nitride (phen-Fe-CN)
[0038] Mix 1,10-phenanthroline (1 g, 5 mmol) and ferrous sulfate heptahydrate (300 mg, 1 mmol), then add 2.5 mL of ethanol and an appropriate amount of water to dissolve. After complete dissolution, pour the mixture into melamine (20 g, 159 mmol). Grind, dry in an oven at 60 °C, then place in a muffle furnace and heat from room temperature to 700 °C at a rate of 5 °C / min and calcine for 2 h. Wash and dry the obtained black solid at room temperature to obtain the phenanthroline-modified single-atom iron-loaded carbon nitride catalyst phen-Fe-CN.
[0039] The structural formula of phen-Fe-CN is shown in the following formula (I):
[0040]
[0041] Example 2: Synthesis of phen-Fe-CN with different ratios
[0042] Mix 1,10-phenanthroline (1 g, 5 mmol) and different contents of ferrous sulfate heptahydrate (100, 200, 300, 400, 500 mg), then add 2.5 mL of ethanol and an appropriate amount of water to dissolve. After complete dissolution, pour the mixture into melamine (20 g, 159 mmol). Grind, dry in an oven at 60 °C, then place in a muffle furnace and calcine for 2 h at a temperature of 700 °C and a heating rate of 5 °C / min. Wash and dry the obtained black solid at room temperature, and name the obtained samples phen-Fe 0.1 -CN, phen-Fe 0.2 -CN, phen-Fe 0.3 -CN (i.e., the product of Example 1), phen-Fe 0.4 -CN and phen-Fe 0.5 -CN.
[0043] Example 3: Preparation of phenanthroline-modified single-atom iron-loaded carbon nitride (phen-Fe-CN)
[0044] Mix 1,10-phenanthroline (1 g, 5 mmol) and ferric chloride (162 mg, 1 mmol), then add 2.5 mL of ethanol and an appropriate amount of water to dissolve. After complete dissolution, pour the mixture into melamine (20 g, 159 mmol). Grind, dry in an oven at 60 °C, then place in a muffle furnace and heat from room temperature to 700 °C at a rate of 5 °C / min and calcine for 2 h. Wash and dry the obtained black solid at room temperature to obtain the phenanthroline-modified single-atom iron-loaded carbon nitride catalyst phen-Fe-CN.
[0045] Comparative example: Preparation of single-atom iron-loaded carbon nitride Fe-CN
[0046] Ferrous sulfate heptahydrate (300 mg, 1 mmol) was dissolved after adding 2.5 mL of ethanol and an appropriate amount of water. After complete dissolution, the solution was poured into melamine (20 g, 159 mmol). It was ground, dried in an oven at 60 °C, and then calcined in a muffle furnace at 700 °C for 2 h with a heating rate of 5 °C / min. The obtained yellow solid was washed and dried at room temperature to obtain the single-atom iron-loaded carbon nitride catalyst Fe-CN.
[0047] Test Example
[0048] Testing the application of the above catalyst in the degradation of tetracycline hydrochloride includes the following steps:
[0049] At room temperature, 30 mg of the catalyst was added to 100 mL of a tetracycline hydrochloride solution with a concentration of 20 mg / L, ultrasonically dispersed, and stirred for 30 min. Then a sample was taken as the initial concentration of the tetracycline hydrochloride solution in the reaction. Subsequently, 20 mg of peroxymonosulfate (PMS) was added to make the PMS concentration in the reaction system 0.65 mmol / L. Timing started, and samples were taken at 1, 2, 4, 7, and 10 minutes, filtered through a 0.22 μm filter, and immediately the absorbance was detected using a UV spectrophotometer.
[0050] Figure 1 XRD patterns of Example 1 and the comparative example.
[0051] Figure 2 XPS of Example 1 and the comparative example
[0052] Figure 3 Degradation activity comparison diagram of phen-Fe-CN with different ratios of single-atom iron loading for tetracycline hydrochloride. The degradation rate change curve of the prepared phenanthroline-modified single-atom iron carbon nitride Fenton-like catalyst for 20 mg / L of tetracycline hydrochloride with time is as Figure 3 shown. After 1 min of reaction, the degradation rate of tetracycline hydrochloride can reach over 50%, and after 10 min of reaction, the degradation rate of tetracycline hydrochloride reaches 80%. The reaction rate is fast and the conditions are mild, indicating that the phenanthroline-modified single-atom iron carbon nitride catalyst of the present invention has good Fenton-like catalytic performance. Compared with other Fe doping ratios, phen-Fe 0.3 -CN is the optimal sample for degradation.
[0053] Changing the pH value in the reaction of degrading tetracycline hydrochloride, the degradation of tetracycline hydrochloride by phen-Fe-CN under different pH conditions was tested, and the results are as Figure 4 shown; from Figure 4It can be seen that in a relatively wide pH range of 1-11, after reacting for 10 minutes, the degradation rate of tetracycline hydrochloride can reach over 70%, which means that the degradation of tetracycline hydrochloride is basically not affected by pH.
[0054] Figure 5 It is a comparison chart of the activities of Example 1 and the comparative example for degrading tetracycline hydrochloride. It can be seen from the figure that the reaction activity of phen-Fe-CN is the best. After reacting for 10 minutes, the degradation rate of tetracycline hydrochloride reaches 94%, and the degradation rate of Fe-CN for tetracycline hydrochloride is only 42%.
[0055] In summary, through the modification of phenanthroline, the uniform dispersion of single-atom iron on carbon nitride is achieved, making full use of the activity of iron atoms, increasing the active sites, improving the catalytic efficiency of the catalyst, and it can be widely used in the degradation of pollutants by the Fenton-like reaction.
[0056] The above embodiments are not limitations on the present invention. The present invention is not limited to the above embodiments. As long as it meets the requirements of the present invention, it belongs to the protection scope of the present invention. In addition, it should be understood that after reading the above description content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.
Claims
1. An efficient Fenton-like catalyst based on phenanthroline-modified single-atom iron supported on carbon nitride, characterized in that, The chemical structural formula is shown as the following formula (I):
2. A preparation method of an efficient Fenton-like catalyst of phenanthroline-modified single-atom iron supported on carbon nitride as described in claim 1, characterized in that, It includes the following steps: Mix 1,10-phenanthroline and an iron source and dissolve them in a solvent. After complete dissolution, pour in melamine and grind. After drying, conduct calcination to obtain the efficient Fenton-like catalyst phen-Fe-CN of 1,10-phenanthroline modified single-atom iron loaded on carbon nitride; wherein, the iron element in the iron source accounts for 0.5%-5% of the mass of phen-Fe-CN.
3. The preparation method according to claim 2, characterized in that, The iron source is a soluble salt of divalent or trivalent iron, and its anion is selected from at least one of chloride ion, nitrate radical, and sulfate radical.
4. The preparation method according to claim 2 or 3, characterized in that, The iron source is ferrous sulfate.
5. The preparation method according to claim 2, wherein, The mass ratio of the 1,10-phenanthroline to melamine is 1:20-22.
6. The preparation method according to claim 2, wherein The solvent is a mixed solvent of ethanol and water.
7. The preparation method according to claim 2, characterized in that, The drying temperature is 60-65 °C.
8. The preparation method according to claim 2, characterized in that, The calcination temperature is 700 °C, and the calcination time is 2-2.5 h.
9. The preparation method according to claim 2, wherein The iron element accounts for 3% of the mass of the efficient Fenton-like catalyst phen-Fe-CN of 1,10-phenanthroline modified single-atom iron loaded on carbon nitride.
10. Application of the efficient Fenton-like catalyst of 1,10-phenanthroline modified single-atom iron loaded on carbon nitride according to claim 1 in the degradation of pollutants by Fenton-like reaction.