A Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst and its preparation method and application

Abstract

The present invention belongs to the technical field of sewage treatment, and specifically relates to a Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, a preparation method thereof, and an application thereof. The embodiment of the present invention discloses a Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, wherein the molar ratio of iron to nickel in the catalyst is 0.5 to 32, and the doping amount of nitrogen is 0.1 to 2wt%. The catalyst of the present invention can degrade organic pollutants in sewage in coordination with the effect of electron beam irradiation, improve the mineralization efficiency and reaction rate of electron beam irradiation, have good application prospects, and are very suitable for application in sewage treatment.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, and specifically relates to an Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst and a preparation method and application thereof. Background Art

[0002] In the process of urbanization, some industries, such as coal chemical industry, printing and dyeing, pharmaceuticals, electronics, metallurgy and pulp, emit a large amount of high-concentration and difficult-to-degrade organic pollutants every year, posing a serious threat to the environment and human health. Although my country's daily sewage treatment scale has exceeded 200 million tons, ranking first in the world, traditional sewage treatment technology has technical bottlenecks and it is difficult to remove high-concentration organic pollutants efficiently, quickly and economically.

[0003] In order to overcome the problems of traditional sewage treatment technology, electron beam irradiation has been widely used and paid attention to as a new sewage treatment technology. Electron beam irradiation can generate hydroxyl radicals to achieve rapid degradation of organic pollutants, and is an efficient method for industrial wastewater treatment and purification.

[0004] Therefore, in order to achieve the goal of zero discharge and wastewater reuse, electron beam irradiation technology has become one of the important directions for improving current wastewater treatment technology. Summary of the invention

[0005] The present invention is based on the inventor's discovery and understanding of the following facts and problems:

[0006] The advantage of electron beam irradiation technology is that it can directly degrade organic pollutants, achieve sewage purification and wastewater resource utilization. This technology can effectively remove various difficult-to-degrade, high-concentration organic pollutants, such as agrochemical organic matter, petroleum hydrocarbons, dyes, nitrosamines, cyanides, etc., and is suitable for various industrial wastewater, urban sewage, rural domestic sewage, insecticides, pesticides and other polluted water bodies. The treatment effect of electron beam irradiation is significant. The treated sewage can meet national and international environmental emission standards, and achieve water intermediate and post-treatment and reuse, which is of great significance to promoting sustainable development. However, the existing electron beam irradiation technology often has the problems of low degradation efficiency and poor degradation effect, resulting in high treatment costs, and still faces great challenges in application.

[0007] The present invention aims to solve at least one of the technical problems in the related art to a certain extent. To this end, the embodiments of the present invention propose a Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, which can cooperate with the effect of electron beam irradiation to degrade organic pollutants in sewage, improve the mineralization efficiency and reaction rate of electron beam irradiation, have good application prospects, and are very suitable for application in sewage treatment.

[0008] The Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst of the embodiment of the present invention has a molar ratio of iron to nickel of 0.5 to 32, and a nitrogen doping amount of 0.1 to 2 wt%.

[0009] The advantages and technical effects brought by the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst of the embodiment of the present invention are as follows: 1. In the embodiment of the present invention, the Fe element can undergo a Fenton-like reaction under ionizing radiation to generate oxidizing components such as hydroxyl radicals. The synergistic effect of Fe and Ni can transfer electrons between the two element atoms, realize the valence change of the iron element, and promote the Fenton-like reaction. The doped nitrogen element can provide unpaired electrons, so that the metal element has more unsaturated chemical bonds in the compound and has higher catalytic activity; 2. In the embodiment of the present invention, the catalyst can cooperate with the effect of electron beam irradiation to degrade organic pollutants in sewage, and can greatly improve the mineralization efficiency and reaction rate of electron beam irradiation; 3. In the embodiment of the present invention, the catalyst can maintain high stability and recyclability under electron beam irradiation, has good economy, and will not cause secondary pollution, and is very suitable for application in sewage treatment.

[0010] In some embodiments, the size of the catalyst is 50-300 nm; and / or the total weight content of iron and nickel in the catalyst is 1-30 wt %.

[0011] The embodiment of the present invention also provides a method for preparing a Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, comprising the following steps:

[0012] (1) Preparation of Fe-Ni bimetallic MOF materials;

[0013] (2) The Fe-Ni bimetallic MOF material obtained in step (1) is calcined under a nitrogen-containing protective gas to obtain a catalyst.

[0014] The advantages and technical effects brought by the preparation method of the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst of the embodiment of the present invention are: 1. The method of the embodiment of the present invention, the prepared catalyst has high-efficiency adsorption performance and catalytic performance, can cooperate with electron beam irradiation technology to improve the degradation effect of organic pollutants in sewage, and has high stability and recyclability, and is very suitable for application in the field of sewage treatment; 2. The method of the embodiment of the present invention has a simple process flow and is easy to operate, and has high production efficiency, which is convenient for promotion and application in industrial production.

[0015] In some embodiments, in step (1), the preparation process of the Fe-Ni bimetallic MOF material includes: mixing iron salt, nickel source, dimethylformamide, and 2-aminoterephthalic acid, and then performing a solvent thermal reaction, and drying and grinding the product obtained by the solvent thermal reaction.

[0016] In some embodiments, the usage ratio of the iron salt, the nickel source, dimethylformamide, and 2-aminoterephthalic acid is (0.8-1.5 g): (0.02-0.4 g): (0.7-1.0 g): (20-30 mL); and / or, the iron salt includes at least one of ferric chloride, ferric sulfate, ferric nitrate, hydrated ferric chloride, hydrated ferric sulfate, and hydrated ferric nitrate, and the nickel source includes at least one of nano-nickel oxide and nano-nickel chloride.

[0017] In some embodiments, the solvothermal reaction temperature is 100-200° C., the reaction pH is 12-14, and the reaction time is 15-20 h.

[0018] In some embodiments, in step (2), the calcination treatment includes increasing the temperature to 600°C to 1000°C at a heating rate of 5 to 10 K / min, and the calcination treatment time is 2 to 4 hours.

[0019] In some embodiments, in step (2), the product obtained by the calcination treatment is cooled and then irradiated with electron beams or gamma rays; preferably, the cooled calcined product is first wetted with deionized water and then irradiated.

[0020] In some embodiments, the absorbed dose of the electron beam or gamma ray irradiation treatment is 0.5 to 3 kGy; and / or, when electron beam irradiation is used, the irradiation energy is 1 to 10 MeV, and the beam intensity is 10 to 300 mA.

[0021] An embodiment of the present invention also provides the use of the above-mentioned Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst or the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared by the above-mentioned preparation method in sewage treatment, comprising adding the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst to sewage and then irradiating it with an electron beam. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the X-ray diffraction (XRD) pattern of the Fe-Ni bimetallic nitrogen-doped MOF derivative material prepared in Example 1;

[0023] Figure 2 This is a transmission electron microscope (TEM) photograph of the Fe-Ni bimetallic nitrogen-doped MOF derivative material prepared in Example 1. DETAILED DESCRIPTION

[0024] Embodiments of the present invention are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.

[0025] The Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst of the embodiment of the present invention has a molar ratio of iron to nickel of 0.5 to 32, and a nitrogen doping amount of 0.1 to 2 wt%.

[0026] The Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst of the embodiment of the present invention, the Fe element can undergo a Fenton-like reaction under ionizing radiation to generate oxidizing components such as hydroxyl radicals, the synergistic effect of Fe and Ni can transfer electrons between the two element atoms, realize the valence change of the iron element, and promote the Fenton-like reaction, the doped nitrogen element can provide unpaired electrons, so that the metal element has more unsaturated chemical bonds in the compound, and has higher catalytic activity; it can cooperate with the effect of electron beam irradiation to degrade organic pollutants in sewage, and can greatly improve the mineralization efficiency and reaction rate of electron beam irradiation; the catalyst can maintain high stability and recyclability under electron beam irradiation, has good economy, and will not cause secondary pollution, and is very suitable for application in sewage treatment.

[0027] In some embodiments, preferably, the molar ratio of iron to nickel in the catalyst is 1-3.

[0028] In some embodiments, preferably, the size of the catalyst is 50-300 nm; and / or, the total weight content of iron and nickel in the catalyst is 1-30 wt %. Further preferably, the size of the catalyst is 50-200 nm.

[0029] The embodiment of the present invention also provides a method for preparing a Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, comprising the following steps:

[0030] (1) Preparation of Fe-Ni bimetallic MOF materials;

[0031] (2) The Fe-Ni bimetallic MOF material obtained in step (1) is calcined under a nitrogen-containing protective gas to obtain a catalyst.

[0032] The preparation method of the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst of the embodiment of the present invention has high-efficiency adsorption and catalytic properties, can cooperate with electron beam irradiation technology to improve the degradation effect of organic pollutants in sewage, and has high stability and recyclability, which is very suitable for application in the field of sewage treatment; the process flow is simple and easy to operate, and the production efficiency is high, which is convenient for promotion and application in industrial production.

[0033] In some embodiments, preferably, in the step (1), the preparation process of the Fe-Ni bimetallic MOF material comprises: mixing iron salt, nickel source, dimethylformamide and 2-aminoterephthalic acid and subjecting the mixture to a solvent thermal reaction, and drying and grinding the product obtained from the solvent thermal reaction.

[0034] In some embodiments, preferably, the iron salt, nickel source, dimethylformamide and 2-aminoterephthalic acid are mixed and then subjected to ultrasonic stirring treatment. Further preferably, the ultrasonic stirring treatment lasts for 20 to 50 minutes.

[0035] In some embodiments, preferably, the ratio of the amount of the iron salt, the nickel source, dimethylformamide, and 2-aminoterephthalic acid is (0.8-1.5 g): (0.02-0.4 g): (0.7-1.0 g): (20-30 mL); and / or, the iron salt includes at least one of ferric chloride, ferric sulfate, ferric nitrate, hydrated ferric chloride, hydrated ferric sulfate, and hydrated ferric nitrate, and the nickel source includes at least one of nano nickel oxide and nano nickel chloride. Further preferably, the ratio of the amount of the iron salt, the nickel source, dimethylformamide, and 2-aminoterephthalic acid is (1.2-1.5 g): (0.05-0.3 g): (0.7-1.0 g): (20-30 mL); the iron salt includes hydrated ferric chloride, and the nickel source includes nano nickel oxide.

[0036] In some embodiments, preferably, the temperature of the solvothermal reaction is 100-200° C., the pH of the reaction is 12-14, and the reaction time is 15-20 hours. Further preferably, the temperature of the solvothermal reaction is 100-150° C. More preferably, sodium hydroxide is used to adjust the pH, and the solvothermal reaction is carried out in an autoclave.

[0037] In the embodiment of the present invention, the conditions of the solvent thermal reaction are optimized, which can promote the formation of iron oxide and nickel oxide particles, while ensuring that the particle size of the particles is within an appropriate range and has good uniformity; if the reaction temperature is too high, the chemical reaction rate is too fast, the generated oxide particles are too large and the uniformity is poor; if the reaction temperature is too low, the reaction is not sufficient, a longer reaction time is required, and other impurity products besides the oxides will be generated.

[0038] In some embodiments, preferably, the drying temperature is 50-70° C., and the drying time is 5-8 hours. Further preferably, the product obtained by the solvent thermal reaction is washed twice with dimethylformamide and deionized water in sequence before the drying.

[0039] In some embodiments, preferably, in step (2), the volume ratio of nitrogen in the protective gas is 60-100%, and the protective gas also contains at least one of argon, neon, krypton and carbon dioxide.

[0040] In some embodiments, preferably, in step (2), the calcination treatment includes raising the temperature to 600°C to 1000°C at a heating rate of 5 to 10K / min, and the calcination treatment time is 2 to 4 hours. Further preferably, the calcination treatment temperature is 650 to 750°C.

[0041] In the embodiments of the present invention, the conditions for calcination treatment are optimized, which can control the composition and morphology of the metal compounds in the catalyst, especially, control the ratio of divalent iron, trivalent iron and zero-valent iron in the iron oxide within an appropriate range; if the temperature of calcination treatment is too high, the generated nanoparticles are too large, and the proportion of zero-valent iron is too low, which restricts the Fenton-like reaction effect and is not conducive to the improvement of catalytic performance; if the temperature of calcination treatment is too low, the generated nanoparticles are too small, which affects the stability of the catalyst; and if the proportion of zero-valent iron is too high, the amount of high-valent iron required in the catalytic oxidation reaction is reduced, which is not conducive to the improvement of catalytic performance.

[0042] In some embodiments, preferably, the calcination process is carried out in a tube furnace. Further preferably, the calcination process is carried out under a vacuum state.

[0043] In some embodiments, preferably, in the step (2), the calcined product is cooled and then irradiated with electron beam or gamma ray; preferably, the cooled calcined product is first wetted with deionized water and then irradiated. Further preferably, the absorbed dose of irradiation when the electron beam or gamma ray irradiation is used is 0.5 to 3 kGy; and / or, when the electron beam irradiation is used, the irradiation energy is 1 to 10 MeV and the beam current intensity is 10 to 300 mA.

[0044] In the embodiment of the present invention, irradiation treatment is performed during the preparation process, and the valence ratio of iron oxide can be further adjusted after irradiation, thereby further improving the catalytic activity of the catalyst and improving the stability of the catalyst during use.

[0045] In some embodiments, preferably, a drying treatment is performed after the electron beam or gamma ray irradiation treatment, and the temperature of the drying treatment is 30-60°C.

[0046] An embodiment of the present invention also provides the use of the above-mentioned Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst or the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared by the above-mentioned preparation method in sewage treatment, comprising adding the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst to sewage and then irradiating it with an electron beam.

[0047] In some embodiments, preferably, the amount of the catalyst is 1 to 50 times the COD concentration in the sewage, more preferably 10 to 20 times.

[0048] In some embodiments, preferably, the liquid level of the sewage is 1 to 5 cm. Further preferably, the liquid level of the sewage is 1 to 3 cm.

[0049] The technical solution of the present invention is described in detail below in conjunction with specific embodiments and drawings.

[0050] Example 1

[0051] (1) Preparation of Fe-Ni bimetallic MOF material: 1.211 g hydrated ferric chloride, 0.2 g nano-nickel oxide, 0.745 g dimethylformamide and 22.5 mL 2-aminoterephthalic acid were added to deionized water in sequence, and 1.8 mL 2M sodium hydroxide was added to adjust the pH to 13; the molar ratio of iron to nickel was 1.672, and after ultrasonic stirring for 30 min, the mixture was transferred to an autoclave and kept at 100 ° C for 18 h; the obtained product was washed twice with DMF and deionized water in sequence, dried in an oven at 60 ° C for 6 h, and ground to obtain Fe-Ni bimetallic MOF material;

[0052] (2) Preparation of Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst: The Fe-Ni bimetallic MOF material was placed in a tubular furnace for vacuum operation, and flowing nitrogen was used as the protective gas. The temperature was increased to 750°C at a heating rate of 5K / min. After calcination for two hours, it was naturally cooled to room temperature. Then, 3 mL of deionized water was added and irradiated with cobalt 60 with an absorbed dose of 1 kGy. The catalyst was then dried in an oven at 40°C for 2 hours to obtain a Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, which was a black powder with magnetic properties.

[0053] In the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared in this embodiment, the molar ratio of iron to nickel is 1.672, the total mass content of iron and nickel is about 15wt%, the doping amount of nitrogen is 0.3wt%, and the size of the catalyst is 50-100nm.

[0054] The Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared in this example was characterized, and the X-ray diffraction pattern was as follows: Figure 1As shown, the crystal diffraction peaks of iron oxide and nickel oxide can be seen; the transmission electron microscope photo is shown in Figure 2 As shown, nanoparticles of iron oxide and nickel oxide can be seen, with a size of about 50 to 100 nm.

[0055] Example 2

[0056] The preparation method of this embodiment is the same as that of Example 1, except that in step (1), the amount of hydrated ferric chloride is 1.081 g, the amount of nano nickel oxide is 0.037 g, and the molar ratio of iron to nickel is 30.8. Finally, a black powder product is obtained, and the morphology, structure and other characteristics of the product are similar to those of the catalyst prepared in Example 1.

[0057] In the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared in this embodiment, the molar ratio of iron to nickel is 30.8, the total mass content of iron and nickel is 12wt%, the doping amount of nitrogen is 0.3wt%, and the size of the catalyst is 50-150nm.

[0058] Example 3

[0059] The preparation method of this embodiment is the same as that of Example 1, except that in step (1), the amount of hydrated ferric chloride is 0.811 g, the amount of nano nickel oxide is 0.312 g, and the molar ratio of iron to nickel is 0.717. Finally, a black powder product is obtained, and the morphology, structure and other characteristics of the product are similar to those of the catalyst prepared in Example 1.

[0060] In the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared in this embodiment, the molar ratio of iron to nickel is 0.717, the total mass content of iron and nickel is 11wt%, the doping amount of nitrogen is 0.3wt%, and the size of the catalyst is 50-150nm.

[0061] Example 4

[0062] The preparation method of this embodiment is the same as that of embodiment 1, except that in step (2), no irradiation treatment of cobalt 60 is performed, that is, the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst is obtained after calcination treatment.

[0063] Example 5

[0064] The preparation method of this embodiment is the same as that of embodiment 1, except that in step (1), the temperature of the autoclave is 200° C., and a black powder product is finally obtained.

[0065] Example 6

[0066] The preparation method of this embodiment is the same as that of Embodiment 1, except that in step (2), flowing air is used as the protective gas.

[0067] Example 7

[0068] The preparation method of this embodiment is the same as that of embodiment 1, except that in step (2), the calcination temperature is 1000°C.

[0069] Example 8

[0070] The preparation method of this embodiment is the same as that of embodiment 1, except that in step (2), after adding 3 mL of deionized water, electron beam irradiation is performed, the absorbed dose is 1 kGy, the irradiation energy is 5 MeV, and the beam intensity is 150 mA.

[0071] Example 9

[0072] The preparation method of this embodiment is the same as that of embodiment 1, except that in step (2), no deionized water is added to the product after calcination and cooling, and cobalt 60 is directly used for irradiation.

[0073] Application Example 1

[0074] The Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared in Example 1 was added to medical wastewater with a COD of 530 mg / L, with an addition amount of 5 g / L, and electron beam irradiation was performed. The energy of the electron beam irradiation was 5 MeV, the absorbed dose was 10 kGy, and the height of the sewage liquid level was 2 cm.

[0075] Application Examples 2 to 9

[0076] The method is the same as that of Example 1, except that the Fe-Ni bimetallic nitrogen-doped MOF derivative catalysts prepared in Examples 2 to 9 are used respectively.

[0077] Application Example 10

[0078] The same as Application Example 1, the only difference is that the addition amount of the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst is 2 g / L.

[0079] Application Comparative Example 1

[0080] The same as Application Example 1, the only difference is that only electron beam irradiation treatment is performed without adding a catalyst.

[0081] The COD content in the wastewater treated by Examples 1 to 10 and Comparative Example 1 was tested by potassium dichromate method, and the results are shown in Table 1.

[0082] Table 1

[0083]

[0084] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" etc. mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0085] Although the above embodiments have been shown and described, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. Changes, modifications, substitutions and variations of the above embodiments by those of ordinary skill in the art are all within the scope of protection of the present invention.

Claims

1. A Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, characterized in that: The molar ratio of iron to nickel in the catalyst is 0.5-32, and the doping amount of nitrogen is 0.1-2 wt%.

2. The Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 1, characterized in that: The size of the catalyst is 50-300 nm; and / or the total mass content of iron and nickel in the catalyst is 1-30 wt %.

3. A method for preparing a Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst, characterized in that: The following steps are involved: (1) Preparation of Fe-Ni bimetallic MOF materials; (2) The Fe-Ni bimetallic MOF material obtained in step (1) is calcined under a nitrogen-containing protective gas to obtain a catalyst.

4. The method for preparing the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 3, characterized in that: In the step (1), the preparation process of the Fe-Ni bimetallic MOF material includes: mixing iron salt, nickel source, dimethylformamide and 2-aminoterephthalic acid, performing a solvent thermal reaction, and drying and grinding the product obtained by the solvent thermal reaction.

5. The method for preparing the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 4, characterized in that: The usage ratio of the iron salt, the nickel source, dimethylformamide and 2-aminoterephthalic acid is (0.8-1.5 g): (0.02-0.4 g): (0.7-1.0 g): (20-30 mL); and / or the iron salt includes at least one of ferric chloride, ferric sulfate, ferric nitrate, hydrated ferric chloride, hydrated ferric sulfate and hydrated ferric nitrate, and the nickel source includes at least one of nano-nickel oxide and nano-nickel chloride.

6. The method for preparing the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 4 or 5, characterized in that: The temperature of the solvent thermal reaction is 100-200° C., the pH of the reaction is 12-14, and the reaction time is 15-20 hours.

7. The method for preparing the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 3, characterized in that: In the step (2), the calcination treatment includes raising the temperature to 600° C. to 1000° C. at a heating rate of 5 to 10 K / min, and the calcination treatment time is 2 to 4 hours.

8. The method for preparing the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 3, characterized in that: In the step (2), the product obtained by the calcination treatment is cooled and then irradiated with electron beams or gamma rays; preferably, the cooled calcined product is first moistened with deionized water and then irradiated.

9. The method for preparing the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 8, characterized in that: When the electron beam or gamma ray irradiation treatment is adopted, the absorbed dose of irradiation is 0.5-3 kGy; and / or, when the electron beam irradiation is adopted, the irradiation energy is 1-10 MeV, and the beam current intensity is 10-300 mA.

10. Use of the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst according to claim 1 or 2 or the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst prepared by the preparation method according to claims 3 to 9 in sewage treatment, characterized in that: The method comprises adding the Fe-Ni bimetallic nitrogen-doped MOF derivative catalyst into sewage and then performing electron beam irradiation.

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