A method for degrading aromatic organic pollutants in water by activating persulfate with a non-metallic heteroatom-coordinated diatomic catalyst

Abstract

The present application belongs to the field of water environment treatment, and particularly relates to a method for activating persulfate to degrade aromatic organic pollutants in water by using a non-metallic heteroatom-coordinated diatomic catalyst. Two transition metals are coordinated by a non-metallic phosphorus atom, doped together on a carbon-based carrier, and calcined at high temperature in an inert gas environment to obtain a non-metallic heteroatom-coordinated diatomic catalyst. The transition metal Fe is combined with any one of Co and Ni; and the carbon-based carrier is a metal organic framework ZIF-8. The preparation method is simple in steps, easy to operate, fast in treatment effect, high in product yield, low in cost, and has good economic value and social benefits. The diatomic catalyst prepared by the present application has the advantages of uniform active sites, atomic-level dispersion, excellent catalytic effect, etc. compared with traditional single-atom catalysts and nano catalysts, and may be a key technology for eliminating organic pollution in water environment in chemical, chemical, pharmaceutical and other industries.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of water environment treatment, and particularly relates to a preparation of a non-metallic heteroatom-coordinated diatomic catalyst and a method and application of the non-metallic heteroatom-coordinated diatomic catalyst in activating persulfate to degrade aromatic organic pollutants in water. BACKGROUND

[0002] Persistent organic pollutants, antibiotics, endocrine disruptors and other organic pollutants are important types of new pollutants launched by the state in recent years. They can enter the aquatic ecosystem through atmospheric dry and wet deposition, surface runoff and direct exchange at the water-air interface, have direct toxicity effects on aquatic organisms and microbial communities, and have effects on human health such as nervous system damage, reproductive system and immune function disorder, neurobehavioral development disorder, endocrine disorder and cancer. At the same time, new organic pollutants also bring potential risks to human health, including increasing human body's resistance to antibiotics and possibly causing immune system abnormalities and fertility problems. Therefore, how to efficiently, completely and non-toxically treat new organic pollutants in the water environment is an important problem.

[0003] The removal of organic pollutants in water usually adopts physicochemical treatment technology or physicochemical treatment coupled with biochemical treatment, and the advanced oxidation technology of Fenton-like reaction is an important treatment means. It mainly produces active oxygen species by activating oxidants (such as hydrogen peroxide and persulfate (PMS)) to oxidatively degrade organic pollutants. Active oxygen species such as hydroxyl radicals and superoxide radicals usually have good degradation effect on electron-rich organic pollutants, but the effect on water body containing refractory aromatic ring organic pollutants is general, especially for aromatic ring compounds containing some electron-withdrawing groups, such as phenol, nitrobenzene and p-chlorophenol, etc. The electron-withdrawing group of the organic pollutants causes the main structure of the organic pollutants to be in an electron-deficient state, and the active oxygen species is difficult to effectively degrade. SUMMARY

[0004] The purpose of the present application is to provide a preparation of a non-metallic heteroatom-coordinated diatomic catalyst and a method and application of the non-metallic heteroatom-coordinated diatomic catalyst in activating persulfate to degrade aromatic organic pollutants in water. The diatomic catalyst prepared in the present application has the characteristics of atomic dispersion, and can efficiently remove aromatic organic pollutants. The non-metallic heteroatom-coordinated diatomic catalyst designed in the present application can realize asymmetric distribution of electrons through hetero-diatomic sites, and realize rapid and efficient removal of various aromatic organic pollutants. It has excellent degradation effect and can realize rapid degradation of various pollutants in 1 minute.

[0005] In order to achieve the above purpose, the present application provides the following technical scheme: a method for degrading aromatic organic pollutants in water by activating persulfate with a non-metallic heteroatom-coordinated diatomic catalyst, comprising the following steps:

[0006] (1) carbon-based carrier ZIF-8 and transition metal compound are dissolved in methanol to react, and the insoluble substance is collected and calcined at high temperature to obtain a diatomic catalyst; the transition metal compound is (1,1'-bis(diphenylphosphine) ferrocene) chloride X, wherein X is one of Co and Ni;

[0007] (2) the diatomic catalyst and persulfate are added to the contaminated water body to oxidize and eliminate the aromatic organic pollutants in the water body.

[0008] Preferably, the mass ratio of the carbon-based carrier ZIF-8 and the transition metal compound is 1:0.01-0.1;

[0009] The mass ratio of the carbon-based carrier ZIF-8 and methanol is 1:10-500;

[0010] The mass concentration / molar concentration of the diatomic catalyst and the persulfate is 0.01-1 g / L:0.1-1.0 mmol / L.

[0011] Preferably, the calcination temperature is 800-1000 ℃, and the time is 2-5 h.

[0012] Preferably, the persulfate is potassium monopersulfate PMS.

[0013] Preferably, the diatomic catalyst is ZIF-Fe-P-Ni or ZIF-Fe-P-Co; the specific preparation method is as follows:

[0014] 2 g of ZIF-8 is weighed, dissolved in 300 mL of methanol, and then 0.44 mmol of (1,1'-bis(diphenylphosphine) ferrocene) nickel dichloride or (1,1'-bis(diphenylphosphine) ferrocene) cobalt dichloride (II) is weighed and dissolved in 200 mL of methanol, then the two are stirred for 5 min respectively, and then ultrasonic is performed for 10 min, and then the solid phase product is collected by suction filtration, washed with methanol for 5 times, and dried; finally, the uniformly ground solid is placed in a tube furnace, heated at a heating rate of 5 ℃ / min under an argon flow of 100 mL / min, heated to 950 ℃ for 3 h, and then cooled to room temperature to obtain the diatomic catalyst ZIF-Fe-P-Ni or ZIF-Fe-P-Co.

[0015] Preferably, the diatomic catalyst has an atomic dispersion effect, and can realize rapid degradation and removal of various aromatic organic pollutants within 1 min.

[0016] Preferably, the method includes the following steps: adding a diatomic catalyst to water containing organic pollutants, mixing thoroughly, and then adding persulfate. The oxidant is activated by the diatomic catalyst, generating a large number of free radicals and non-free radicals, which attack and destroy the structure of aromatic organic pollutants, thereby achieving efficient degradation.

[0017] Preferably, the contaminants include fluoroquinolone antibiotics, sulfonamide antibacterial drugs, and p-chlorophenol organic contaminants.

[0018] Preferably, uniformly ground ZIF-Fe-P-Ni is added to water bodies contaminated by SMX, NOR, and 4-CP, respectively, so that the concentration of ZIF-Fe-P-Ni in the reaction system is 0.1 g / L. Then, PMS is added to make the concentration of PMS in the reaction system 0.1-0.4 mM. Stirring for 1 min can complete the removal of 100% of organic pollutants in the SMX and 4-CP contaminated water bodies, and stirring for 5 min can complete the removal of 100% of organic pollutants in the NOR contaminated water bodies.

[0019] Compared with the prior art, the features and beneficial effects of this invention are as follows:

[0020] (1) It can be mass-produced and applied on a large scale.

[0021] (2) Unlike the general multi-step calcination method, the present invention adopts a one-step calcination method, which has simple synthesis steps and easy synthesis reaction conditions.

[0022] (3) The material itself is non-toxic and can be repeatedly recycled.

[0023] (4) Multiple metals are uniformly dispersed on the carrier to achieve high atomic utilization.

[0024] (5) The process of removing aromatic organic pollutants from water is simple and easy to implement, and it is easy to achieve 100% removal rate of pollutants under natural conditions.

[0025] (6) The diatomic catalyst prepared in this invention can activate persulfate and oxidize and degrade various types of organic pollutants in water that are difficult to remove, such as quinolone antibiotics, sulfonamide antibiotics and phenolic compounds.

[0026] (7) This technical method has a high rate of oxidative degradation of aromatic organic pollutants in polluted water bodies, achieving 100% degradation efficiency within 1 minute.

[0027] (8) The present invention uses a metal ligand compound containing P to react with ZIF-8 to prepare a diatomic catalyst with non-metallic P heteroatom coordination. The doping of non-metals leads to uneven electron distribution of transition metal atoms, which makes it easier to induce electron migration, thereby promoting the catalytic effect.

[0028] (9) This technique can prepare a variety of high-performance diatomic catalysts, such as ZIF-Fe-P-Co and ZIF-Fe-P-Ni.

[0029] (10) Figure 4 The image shows the adsorption efficiency of 0.1 g / L single-atom and diatom catalysts for 10 mg / L 4-CP without the addition of PMS. The catalyst's adsorption efficiency for the pollutant is approximately 20%. Figure 5 The figure shows the degradation of 4-CP by 0.1 g / L single and double atom catalysts. Among them, ZIF-Fe-P-Ni can achieve 100% removal of 4-CP in about 30 seconds, and the degradation effect is very obvious. This indicates that the oxidative degradation step makes the main contribution to the removal of aromatic organic pollutants, rather than a simple adsorption process that may cause secondary pollution to the environment.

[0030] Furthermore, compared to existing aromatic organic pollutant removal technologies, the method provided by this invention does not require long-term premixing of the catalyst and pollutants. Instead, the diatomic catalyst and persulfate are directly added to the polluted water, achieving 100% removal of aromatic pollutants in a short time. Regarding the elimination mechanism of aromatic organic pollutants, this invention uses a phosphorus-containing metal ligand compound to react with ZIF-8 to prepare a diatomic catalyst with non-metallic phosphorus heteroatoms. The non-metallic doping leads to uneven electron distribution of transition metal atoms, making electron migration more likely and disrupting the chemical structure of aromatic organic pollutants, thereby promoting catalytic oxidation degradation. Therefore, the diatomic material described in this invention can remove various aromatic organic pollutants, such as quinolone antibiotics, sulfonamide antibiotics, and phenolic compounds, without specifically targeting a single organic pollutant. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 XRD patterns of single- and diatomic catalysts with different coordination environments and different amounts of transition metals.

[0033] Figure 2 Fourier transform infrared (FTIR) spectra of single- and diatomic catalysts with different coordination environments and different amounts of transition metals.

[0034] Figure 3The graph shows the effect of 0.1 g / L ZIF-Fe-P-Ni diatomic catalyst on the degradation of 10 mg / L sulfamethoxazole (SMX, a sulfonamide antibacterial agent), norfloxacin (NOR, a quinolone antibiotic) and p-chlorophenol (4-CP) by 0.4 mM PMS.

[0035] Figure 4 The effect of single and diatomic catalysts with different coordination environments at 0.1 g / L on the degradation of 10 mg / L 4-CP by 0.1 mM PMS.

[0036] Figure 5 The adsorption effects of single and diatomic catalysts with different coordination environments at 0.1 g / L on 10 mg / L 4-CP are shown in the figure.

[0037] Figure 6 The graph shows the effect of 0.1 g / L ZIF-Fe-P-Ni atomic catalyst on the degradation of 10 mg / L 4-CP by different concentrations of PMS.

[0038] Figure 7 The graph shows the effect of different dosages of ZIF-Fe-P-Ni diatomic catalyst on the degradation of 10 mg / L 4-CP by 0.1 mM PMS.

[0039] Figure 8 The effect of different mass transition metal-coordinated diatomic catalysts (0.1 g / L) on the degradation of 10 mg / L 4-CP by 0.1 mM PMS. Detailed Implementation

[0040] The present invention is further illustrated below by way of examples. The preparation of the diatomic catalyst and the technical method for degrading aromatic organic pollutants provided by the present invention are described in detail with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0041] Example 1

[0042] Weigh out 12.75 g of Zn(NO3). Dissolve 6H2O in 1 L of purified water, then weigh 29.15 g of 2-methylimidazole and dissolve it in 1 L of purified water. Stir each for 5 min and then mix them. Stir rapidly for 2 h and let stand for 12 h. Discard the supernatant, centrifuge and wash with water 3 times, collect the precipitate and dry it to obtain the carbon-based support ZIF-8.

[0043] 2 g of ZIF-8 was weighed and dissolved in 300 mL of methanol. 0.44 mmol of (1,1'-bis(diphenylphosphine)ferrocene) nickel dichloride was weighed and dissolved in 200 mL of methanol. The two solutions were stirred separately for 5 min, then mixed and sonicated for 10 min. The mixture was then vigorously stirred at 40 °C for 16 h. The solid product was collected by filtration, washed five times with methanol, and dried. Finally, the homogenized solid was placed in a tube furnace and heated at a rate of 5 °C / min with argon gas at a flow rate of 100 mL / min to 950 °C for 3 h. After cooling to room temperature, the diatomic catalyst ZIF-Fe-P-Ni was obtained.

[0044] Uniformly ground ZIF-Fe-P-Ni was added to water bodies contaminated with SMX, NOR, and 4-CP at concentrations of 10 mg / L, respectively, to achieve a ZIF-Fe-P-Ni concentration of 0.1 g / L in the reaction system. Then, PMS was added to achieve a PMS concentration of 0.4 mM in the reaction system. Stirring for 1 min achieved 100% removal of organic pollutants from the SMX and 4-CP contaminated water bodies, while stirring for 5 min achieved 100% removal of organic pollutants from the NOR contaminated water bodies. Figure 3 As shown.

[0045] Example 2

[0046] Weigh out 12.75 g of Zn(NO3). Dissolve 6H2O in 1 L of purified water, then weigh 29.15 g of 2-methylimidazole and dissolve it in 1 L of purified water. Stir each for 5 min and then mix them. Stir rapidly for 2 h and let stand for 12 h. Discard the supernatant, centrifuge and wash with water 3 times, collect the precipitate and dry it to obtain the carbon-based support ZIF-8.

[0047] 2 g of ZIF-8 was weighed and dissolved in 300 mL of methanol. 0.44 mmol of (1,1'-bis(diphenylphosphine)ferrocene) nickel / cobalt(II) chloride was weighed and dissolved in 200 mL of methanol. Both solutions were stirred separately for 5 min, then mixed and sonicated for 10 min. The mixture was then vigorously stirred at 40 °C for 16 h. The solid product was collected by filtration, washed five times with methanol, and dried. Finally, the homogenized solid was placed in a tube furnace and heated at 5 °C / min with argon gas at a flow rate of 100 mL / min to 950 °C for 3 h. After cooling to room temperature, the diatomic catalysts ZIF-Fe-P-Ni and ZIF-Fe-P-Co were obtained.

[0048] The synthesis of other single-atom catalysts mainly changes the types of metal ligand compounds, but the total molar number of metal ions remains the same as that of the dual-atom catalysts. That is, the ZIF-Fe catalyst is synthesized using 0.88 mmol of ferrocene, the ZIF-Fe-P catalyst is synthesized using 0.888 mmol of (1,1'-bis(diphenylphosphino)ferrocene), and the ZIF-Ni catalyst is synthesized using 0.88 mmol of nickel dichloride hexahydrate. The remaining steps are the same as those for the synthesis of the dual-atom catalysts;

[0049] Add the well-ground ZIF, ZIF-Fe, ZIF-Ni, ZIF-Fe-P, ZIF-Fe-P-Co, and ZIF-Fe-P-Ni to the water body contaminated with 4-CP, so that the concentration of the above catalysts in the reaction system is 0.1 g / L, and then add PMS so that the concentration of PMS in the reaction system is 0.1 mM. In addition, the adsorption performance of the above catalysts on 4-CP without adding PMS was also investigated. As Figure 4 shown, when no PMS is added, the adsorption and removal rate of all catalysts on 4-CP is about 20%, indicating that the adsorption ability of the above single-atom catalysts on 4-CP is relatively weak. When PMS is added, as Figure 5 shown, the removal rate of 4-CP by the above single-atom catalysts increases, indicating that the catalytic oxidation process occurs. Among them, the catalytic effect order is: ZIF < ZIF-Fe < ZIF-Ni < ZIF-Fe-P < ZIF-Fe-P-Co < ZIF-Fe-P-Ni. It can be seen that ZIF-Fe-P-Ni has the best removal effect on 4-CP and can complete 100% removal efficiency of organic pollutants in the 4-CP contaminated water body within 30 seconds.

[0050] Example 3

[0051] Weigh 12.75 g of Zn(NO3) 6H2O, dissolve it in 1 L of pure water, then weigh 29.15 g of 2-methylimidazole and dissolve it in 1 L of pure water. After stirring each of them for 5 min, mix them, stir rapidly for 2 h, then let it stand for 12 h. Pour off the supernatant, wash it by centrifugation 3 times, collect the precipitate and dry it to obtain the carbon-based carrier ZIF-8.

[0052] 2 g of ZIF-8 was weighed and dissolved in 300 mL of methanol. Then, 0.09, 0.18, 0.26, and 0.44 mmol of (1,1'-bis(diphenylphosphine)ferrocene) nickel dichloride were weighed and dissolved in 200 mL of methanol. The two solutions were stirred separately for 5 min, then mixed and sonicated for 10 min. The mixture was then vigorously stirred at 40 °C for 16 h. The solid products were collected by filtration, washed five times with methanol, and dried. Finally, the homogenized solid was placed in a tube furnace and heated to 950 °C for 3 h at an argon flow rate of 100 mL / min and a heating rate of 5 °C / min. After cooling to room temperature, diatomic catalysts ZIF-Fe-P-Ni with different ratios were obtained.

[0053] Grind ZIF-Fe-P-Ni to a uniformly homogenous concentration of 0.1 g / L in the reaction system, then add PMS to a concentration of 0.1 mM in the reaction system. Figure 6 As shown, all ZIF-Fe-P-Ni formulations achieved nearly 100% removal of 4-CP within 4 minutes. Among them, the ZIF-Fe-P-Ni formulation with 0.44 mmol (1,1'-bis(diphenylphosphine)ferrocene) nickel dichloride showed the best effect, achieving 100% removal of 4-CP within 30 seconds.

[0054] Example 4

[0055] Weigh out 12.75 g of Zn(NO3). Dissolve 6H2O in 1 L of purified water, then weigh 29.15 g of 2-methylimidazole and dissolve it in 1 L of purified water. Stir each for 5 min and then mix them. Stir rapidly for 2 h and let stand for 12 h. Discard the supernatant, centrifuge and wash with water 3 times, collect the precipitate and dry it to obtain the carbon-based support ZIF-8.

[0056] 2 g of ZIF-8 was weighed and dissolved in 300 mL of methanol. 0.44 mmol of (1,1'-bis(diphenylphosphine)ferrocene) nickel dichloride was weighed and dissolved in 200 mL of methanol. Both solutions were stirred separately for 5 min, then mixed and sonicated for 10 min. The mixture was then vigorously stirred at 40 °C for 16 h. The solid product was collected by filtration, washed five times with methanol, and dried. Finally, the homogenized solid was placed in a tube furnace and heated to 950 °C for 3 h at an argon flow rate of 100 mL / min and a heating rate of 5 °C / min. After cooling to room temperature, the diatomic catalyst ZIF-Fe-P-Ni was obtained.

[0057] Grind ZIF-Fe-P-Ni to a uniformly homogenous concentration of 0.1 g / L in a reaction system, then add PMS to achieve concentrations of 0.05, 0.1, 0.15, 0.2, and 0.4 mM in the reaction system. Figure 7 As shown, the removal efficiency of ZIF-Fe-P-Ni for 4-CP gradually increases with increasing PMS concentration, with the best effect observed at a PMS concentration of 0.4 mM. However, considering cost savings, 0.1 mM PMS was used.

[0058] Example 5

[0059] Weigh out 12.75 g of Zn(NO3). Dissolve 6H2O in 1 L of purified water, then weigh 29.15 g of 2-methylimidazole and dissolve it in 1 L of purified water. Stir each for 5 min and then mix them. Stir rapidly for 2 h and let stand for 12 h. Discard the supernatant, centrifuge and wash with water 3 times, collect the precipitate and dry it to obtain the carbon-based support ZIF-8.

[0060] 2 g of ZIF-8 was weighed and dissolved in 300 mL of methanol. 0.44 mmol of (1,1'-bis(diphenylphosphine)ferrocene) nickel dichloride was weighed and dissolved in 200 mL of methanol. Both solutions were stirred separately for 5 min, then mixed and sonicated for 10 min. The mixture was then vigorously stirred at 40 °C for 16 h. The solid product was collected by filtration, washed five times with methanol, and dried. Finally, the homogenized solid was placed in a tube furnace and heated to 950 °C for 3 h at an argon flow rate of 100 mL / min and a heating rate of 5 °C / min. After cooling to room temperature, the diatomic catalyst ZIF-Fe-P-Ni was obtained.

[0061] Uniformly ground ZIF-Fe-P-Ni was added to water contaminated with 4-CP, resulting in ZIF-Fe-P-Ni concentrations of 0.025, 0.05, 0.075, and 0.1 g / L in the reaction system. Then, PMS was added, with a concentration of 0.1 mM in the reaction system. Figure 8 As shown, the removal effect of ZIF-Fe-P-Ni on 4-CP gradually increases with the increase of ZIF-Fe-P-Ni dosage, and the effect is best when the ZIF-Fe-P-Ni dosage is 0.1 g / L.

[0062] Performance testing

[0063] To further illustrate the effects of the present invention, X-ray diffraction (XRD) was performed on the catalyst described in the present invention. Figure 1The XRD patterns of the catalyst samples ZIF, ZIF-Fe, ZIF-Fe-P, ZIF-Ni, ZIF-Fe-P-Ni, and ZIF-Fe-P-Co prepared according to the above embodiments are shown. Figure 1 The diffraction peaks of the prepared ZIF-Fe, ZIF-Fe-P, ZIF-Fe-P-Ni, and ZIF-Fe-P-Co are the same as those of ZIF, and no peaks of Fe or Ni nanoparticles were detected, indicating that Fe and Ni exist in the form of single atoms.

[0064] Figure 2 Fourier transform infrared (FTIR) spectra of the catalyst samples ZIF, ZIF-Fe, ZIF-Fe-P, ZIF-Ni, ZIF-Fe-P-Ni, and ZIF-Fe-P-Co described in this invention. From... Figure 2 It can be seen from the diffraction peaks of the prepared ZIF-Fe, ZIF-Fe-P, ZIF-Ni, ZIF-Fe-P-Ni, and ZIF-Fe-P-Co are the same as those of ZIF. No peaks of Fe or Ni nanoparticles were detected, indicating that Fe and Ni exist in the form of single atoms.

[0065] Figure 4 The image shows the adsorption efficiency of 0.1 g / L single-atom and diatom catalysts for 10 mg / L 4-CP without the addition of PMS. The catalyst's adsorption efficiency for the pollutant is approximately 20%. Figure 5 The figure shows the degradation of 4-CP by 0.1 g / L single and double atom catalysts. Among them, ZIF-Fe-P-Ni can achieve 100% removal of 4-CP in about 30 seconds, and the degradation effect is very obvious. This indicates that the oxidative degradation step makes the main contribution to the removal of aromatic organic pollutants, rather than a simple adsorption process that may cause secondary pollution to the environment.

[0066] Furthermore, compared to existing aromatic organic pollutant removal technologies, the method provided in this patent does not require long-term premixing of the catalyst and pollutants. Instead, the diatomic catalyst and persulfate are directly added to the polluted water, achieving 100% removal of aromatic pollutants in a short time. Regarding the elimination mechanism of aromatic organic pollutants, this invention uses a phosphorus-containing metal ligand compound to react with ZIF-8 to prepare a diatomic catalyst with non-metallic phosphorus heteroatoms. The non-metallic doping leads to uneven electron distribution of transition metal atoms, making electron migration more likely and disrupting the chemical structure of aromatic organic pollutants, thereby promoting catalytic oxidation degradation. Therefore, the diatomic material described in this invention can remove various aromatic organic pollutants, such as quinolone antibiotics, sulfonamide antibiotics, and phenolic compounds, without specifically targeting a single organic pollutant.

[0067] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. Other embodiments can be obtained without inventiveness based on these embodiments, and all equivalent changes and modifications made in accordance with the scope of the claims of the present invention should be protected within the scope of the present invention.

Claims

1. A method for activating a non-metallic heteroatom-coordinated diatomic catalyst to degrade aromatic organic pollutants in water using persulfate, characterized in that, Includes the following steps: (1) The carbon-based support ZIF-8 and the transition metal compound were dissolved in methanol and reacted. The insoluble matter was collected and calcined at high temperature to obtain a diatomic catalyst. The transition metal compound was (1,1'-bis(diphenylphosphine)ferrocene) chloride X, wherein X was one of Co and Ni. The diatomic catalyst was ZIF-Fe-P-Ni or ZIF-Fe-P-Co. (2) Add the diatomic catalyst and persulfate to the polluted water body to oxidize and eliminate the aromatic organic pollutants in the water body; the mass ratio of the carbon-based support ZIF-8 and the transition metal compound is 1:0.01~0.1; The mass ratio of the carbon-based carrier ZIF-8 to methanol is 1:10~500; The mass concentration of the diatomic catalyst is 0.01~1 g / L, and the molar concentration of persulfate is 0.1~1.0 mmol / L; The pollutants are fluoroquinolone antibiotics, sulfonamide antibacterial drugs, or p-chlorophenol organic pollutants.

2. The method for activating persulfate degradation of aromatic organic pollutants in water using a non-metallic heteroatom-coordinated diatomic catalyst according to claim 1, characterized in that, The calcination temperature is 800~1000 ℃, and the time is 2~5 h.

3. The method for activating persulfate degradation of aromatic organic pollutants in water using a non-metallic heteroatom-coordinated diatomic catalyst according to claim 1, characterized in that, The persulfate is potassium peroxymonosulfate.

4. The method for activating persulfate degradation of aromatic organic pollutants in water using a non-metallic heteroatom-coordinated diatomic catalyst according to claim 1, characterized in that, The diatomic catalyst is ZIF-Fe-P-Ni or ZIF-Fe-P-Co; the specific preparation method is as follows: Weigh 2 g of ZIF-8 and dissolve it in 300 mL of methanol. Then weigh 0.44 mmol of (1,1'-bis(diphenylphosphine)ferrocene)nickel chloride or (1,1'-bis(diphenylphosphine)ferrocene)cobalt(II) chloride and dissolve it in 200 mL of methanol. After stirring each for 5 min, mix and sonicate for 10 min. Stir vigorously at 40 °C for 16 h. Collect the solid product by vacuum filtration, wash it 5 times with methanol, and dry it. Finally, put the uniformly ground solid into a tube furnace and heat it at a rate of 5 °C / min with an argon flow rate of 100 mL / min to 950 °C for 3 h. After cooling to room temperature, the diatomic catalysts ZIF-Fe-P-Ni or ZIF-Fe-P-Co are obtained.

5. The method for activating persulfate degradation of aromatic organic pollutants in water using a non-metallic heteroatom-coordinated diatomic catalyst according to claim 1, characterized in that: The diatomic catalyst has an atomic dispersion effect, enabling the rapid degradation and removal of various aromatic organic pollutants within 1 minute.

6. The method for activating persulfate degradation of aromatic organic pollutants in water using a non-metallic heteroatom-coordinated diatomic catalyst according to claim 1, characterized in that, The process includes the following steps: adding a diatomic catalyst to water containing organic pollutants, mixing thoroughly, then adding persulfate. The oxidant is activated by the diatomic catalyst, generating a large number of free radicals and non-free radicals, which attack and destroy the structure of aromatic organic pollutants, thereby achieving efficient degradation.

7. The method for activating a non-metallic heteroatom-coordinated diatomic catalyst to degrade aromatic organic pollutants in water using persulfate, as described in claim 5, is characterized in that... Grind ZIF-Fe-P-Ni evenly to be added to water bodies contaminated with SMX, NOR, and 4-CP respectively, so that the concentration of ZIF-Fe-P-Ni in the reaction system is 0.1 g / L. Then PMS is added to make the concentration of PMS in the reaction system 0.1-0.4 mM. Stirring for 1 min can complete the removal of organic pollutants from SMX and 4-CP contaminated water bodies, and stirring for 5 min can complete the removal of organic pollutants from NOR contaminated water bodies.

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