Single-site catalyst with asymmetric coordination as well as preparation method and application of single-site catalyst

Abstract

The invention discloses a single-site catalyst with asymmetric coordination as well as a preparation method and application of the single-site catalyst. An oxidation pathway dominated by singlet oxygen can be realized. The Co-N2C2 is dominated by singlet oxygen, has excellent degradation performance on ARG and various antibiotics in the environment, and still keeps good degradation performance on the ARG under the interference of various ions. The preparation method of the asymmetric coordination single-site catalyst is simple, the preparation cost is low, the asymmetric coordination single-site catalyst has good activity on numerous organic pollutants, the application of Co-N2C2 in the advanced oxidation technology is never reported, and the asymmetric coordination single-site catalyst has good application prospects.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation and application technology, specifically relating to a highly active asymmetric coordinated single-site catalyst, its preparation method, and its application. Background Technology

[0002] With the rapid development of modern industry and agriculture and the widespread use of antibiotics, antibiotic and antibiotic resistance gene pollution in the aquatic environment has become a serious global environmental and health problem. Antibiotic resistance genes, as a new type of persistent pollutant, are environmentally persistent and can undergo horizontal gene transfer between different bacterial populations via mobile genetic elements such as plasmids, transposons, and bacteriophages, thereby accelerating the spread and diffusion of resistance. This makes conventional wastewater treatment technologies ineffective in removing them; therefore, the development of novel water treatment technologies capable of efficiently degrading and inactivating antibiotic resistance genes is particularly urgent.

[0003] Among numerous advanced oxidation technologies, persulfate-based advanced oxidation processes have attracted widespread attention due to their ability to generate reactive oxygen species. Traditional persulfate activation pathways typically rely on free radical pathways, such as sulfate radicals and hydroxyl radicals. These free radical species can cleave antibiotic resistance genes by indiscriminately attacking DNA molecular structures. However, this free radical-based oxidation pathway has certain limitations in practical aquatic applications. For example, free radicals are easily quenched by coexisting anions or natural organic matter in the water, leading to reduced oxidant utilization efficiency; simultaneously, non-selective strong oxidation may also lead to the generation of byproducts, potentially increasing environmental risks.

[0004] Compared to free radical pathways, non-radical oxidation pathways, such as those using reactive species like singlet oxygen, may exhibit better resistance to interference and higher oxidant utilization in complex aquatic matrices due to their selective oxidation of electron-rich organic matter. Non-radical species can target electron-rich base units in antibiotic resistance genes, potentially disrupting their genetic function more precisely. However, in current technologies, precisely controlling the persulfate activation pathway to stably generate a non-radical-dominated oxidation environment, particularly for the efficient and selective degradation of antibiotic resistance genes, remains a challenging technical problem requiring further exploration and resolution.

[0005] The microstructure of a catalyst is a core factor determining its activation pathway and catalytic performance. In recent years, the emergence of single-site catalysts has provided a new approach to solving these problems. With their high atom utilization and well-defined, tunable active site structures, single-site catalysts offer the possibility of achieving efficient and targeted non-radical species generation. Theoretically, by carefully designing the local coordination environment of the metal center, its electronic structure can be precisely controlled, thereby guiding the activation of persulfate via a non-radical pathway. Although single-site catalysts have shown potential in fields such as energy catalysis, their application to the activation of persulfate to degrade antibiotic resistance genes, especially the construction of cobalt-based single-site catalysts with specific asymmetric coordination structures, and the systematic elucidation of their mechanism for gene inactivation via a singlet oxygen-dominated non-radical pathway, remains a gap in current technology. Therefore, developing a single-site catalyst with a specific asymmetric coordination structure that can efficiently activate persulfate and target the degradation of antibiotic resistance genes via a non-radical pathway not only has significant theoretical value but also holds considerable practical application potential. Summary of the Invention

[0006] Technical Problem Solved: To address the aforementioned problems, this invention aims to provide a single-site catalyst with an asymmetric cobalt-nitrogen-carbon coordination structure, its preparation method, and its applications. This catalyst can efficiently activate persulfate and achieve efficient and stable degradation of various organic pollutants, especially antibiotic resistance genes, primarily through non-radical pathways (particularly the singlet oxygen pathway). This invention further solves the technical problems of existing catalysts being easily inhibited under complex water quality conditions and having poor cycle stability, thus providing a more reliable and efficient solution for the application of advanced oxidation technologies in practical wastewater treatment.

[0007] Technical solution: A single-site catalyst with an asymmetric cobalt-nitrogen-carbon coordination structure, wherein cobalt atoms are dispersed in a single-site manner and characterized by X-ray absorption fine structure spectroscopy, the first coordination layer consists of two nitrogen atoms and two carbon atoms, forming a Co-N2C2 coordination configuration, wherein the cobalt-nitrogen bond length is 1.5 Å and the cobalt-carbon bond length is 1.8 Å; the catalyst has a plate-like structure and a BET specific surface area of ​​70-280 m². 2 / g, with a pore size of 2-10 nm; the catalyst exhibits a first-order degradation rate constant k ≥ 2.0 min~12.0 min in the reaction of activating persulfate to degrade antibiotic resistance genes. -1 .

[0008] A method for preparing the single-site catalyst includes the following steps: mixing and grinding a cobalt source, trimesic acid, and dicyandiamide to obtain a precursor mixture; calcining the precursor mixture under an inert atmosphere to obtain a calcined product; and acid washing, washing, and drying the calcined product to obtain the single-site catalyst; wherein the mass ratio of the cobalt source, trimesic acid, and dicyandiamide is 1:(13~50):(167~500), and the single-site catalyst has an asymmetric Co-N2C2 coordination structure characterized by X-ray absorption spectroscopy.

[0009] Preferably, the cobalt source is cobalt chloride.

[0010] Preferably, the above calcination process is as follows: the temperature is increased to 800°C at a heating rate of 5°C / min and held for 3 hours.

[0011] Preferably, the pickling process uses a 1 mM sulfuric acid solution and is carried out at 60°C for 8 hours.

[0012] The above-mentioned unit point catalyst is used in the activation of persulfate in Fenton-like reactions to degrade organic pollutants in water.

[0013] The aforementioned organic pollutants include at least one of the following: antibiotic resistance genes, tetracycline, carbamazepine, sulfamethoxazole, ciprofloxacin, or oxytetracycline.

[0014] When the aforementioned organic pollutant is an antibiotic resistance gene, its initial concentration is 10. 10 Up to 10 13 copies / mL.

[0015] In the reaction system, the concentration of the above catalyst is 50-200 mg / L.

[0016] In the reaction system, the concentration of persulfate is 0.5-2 mM, and the pH value of the reaction is 3-9.

[0017] Beneficial Effects: The single-site catalyst with an asymmetric Co-N2C2 structure provided by this invention exhibits a series of significant beneficial effects in Fenton-like reactions. First, when activating persulfate to degrade antibiotic resistance genes, this catalyst demonstrates a catalytic efficiency far exceeding that of other metal-centered single-site catalysts (such as Fe-N2C2, Cu-N2C2, etc.), with a significantly improved first-order reaction kinetic constant. This is attributed to the synergistic effect between the cobalt active center and the unique asymmetric N2C2 coordination environment, which jointly optimizes the electronic structure of the active site, making it easier for the reaction to be dominated by a non-radical pathway. Second, this catalyst system mainly relies on the non-radical oxidation pathway of singlet oxygen. This pathway not only gives it a specific attack capability on electron-rich antibiotic resistance gene bases (such as guanine), effectively disrupting their genetic function and achieving deep disinfection; but also, this non-radical mechanism endows the catalytic system with excellent resistance to interference from the aqueous matrix. In complex aquatic environments containing high concentrations of chloride ions, bicarbonate ions, and other coexisting ions, its catalytic degradation performance remains stable, overcoming the inherent defect of traditional free radical pathways being easily quenched by background components, demonstrating stronger adaptability to practical applications. Furthermore, after ten cycles of reuse, the degradation kinetic constant for characteristic pollutants only shows a slight decrease, indicating its excellent structural stability and recyclability, which is closely related to its robust carbon-based framework and stable atomic-level coordination structure. Simultaneously, the catalyst has a broad spectrum of applicable pollutants, not only targeting various typical antibiotic resistance genes but also exhibiting good degradation and removal rates for structurally diverse organic pollutants such as tetracycline, sulfamethoxazole, and bisphenol A, demonstrating its potential as a broad-spectrum advanced oxidation catalyst. Attached Figure Description

[0018] Figure 1 Characterization of Co-N2C2 single-site catalyst. (a) Transmission electron microscopy image of Co-N2C2, (b) Scanning electron microscopy image of Co-N2C2.

[0019] Figure 2 (a) K-edge XANES spectrum of cobalt (normalized): comparative analysis of Co-N2C2 material and reference sample. (b) K-edge Fourier transform extended X-ray absorption fine structure spectrum of cobalt: comparative study of Co-N2C2 material and reference sample. (c) Cobalt K-edge EXAFS fitting analysis of Co-N2C2 material. (d) Formation energy calculation of three different configurations of Co-N2C2. (e) Wavelet transform spectrum analysis of Co-N2C2. These results indicate that the catalyst's structural configuration is Co-N2C2.

[0020] Figure 3(a) Nitrogen adsorption-desorption isotherms of the Co-N2C2 material, and (b) pore size distribution curves of the Co-N2C2 material. All prepared catalysts exhibited type IV isotherms and significant type H3 hysteresis curves, indicating a well-defined mesoporous structure. The specific surface areas of Co-N2C2 were similar.

[0021] Figure 4 For (a) Co-N2C2 against ARG (bla TEM-1 (a) Degradation performance of Co-N2C2 on ARG (ampR), (b) Degradation performance of Co-N2C2 on ARG (tetA).

[0022] Figure 5 This refers to the survival status of bacteria after the degraded ARG is introduced into the bacteria. Detailed Implementation

[0023] Example 1

[0024] 1. Investigate the effect of different metal loadings on the catalyst activity per unit site.

[0025] Preparation of unit point catalysts by calcination method

[0026] The drugs were mixed using physical methods: ferrous chloride (7 mg), cobalt chloride (6 mg), copper chloride (3.5 mg), and nickel chloride (6 mg) were mixed with pyromellitic acid (100 mg) and dicyandiamide (1.0 g) in a mortar and ground thoroughly until homogeneous; the mixture was then heated at 5°C for 1 min under a nitrogen atmosphere. -1 The catalysts were heated to 800℃ at a certain rate and held at this temperature for 3 h to obtain highly active and stable single-site catalysts with different metal supports: Co-N2C2, Fe-N2C2, Cu-N2C2, and Cu-N2C2. The obtained single-site catalysts were acid-washed at 60℃ for 8 h using a 1 mM sulfuric acid solution. After acid washing, they were washed with deionized water to a neutral pH and dried at 60℃ for 36 h. The obtained single-site catalysts had a plate-like morphology, as shown in Figure 1:ab. Furthermore, X-ray absorption spectroscopy (XAS) was used to investigate the electronic structure and coordination environment of cobalt atoms in Co-N2C2. For example, the normalized cobalt K-edge XAS spectrum (…) Figure 2 As shown in a), the absorption edge of Co-N2C2 lies between the cobalt foil and cobalt phthalocyanine (CoPc), and is closer to the latter, indicating that cobalt exists primarily in the +2 oxidation state. This conclusion is supported by the high-resolution electron paramagnetic resonance (XPS) spectrum of cobalt 2p, which shows the relationship with Co... 2+ Species-consistent characteristic cobalt 2p 3 / 2 and cobalt 2p 1 / 2 doublets. Fourier transform k3-weighted X-ray absorption fine structure (EXAFS) spectrum. Figure 2 b) No cobalt-cobalt scattering peak was detected near 2.18 Å, confirming the absence of metallic cobalt clusters. Instead, a significant peak was observed at approximately 1.5 Å, corresponding to cobalt-nitrogen coordination, a result also supported by wavelet transform (WT) analysis. Figure 2 The presence of cobalt nanoparticles or sub-nano clusters was further ruled out by the support of (cd). A clear leading-edge peak is visible at approximately 7710 eV, indicating a low-symmetry and non-centrosymmetric coordination structure. EXAFS fitting ( Figure 1 (f) The cobalt-nitrogen coordination number is approximately 2.3 and the cobalt-carbon coordination number is approximately 1.8, indicating that the coordination configuration of Co-N2C2 is embedded in the carbon matrix. In the three possible Co-N2C2 structural units ( Figure 2 In section e), formation energy calculations based on density functional theory (DFT) indicate that structure I is thermodynamically the most stable and therefore the most likely to form. Therefore, in the subsequent discussion, structure I is designated as the representative model for Co–N₂C₂ coordination. The specific surface area is 220.738 m², as determined by BET. 2 / g, with a pore size of 6.095nm.

[0027] In the activity test of the catalyst under different reaction conditions, the oxidation reaction of antibiotic resistance genes (ARGs) with potassium persulfate was used as a probe reaction, and the first-order degradation rate constant k was used as a comparison; the higher the k value, the better the activity. Different catalysts (Co-N2C2, Fe-N2C2, Cu-N2C2, Cu-N2C2) were added, the reaction temperature was controlled at 25℃, and the substrate was 10... 12 A solution of antibiotic resistance gene (ARG) copies / mL was prepared. 0.1 mL of 60 mg / mL potassium persulfate (PMS) solution was added to 20 mL of reaction solution containing 0.1 g / L catalyst to initiate the reaction. The stirring speed was 500 rpm. 0.2 mL of the reaction solution was collected at the set reaction time intervals (0 min, 10 s, 30 s, 1 min, 2 min, 3 min, 5 min, 10 min, 20 min, and 30 min). 10 μL of 20 g / L sodium thiosulfate was added to the collected samples as a reaction quencher. After thorough mixing, online analysis was performed using qPCR.

[0028] Table 1. Effect of different metal loadings on the activity of catalysts per unit site

[0029]

[0030] Table 1 shows that M-N2C2 with different metal loadings has a crucial impact on the reaction. It can be found that when cobalt metal is loaded on a nitrogen-doped carbon base, it has the best ARG degradation performance and can achieve a large amount of pollutant degradation in a short time.

[0031] 2. Investigate the effect of different reaction conditions on the activity of the catalyst Co-N2C2.

[0032] In the activity test of the catalyst under different reaction conditions, the oxidation of antibiotic resistance genes (ARGs) with potassium persulfate was used as a probe reaction, and the first-order degradation rate constant k was used as a comparison; a higher k value indicates better activity. The reaction temperature was controlled at 25℃, and Co-N2C2 catalyst was used as a model catalyst. The reaction substrate was 20 mL of 10 12 A solution of antibiotic resistance genes (ARGs) was prepared at 1000 copies / mL. A certain amount of potassium persulfate (PMS) solution was added to the reaction solution to initiate the reaction. The pH of the reaction system was controlled by increasing the pH with 1 mmol / L sodium hydroxide solution and decreasing the pH with 1 mmol / L hydrochloric acid solution. The concentrations of PMS and catalyst were controlled by changing the concentrations of PMS (0.1 g / L, 0.2 g / L, 0.3 g / L, 0.6 g / L) and the concentrations of catalyst (0.05 g / L, 0.1 g / L, 0.2 g / L, 0.1 g / L) at 500 rpm and 25℃. 0.2 mL of the reaction solution was taken at set reaction time intervals (0 min, 0.15 min, 0.5 min, 1 min, 2 min, 3 min, 5 min, 10 min, 20 min, 30 min), and 10 μL of each sample was added to the sample. Sodium thiosulfate at a concentration of 20 g / L was used as a reaction quencher. The mixture was thoroughly mixed and then analyzed online using assembly-based qPCR.

[0033] Table 2 Effect of different reaction conditions on the activity of the catalyst Co-N2C2

[0034]

[0035] As shown in Table 2, the reaction activity is poor when the pH is too high or too low, while the activity is optimal when the pH is neutral, weakly acidic, or weakly alkaline. However, as the concentration of PMS and catalyst increases, the activity first improves and then deteriorates. This is because excessively high PMS concentrations cause PMS to react and generate reactive species with poor reactivity, thus reducing the concentration of PMS that can effectively participate in the reaction.

[0036] 3. Investigate the effect of different ions on the reaction activity of the catalyst Co-N2C2.

[0037] In the activity test of the catalyst under different reaction conditions, the oxidation of antibiotic resistance genes (ARGs) with potassium persulfate was used as a probe reaction, and the first-order degradation rate constant k was used as a comparison; a higher k value indicates better activity. The reaction temperature was controlled at 25℃, and Co-N2C2 catalyst was used as a model catalyst. The reaction substrate was 20 mL of 10 12 Antibiotic resistance gene (ARG) solutions of copies / mL were prepared by altering water quality conditions through the addition of different ionic salts to the reaction system. The added ionic salts were sodium chloride, sodium bicarbonate, sodium sulfate, sodium carbonate, sodium dihydrogen phosphate, sodium nitrate, and sodium phosphate (NaCl, NaHCO3, Na2SO4, Na2CO3, H2PO4, NaNO3, Na2PO4). The concentration of the added ionic salts in the reaction system was uniformly controlled at 20 mmol / L. 0.1 mL of 60 mg / mL potassium persulfate (PMS) solution was added to 20 mL of the reaction solution containing 0.1 g / L catalyst to initiate the reaction. The stirring speed was 500 rpm. 0.2 mL of the reaction solution was taken at set reaction time intervals (0 min, 0.15 min, 0.5 min, 1 min, 2 min, 3 min, 5 min, 10 min, 20 min, and 30 min), and 10 μL of each sample was added to the collected sample. Sodium thiosulfate at a concentration of 20 g / L was used as a reaction quencher. The mixture was thoroughly mixed and then analyzed online using assembly-based qPCR.

[0038] Table 3 Effect of different reaction conditions on the activity of the catalyst Co-N2C2

[0039]

[0040] As shown in Table 3, apart from nitrate ions, chloride ions, bicarbonate ions, sulfate ions, carbonate ions, dihydrogen phosphate ions, and phosphate ions have little effect on catalytic performance. The catalytic efficiency did not change significantly after the addition of sulfate ions and carbonate ions.

[0041] 4. Investigate the catalytic performance of the unit-point catalyst Co-N2C2 for different pollutants.

[0042] In the activity test of the composite catalyst for different pollutants, the selected pollutants mainly included tetracycline, sulfamethoxazole, bisphenol A, p-hydroxybenzoic acid, nitrobenzene, and phenol. The potassium persulfate oxidation reaction of these pollutants was used as a probe reaction, and the degradation rate η at 60 min was used as a comparison. The degradation rate η was calculated using the formula: η = 1 - Ct / C0, where Ct is the concentration of different pollutants at sampling time t, and C0 is the concentration of different pollutants in the solution at the beginning of the reaction. A higher degradation rate η indicates better activity. Using Co-N2C2 catalyst as a model catalyst, the reaction substrate was 40 mL of 50 µM solution containing different pollutants. 0.1 mL of 60 mg / mL potassium persulfate (PMS) solution was added to 20 mL of the reaction solution containing 0.1 g / L catalyst to start the reaction. The stirring speed was 500 rpm, and the reaction temperature was controlled at 25 °C. 1 mL of the reaction solution was then taken at set reaction time intervals (0 min, 1 min, 2 min, 3 min, 5 min, 10 min, 20 min, 30 min, and 60 min), and analyzed online using high-performance liquid chromatography (HPLC) with a C18 column.

[0043] Table 4 Effect of different reaction conditions on the activity of the catalyst Co-N2C2

[0044]

[0045] As shown in Table 4, the catalyst at a single point exhibits certain catalytic degradation performance for various pollutants, demonstrating a certain degree of universality.

[0046] 5. Investigate the irreversible damage to ARG caused by the unit-point catalyst Co-N2C2.

[0047] In the test to examine the regeneration capacity of ARGs, the potassium persulfate oxidation reaction of antibiotic resistance genes (ARGs) was used as a probe reaction, and the first-order degradation rate constant k was used as a comparison; the higher the k value, the better the activity. Co-N2C2, Fe-N2C2, and Cu-N2C2 were added, the reaction temperature was controlled at 25℃, and the reaction substrate was 10... 12A solution of antibiotic resistance gene (ARG) of copies / mL was added to 20 mL of reaction solution containing 0.1 g / L catalyst. 0.1 mL of 60 mg / mL potassium persulfate (PMS) solution was added to initiate the reaction at 500 rpm. 0.2 mL of the reaction solution was collected at set reaction time intervals (0 min, 10 s, 30 s, 1 min, 2 min, 3 min, 5 min, 10 min, 20 min, and 30 min). 10 μL of 20 g / L sodium thiosulfate was added to each sample as a reaction quencher, and the mixture was thoroughly mixed. Subsequently, 5 μL of the reaction sample was added to 100 μL of capable host bacteria and incubated on ice for 30 min, followed by heat shock at 42 °C for 90 s, and then incubated on ice for 2 min. Under aseptic conditions, 500 μL of non-resistant culture medium was added, and the mixture was incubated at 37 °C with shaking for 60 min. The cultures were then centrifuged, mixed, and fractions of the suspension were plated onto LB agar plates containing appropriate antibiotics. The inoculated plates were incubated at 37°C for 12–16 hours to allow colony formation. Plating was then performed using the plate count method.

[0048] Depend on Figure 5 It was observed that no antibiotic-resistant bacteria were generated after 3 minutes of reaction, indicating that the oxidation of ARG by the Co-N2C2 / PMS system causes irreversible damage.

[0049] 6. Investigate the cycle characteristics of the unit-point catalyst Co-N2C2.

[0050] In the experiment investigating the cyclic catalytic properties of the catalyst, the oxidation of antibiotic resistance genes (ARGs) with potassium persulfate was used as a probe reaction, and the degradation rate of ARGs over 30 minutes was used as a reference for comparison. The first-order degradation rate constant k was used as a comparison; a higher k value indicates better activity. The catalyst after reaction was centrifuged, washed with deionized water and anhydrous ethanol, and dried in a 60℃ oven for 12 hours before being used in the next reaction, for a total of ten cycles. The reaction temperature was controlled at 25℃, with a Co-N2C2 catalyst as the model catalyst, and the substrate being 20 mL of 10... 12The antibiotic resistance gene (ARG) solution was prepared in copies / mL. 0.1 mL of 60 mg / mL potassium persulfate (PMS) solution was added to the reaction solution to initiate the reaction. The stirring speed was 500 rpm, and the reaction temperature was controlled at 25℃. Then, 0.2 mL of the reaction solution was taken at the set reaction time intervals (0 min, 0.15 min, 0.5 min, 1 min, 2 min, 3 min, 5 min, 10 min, 20 min, and 30 min). 10 μL of 20 g / L sodium thiosulfate was added to the taken samples as a reaction quencher, and the mixture was thoroughly mixed. Online analysis was then performed using assembly-based qPCR.

[0051] Table 5. Recycling characteristics of the Co-N2C2 catalyst

[0052]

[0053] As shown in Table 5, the degradation rate of ARGs by the catalyst gradually decreases with the increase of the number of cycles, which may be due to the introduction of catalyst impurities during the recovery process. However, even under these circumstances, Co-N2C2 can still maintain its high catalytic activity after ten cycles.

Claims

1. A single-site catalyst with asymmetric coordination, characterized in that, In the catalyst, cobalt atoms are dispersed in unit-point form, and their structure is characterized by X-ray absorption fine structure spectroscopy. The first coordination layer consists of two nitrogen atoms and two carbon atoms, forming a Co-N₂C₂ coordination configuration, with a cobalt-nitrogen bond length of 1.5 Å and a cobalt-carbon bond length of 1.8 Å. The catalyst has a plate-like structure and a BET specific surface area of ​​70-280 m². 2 / g, with a pore size of 2-10 nm; the catalyst exhibits a first-order degradation rate constant k ≥ 2.0 min~12.0 min in the reaction of activating persulfate to degrade antibiotic resistance genes. -1 .

2. A method for preparing the asymmetric coordination unit site catalyst as described in claim 1, characterized in that, Includes the following steps: Cobalt source, trimesic acid and dicyandiamide were mixed and ground to obtain a precursor mixture; The precursor mixture is calcined under an inert atmosphere to obtain a calcined product; the calcined product is acid-washed, washed and dried to obtain the unit site catalyst; wherein the mass ratio of the cobalt source, trimesic acid and dicyandiamide is 1:(13~50):(167~500), and the asymmetric coordination unit site catalyst has an asymmetric Co-N2C2 coordination structure characterized by X-ray absorption spectroscopy.

3. The method according to claim 2, characterized in that, The cobalt source is cobalt chloride.

4. The method according to claim 2, characterized in that, The calcination process is as follows: the temperature is increased to 800°C at a rate of 5°C / min and held for 3 hours.

5. The method according to claim 2, characterized in that, The pickling process uses a 1 mM sulfuric acid solution and is carried out at 60°C for 8 hours.

6. The application of the asymmetric coordination unit site catalyst as described in claim 1 in activating persulfate in a Fenton-like reaction to degrade organic pollutants in water.

7. The application according to claim 6, characterized in that, The organic pollutants include at least one of antibiotic resistance genes, tetracycline, carbamazepine, sulfamethoxazole, ciprofloxacin, or oxytetracycline.

8. The application according to claim 7, characterized in that, When the organic pollutant is an antibiotic resistance gene, its initial concentration is 10. 10 Up to 10 13 copies / mL.

9. The application according to claim 6, characterized in that, In the reaction system, the concentration of the catalyst is 50-200 mg / L.

10. The application according to claim 6, characterized in that, In the reaction system, the concentration of persulfate is 0.5-2 mM, and the pH value of the reaction is 3-9.

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