Ion-interference-resistant high-load copper monatomic catalyst as well as preparation method and application thereof

Abstract

The invention discloses an anti-ion interference high-load copper monatomic catalyst as well as a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: dissolving a copper source and a carbon-nitrogen carrier in deionized water, fully mixing, and slowly and completely evaporating the deionized water to obtain catalyst precursor powder; and carrying out temperature programming sintering molding on the catalyst precursor powder in a protective atmosphere to obtain the catalyst. The copper source is copper chloride dihydrate and / or copper sulfide. According to the catalyst, through metal-carrier directional coordination engineering, in-situ anchoring of a copper source is carried out to obtain copper monatomic atoms, high loading capacity of the catalyst is achieved while high dispersity of the copper element is guaranteed, in addition, the catalyst further has excellent cycling stability and ion interference resistance, and the catalyst is used for degrading organic matter in waste water and has good application prospects. The method has the advantages that the consumption of the oxidizing agent is greatly reduced, rapid degradation of the antibiotics is realized, the wastewater treatment period is greatly shortened, and the operation cost is reduced when the method is used for treating the wastewater, especially the wastewater containing the antibiotics.

Description

Technical Field

[0001] The invention relates to a copper single atom catalyst, in particular to an ion interference resistant high-load copper single atom catalyst and a preparation method and application thereof, belonging to the technical field of water pollution treatment. Background Art

[0002] The pharmaceutical industry produces a huge amount of wastewater, and a large proportion of it contains antibiotic wastewater, which poses serious safety hazards to the environment and human health. Fenton-like systems based on hydrogen peroxide are gradually becoming an important technology in the field of water treatment, especially in the treatment of difficult-to-degrade organic pollutants. As heterogeneous catalysts for activating hydrogen peroxide, nanomaterials have played a huge role in this process. It is generally believed that the key to achieving efficient hydrogen peroxide activation and removing difficult-to-degrade pollutants is to develop highly active, highly stable and cost-effective catalysts. Although traditional metal nanoparticle catalysts perform well in this field, they face problems such as catalyst loss into product water, large mass transfer resistance and easy damage under strong shear force. These limitations have hindered the widespread application of hydrogen peroxide in actual water treatment processes to a certain extent. Therefore, the development of an efficient catalyst that can effectively treat new pollutants in the environment has important research value and broad application prospects.

[0003] Single-atom catalysts are mainly composed of three elements: metal, carbon, and nitrogen. This type of catalyst has the characteristic of high loading. Due to its unique structure, single-atom catalysts show excellent catalytic activity, especially in the fields of organic synthesis, energy conversion, and environmental protection. It has broad application prospects. In addition, the composite structure of single-atom catalysts gives them a higher specific surface area, which helps to improve their efficiency in adsorption, catalysis, energy storage, etc. Although single-atom catalysts have significant advantages in conductivity, mechanical properties, catalytic performance, etc., they also face many challenges such as synthesis complexity, high cost, environmental impact, aggregation, and structural heterogeneity. These shortcomings limit their promotion and use in some practical applications.

[0004] JianrongQiu (Chemical Engineering Journal, 2024, 479, 147841) from Guangxi University et al. used the affinity of nitrogen atoms generated by carbon vacancies to anchor single-atom Cu, achieving precise regulation of Cu, reducing agglomeration, maximizing exposure of active sites, and enhancing the activation of H2O2, achieving 100% removal of tetracycline in 20 min.

[0005] A Chinese patent (CN112264064B) discloses a method for preparing a copper single-atom carbon-based catalyst and its application in degrading phenolic organic pollutants. The catalyst has a Cu loading of 8 wt%, a wide pH adaptability range (pH1~11) and a strong ability to resist ion interference in water. However, the existing technology has the following problems: the synthesis process relies on high-concentration acid solution for metal etching and carrier purification, and a single batch produces 50-100 L / t of copper-containing acidic waste liquid, which has a significant environmental footprint; the multi-step separation and purification operation complicates the process flow, and is limited by the metal agglomeration effect, and the copper atom loading is usually less than 10 wt%. Therefore, the market urgently needs a single-atom catalyst with simple process, high metal loading and good dispersion to achieve industrial application. Summary of the invention

[0006] In view of the problems existing in the prior art, the first object of the present invention is to provide a high-load copper single-atom catalyst with resistance to ion interference. The catalyst anchors the copper source in situ to obtain copper single atoms through metal-carrier directional coordination engineering, while ensuring the high dispersibility of the copper element, it also achieves its high loading amount, reaching 25.9wt%, which is significantly higher than the prior art, and greatly improves the density of active sites; in addition, due to the metal-carrier directional coordination, the catalyst is also endowed with excellent cycle stability and anti-ion interference characteristics, that is, it still maintains efficient catalytic degradation ability in a complex system where multiple ions coexist.

[0007] The second object of the present invention is to provide a method for preparing a high-load copper single-atom catalyst that is resistant to ion interference. The method creatively obtains a copper single-atom catalyst by directional coordination between a copper source and a carrier only through "coordination-drying-sintering", without the need for acid etching or acid purification, without involving any other chemical reagents, and without emitting any waste gas or waste liquid, and has the advantages of simple process, green and high efficiency, etc.

[0008] The third object of the present invention is to provide an application of a high-load copper single-atom catalyst resistant to ion interference for catalytic degradation of organic pollutants in wastewater. Based on the excellent performance of the above copper single-atom catalyst, it is used to degrade organic matter in wastewater, especially wastewater containing antibiotics, with excellent technical effects. While greatly reducing the amount of oxidant used, it also achieves rapid degradation of antibiotics. After testing, only 0.3M hydrogen peroxide can be used to achieve complete degradation of 10mg / L tetracycline solution within 10 minutes, which greatly shortens the wastewater treatment cycle and reduces operating costs.

[0009] To achieve the above technical objectives, the present invention provides a method for preparing a highly loaded copper single atom catalyst resistant to ion interference, comprising: dissolving a copper source and a carbon-nitrogen carrier in deionized water and fully mixing them, then slowly and completely evaporating the deionized water to obtain a catalyst precursor powder; sintering the catalyst precursor powder under a protective atmosphere by programmed temperature rise to obtain a catalyst precursor powder; the copper source is cupric chloride dihydrate and / or copper sulfide.

[0010] The method provided by the present invention uses water as a solvent, thereby avoiding the generation of a large amount of acidic waste liquid due to the metal etching process in the prior art, and in-situ anchoring of copper single atoms through high-temperature pyrolysis of a carbon-nitrogen carrier, thereby avoiding metal agglomeration and greatly increasing the metal loading of the catalyst.

[0011] It should be noted that the selection of the copper source is one of the key parameters for achieving the waste-free preparation of the copper single-atom catalyst of the present invention. The decomposition of copper chloride and copper sulfide at high temperature will neither produce a large amount of gas to destroy the stability of the carrier structure, nor produce a large amount of anion residues to compete with copper ions for the active sites of the carrier. The cuprous ligands formed by them can easily form a stable coordination structure with the carbon nitride produced by the high-temperature sintering of the carbon-nitrogen carrier. Therefore, the one-step sintering method can be achieved to obtain a high-load copper single-atom catalyst through the directional coordination between the copper source and the carrier.

[0012] As a preferred solution, the mass ratio of the copper source to the carbon nitrogen carrier is 1:20~50.

[0013] As a preferred solution, the carbon-nitrogen carrier is urea and / or melamine. Urea and melamine will decompose to produce a large amount of -CN under high temperature and oxygen-free conditions, which can not only form a large number of defect vacancies, but also achieve efficient coordination with copper elements, thereby anchoring the copper elements in the defect sites and avoiding agglomeration under high loading.

[0014] As a preferred solution, the method of sufficient mixing is stirring mixing, and the stirring time is ≥ 1h.

[0015] As a preferred solution, the method of completely evaporating the deionized water is one of rotary evaporation, freeze drying, oven drying and vacuum drying;

[0016] As a preferred solution, the method of completely evaporating the deionized water is oven drying, and the conditions are: temperature of 50-100° C. and time of 8-20 hours.

[0017] As a preferred solution, the conditions for the programmed temperature sintering molding are: heating from room temperature to 300-1000°C at a rate of 2-10°C / min, keeping the temperature for 1-5 hours, and then cooling to room temperature with the furnace.

[0018] As a preferred solution, the protective atmosphere is nitrogen and / or argon.

[0019] As a preferred solution, the programmed temperature rising sintering molding is carried out with continuous blowing throughout the entire process, and the protective atmosphere flow rate is 50-200 L / min.

[0020] The present invention also provides a high-loaded copper single atom catalyst resistant to ion interference, obtained by any of the methods described above; the catalyst is composed of copper single atoms and a nitrogen carbide carrier, and the copper loading is 22~27wt% based on the mass of copper element.

[0021] The present invention also provides an application of a high-load copper single-atom catalyst resistant to ion interference, which is used for catalytic degradation of organic pollutants in wastewater. The process is: after the copper atom catalyst is fully mixed with the wastewater, an oxidant is added to carry out a catalytic degradation reaction, and the catalyst is recovered after the reaction is completed.

[0022] As a preferred solution, the mass volume ratio of the copper single atom catalyst to the wastewater is 0.1~0.5g / L; the oxidant is at least one of hydrogen peroxide, ozone and oxygen; and the pH of the catalytic degradation reaction is 3~11.

[0023] As a preferred solution, the concentration of organic pollutants in the wastewater is 5-20 mg / L. Further preferably, the organic pollutants are antibiotics and / or organic pigments.

[0024] As a preferred solution, when the oxidant is hydrogen peroxide, its concentration is 0.01-0.5 mol / L; the mass volume ratio of the copper single atom catalyst to hydrogen peroxide is 10-20 g / L.

[0025] Compared with the prior art, the beneficial technical effects of the technical solution provided by the present invention are:

[0026] 1) The copper single-atom catalyst provided by the present invention realizes the stable loading of copper atoms on the carbon nitride carrier in an atomically dispersed form through metal-carrier directional coordination engineering, and the copper loading capacity has reached a breakthrough of 25.9wt%, which is 3 to 5 times higher than that of conventional single-atom catalysts. This high-density atomic dispersion structure significantly increases the density of active sites on the catalyst surface.

[0027] 2) The preparation method provided by the present invention uses a copper source and a carbon-nitrogen carrier for in-situ synthesis through "coordination-drying-sintering", which greatly shortens the process flow of the copper single-atom catalyst and does not require acid leaching and solvent washing. It not only eliminates acidic waste liquid pollution, but also greatly reduces energy consumption costs. This method achieves in-situ composite of metal and carrier through molecular self-assembly, ensuring uniform dispersion of active components. The whole process does not involve any other chemical reagents and does not emit any waste gas or waste liquid. It has the advantages of simple process, green and high efficiency.

[0028] 3) The technical solution provided by the present invention is based on the excellent performance of the above-mentioned copper single-atom catalyst, and is used to degrade organic matter in wastewater, especially wastewater containing antibiotics, with excellent technical effects. While greatly reducing the amount of oxidant used, it also achieves rapid degradation of antibiotics. According to tests, only 0.3M hydrogen peroxide can be used to achieve complete degradation of a 10mg / L tetracycline solution within 10 minutes, which greatly shortens the wastewater treatment cycle and reduces operating costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The X-ray diffraction pattern of the catalyst prepared in Example 1;

[0030] Figure 2 This is a scanning electron microscope photo of the catalyst prepared in Example 1;

[0031] in, Figure 2 (a) is a scanning electron microscope image of the catalyst prepared in Example 1 at a magnification of 2000 times. Figure 2 (b) is a scanning electron microscope image of the catalyst prepared in Example 1 at a magnification of 20,000 times. Figure 2 (c) is a scanning electron microscope (EDS) image of the catalyst prepared in Example 1 at a magnification of 2000 times. Figure 2 (d) is a Cu scanning electron microscope EDS image of the catalyst prepared in Example 1 at a magnification of 2000 times. Figure 2 (e) is a C scanning electron microscope EDS image of the catalyst prepared in Example 1 at a magnification of 2000 times. Figure 2 (f) is a N scanning electron microscope EDS image of the catalyst prepared in Example 1 at a magnification of 2000 times;

[0032] Figure 3 This is the XPS graph of the catalyst prepared in Example 1;

[0033] in, Figure 3 (a) is the N 1s fine spectrum of the catalyst prepared in Example 1, Figure 3 (b) is the Cu 2p fine spectrum of the catalyst prepared in Example 1;

[0034] Figure 4 The effect diagram of tetracycline degradation under different conditions of Example 1 and Comparative Examples 1 and 2;

[0035] Figure 5 The effect of the catalyst prepared in Example 1 on the degradation of tetracycline under different degradation conditions;

[0036] in, Figure 5 (a) Effect of different catalyst dosages on tetracycline degradation. Figure 5 (b) Effects of different amounts of hydrogen peroxide added on tetracycline degradation. Figure 5(c) Effect of different pH on the degradation of tetracycline. Figure 5 (b) Effect of catalyst on tetracycline degradation at different tetracycline concentrations;

[0037] Figure 6 This is a diagram showing the recycling effect of the catalyst prepared in Example 1;

[0038] Figure 7 This is a diagram showing the effect of degrading different organic pollutants in Example 2;

[0039] Figure 8 The degradation effect diagram of tetracycline by the catalyst of Example 3 under the interference of different anions;

[0040] Fig. 9 The figure is a diagram showing the degradation effect of the catalysts prepared in Examples 4 and 5 on tetracycline. DETAILED DESCRIPTION

[0041] For ease of understanding of the present invention, the present invention will be described more fully below with reference to specific implementation cases. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.

[0042] Example 1

[0043] A method for preparing a high-load copper single-atom catalyst comprises the following steps:

[0044] Dissolve 0.3 g of copper chloride dihydrate and 12 g of urea in 20 mL of deionized water and stir for 1 h.

[0045] The solution was placed in a forced air drying oven for drying, the heating temperature was set to 80 °C and kept warm for 12 h.

[0046] The dried powder was transferred to a porcelain boat and placed in a tube furnace. −1 The samples were heated to 550 °C at a heating rate of 100 °C, kept warm for 2 h under a flowing Ar atmosphere, and finally naturally cooled to room temperature to obtain a highly loaded copper single atom catalyst.

[0047] Figure 1~Figure 3This is the basic physicochemical information characterization of the copper single atom catalyst obtained in this example. It can be seen from the figure that the catalyst has no Cu diffraction peak, and the distribution of Cu is consistent with that of C and N, and is relatively dispersed. In addition, the valence of Cu in XPS is mainly +1.

[0048] Method for degrading tetracycline (TC) by activating hydrogen peroxide using the above-mentioned high-load copper single-atom catalyst:

[0049] Weigh 0.025g of high-load copper single-atom catalyst using an analytical balance and add it to 50mL of 10mg / L tetracycline solution. Stir the resulting solution with a magnetic stirrer for 15min to allow the adsorption-desorption equilibrium between the catalyst and the pollutant to be reached, then add 1.53mL of hydrogen peroxide (about 0.3M) and start the timing reaction.

[0050] Samples were taken from the reaction solution at set time intervals, filtered using a 0.22 μm filter membrane, and the supernatant was subjected to high performance liquid chromatography to detect the residual tetracycline concentration to determine the removal efficiency. Figure 5 It can be seen that the catalyst prepared by the present invention has a relatively fast degradation ability, that is, 100% degradation of tetracycline can be completed in 10 minutes. At the same time, it has a good degradation ability under different pH conditions. Even when the pH of the system is 11, 100% degradation of tetracycline can still be completed in 60 minutes.

[0051] Furthermore, the present invention also conducts a cyclic experiment on the obtained high-load copper single-atom catalyst / hydrogen peroxide system:

[0052] For the cycle test, 0.025 g of highly loaded copper single atom catalyst was weighed with an analytical balance and added to 50 mL of a tetracycline solution with a concentration of 10 mg / L. The resulting solution was stirred with a magnetic stirrer for 90 min. After each experiment, the catalyst was recovered by centrifugation in a centrifuge and thoroughly washed with a large amount of deionized water. In order to make up for the inevitable loss of catalyst mass during the recovery process, multiple sets of parallel experiments were carried out in the first cycle test to recover enough catalyst for subsequent cycles. In order to restore the catalytic performance, the used catalyst was filtered, collected and dried in a forced air drying oven at 60 °C overnight. The results are shown in Figure 2. Figure 6 The results show that after eight recycling cycles, the degradation effect of tetracycline is still more than 85% in 10 minutes. This shows that the high-load copper single-atom catalyst prepared in Example 1 has excellent recycling ability.

[0053] Comparative Example 1

[0054] Method of using hydrogen peroxide alone to degrade tetracycline:

[0055] Use a pipette to measure 1.53 mL of hydrogen peroxide and add it to 50 mL of 10 mg / L tetracycline solution. Stir the resulting solution with a magnetic stirrer for 10 min.

[0056] Samples were taken from the reaction solution at set time intervals and filtered using a 0.22 μm filter membrane. The supernatant was subjected to high performance liquid chromatography to detect the residual tetracycline concentration to determine the removal efficiency. The results showed that the degradation rate of tetracycline was 3.4% when only 1.53 mL of hydrogen peroxide was added.

[0057] Comparative Example 2

[0058] Method for degrading tetracycline using the high-load copper single-atom catalyst obtained in Example 1 alone:

[0059] 0.025 g of highly loaded copper single atom catalyst was weighed using an analytical balance and added to 50 mL of a 10 mg / L tetracycline solution. The resulting solution was stirred using a magnetic stirrer for 90 min.

[0060] 5 mL of the reaction solution was sampled and filtered using a 0.22 μm filter membrane. The supernatant was injected into a high-performance liquid chromatography to detect the residual tetracycline concentration to determine the removal efficiency. The results showed that the degradation rate of tetracycline was 7.1% when only 0.025 g of high-loaded copper single-atom catalyst was added.

[0061] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0062] Example 2

[0063] Method for degrading different organic pollutants using highly loaded copper single atom catalyst to activate hydrogen peroxide:

[0064] 0.025 g of the high-load copper single-atom catalyst prepared in Example 1 was weighed with an analytical balance and added to 50 mL of 10 mg / L methylene blue, rhodamine B, sulfamethoxazole, and sulfasalazine solutions. The resulting solution was stirred with a magnetic stirrer for 15 min to allow the catalyst and the pollutants to reach adsorption-desorption equilibrium, and then 1.53 mL of hydrogen peroxide (about 0.3 M) was added to start the timing reaction.

[0065] Samples were taken from the reaction solution at set time intervals, filtered using a 0.22 μm filter membrane, and the supernatant was tested in a high performance liquid chromatography to determine the concentration of residual organic pollutants to determine the removal efficiency. Figure 7As shown in the figure, the degradation rates of the four types of pollutants can reach 100% within 20 min, which proves that the catalyst has excellent broad-spectrum oxidation adaptability and engineering application potential.

[0066] Example 3

[0067] In order to verify the applicability of the catalyst in actual water bodies, this example simulates an industrial wastewater environment containing high concentrations of inorganic anions, and evaluates the method of activating hydrogen peroxide to degrade tetracycline using a high-load copper single atom catalyst under conditions of different inorganic ion interferences:

[0068] Sodium chloride, sodium nitrate, sodium sulfate and sodium bicarbonate were used as ion sources to prepare tetracycline solutions containing 10.0 mM chloride ion, nitrate ion, sulfate ion and bicarbonate ion, respectively. The control group was a pure TC solution without ion addition.

[0069] First, 10 mM of inorganic salt corresponding to inorganic ions was weighed and added to 50 mL of a 10 mg / L tetracycline solution, and then 0.025 g of the high-load copper single-atom catalyst prepared in Example 1 was weighed using an analytical balance and added to the above solution. The obtained solution was stirred with a magnetic stirrer for 15 min to allow the catalyst and the pollutant to reach an adsorption-desorption equilibrium, and then 1.53 mL of hydrogen peroxide (about 0.3 M) was added to start the timing reaction.

[0070] Samples were taken from the reaction solution at set time intervals, filtered using a 0.22 μm filter membrane, and the supernatant was subjected to high performance liquid chromatography to detect the concentration of residual organic pollutants to determine the removal efficiency.

[0071] like Figure 8 As shown, under different ion interferences, the single-atom catalysts prepared by the present invention can be completely degraded within 10 minutes, proving that the catalyst still maintains excellent stability and anti-interference ability in complex water quality.

[0072] Example 4

[0073] A method for preparing a high-load copper single-atom catalyst comprises the following steps:

[0074] Dissolve 0.1 g of copper chloride dihydrate and 12 g of urea in 20 mL of deionized water and stir for 1 h.

[0075] The solution was placed in a forced air drying oven for drying, the heating temperature was set to 80 °C and kept warm for 12 h.

[0076] The dried powder was transferred to a porcelain boat and placed in a tube furnace. The samples were then heated to 550°C at a heating rate of 5°C•min−1, kept warm for 2 h under an Ar gas atmosphere, and finally cooled naturally to room temperature to obtain a high-load copper single atom catalyst.

[0077] Method for degrading tetracycline (TC) using highly loaded copper single atom catalyst to activate hydrogen peroxide:

[0078] Weigh 0.025 g of highly loaded copper single atom catalyst using an analytical balance and add it to 50 mL of 10 mg / L tetracycline solution. Stir the resulting solution with a magnetic stirrer for 15 min to allow the catalyst and pollutants to reach adsorption-desorption equilibrium, then add 1.53 mL of hydrogen peroxide (about 0.3 M) and start the timing reaction.

[0079] Samples were taken from the reaction solution at set time intervals, and then filtered using a 0.22 μm filter membrane. The supernatant was taken in a high performance liquid chromatography to detect the residual tetracycline concentration to determine the removal efficiency. The results showed that the high-load copper single-atom catalyst prepared by the present invention could achieve 100% removal of tetracycline in 60 min.

[0080] Example 5

[0081] A method for preparing a high-load copper single-atom catalyst comprises the following steps:

[0082] Dissolve 0.3 g of copper chloride dihydrate and 12 g of urea in 20 mL of deionized water and stir for 1 h.

[0083] The solution was placed in a forced air drying oven for drying, the heating temperature was set to 80 °C and kept warm for 12 h.

[0084] The dried powder was transferred to a porcelain boat and placed in a tube furnace. The samples were then heated to 650°C at a heating rate of 5°C•min−1, kept warm for 2 h under an Ar gas atmosphere, and finally cooled naturally to room temperature to obtain a high-load copper single atom catalyst.

[0085] Method for degrading tetracycline (TC) using highly loaded copper single atom catalyst to activate hydrogen peroxide:

[0086] Weigh 0.025 g of highly loaded copper single atom catalyst using an analytical balance and add it to 50 mL of 10 mg / L tetracycline solution. Stir the resulting solution with a magnetic stirrer for 15 min to allow the catalyst and pollutants to reach adsorption-desorption equilibrium, then add 1.53 mL of hydrogen peroxide (about 0.3 M) and start the timing reaction.

[0087] Samples were taken from the reaction solution at set time intervals, and then filtered using a 0.22 μm filter membrane. The supernatant was subjected to high performance liquid chromatography to detect the residual tetracycline concentration to determine the removal efficiency. The results showed that the Cu single atom catalyst prepared by the present invention could achieve 96.2% removal of tetracycline in 90 min.

[0088] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing a highly loaded copper single atom catalyst resistant to ion interference, characterized in that: include: The copper source and the carbon-nitrogen carrier are dissolved in deionized water and fully mixed, and then the deionized water is slowly evaporated to obtain a catalyst precursor powder; the catalyst precursor powder is sintered in a protective atmosphere at a programmed temperature to obtain a catalyst precursor powder; The copper source is copper chloride dihydrate and / or copper sulfide.

2. The method for preparing a highly loaded copper single atom catalyst resistant to ion interference according to claim 1, characterized in that: The mass ratio of the copper source to the carbon-nitrogen carrier is 1:20-50; the carbon-nitrogen carrier is urea and / or melamine.

3. The method for preparing a highly loaded copper single atom catalyst resistant to ion interference according to claim 1, characterized in that: The method of fully mixing is stirring and mixing, and the stirring time is ≥1h; the method of completely evaporating the deionized water is one of rotary evaporation, freeze drying, oven drying and vacuum drying.

4. The method for preparing a highly loaded copper single atom catalyst resistant to ion interference according to claim 3, characterized in that: The method of completely evaporating the deionized water is oven drying, and the conditions are: temperature of 50-100° C. and time of 8-20 hours.

5. The method for preparing a highly loaded copper single atom catalyst resistant to ion interference according to claim 1, characterized in that: The conditions for the programmed temperature sintering molding are: heating from room temperature to 300-1000° C. at 2-10° C. / min, keeping the temperature for 1-5 hours, and then cooling to room temperature with the furnace.

6. The method for preparing a highly loaded copper single atom catalyst resistant to ion interference according to any one of claims 1 to 5, characterized in that: The protective atmosphere is nitrogen and / or argon; the air is blown continuously throughout the programmed temperature rising sintering process, and the protective atmosphere flow rate is 50-200 L / min.

7. A highly loaded copper single atom catalyst resistant to ion interference, characterized in that: Obtained by the method described in any one of claims 1 to 6; the catalyst consists of copper atoms and a carbonized nitrogen carrier, and the copper loading is 22 to 27 wt% based on the mass of the copper element.

8. The use of a highly loaded copper single atom catalyst resistant to ion interference as claimed in claim 7, characterized in that: It is used for catalytic degradation of organic pollutants in wastewater, and the process is: after the copper atom catalyst is fully mixed with the wastewater, an oxidant is added to carry out catalytic degradation reaction, and the catalyst is recovered after the reaction is completed.

9. The use of a highly loaded copper single atom catalyst resistant to ion interference according to claim 8, characterized in that: The mass volume ratio of the copper single atom catalyst to the wastewater is 0.1-0.5 g / L; the oxidant is at least one of hydrogen peroxide, ozone and oxygen; and the pH of the catalytic degradation reaction is 3-11.

10. The use of a highly loaded copper single atom catalyst resistant to ion interference according to claim 9, characterized in that: When the oxidant is hydrogen peroxide, its concentration is 0.01-0.5 mol / L; the mass volume ratio of the copper single atom catalyst to hydrogen peroxide is 10-20 g / L.

Images