Preparation method and application of persulfate activator for efficiently removing drug-resistant bacteria and drug-resistant genes in water

Abstract

The invention relates to the technical field of environmental functional materials and water treatment, and discloses a preparation method and application of a persulfate activator for efficiently removing drug-resistant bacteria and drug-resistant genes in water. Waste biomass and waste plastics are used as raw materials, solid waste resource utilization is achieved through synergistic pyrolysis, compared with a traditional catalyst, the preparation cost can be reduced by more than 40%, and remarkable economic and environmental benefits are achieved. The catalyst has the following advantages: 1) the limitation of a traditional single-active-site catalyst is broken through through the triple synergistic effect of transition metal oxide variable valence activation, nonmetal doped carbon electron conduction and an oxygen vacancy non-free radical path; 2) physical interception of ARB and enrichment of ARGs can be realized at the same time by utilizing a multi-stage pore channel structure; and (3) activating persulfate to generate free radicals (SO4 <->. / . OH) and non-free radicals (1O2 / electron transfer) to generate a double-path synergistic effect, thereby realizing efficient removal of ARB / ARGs in water.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental functional materials and water treatment, and in particular to a preparation method and application of a persulfate activator for efficiently removing drug-resistant bacteria and drug-resistant genes in water. Background Art

[0002] Antibiotic-resistant bacteria (ARB) and antibiotic-resistant genes (ARGs) have become a global environmental problem. With the widespread use of antibiotics, a large amount of undegraded antibiotics enters water bodies, promoting the generation and spread of ARB and ARGs.

[0003] Research has shown that ARGs are widely present in surface water, groundwater, hospital wastewater, farm wastewater, and sewage treatment plant discharge, with surface water pollution being particularly serious. ARGs can spread between microorganisms through horizontal gene transfer, increasing the risk of drug resistance and potentially contributing to the emergence of "superbugs" resistant to multiple antibiotics, posing a serious threat to human health. Furthermore, ARGs can persist in the environment for long periods of time and potentially spread through the food chain, further exacerbating ecological risks.

[0004] Traditional water treatment technologies, such as chlorine disinfection, ultraviolet disinfection, and biological treatment processes, have significant shortcomings in removing ARGs. Chlorine disinfection may promote the exchange of ARGs between bacteria, while resistant bacteria can potentially regenerate after UV disinfection. While biological treatment processes have some effectiveness in removing some ARGs, complete elimination is difficult. Therefore, the development of new and efficient water treatment technologies is a pressing priority.

[0005] Studies have shown that persulfate advanced oxidation technology (PS-AOPs) has significant advantages in removing ARBs and ARGs. - ) and hydroxyl radicals (·OH) to achieve efficient oxidation, and combined with singlet oxygen ( 1 O2) and superoxide (O2· - ) and other non-free radical pathways to improve the degradation effect.

[0006] PS-AOPs are suitable for different pH conditions and have strong mineralization capabilities, avoiding secondary contamination that may be caused by traditional disinfection technologies. In addition, this technology can be activated by various methods such as heat, ultraviolet light, electrochemistry, and transition metal catalysis, and has a wide range of adaptability. Compared with hydroxyl radicals, sulfate radicals have a longer lifespan and a larger diffusion radius, which enables them to exhibit more persistent oxidizing ability in complex environments. Therefore, this technology is considered one of the important strategies for the control and removal of ARBs / ARGs due to its high efficiency, broad spectrum, and stability.

[0007] However, the concentration of ARB / ARGs pollutants in water bodies is usually at trace levels, and traditional catalysts have limited selective adsorption capacity for them. In addition, the synergistic effect of activated persulfate to generate free radicals and non-free radicals is insufficient, making it difficult to achieve efficient targeted removal of ARB / ARGs. In addition, the competitive interference of coexisting substances in water bodies on oxidants further reduces the catalytic efficiency, resulting in the need for excessive use of catalysts to achieve the removal effect of target pollutants, increasing technical costs and limiting the promotion of PS-AOPs technology in practical applications. Therefore, the development of catalysts with good selective adsorption for ARB / ARGs, low cost, high efficiency and stability is the key to promoting the practical application of PS-AOPs technology.

[0008] Waste biomass, including organic matter from a wide range of sources, including agriculture, forestry, food processing, livestock and poultry farming, urban organic waste, and industrial byproducts, is renewable and biodegradable. Through pyrolysis and catalysis, it can be converted into energy, materials, and environmental remediation agents, achieving resource utilization and high-value utilization. The massive accumulation of waste plastics (such as polyethylene and polypropylene) has become a global environmental problem.

[0009] However, these wastes contain rich carbon resources and energy potential, and have important resource value. How to achieve their high-value utilization is one of the hot topics in solid waste resource utilization. Biomass pyrolytic carbon has excellent performance in pollutant adsorption due to its rich pore structure and surface functional groups, but its poor electrical conductivity limits its derivative catalytic activity. In contrast, the pyrolysis of waste plastics can generate reducing gases such as H2 and CH4, and release tar, which can effectively promote the pore formation and reduction regulation of the material. Through the synergistic pyrolysis of the two, the pore structure, carbon phase composition and surface chemical properties of the pyrolytic carbon can be effectively regulated, thereby improving its derivative catalytic activity.

[0010] Furthermore, the introduction of metal oxides for modification can give the material higher redox properties and electron transfer capabilities, and construct a composite material with both efficient adsorption and catalytic degradation functions. This strategy can be effectively used for the efficient removal of ARB / ARGs. Summary of the Invention

[0011] The purpose of the present invention is to solve the problems of insufficient activity of existing catalysts and low removal rate of drug-resistant bacteria and drug-resistant genes in water. It is proposed to use waste biomass, waste plastics and transition metals as raw materials, generate reducing gas through high-temperature co-pyrolysis, and prepare transition metal oxide-porous carbon catalyst co-doped with non-metallic elements such as nitrogen, phosphorus, sulfur and boron; the catalyst has the functions of multi-level pore adsorption, oxygen vacancy activation, and non-metallic structure multi-active center catalysis, can efficiently activate persulfate (PMS / PDS), and achieve efficient removal of ARB / ARGs through nano-confined adsorption and synergistic action of multiple metal active centers.

[0012] To achieve the above object, a first aspect of the present invention provides a method for preparing a transition metal oxide-non-metal element co-doped porous carbon catalyst, the method comprising:

[0013] Crush the dried waste biomass and waste plastics to a particle size > 50 mesh respectively to obtain waste biomass powder and waste plastic particles;

[0014] Mix the waste biomass powder, the waste plastic particles, a transition metal salt, and a non-metal element compound evenly, then add deionized water, adjust the pH of the system to 8-10, stir at 50-80 °C for 2-8 h, then let stand for 4-8 h, filter, take the filter residue, place it in an oven at 105 °C and dry for 8-16 h, grind it into a uniform powder, and then under a nitrogen atmosphere, heat it to 500-900 °C at a rate of 5-10 °C / min and calcine at this temperature for 4-8 h, and cool naturally to obtain a transition metal oxide-non-metal element co-doped porous carbon catalyst;

[0015] Based on the total amount of the waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metal element compound, the dosage of the waste biomass powder is 70-90 wt%, the dosage of the waste plastic particles is 8-15 wt%, the dosage of the transition metal salt is 5-10 wt%, and the dosage of the non-metal element compound is 3-5 wt%.

[0016] A second aspect of the present invention provides a transition metal oxide-non-metal element co-doped porous carbon catalyst prepared by the method described in the first aspect of the present invention.

[0017] A third aspect of the present invention provides the application of the transition metal oxide-non-metal element co-doped porous carbon catalyst described in the second aspect of the present invention in removing drug-resistant bacteria and drug-resistant genes in water by persulfate. Add the transition metal oxide-non-metal element co-doped porous carbon catalyst and persulfate to the water containing ARB and ARGs, and react at a pH of 3-10 for 10-60 min.

[0018] The method provided by the present invention at least further has the following beneficial effects:

[0019] (1) Resource utilization and low-cost advantages: The present invention uses waste biomass and waste plastics as raw materials to realize the resource utilization of solid waste through synergistic pyrolysis. Compared with traditional catalysts, the raw material cost is reduced by more than 40%, and it has significant economic and environmental benefits.

[0020] (2) Efficient synergistic catalytic mechanism: The present invention breaks through the limitation of a single active site of traditional catalysts through the synergistic effect of variable valence activation of transition metal oxides, electron conduction of nitrogen-doped carbon, and non-free radical pathways of oxygen vacancies. Its activation of persulfate can be achieved through free radicals (SO4 -· / ·OH) and non-free radicals ( 1 O2 / electron transfer) dual-path efficient coupling to achieve efficient inactivation and removal of ARB / ARGs in water.

[0021] (3) Environmental adaptability and stability: The hierarchical pore structure of the catalyst of the present invention effectively shields the interference of humic acid and inorganic ions, and the nitrogen doping buffers the pH fluctuation, so that it maintains high activity in a wide pH range (3-10); oxygen vacancies and metal-nitrogen-carbon (M-N-C) structures inhibit metal leaching and inactivation of active sites. After 5 cycles of use, the performance decay is <8%, significantly improving the reuse performance and reducing the operation cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the SEM scanning electron microscope test diagram of Fe-N@BC obtained in Example 1 of the present invention;

[0023] Figure 2 is the SEM scanning electron microscope test diagram of Co-S@BC obtained in Example 2 of the present invention;

[0024] Figure 3 is the SEM scanning electron microscope test diagram of NiFe-N@BC obtained in Example 3 of the present invention;

[0025] Figure 4 is the SEM scanning electron microscope diagram of the ARB cell membrane during the activation of PMS by Fe-N@BC;

[0026] Figure 5 is the SEM scanning electron microscope diagram of the ARB cell membrane during the activation of PMS by Co-S@BC;

[0027] Figure 6 is the SEM scanning electron microscope diagram of the ARB cell membrane during the activation of PMS by NiFe-N@BC;

[0028] Figure 7 is the DNA gel electrophoresis change diagram during the activation of PMS by NiFe-N@BC. DETAILED DESCRIPTION OF THE INVENTION

[0029] The endpoints and any values in the ranges disclosed herein are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0030] In the present invention, ARB represents antibiotic-resistant bacteria; ARGs represents antibiotic resistance genes; and PMS or PDS represents persulfate.

[0031] As mentioned above, the first aspect of the present invention provides a method for preparing a transition metal oxide-non-metallic element co-doped porous carbon catalyst, the method comprising:

[0032] The dried waste biomass and waste plastics are crushed to a particle size of >50 mesh to obtain waste biomass powder and waste plastic particles;

[0033] The waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metallic element compound are uniformly mixed, deionized water is added, the pH of the system is adjusted to 8-10, the mixture is stirred at 50-80° C. for 2-8 hours, the mixture is allowed to stand for 4-8 hours, filtered, the filter residue is taken, and the mixture is dried in a 105° C. oven for 8-16 hours, ground into a uniform powder, and then heated to 500-900° C. at a rate of 5-10° C. / min under a nitrogen atmosphere, and calcined at this temperature for 4-8 hours, and naturally cooled to obtain a transition metal oxide-non-metallic element co-doped porous carbon catalyst;

[0034] Based on the total amount of the waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metallic element compound, the amount of the waste biomass powder is 70-90wt%, the amount of the waste plastic particles is 8-15wt%, the amount of the transition metal salt is 5-10wt%, and the amount of the non-metallic element compound is 3-5wt%.

[0035] In the present invention, there is no particular requirement for the type of waste biomass, which can be at least one of organic materials from a wide range of sources, such as agriculture, forestry, food processing, livestock and poultry farming, urban organic waste, and industrial by-products. Exemplarily, the waste biomass is rice husk powder, sawdust, or coconut shell powder.

[0036] Preferably, the waste plastic is at least one of PE, PP, and PS.

[0037] More preferably, the transition metal salt is at least one of an iron salt, a cobalt salt, a nickel salt, and a copper salt.

[0038] Preferably, the transition metal salt is at least one of NiSO4, Fe(NO3)3, and CoCl2.

[0039] Preferably, the non-metallic element compound is at least one of a nitrogen-containing compound, a phosphorus-containing compound, a sulfur-containing compound, and a boron-containing compound.

[0040] Further preferably, the nitrogen-containing compound is urea, melamine or ammonium nitrate.

[0041] Preferably, the phosphorus-containing compound is ammonium dihydrogen phosphate.

[0042] More preferably, the sulfur-containing compound is thiourea, ammonium sulfate or thioacetamide.

[0043] Preferably, the boron-containing compound is boric acid or borax.

[0044] Preferably, based on the total amount of the waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metal element compound, the content of the waste biomass powder is 75-80 wt%, the content of the waste plastic particles is 10 wt%, the content of the transition metal salt is 6-10 wt%, and the content of the non-metal element compound is 3-5 wt%.

[0045] Preferably, the ratio of the total amount of the waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metal element compound to the amount of deionized water used is 1:10.

[0046] In the present invention, waste biomass and waste plastics are used as raw materials, and a transition metal oxide - porous carbon catalyst (M-X@BC) co-doped with non-metal elements such as nitrogen, phosphorus, sulfur, and boron is prepared by a co-precipitation - high-temperature calcination method. The reducing gases (H2 / CH4) generated by the pyrolysis of waste plastics not only promote the formation of hierarchical pores (micropores - mesopores - macropores), but also induce the generation of abundant oxygen vacancies. The doping of non-metal elements constructs multiple active sites: nitrogen (N) forms M-N-C active centers, phosphorus (P) constructs M-Px coordination structures, sulfur (S) introduces thiophene sulfur to enhance π-electron delocalization, and boron (B) stabilizes the carbon skeleton and regulates the metal electronic state. This catalyst physically intercepts ARBs through hierarchical pores and enriches ARGs using surface characteristics. During the catalytic process, oxygen vacancies and variable-valence metals synergistically activate persulfate (PMS / PDS), triggering a synergistic degradation path of free radicals (SO4 - · / ·OH) and non-free radicals ( 1 O2, electron transfer), effectively destroying the bacterial cell membrane and degrading DNA strands. The co-doping of multiple elements not only broadens the pH adaptation range (3 - 10), but also improves the electron conduction efficiency and catalytic stability, providing a low-cost, high-performance, and environmentally friendly solution for the treatment of waterborne antibiotic resistance pollution.

[0047] As described above, the second aspect of the present invention provides a transition metal oxide - non-metal element co-doped porous carbon catalyst prepared by the method described in the first aspect of the present invention.

[0048] As described above, the third aspect of the present invention provides an application of the transition metal oxide-non-metal element co-doped porous carbon catalyst described in the second aspect of the present invention in removing drug-resistant bacteria and drug-resistant genes in water. A transition metal oxide-non-metal element co-doped porous carbon catalyst and persulfate are added to a water body containing ARB and ARGs, and the reaction is carried out at a pH of 3 to 10 for 10 to 60 minutes.

[0049] Preferably, the dosage of the transition metal oxide-non-metal element co-doped porous carbon catalyst is 0.1 to 0.5 g / L.

[0050] More preferably, the concentration of the persulfate is 0.5 to 2 mmol / L.

[0051] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, the raw materials are commercially available products.

[0052] Example 1

[0053] This example is used to provide a method for preparing an iron oxide-nitrogen element co-doped porous carbon catalyst, and the method includes the following steps:

[0054] The dried rice husk and polypropylene waste plastic are respectively crushed to a particle size of 200 mesh to obtain rice husk powder and PP particles;

[0055] According to the mass percentage, 80 wt% of the rice husk powder, 10 wt% of the PP particles, 7 wt% of Fe(NO3)3, and 3 wt% of urea are weighed and mixed evenly. Then, deionized water is added, and the pH of the system is adjusted to 8 with sodium hydroxide solution. Stir at 60 °C for 4 h, then stand for 4 h, filter, take the filter residue, dry it in an oven at 105 °C for 12 h, grind it into a uniform powder, and then, under a nitrogen atmosphere, heat it to 600 °C at a rate of 5 °C / min and calcine it at this temperature for 4 h, and cool it naturally to obtain an iron oxide-nitrogen element co-doped porous carbon catalyst, denoted as Fe-N@BC;

[0056] Among them, the dosage of the deionized water is 10 mL (that is, the ratio of the total dosage of the rice husk powder, the PP particles, the Fe(NO3)3, and the urea to the dosage of the deionized water is 1:10).

[0057] Example 2

[0058] This example is used to provide a method for preparing a cobalt oxide-sulfur element co-doped porous carbon catalyst, and the method includes:

[0059] The dried wood chips and polyethylene waste plastic are respectively crushed to a particle size of 200 mesh to obtain wood chip powder and PE particles;

[0060] According to the mass percentage, 75wt% of the sawdust powder, 10wt% of the PE particles, 10wt% of CoCl2, and 5wt% of thiourea were weighed and mixed evenly, and then deionized water was added. The pH of the system was adjusted to 9 with sodium hydroxide solution, and the mixture was stirred at 60°C for 2h, and then allowed to stand for 4h. The mixture was filtered, and the filter residue was taken and dried in an oven at 105°C for 10h. The residue was ground into a uniform powder, and then heated to 800°C at a rate of 5°C / min under a nitrogen atmosphere, and calcined at this temperature for 4h. The mixture was naturally cooled to obtain a cobalt oxide-sulfur co-doped porous carbon catalyst, which was recorded as Co-S@BC;

[0061] The amount of deionized water used is 10 mL (that is, the ratio of the total amount of the sawdust powder, the PE particles, the CoCl2, and the thiourea to the amount of the deionized water is 1:10).

[0062] Example 3

[0063] This example is used to provide a method for co-doping porous carbon catalyst with periron nickel oxide and nitrogen, and the method includes:

[0064] The dried corn cobs and polyethylene waste plastics were crushed to a particle size of 200 mesh to obtain corn cob powder and PE particles;

[0065] According to the mass percentage, 80wt% of the corn cob powder, 10wt% of the PE particles, 3wt% Fe(NO3)3, 3wt% NiSO4, and 4wt% urea were weighed and mixed evenly, and then deionized water was added. The pH of the system was adjusted to 9 with sodium hydroxide solution, stirred at 50°C for 4h, and then allowed to stand for 4h. The mixture was filtered, and the filter residue was taken and placed in a 105°C oven to dry for 16h. The residue was ground into a uniform powder, and then heated to 800°C at a rate of 5°C / min under a nitrogen atmosphere, and calcined at this temperature for 4h. The mixture was naturally cooled to obtain an iron nickel oxide-nitrogen element co-doped porous carbon catalyst, which was recorded as NiFe-N@BC;

[0066] Among them, the amount of deionized water used is 10 mL (that is, the total amount of the corn cob powder, the PE particles, the Fe(NO3)3, the NiSO4, and the urea is in a ratio of 1:10 to the amount of deionized water).

[0067] Comparative Example 1

[0068] The method of Example 1 was followed, except that no rice husk powder, PP particles, or urea were added, and only Fe(NO3)3 was used as the raw material. The remaining steps and parameters were the same as those of Example 1.

[0069] Comparative Example 2

[0070] It was carried out according to the method of Example 1, except that no PP particles were added and the amount of rice husk powder was 90 wt%, and the remaining steps and parameters were the same as those in Example 1.

[0071] Comparative Example 3

[0072] It was carried out according to the method of Example 1, except that no urea was added and the amount of rice husk powder was 83 wt%, and the remaining steps and parameters were the same as those in Example 1.

[0073] Test Example 1

[0074] The catalysts prepared in the above examples and comparative examples were tested by SEM (scanning electron microscope), and the results are as Figures 1 to 3 shown.

[0075] Figure 1 This is the SEM test diagram of Fe-N@BC obtained in Example 1 of the present invention. It can be seen from Figure 1 this that the Fe-N@BC obtained in Example 1 of the present invention has curved carbon nanotubes with uneven pore diameters, so this catalyst has micropores-mesopores-macropores.

[0076] Figure 2 This is the SEM test diagram of Co-S@BC obtained in Example 2 of the present invention. It can be seen from Figure 2 this that the Co-S@BC obtained in Example 2 of the present invention has carbon nanotubes with uneven pore diameters, and the morphology of the carbon nanotubes is mainly linear, and this catalyst has hierarchical pores.

[0077] Figure 3 This is the SEM test diagram of NiFe-N@BC obtained in Example 3 of the present invention. It can be seen from Figure 3 this that the NiFe-N@BC obtained in Example 3 of the present invention has straight or curved carbon nanotubes with relatively uniform thickness.

[0078] Application Example 1

[0079] 0.3 g / L of Fe-N@BC and 1 mmol / L of PMS were added to the water sample containing Escherichia coli (carrying the tetA gene). After reacting for 30 min, during the activation of PMS by Fe-N@BC (in this application example, 0 min, 5 min, 10 min, and 30 min were recorded respectively), the morphological changes of the ARB cell membrane were observed by SEM (scanning electron microscope) (the results are as Figure 4 shown), and the colony count and the degradation rate of the tetA gene were calculated.

[0080] In this application example, the colony count decreased by 4.5 log, and the degradation rate of the tetA gene reached 98.7%.

[0081] FromFigure 4 It can be seen that the cell membrane of Escherichia coli is smooth and intact on the surface at 0 min of treatment. After 5 min of reaction, depressions and wrinkles appear on the cell membrane on the surface of the bacteria. After 30 min of reaction, the degree of depression and wrinkle of the cell membrane increases, indicating that the cell membrane structure is damaged.

[0082] Application Example 2

[0083] To a high-salt wastewater (with a NaCl content of 3 g / L) containing Pseudomonas aeruginosa (carrying the blaCTX-M gene), 0.4 g / L of Co-S@BC and 1.5 mmol / L of PMS were added, with a pH of 9. After 40 min of reaction, during the activation of PMS by Co-S@BC (in this application example, at 0 min, 5 min, 10 min, and 40 min respectively), the morphological changes of the ARB cell membrane were observed by SEM scanning electron microscopy (the results are as Figure 5 shown), and the colony count and the degradation rate of the blaCTX-M gene were calculated.

[0084] In this application example, the inactivation rate of ARB was 99.95%, that is, the colony count decreased by 4.3 log, and the degradation rate of the blaCTX-M gene was 96.5%.

[0085] From Figure 5 it can be seen that the cell membrane of Pseudomonas aeruginosa is smooth and plump at 0 min. After 5 min of treatment, the surface is still smooth but shrinks and becomes shorter; after 10 min of treatment, the cell membrane loses its smooth surface and further shrinks and becomes wrinkled; at 40 min, damage to the cell membrane and the outflow of intracellular substances are observed.

[0086] Application Example 3

[0087] To a humic acid-polluted water body (with a humic acid content of 10 mg / L) containing methicillin-resistant Staphylococcus aureus (carrying the mecA gene), 0.2 g / L of NiFe-N@BC and 2 mmol / L of PMS were added, with a pH of 5, and the reaction time was 90 min. During the activation of PMS by NiFe-N@BC (in this application example, at 0 min, 5 min, 30 min, and 90 min respectively), the morphological changes of the ARB cell membrane were observed by SEM scanning electron microscopy (the results are as Figure 6 shown), and the changes in DNA gel electrophoresis during the activation treatment of PMS by NiFe-N@BC (in this application example, at 0 min, 5 min, 10 min, 30 min, 60 min, and 90 min respectively) were recorded (the results are as Figure 7 shown), and the colony count and the degradation rate of the mecA gene were calculated.

[0088] In the embodiment of this application, the ARB inactivation rate is 99.98%, that is, the colony count is reduced by 4.6 log, and the degradation rate of the mecA gene is 97.3%.

[0089] It can be seen from Figure 6 that after 5 minutes of treatment, the bacterial morphology was observed to shorten in length due to shrinkage and wrinkling; after 30 minutes of treatment, the cell membrane structure was significantly ruptured, and some cell structures were completely destroyed, presenting an irregular cell debris structure.

[0090] It can be seen from Figure 7 that as the treatment time increases, the brightness of the gene band of iDNA gradually weakens, and a tailing phenomenon appears, indicating that the concentration of iDNA gradually decreases, and there is a phenomenon of degradation and rupture of the DNA strand structure. The brightness of the eDNA band shows a trend of first increasing and then decreasing, indicating that the concentration of eDNA also first increases and then decreases. This phenomenon is due to the leakage of iDNA leading to an increase in eDNA. After the treatment time exceeds 60 minutes, the brightness of the eDNA band almost disappears, indicating that eDNA is completely destroyed.

[0091] Application test example 1

[0092] Recover Fe-N@BC of Application Example 1 and conduct a stability test. Specifically, after drying the recovered Fe-N@BC, without any treatment, it was put into a water sample containing Escherichia coli (carrying the tetA gene), 1 mmol / L PMS was added, and the reaction was carried out for 30 minutes. The colony count and the degradation rate of the tetA gene were calculated. After 5 cycles of use, the activity of Fe-N@BC decreased by 5.3%.

[0093] Application test example 2

[0094] Recover Co-S@BC of Application Example 2 and conduct a stability test. Specifically, after drying the recovered Co-S@BC, without any treatment, it was put into high-salt wastewater containing Pseudomonas aeruginosa (carrying the blaCTX-M gene), 1 mmol / L PMS was added, and the reaction was carried out for 40 minutes. The colony count and the degradation rate of the blaCTX-M gene were calculated. After 5 cycles of use, the activity of Co-S@BC decreased by 5.8%.

[0095] Application test example 3

[0096] Recover NiFe-N@BC of Application Example 3 and conduct a stability test. Specifically, after drying the recovered NiFe-N@BC, without any treatment, it was put into humic acid-polluted water containing methicillin-resistant Staphylococcus aureus (carrying the mecA gene), 1 mmol / L PMS was added, and the reaction was carried out for 90 minutes. The colony count and the degradation rate of the mecA gene were calculated. After 5 cycles of use, the activity of NiFe-N@BC decreased by 5.5%.

[0097] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A preparation method of a transition metal oxide-non-metal element co-doped porous carbon catalyst, characterized in that, The method includes: Crushing the dry waste biomass and waste plastics to a particle size >50 mesh respectively to obtain waste biomass powder and waste plastic particles; Mixing the waste biomass powder, the waste plastic particles, a transition metal salt, and a non-metal element compound evenly, then adding deionized water, adjusting the pH of the system to 8-10, stirring at 50-80 °C for 2-8 h, then standing for 4-8 h, filtering, taking the filter residue, drying it in an oven at 105 °C for 8-16 h, grinding it into a uniform powder, and then heating it to 500-900 °C at a rate of 5-10 °C / min under a nitrogen atmosphere and calcining at this temperature for 4-8 h, and naturally cooling to obtain a transition metal oxide-non-metal element co-doped porous carbon catalyst; Based on the total amount of the waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metal element compound, the dosage of the waste biomass powder is 70-90 wt%, the dosage of the waste plastic particles is 8-15 wt%, the dosage of the transition metal salt is 5-10 wt%, and the dosage of the non-metal element compound is 3-5 wt%.

2. The method according to claim 1, wherein, The waste plastic is at least one of PE, PP, and PS.

3. The method according to claim 1 or 2, wherein The transition metal salt is at least one of iron salt, cobalt salt, nickel salt, and copper salt.

4. The method according to claim 1 or 2, wherein The non-metal element compound is at least one of a nitrogen-containing compound, a phosphorus-containing compound, a sulfur-containing compound, and a boron-containing compound; and / or, the nitrogen-containing compound is urea, melamine, or ammonium nitrate; and / or, the phosphorus-containing compound is ammonium dihydrogen phosphate; and / or, the sulfur-containing compound is thiourea, ammonium sulfate, or thioacetamide; and / or, the boron-containing compound is boric acid or borax.

5. The method according to claim 1 or 2, wherein, Based on the total amount of the waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metal element compound, the content of the waste biomass powder is 75-80 wt%, the content of the waste plastic particles is 10 wt%, the content of the transition metal salt is 6-10 wt%, and the content of the non-metal element compound is 3-5 wt%.

6. The method according to claim 1 or 2, wherein The ratio of the total amount of the waste biomass powder, the waste plastic particles, the transition metal salt, and the non-metal element compound to the dosage of the deionized water is 1:

10.

7. A transition metal oxide-non-metal element co-doped porous carbon catalyst prepared by the method according to any one of claims 1-6.

8. Use of the transition metal oxide-non-metal element co-doped porous carbon catalyst described in claim 7 in removing drug-resistant bacteria and drug-resistant genes in water, characterized in that, Adding a transition metal oxide-non-metal element co-doped porous carbon catalyst and persulfate to a water body containing ARB and ARGs and reacting at a pH of 3-10 for 10-60 min.

9. The application according to claim 8, wherein The dosage of the transition metal oxide-non-metal element co-doped porous carbon catalyst is 0.1-0.5 g / L.

10. The application according to claim 8 or 9, wherein, The concentration of the persulfate is 0.5-2 mmol / L.

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