Method for degrading antibiotics by transition bimetallic catalyst rubbing activation monopersulfate and application thereof

Abstract

The application relates to a method for degrading antibiotics by friction-activated peroxymonosulfate of a transition bimetallic catalyst and application. 1 Compared with the prior art, the application has better degradation effect on antibiotics, has the advantages of promoting multi-path O2 generation, realizing non-radical dominant selective degradation of electron-rich antibiotics, etc., and has great potential in practical application of antibiotic wastewater treatment.

Description

Technical Field

[0001] This invention relates to the field of antibiotic degradation technology, and in particular to a method and application of antibiotic degradation by triboelectric activation of peroxymonosulfate using a transition bimetallic catalyst. Background Technology

[0002] The widespread use of antibiotics in various fields has led to their prevalence in water bodies, posing a potential threat to ecosystems and human health. Efficiently degrading antibiotics in water bodies can reduce their toxicity to aquatic organisms and their potential impact on humans.

[0003] Traditional wastewater treatment plants and biological treatment processes are inefficient at removing antibiotics. In recent decades, technologies based on SO4 generated after peroxymonosulfate activation have become increasingly important. ·- Its stronger oxidizing capacity has attracted much attention. To improve the removal efficiency of antibiotics, coupled technologies such as photo / electrochemical methods have been studied simultaneously, but these are limited by the high requirements for catalysts. Meanwhile, in recent years, researchers, including our team, have also discovered that SO42- is involved in the antibiotic degradation process. ·- It is not the primary active species, but rather other active species involved in the activation process of peroxymonosulfate (PMS), such as singlet oxygen (…). 1 O2) or direct electron transfer, this non-radical-dominated degradation pathway offers entirely new insights into water treatment technologies, in which 1 O2, as an electrophilic and reactive excited-state oxygen, possesses a highly efficient and selective electrophilic attack capability against electron-rich antibiotics. Therefore, [this is relevant to...] 1 The non-radical process of O2 is more advantageous for practical applications because it exhibits strong resistance to interference and a wider pH adaptability.

[0004] Patent publication number CN114713228A discloses a method for preparing a novel material, CNTs-TiO2@CuFe2O4, and its application. It constructs a novel advanced oxidation system of CNTsTiO2@CuFe2O4 / light / PMS, achieving complete mineralization of antibiotics through photocatalytic synergistic activation of PMS to generate long-lived and highly oxidizing sulfate and hydroxyl radicals. This patent uses composite materials and a photosensitive catalyst for synergistic photocatalysis, which increases the cost and complexity of catalyst preparation. Furthermore, the patent demonstrates the in-situ coupling of SO4 with PMS activation under light-assisted conditions. ·- and HO · This is to remove recalcitrant organic pollutants. Although the composite catalyst has certain adsorption properties, its degradation efficiency for ciprofloxacin is over 95% within 30 minutes. While photocatalytic degradation of wastewater is a promising and environmentally friendly technology, current issues such as low light utilization efficiency and low energy conversion efficiency of catalysts still prevent the large-scale application of light energy in wastewater treatment.

[0005] CuFe₂O₄, a catalyst with two active sites, has been studied as a dual-transition metal ferroelectric material, but SO₄... ·- or HO · It is considered to be the main active substance in the CuFe2O4 / PMS system, or... 1 O2 exists as a coexisting substance. Many researchers have attempted to modulate the electronic structure of catalysts by adjusting their surface or interface engineering, aiming to overcome the free radical generation pathway and achieve 100% production. 1 O2, however, requires complex synthesis conditions for catalyst coordination environment and precise control to ensure uniform atomic distribution, which significantly increases the cost and time of catalyst preparation. However, the application of triboelectric technology to dye degradation for the first time in 2019 has become a new direction for using mechanical energy in wastewater treatment. Especially during ball milling, temporary polarized surfaces with opposite charges can be generated, meaning that triboelectric catalysis can adjust the local electronic structure and enhance electron transfer. This holds promise for regulating the CuFe2O4 / PMS system. 1 The generation of O2. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the existing technology, especially the problem of requiring additional photosensitive catalysts for synergistic photocatalysis and the degradation pathway dominated by free radicals. This invention provides a simpler, lower-energy method and application for the triboelectric activation of peroxymonosulfate by a transition bimetallic catalyst to degrade antibiotics, which has a better degradation effect on antibiotics and promotes multi-pathway degradation. 1 The 100% generation of O2 enables the selective degradation of electron-rich antibiotics dominated by non-free radicals. Furthermore, its good resistance to acid and base and stability among organic and inorganic ions have great potential for practical applications in antibiotic wastewater treatment.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] In one aspect, the present invention provides a method for the triboelectric degradation of antibiotics by peroxymonosulfate using a transition bimetallic catalyst. The antibiotic solution to be degraded is placed in a ball mill jar, and a transition bimetallic catalyst, milling beads, and PMS are added before ball milling to achieve triboelectric electrocatalytic degradation of antibiotics.

[0009] Furthermore, the antibiotics include electron-rich sulfonamides, β-lactam antibiotics, diaminopyrimidine antibiotics, and tetracycline antibiotics.

[0010] The electron-rich sulfonamide antibiotics include sulfadiazine (SDZ) and sulfamethoxazole (SMX);

[0011] The β-lactam antibiotics mentioned include 6-aminopenicillanic acid (6-APA);

[0012] The diaminopyrimidine antibiotics mentioned include methoxypyrimidine (TMP);

[0013] The tetracycline antibiotics mentioned include p-chlorophenol (4-CP).

[0014] Furthermore, the solvent in the antibiotic solution includes aqueous solutions, aqueous solutions containing inorganic anions, metal cations, and natural organic compounds.

[0015] Furthermore, the inorganic anion includes NO3. - HCO3 - Cl - Metal cations include Ca 2+ Mg 2 Natural organic compounds include hyaluronic acid (HA).

[0016] Furthermore, the pH of the antibiotic solution is 4–10.

[0017] Furthermore, the ratio of the transition bimetallic catalyst dispersion to PMS is 10–100 mL: 0.28–16 mg, preferably 100 mL: 7–10 mg;

[0018] The concentration of the antibiotic solution is 5–30 mg / L, preferably 5–20 mg / L; the concentration of the PMS is 0.25–1 mM, preferably 0.4–0.6 mM.

[0019] Furthermore, the chemical formula of the aforementioned transition bimetallic catalyst is AB₂O₄. AB₂O₄ spinel is a special cubic crystal structure, exhibiting superior redox capabilities and stability. A is manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), or copper (Cu), and B is iron (Fe), titanium (Ti), chromium (Cr), or molybdenum (Mo).

[0020] Furthermore, the chemical formula of the aforementioned transition bimetallic catalyst is AFe₂O₄. The magnetic AFe₂O₄ nanoparticles have a spinel structure, wherein Fe... 3+ Spinel-structured materials, with ions occupying octahedral B sites and divalent ions located at tetrahedral A sites, are widely used in fields such as optics and catalysts, for example, in magnetic storage media, magnetic nanoparticles, and photocatalytic materials.

[0021] Furthermore, the chemical formula of the aforementioned transition bimetallic catalyst is CuFe2O4.

[0022] Furthermore, the preparation process of the transition bimetallic catalyst is as follows: A salt solution and B salt solution are ultrasonically mixed, and an alkaline solution is added dropwise to form a dark brown solution. The dark brown solution is subjected to a hydrothermal reaction, and the precipitated product obtained is the transition bimetallic catalyst.

[0023] Furthermore, the A salt solution includes Mn salt solution, Co salt solution, Ni salt solution, Zn salt solution or Cu salt solution, the B salt solution includes Fe salt solution, and the alkaline solution includes NaOH solution and KOH solution;

[0024] The molar ratio of A to B in the A salt solution and B salt solution is 1:1 to 4, preferably 1:1.8 to 2.2; the concentration of the alkali solution is 1 to 10 mol / L, preferably 1 to 5 mol / L; the volume ratio of the A salt solution to the alkali solution is 1 to 10:1, preferably 1 to 5:1.

[0025] The hydrothermal reaction is carried out at a temperature of 160–200°C for a duration of 12–48 hours.

[0026] Furthermore, the concentration of the A salt solution is 0.1–2 mol / L, preferably 0.1–1 mol / L; the concentration of the B salt solution is 0.05–2 mol / L, preferably 0.05–1 mol / L; and the concentration of the alkali solution is 1–10 mol / L, preferably 1–5 mol / L.

[0027] Furthermore, the A salt solution is uniformly dispersed by ultrasound for 5–30 minutes; the B salt solution is uniformly dispersed by ultrasound for 5–10 minutes; and the A salt solution and the B salt solution are ultrasonically mixed for 10–30 minutes.

[0028] Furthermore, after adding alkaline solution dropwise and stirring, a dark brown solution is obtained, and the stirring time is 60 to 150 minutes.

[0029] Furthermore, the obtained precipitate is washed and dried at a temperature of 60–70°C for 10–20 hours.

[0030] Furthermore, the milling jar includes a zirconia milling jar, the milling beads include zirconia milling beads, the particle size of the milling beads is 1-10 mm, and the powder-to-bead ratio is 1:300-800. The powder-to-bead ratio represents the mass ratio of the transition bimetallic catalyst to the milling beads.

[0031] Furthermore, the rotational speed of the ball mill is 50 to 1200 rpm, preferably 100 to 400 rpm.

[0032] Furthermore, the degradation time is 0.01–180 min, preferably 5–180 min.

[0033] In another aspect, the present invention also provides an application of a method for degrading antibiotics by triboelectric activation of a transition bimetallic catalyst with peroxymonosulfate in the field of antibiotic wastewater treatment.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] (1) For electron-rich antibiotics, this invention promotes the oxidation of non-radical intermediates formed by heterogeneous tribocatalysis and PMS activation; and utilizes a transition bimetallic catalyst to promote multi-pathway oxidation by leveraging the contact electrification effect under ball milling in conjunction with PMS activation. 1 The generation of O2 enables the non-free radical-dominated selective degradation of electron-rich sulfonamide antibiotics (SDZ).

[0036] (2) The transition bimetallic catalyst of the present invention is prone to surface polarization under ball milling conditions, and the redox potential of the catalyst decreases under bimetallic synergy. In addition, PMS is introduced into the friction system of the transition bimetallic catalyst to make full use of the excellent potential and electron transfer characteristics of the transition bimetallic catalyst, effectively activate PMS, and further improve the catalytic activity of the entire reaction system.

[0037] (3) The formation of A-PMS* (especially Cu-PMS*) and B-PMS* (especially Fe-PMS*) between the transition bimetallic catalyst AB2O4 and PMS in this invention is 1 The key to O2 generation, even though the production of HO is unavoidable, lies in inducing its generation of nearly 100% single HO particles under conditions of high electron-hole mass transfer capability. 1 O2 is crucial for the efficient and selective removal of antibiotics in a short time. While mass transfer in antibiotic degradation research may often be overlooked, it significantly impacts reaction rates. Current research on improving mass transfer efficiency largely focuses on interfacial manipulation of materials, and ball milling can minimize mass transfer losses between the catalyst, PMS, and antibiotics. Furthermore, triboelectric electrocatalysis is an emerging antibiotic degradation technology that, compared to piezoelectric catalysis, has fewer material limitations, especially given the contact electrification effect generated during ball milling. Currently, there are no reports on using ball milling for transition metal-activated PMS degradation of organic pollutants, providing new research avenues for developing more environmentally friendly wastewater treatment technologies to achieve effective and efficient antibiotic removal.

[0038] (4) The redox reactions of A(III) / A(II) and B(III) / B(II) on the surface of the transition bimetallic catalyst AB2O4 of this invention significantly contribute to the decomposition of PMS. Combined with triboelectric contact electrocatalytic degradation technology, compared to piezoelectric catalysis, it has fewer material limitations. The catalyst generates a contact electrification effect during ball milling, and the catalyst surface undergoes transient polarization, generating holes (h... +) and electrons (e - This further promotes the activation of PMS.

[0039] (5) The preparation process of the transition bimetallic catalyst of the present invention is simple, the production cost is low, and the catalyst has high stability, which has great potential in practical applications.

[0040] (6) The material preparation and pollution control of this invention break through the bottlenecks of existing technologies. First, a spinel-structured dual transition metal catalyst is prepared using a simple one-step hydrothermal method. Second, an external mechanical ball milling environment is used to improve the electronic structure of the catalyst surface, thereby inducing multi-pathway synthesis. 1 The generation of O2 overcomes the problem of generating other reactive free radicals in the current transition metal-activated PMS process. 1 The problem of low O2 production efficiency. Finally, this mechanical ball mill environment system has high mass transfer and high efficiency. 1 It exhibits high antibiotic removal efficiency due to its high O2 yield. It is characterized by simple operation and low cost, and holds promise for large-scale wastewater treatment. Attached Figure Description

[0041] Figure 1 The XRD patterns of the CuFe2O4 catalysts in Examples 1-4 of this invention are shown below.

[0042] Figure 2 The SEM images and particle size distribution maps of the CuFe2O4 catalysts (a) CFO-1, (b) CFO-1.5, (c) CFO-2 and (d) CFO-4 in Examples 1-4 of this invention are shown.

[0043] Figure 3 The following are the (a) HRTEM and (b) EDS mapping spectra of CFO-2 of this invention;

[0044] Figure 4 The BET spectra of the CuFe2O4 catalysts in Examples 1-4 of this invention are shown.

[0045] Figure 5 The images show the triboelectric synergistic PMS ball milling degradation performance of CuFe2O4 catalyst in Examples 1-4 of this invention. (a) shows the triboelectric synergistic PMS ball milling degradation of SDZ by CuFe2O4, Fe2O3, CuO, and Fe2O3 / CuO synthesized from raw materials with different molar ratios. (b) shows the triboelectric synergistic PMS ball milling degradation of SDZ by CuFe2O4 under different conditions.

[0046] Figure 6The graphs show the degradation performance and resistance to environmental interference of CFO-2 of the present invention against different pollutants. (a) shows the degradation experiment of different pollutants, (b) shows the effect experiment of 5mM anions and 5mM metal cations, (c) shows the effect experiment of humic acid (HA) at different concentrations of 5-20ppm, and (d) shows the effect experiment of initial pH.

[0047] Figure 7 This is a graph showing the TOC removal rate of SDZ pollutants by CFO-2 of the present invention;

[0048] Figure 8 The optimal reaction conditions for the CFO-2 synergistic PMS ball milling system of this invention were tested, including (a) the effect of different ball milling speeds, (b) the effect of different PMS concentrations, (c) the effect of different catalyst dosages, and (d) the effect of different contaminant concentrations.

[0049] Figure 9 This is a stability graph of the CFO-2 reaction.

[0050] Figure 10 The effect of different quenchers on SDZ degradation. Detailed Implementation

[0051] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments. All other embodiments obtained by those skilled in the art based on the given embodiments without creative effort are within the scope of protection of this application. Unless otherwise specified, the reagents, methods, instruments, and equipment used in the present invention are conventional reagents, methods, instruments, and equipment in the art.

[0052] Example 1

[0053] A method for the degradation of antibiotics by peroxymonosulfate using a transition bimetallic catalyst via triboelectric activation includes the following steps:

[0054] (1) Preparation of CuFe2O4 catalyst

[0055] At room temperature, 0.826 g of FeCl3·6H2O and 0.5115 g of CuCl2·2H2O (molar ratio 1:1) (all reagents were analytical grade, purchased from Adamas Reagent Co., Ltd.) were dissolved in 30 mL of deionized water, and the solutions were sonicated for 5 min to form homogeneous FeCl3 and CuCl2 solutions, respectively. The FeCl3 solution was then added dropwise to the CuCl2 solution with stirring. Meanwhile, 20 mL of 1.4 mol / L KOH solution (analytical grade, purchased from Adamas Reagent Co., Ltd.) was added dropwise with stirring for 60 min. The resulting solution was then placed in a polytetrafluoroethylene-lined autoclave and reacted at 200 °C for 3 h. After the autoclave cooled to room temperature, the precipitate was collected. The precipitate was washed three times each with deionized water and ethanol, and then dried at 60 °C for 12 h to obtain the CuFe2O4 catalyst, denoted as CFO-1.

[0056] (2) Friction-activated peroxymonosulfate degradation of antibiotics

[0057] A 50 mL solution of SDZ (10 mg / L) to be degraded (reagent was analytical grade, purchased from Adamas Reagent Co., Ltd.) was placed in a 50 mL zirconia ball mill jar. 20 mg of CFO-1 was added and dispersed in the solution. Zirconia ball milling beads of 3 mm (powder to ball ratio of 1:500) were added. PMS (0.5 mM, reagent purity 98%+, purchased from Adamas Reagent Co., Ltd.) was added, and the jar was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve the triboelectric electrocatalytic degradation of antibiotics.

[0058] Example 2

[0059] A method for the degradation of antibiotics by peroxymonosulfate using a transition bimetallic catalyst via triboelectric activation includes the following steps:

[0060] (1) Preparation of CuFe2O4 catalyst

[0061] At room temperature, 1.239 g of FeCl3·6H2O and 0.5115 g of CuCl2·2H2O (molar ratio 1.5:1) (all reagents were analytical grade, purchased from Adamas Reagents Ltd.) were dissolved in 30 mL of deionized water, respectively, and sonicated for 5 min to form homogeneous FeCl3 and CuCl2 solutions. The FeCl3 solution was then added dropwise to the CuCl2 solution under stirring. Simultaneously, 20 mL of 1.4 mol / L KOH solution (analytical grade, purchased from Adamas Reagents Ltd.) was added dropwise under stirring for 60 min. The resulting solution was then placed in a polytetrafluoroethylene-lined autoclave and reacted at 200 °C for 3 h. After the autoclave cooled to room temperature, the precipitate was collected. The precipitate was washed three times each with deionized water and ethanol, and then dried at 60 °C for 12 h to obtain the CuFe2O4 catalyst, denoted as CFO-1.5.

[0062] (2) Friction-activated peroxymonosulfate degradation of antibiotics

[0063] A 50 mL solution of SDZ (10 mg / L) to be degraded (analytical grade, purchased from Adamas Reagents Ltd.) was placed in a 50 mL zirconia ball mill jar. 20 mg of CFO-1.5 was added and dispersed in the solution. 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, followed by PMS (0.5 mM, reagent purity 98%+, purchased from Adamas Reagents Ltd.). The jar was then placed in a planetary ball mill for ball milling degradation experiments (400 rpm) for 5 min, achieving the triboelectric electrocatalytic degradation of the antibiotic.

[0064] Example 3

[0065] A method for the degradation of antibiotics by peroxymonosulfate using a transition bimetallic catalyst via triboelectric activation includes the following steps:

[0066] (1) Preparation of CuFe2O4 catalyst

[0067] At room temperature, 1.652 g of FeCl3·6H2O and 0.5115 g of CuCl2·2H2O (molar ratio 2:1) (all reagents were analytical grade, purchased from Adamas Reagent Co., Ltd.) were dissolved in 30 mL of deionized water, and the solutions were sonicated for 5 min to form homogeneous FeCl3 and CuCl2 solutions, respectively. The FeCl3 solution was then added dropwise to the CuCl2 solution with stirring. Meanwhile, 20 mL of 1.4 mol / L KOH solution (analytical grade, purchased from Adamas Reagent Co., Ltd.) was added dropwise with stirring for 60 min. The resulting solution was then placed in a polytetrafluoroethylene-lined autoclave and reacted at 200 °C for 3 h. After the autoclave cooled to room temperature, the precipitate was collected. The precipitate was washed three times each with deionized water and ethanol, and then dried at 60 °C for 12 h to obtain the CuFe2O4 catalyst, denoted as CFO-2.

[0068] (2) Friction-activated peroxymonosulfate degradation of antibiotics

[0069] A 50 mL solution of SDZ (10 mg / L) to be degraded (reagent was analytical grade, purchased from Adamas Reagent Co., Ltd.) was placed in a 50 mL zirconia ball mill jar. 20 mg of CFO-2 was added and dispersed in the solution. 3 mm zirconia ball milling beads (powder to ball ratio of 1:500) were added. PMS (0.5 mM) (reagent purity of 98%+, purchased from Adamas Reagent Co., Ltd.) was added, and the jar was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve the triboelectric electrocatalytic degradation of antibiotics.

[0070] Example 4

[0071] A method for the degradation of antibiotics by peroxymonosulfate using a transition bimetallic catalyst via triboelectric activation includes the following steps:

[0072] (1) Preparation of CuFe2O4 catalyst

[0073] At room temperature, 3.304 g of FeCl3·6H2O and 0.5115 g of CuCl2·2H2O (molar ratio 4:1) (all reagents were analytical grade, purchased from Adamas Reagents Ltd.) were dissolved in 30 mL of deionized water, respectively, and sonicated for 5 min to form homogeneous FeCl3 and CuCl2 solutions. The FeCl3 solution was then added dropwise to the CuCl2 solution under stirring. Simultaneously, 20 mL of 1.4 mol / L KOH solution (analytical grade, purchased from Adamas Reagents Ltd.) was added dropwise under stirring for 60 min. The resulting solution was then placed in a polytetrafluoroethylene-lined autoclave and reacted at 200 °C for 3 h. After the autoclave cooled to room temperature, the precipitate was collected. The precipitate was washed three times each with deionized water and ethanol, and then dried at 60 °C for 12 h to obtain the CuFe2O4 catalyst, denoted as CFO-4.

[0074] (2) Friction-activated peroxymonosulfate degradation of antibiotics

[0075] A 50 mL solution of SDZ (10 mg / L) to be degraded (reagent was analytical grade, purchased from Adamas Reagent Co., Ltd.) was placed in a 50 mL zirconia ball mill jar. 20 mg of CFO-4 was added and dispersed in the solution. 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added. PMS (0.5 mM) (reagent purity of 98%+, purchased from Adamas Reagent Co., Ltd.) was added, and the jar was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve the triboelectric electrocatalytic degradation of antibiotics.

[0076] Example 5

[0077] Compared with Example 3, most of the steps are the same, except that the antibiotic being degraded is SMX (the reagent is of analytical grade and purchased from Adamas Reagent Co., Ltd.). Step (2) triboelectric activation of peroxymonosulfate to degrade antibiotic: 50 mL of SMX (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (the mass ratio of catalyst to ball milling beads is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm) for 5 min, so as to achieve triboelectric contact electrocatalytic degradation of antibiotic.

[0078] Example 6

[0079] Compared with Example 3, most of the steps are the same, except that the antibiotic being degraded is TMP (analytical grade, purchased from Adamas Reagent Co., Ltd.). Step (2) is the triboelectric activation of peroxymonosulfate to degrade antibiotics: 50 mL of TMP (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (the mass ratio of catalyst to ball milling beads is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm), and the degradation time is 5 min, thus realizing the triboelectric contact electrocatalytic degradation of antibiotics.

[0080] Example 7

[0081] Compared with Example 3, most of the steps are the same, except that the antibiotic being degraded is 4-CP (the reagent is of analytical grade and purchased from Adamas Reagent Co., Ltd.). Step (2) is the triboelectric activation of peroxymonosulfate to degrade antibiotics: 50 mL of 4-CP (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (the mass ratio of catalyst to ball milling beads is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm) for 5 min, so as to achieve triboelectric contact electrocatalytic degradation of antibiotics.

[0082] Example 8

[0083] Most of the components were the same as in Example 3, except that 5 mM Cl was added to the degradation solution. - Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 18.625 mg KCl (analytical grade reagent, purchased from Adamas Reagent Co., Ltd.) was added, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve friction-contact electrocatalytic degradation of antibiotics.

[0084] Example 9

[0085] The process was largely the same as in Example 3, except that 5 mM HCO3 was added to the degradation solution. –Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 25 mg KHCO3 (analytical grade reagent, purchased from Adamas Reagent Co., Ltd.) was added, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve friction-contact electrocatalytic degradation of antibiotics.

[0086] Example 10

[0087] The process was largely the same as in Example 3, except that 5 mM NO3 was added to the degradation solution. – Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 25.25 mg KNO3 (analytical grade reagent, purchased from Sinopharm Chemical Reagent Co., Ltd.) was added, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve friction-contact electrocatalytic degradation of antibiotics.

[0088] Example 11

[0089] The process was largely the same as in Example 3, except that 5 mM Ca was added to the degradation solution. 2+ Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 36.75 mg CaCl2·2H2O (analytical grade, purchased from Adamas Reagent Co., Ltd.) was added, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve friction-contact electrocatalytic degradation of antibiotics.

[0090] Example 12

[0091] The process was largely the same as in Example 3, except that 5 mM Mg was added to the degradation solution. 2+Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 32.75 mg MgCl2·6H2O (analytical grade, purchased from Adamas Reagent Co., Ltd.) was added, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve friction-contact electrocatalytic degradation of antibiotics.

[0092] Example 13

[0093] Compared with Example 3, most of the steps are the same, except that 5 ppm of humic acid (HA) (analytical grade, purchased from Macklin Biotechnology Co., Ltd.) is added to the degradation solution. Step (2) is to degrade antibiotics by friction activation of peroxymonosulfate: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 2.5 mL of 100 ppm HA solution is added, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve the friction contact electrocatalytic degradation of antibiotics.

[0094] Example 14

[0095] Compared with Example 3, most of the steps are the same, except that 10 ppm of humic acid (HA) (analytical grade, purchased from Macklin Biotechnology Co., Ltd.) is added to the degradation solution. Step (2) is to degrade antibiotics by friction activation of peroxymonosulfate: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 5 mL of pre-prepared 200 ppm HA solution is added, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (the mass ratio of catalyst to ball milling beads is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm) for 5 min to achieve the friction contact electrocatalytic degradation of antibiotics.

[0096] Example 15

[0097] Compared with Example 3, most of the steps are the same except that 0.1 mol / L HCl (analytical grade, purchased from Sinopharm Chemical Reagent Co., Ltd.) was used to adjust the initial pH of the solution to 4. Step (2) Frictionally activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, HCl solution was added dropwise until the pH of the solution was 4, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve frictional contact electrocatalytic degradation of antibiotics.

[0098] Example 16

[0099] Compared with Example 3, most of the steps are the same, except that 0.1 mol / L NaOH (analytical grade, purchased from Adamas Reagent Co., Ltd.) was used to adjust the initial pH of the solution to 8. Step (2) Frictionally activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, NaOH solution was added dropwise until the solution pH was 8, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve frictional contact electrocatalytic degradation of antibiotics.

[0100] Example 17

[0101] Compared with Example 3, most of the steps are the same, except that 0.1 mol / L NaOH (analytical grade, purchased from Adamas Reagent Co., Ltd.) was used to adjust the initial pH of the solution to 10. Step (2) Frictionally activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, NaOH solution was added dropwise until the solution pH was 10, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) were added, PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve frictional contact electrocatalytic degradation of antibiotics.

[0102] Example 18

[0103] Compared with Example 3, most of the steps are the same, except that the rotation speed of the planetary ball mill is adjusted to 100 rpm in step (2): 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 100 rpm) for 5 min, thus achieving the triboelectric electrocatalytic degradation of antibiotics.

[0104] Example 19

[0105] Compared with Example 3, most of the steps are the same, except that the rotation speed of the planetary ball mill is adjusted to 200 rpm in step (2): 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 200 rpm) for 5 min to achieve the triboelectric contact electrocatalytic degradation of antibiotics.

[0106] Example 20

[0107] Compared with Example 3, most of the steps are the same, except that the rotation speed of the planetary ball mill is adjusted to 300 rpm in step (2): 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in the planetary ball mill for ball milling degradation experiment (rotation speed of 300 rpm) for 5 min, thus achieving the triboelectric electrocatalytic degradation of antibiotics.

[0108] Example 21

[0109] Compared with Example 3, most of the contents are the same, except that the concentration of PMS in step (2) is adjusted to 0.25mM: 50mL of SDZ (10mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, 20mg of CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.25mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min, so as to achieve the triboelectric contact electrocatalytic degradation of antibiotics.

[0110] Example 22

[0111] Compared with Example 3, most of the contents are the same, except that the concentration of PMS in step (2) is adjusted to 1mM: 50mL of SDZ (10mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, 20mg of CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (1mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min, so as to achieve the triboelectric contact electrocatalytic degradation of antibiotics.

[0112] Example 23

[0113] Compared with Example 3, most of the steps are the same, except that the amount of CFO-2 in step (2) is adjusted to 5 mg: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 5 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min, so as to achieve the triboelectric contact electrocatalytic degradation of antibiotics.

[0114] Example 24

[0115] Compared with Example 3, most of the steps are the same, except that the amount of CFO-2 in step (2) is adjusted to 10 mg: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 10 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve the triboelectric electrocatalytic degradation of antibiotics.

[0116] Example 25

[0117] Compared with Example 3, most of the steps are the same, except that the amount of CFO-2 in step (2) is adjusted to 30 mg: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 30 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min, so as to achieve the triboelectric contact electrocatalytic degradation of antibiotics.

[0118] Example 26

[0119] Compared with Example 3, most of the contents are the same, except that the concentration of SDZ in step (2) is adjusted to 5 mg / L: 50 mL of SDZ (5 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 2 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min, so as to achieve the triboelectric contact electrocatalytic degradation of antibiotics.

[0120] Example 27

[0121] Compared with Example 3, most of the contents are the same, except that the concentration of SDZ in step (2) is adjusted to 20 mg / L: 50 mL of SDZ (20 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 2 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min, so as to achieve the triboelectric contact electrocatalytic degradation of antibiotics.

[0122] Example 28

[0123] Compared with Example 3, most of the contents are the same, except that methanol (MeOH) (99.9% purity, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 0.2M. Step (2) Friction activation of peroxymonosulfate to degrade antibiotics: 50mL of SDZ (20mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, 99.9% methanol is added to a concentration of 0.2M, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min to achieve friction contact electrocatalytic degradation of antibiotics.

[0124] Example 29

[0125] Compared with Example 3, most of the steps are the same, except that methanol (MeOH) (99.9% purity, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 0.5mM. Step (2) Friction activation of peroxymonosulfate to degrade antibiotics: 50mL of SDZ (20mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, 99.9% methanol is added to a concentration of 0.5M, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min to achieve friction contact electrocatalytic degradation of antibiotics.

[0126] Example 30

[0127] Compared with Example 3, most of the process is the same except that methanol (MeOH) (99.9% purity, purchased from Adamas Reagents Ltd.) is used and the amount is adjusted to 2M. Step (2) Friction activation of peroxymonosulfate degradation of antibiotics: 50mL of SDZ (20mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, 99.9% methanol is added to a concentration of 2M, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min to achieve friction contact electrocatalytic degradation of antibiotics.

[0128] Example 31

[0129] Compared with Example 3, most of the steps are the same except that tert-butanol (TBA) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 0.2 mM. Step (2) Friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (20 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, TBA is added to a concentration of 0.2 mM, 2 mg CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0130] Example 32

[0131] Compared with Example 3, most of the steps are the same except that tert-butanol (TBA) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 0.5 mM. Step (2) Friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (20 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, tert-butanol is added to a concentration of 0.5 mM, 2 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0132] Example 33

[0133] Compared with Example 3, most of the steps are the same except that tert-butanol (TBA) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 1M. Step (2) Friction activation of peroxymonosulfate to degrade antibiotics: 50mL of SDZ (20mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, tert-butanol is added to a concentration of 1M, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min to achieve friction contact electrocatalytic degradation of antibiotics.

[0134] Example 34

[0135] Compared with Example 3, most of the steps are the same except that L-histidine (L-his) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 1mM. Step (2) Friction activation of peroxymonosulfate to degrade antibiotics: 50mL of SDZ (20mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, L-histidine is added to a concentration of 1mM, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min to achieve friction contact electrocatalytic degradation of antibiotics.

[0136] Example 35

[0137] Compared with Example 3, most of the steps are the same except that L-histidine (L-his) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 2mM. Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50mL of SDZ (20mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, L-histidine is added to a concentration of 2mM, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min to achieve friction-contact electrocatalytic degradation of antibiotics.

[0138] Example 36

[0139] Compared with Example 3, most of the steps are the same except that L-histidine (L-his) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the amount is adjusted to 5mM. Step (2) Friction activation of peroxymonosulfate to degrade antibiotics: 50mL of SDZ (20mg / L) solution to be degraded is placed in a 50mL zirconia ball mill jar, L-histidine is added to a concentration of 5mM, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio of 1:500) are added, PMS (0.5mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400rpm) for 5min to achieve friction contact electrocatalytic degradation of antibiotics.

[0140] Comparative Example 1

[0141] A method for Fe2O3-tribosensitive activation of peroxymonosulfate degradation of antibiotics includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar; 20 mg of Fe2O3 (analytical grade, purchased from Adamas Reagent Co., Ltd.) is added and dispersed in the solution; 3 mm zirconia ball milling beads are added (catalyst to ball milling beads mass ratio is 1:500); PMS (0.5 mM) is added; and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed 400 rpm) for 5 min, thereby achieving tribosensitive electrocatalytic degradation of antibiotics.

[0142] Comparative Example 2

[0143] A method for CuO-triboelectrically activated peroxymonosulfate degradation of antibiotics includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar; 20 mg of CuO (analytical grade, purchased from Adamas Reagents Ltd.) is added and dispersed in the solution; 3 mm zirconia ball milling beads are added (catalyst to ball milling beads mass ratio is 1:500); PMS (0.5 mM) is added; and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed 400 rpm) for 5 min, thereby achieving triboelectric contact electrocatalytic degradation of antibiotics.

[0144] Comparative Example 3

[0145] A method for the triboelectric degradation of antibiotics using Fe2O3 / CuO, comprising the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar; 20 mg of a mixture of Fe2O3 and CuO (molar ratio 1:1) (all reagents are analytical grade, purchased from Adamas Reagents Ltd.) is added and dispersed in the solution; 3 mm zirconia ball milling beads are added (catalyst to ball milling beads mass ratio 1:500); PMS (0.5 mM) is added; and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed 400 rpm) for 5 min, thereby achieving triboelectric electrocatalytic degradation of antibiotics.

[0146] Comparative Example 4

[0147] A method for degrading antibiotics with peroxymonosulfate includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 3 mm zirconia grinding beads are added (the mass ratio of catalyst to grinding beads is 1:500), PMS (0.5 mM) is added, and then the jar is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm) for 5 min, thereby achieving the triboelectric electrocatalytic degradation of antibiotics.

[0148] Comparative Example 5

[0149] A method for the triboelectric degradation of antibiotics using CFO-2 includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar; 20 mg of CFO-2 is added and dispersed in the solution; 3 mm zirconia ball milling beads (catalyst to ball milling beads mass ratio of 1:500) are added; and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm) for 5 min, thereby achieving triboelectric contact electrocatalytic degradation of antibiotics.

[0150] Comparative Example 6

[0151] A Fe 3+ A method for the triboelectric activation of peroxymonosulfate degradation of antibiotics includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of FeCl3·6H2O (analytical grade reagent, purchased from Adamas Reagent Co., Ltd.) is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (catalyst to ball milling beads mass ratio is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm), and the degradation time is 5 min, thereby achieving triboelectric contact electrocatalytic degradation of antibiotics.

[0152] Comparative Example 7

[0153] A Cu 2+ A method for the triboelectric activation of peroxymonosulfate degradation of antibiotics includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CuCl2·2H2O (analytical grade reagent, purchased from Adamas Reagent Co., Ltd.) is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (catalyst to ball milling beads mass ratio is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm), degradation time is 5 min, thereby achieving triboelectric contact electrocatalytic degradation of antibiotics.

[0154] Comparative Example 8

[0155] A method for CFO-2-triboelectro-activated peroxymonosulfate degradation of antibiotics includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar; 0.2 mM EDTA (analytical grade, purchased from Adamas Reagents Ltd.) is added and dispersed in the solution; 20 mg of CFO-2 is added and dispersed in the solution; 3 mm zirconia ball milling beads are added (catalyst to ball milling beads mass ratio is 1:500); PMS (0.5 mM) is added; and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed 400 rpm) for 5 min, achieving triboelectro-induced electrocatalytic degradation of antibiotics.

[0156] Comparative Example 9

[0157] A method for the triboelectric activation of preoxidation-CFO to degrade antibiotics with peroxymonosulfate includes the following steps: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar; 20 mg of CFO-2 and PMS (0.5 mM) are added, thoroughly mixed, dried, and dispersed in the solution; 3 mm zirconia ball milling beads are added (catalyst to ball milling beads mass ratio is 1:500); and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed 400 rpm) for 5 min, achieving triboelectric contact electrocatalytic degradation of antibiotics.

[0158] Comparative Example 10

[0159] Compared with Example 3, most of the steps are the same, except that the antibiotic being degraded is CAP (analytical grade, purchased from Adamas Reagent Co., Ltd.). Step (2) is the triboelectric activation of peroxymonosulfate to degrade antibiotics: 50 mL of CAP (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (the mass ratio of catalyst to ball milling beads is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm) for 5 min, thus realizing the triboelectric contact electrocatalytic degradation of antibiotics.

[0160] Comparative Example 11

[0161] The process was largely the same as in Example 3, except that 5 mM CO3 was added to the degradation solution. 2– Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 34.5 mg K2CO3 (analytical grade reagent, purchased from Adamas Ltd.) was added, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads were added (the mass ratio of catalyst to ball milling beads was 1:500), PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed was 400 rpm) for 5 min to achieve the friction-contact electrocatalytic degradation of antibiotics.

[0162] Comparative Example 12

[0163] The process was largely the same as in Example 3, except that 5 mM PO4 was added to the degradation solution. 3–Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 41 mg of Na3PO4 (analytical grade reagent, purchased from Adamas Ltd.) was added, 20 mg of CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads were added (the mass ratio of catalyst to ball milling beads was 1:500), PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed was 400 rpm) for 5 min to achieve the friction-contact electrocatalytic degradation of antibiotics.

[0164] Comparative Example 13

[0165] The process was largely the same as in Example 3, except that 5 mM of H2PO4 was added to the degradation solution. – Step (2) Friction-activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 34 mg KH2PO4 (analytical grade reagent, purchased from Adamas Ltd.) was added, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads were added (the mass ratio of catalyst to ball milling beads was 1:500), PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed was 400 rpm) for 5 min, so as to realize the friction-contact electrocatalytic degradation of antibiotics.

[0166] Comparative Example 14

[0167] Compared with Example 3, most of the steps are the same, except that 20 ppm humic acid (HA) (analytical grade, purchased from Macklin Biotechnology Co., Ltd.) is added to the degradation solution. Step (2) is to degrade antibiotics by friction activation of peroxymonosulfate: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill jar, 5 mL of 100 ppm HA solution is added, 20 mg CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (the mass ratio of catalyst to ball milling beads is 1:500), PMS (0.5 mM) is added, and then the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400 rpm) for 5 min to achieve the friction contact electrocatalytic degradation of antibiotics.

[0168] Comparative Example 15

[0169] Compared with Example 3, most of the steps are the same, except that 0.1 mol / L HCl (analytical grade, purchased from Sinopharm Chemical Reagent Co., Ltd.) was used to adjust the initial pH of the solution to 2. Step (2) Frictionally activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, HCl solution was added dropwise until the pH of the solution was 2, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads were added (the mass ratio of catalyst to ball milling beads was 1:500), PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed was 400 rpm) for 5 min to achieve the frictional contact electrocatalytic degradation of antibiotics.

[0170] Comparative Example 16

[0171] Compared with Example 3, most of the steps are the same, except that 0.1 mol / L NaOH (analytical grade, purchased from Adamas Reagent Co., Ltd.) was used to adjust the initial pH of the solution to 12. Step (2) Frictionally activated peroxymonosulfate degradation of antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, NaOH solution was added dropwise until the solution pH was 12, 20 mg CFO-2 was added and dispersed in the solution, 3 mm zirconia ball milling beads were added (the mass ratio of catalyst to ball milling beads was 1:500), PMS (0.5 mM) was added, and then the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed was 400 rpm) for 5 min, so as to achieve the frictional contact electrocatalytic degradation of antibiotics.

[0172] Performance testing:

[0173] I. The CuFe2O4 catalysts in Examples 1-4 were characterized by XRD, as follows:

[0174] The crystal structure of the samples was measured using a Bruker D8 advanced Cu-Kα (λ = 0.15406 nm) Rigaku Ultimate IV X-ray diffractometer with a diffraction target. Data collection was performed in 2-theta scanning mode, with continuous scanning completed within the range of 10° to 80° at a scanning speed of 6° / min. Figure 1XRD patterns of CuFe2O4 catalysts synthesized from raw materials with different molar ratios, as well as Fe2O3 and CuO samples, are presented. XRD comparisons with CuFe2O4 (PDF#77-0010), CuO, and Fe2O3 revealed varying degrees of CuO and Fe2O3 doping. However, only the CFO-2 sample exhibited crystal planes consistent with CuFe2O4 at 18.344°, 30.175°, 35.543°, 27.180°, and 43.199°, corresponding to the (111), (220), (311), (222), and (400) crystal planes, respectively. Therefore, to better explore the heterogeneous catalytic mechanism of CuFe2O4, CFO-2 was used as the primary catalyst model.

[0175] II. The SEM morphology of the CuFe2O4 catalysts in Examples 1-4 was determined as follows:

[0176] The surface morphology of CuFe2O4 was observed using a scanning electron microscope (SEM 300).

[0177] Figure 2 The morphology of CuFe2O4 catalysts synthesized at different molar ratios of raw materials is shown. It is clearly demonstrated that CuFe2O4 is composed of uniformly and regularly stacked spherical particles. The particle size tends to decrease with increasing raw material molar ratio, but the particle size increases when the molar ratio of FeCl3·6H2O to CuCl2·2H2O is 4:1. The particle size of CFO-1 sample is mainly distributed in the range of 20 nm to 70 nm, CFO-1.5 sample in the range of 20 nm to 60 nm, CFO-2 sample in the range of 15 nm to 40 nm, and CFO-4 sample in the range of 60 nm to 140 nm. This indicates that the CFO sample obtained with a FeCl3·6H2O to CuCl2·2H2O molar ratio of 2:1 (Example 3) has a relatively small and uniform particle size distribution.

[0178] III. TEM tests were performed on the CuFe2O4 catalyst in Example 3, as detailed below:

[0179] The surface morphology and lattice fringes of CuFe2O4 were observed using a transmission electron microscope equipped with EDS (TEM, FEI Talos F200S, USA). Figure 3The morphology of the CuFe2O4 catalyst is shown, demonstrating that it is granular. TEM images reveal clear lattice fringes, further confirming the high crystallinity of the CFO-2 catalyst. Interlayer distances of 0.2944, 0.2112, and 0.2520 nm correspond to the (220), (440), and (311) crystal planes of CuFe2O4, respectively. These lattice fringes further confirm that the CFO-2 nanoparticles mainly exist in the CuFe2O4 crystalline phase, and the uniform elemental distribution is clearly shown in the EDS mapping diagram.

[0180] IV. BET tests were performed on the CuFe2O4 catalysts in Examples 1-4, as detailed below:

[0181] The specific surface area, pore volume, and pore size of the sample were measured using a specific surface area analyzer (BET, Autosorb IQ). For example... Figure 4 As shown in Table 1, different molar ratios of raw materials had no significant effect on the pore volume, pore size, and specific surface area of ​​CuFe₂O₄. The specific surface areas of samples CFO-1, CFO-1.5, CFO-2, and CFO-4 were 32.947, 26.387, 41.828, and 29.059 m², respectively. 2 / g, CFO-2 has the largest specific surface area, pore volume and smallest pore size.

[0182] Table 1. Pore volume, pore size, and specific surface area of ​​CuFe2O4 with different molar ratios of raw materials.

[0183]

[0184] V. Test on the effect of CuFe2O4 catalyst synergistic with PMS in the triboelectric degradation of SDZ.

[0185] Figure 5 The results show the performance of CuFe2O4 catalyst in synergistic PMS triboelectric degradation of SDZ. During the degradation reaction, a certain volume of reaction solution was taken every 1 minute at fixed time intervals, with a total reaction time of 5 minutes. 1.5 mL of the suspension was filtered through a 0.22 μm MCE filter and then quenched with 40 μL of sodium thiosulfate for further analysis.

[0186] in, Figure 5(a) shows that, within 5 min, comparisons were made between Fe2O3 (Comparative Example 1), CuO (Comparative Example 2), a mixture of Fe2O3 and CuO (Comparative Example 3), and CuFe2O4 catalysts with different molar ratios (Examples 1-4). It was found that CuFe2O4 catalysts with different molar ratios could achieve 100% degradation of SDZ solution. However, the degradation effects of catalysts Fe2O3, CuO, and Fe2O3 / CuO (1:1) on SDZ solution within 5 min were 50%, 98%, and 90%, respectively. Furthermore, based on the characterization results, the CuFe2O4 catalyst in Example 3 showed higher activity; therefore, CFO-2 was used as a model for further investigation.

[0187] Figure 5 (b) The oxidation process of SDZ alone by PMS (Comparative Example 4) showed almost no degradation, indicating that PMS can only be activated in the presence of CFO-2, with Cu as the main active site and Fe sites working synergistically. Under CFO-2 catalyst conditions (Comparative Example 5), desorption occurred after adsorption, showing almost no effect on pollutant removal. Under the same conditions, the degradation results of SDZ in the filtrate containing excess PMS and after the addition of PMS indicate that the degradation of SDZ by the CFO-2 / PMS system (Example 3) follows a heterogeneous catalytic reaction. EDTA, as an ion coupling agent, showed no significant hindrance effect in the EDTA / PMS (Comparative Example 8) reaction after 5 min, further demonstrating that this system is non-Fe... 3+ / PMS (Comparative Example 6) and Cu 2+ The homogeneous system of PMS / PMS (Comparative Example 7) demonstrates the availability of the catalyst for further recycling. Further reaction was conducted using the filtrate after the reaction; SDZ showed almost no degradation, indicating that there were virtually no leached ions or excess PMS in the solution for further reaction. Using pre-oxidized CFO-2 (Comparative Example 9), i.e., mixing the same concentration of PMS with the CFO-2 catalyst, drying, and then ball milling, without adding any more PMS solution, the results showed 50% degradation of SDZ. This indicates that during the CFO / PMS degradation of SDZ, PMS first forms a PMS* complex with the catalyst, subsequently further degrading SDZ.

[0188] VI. Effects of CuFe2O4 catalyst synergistic with PMS ball milling on the degradation of different antibiotics and common aqueous matrices of SDZ by CuFe2O4 catalyst synergistic with PMS. During the degradation reaction at fixed time intervals, 1.5 mL of the suspension was filtered through a 0.22 μm MCE filter and then quenched with 40 μL of sodium thiosulfate for further analysis.

[0189] Figure 6(a) shows the ball milling degradation of different antibiotics by CFO-2 in conjunction with PMS, including SDZ (Example 3), SMX (Example 5), TMP (Example 6), 4-CP (Example 7), and chloramphenicol (CAP) (Comparative Example 10). The results show that, under ball milling conditions, the CuFe2O4 catalyst, in conjunction with PMS, achieved a 100% degradation rate for SDZ, SMX, and 4-CP within 5 minutes, a 50% degradation rate for TMP, and almost no degradation for CAP. This indicates that the CuFe2O4 catalyst has a certain degree of general applicability, especially its highly selective removal capability for electron-rich pollutants. This is because singlet oxygen is an electron-deficient free radical that readily attacks electron-rich pollutants.

[0190] Figure 6 (b) shows the metal cation (Ca) 2+ Mg 2+ ), anionic salts (Cl) - HCO3 - NO3 - CO3 2- PO4 3- H2PO4 - The effect of CuFe2O4 catalyst on the triboelectric synergistic degradation of SDZ by PMS was investigated (Examples 3, 8-12, Comparative Examples 11-13). The concentration of the organic pollutant SDZ was determined using a high-performance liquid chromatograph (UHPLC, Ultimate 3000, Thermo Scientific USA) equipped with a UV-Vis detector and a C18 reversed-phase column. The mobile phase consisted of 70% 0.1% phosphoric acid solution and 30% acetonitrile. The detection wavelength was 270 nm, and the flow rate was 1 mL / min. The results showed that, compared with the control (Example 3), SDZ degradation was almost unaffected by Cl-. - HCO3 - NO3 - The impact of CO3 2- PO4 3- H2PO4 - These anions have some impact on SDZ degradation because they compete with reactive free radicals to varying degrees. Metal cations Ca... 2+ Mg 2+ The CFO-2 / PMS ball milling system was unaffected by SDZ degradation, demonstrating its strong anti-interference capability.

[0191] Figure 6(c) The effect of natural organic compounds (5, 10, and 20 ppm hyaluronic acid (HA)) on the triboelectric synergistic degradation of SDZ by CuFe₂O₄ catalyst using PMS is shown (Examples 3, 13, and 14; Comparative Example 14). The concentration of the organic pollutant SDZ was determined using a high-performance liquid chromatograph (UHPLC, Ultimate 3000, Thermo Scientific USA) equipped with a UV-Vis detector and a C18 reversed-phase column. The mobile phase was 70% 0.1% phosphoric acid solution and 30% acetonitrile, the detection wavelength was 270 nm, and the flow rate was 1 mL / min. The results showed the effect of 5-20 ppm HA on SDZ degradation compared to the control (Example 3). The results indicated that HA had no significant inhibitory effect on SDZ degradation within the range of 10 ppm. Only at a high concentration of 20 ppm did it have a certain inhibitory effect, with the SDZ degradation rate decreasing from 100% to 75% within 5 min. This is because the high concentration of humic acid increased the consumption of PMS oxidant, but at low concentrations, it had almost no effect, demonstrating the strong tolerance of the system to the background environment of natural organic compounds.

[0192] Figure 6 (d) The effect of initial pH on the triboelectric synergistic degradation of SDZ by CuFe2O4 catalyst using PMS (Examples 3, 15-17; Comparative Examples 15, 16). In Example 3, the pH was measured to be 6. The results showed that the initial pH of 4-10 had almost no effect on the degradation of SDZ. Under strongly acidic conditions (pH=2) and strongly alkaline conditions (pH=12), the degradation of SDZ was inhibited to some extent, with degradation rates of approximately 70% and 60%, respectively. This indicates that the reaction can proceed over a relatively wide pH range without affecting the degradation of SDZ.

[0193] VII. TOC removal rate of SDZ by triboelectric degradation under ball milling with CuFe2O4 catalyst and PMS synergistic.

[0194] During the degradation reaction process at fixed time intervals (Example 3, CFO-2), samples were taken every 60 minutes. 20 mL of the solution was filtered through a 0.22 μm MCE filter and tested using a TOC-2000 analyzer (Metash, China). Figure 7 The results showed that CuFe2O4 catalyst synergistically with PMS ball milling degradation could effectively remove SDZ, with a TOC removal rate of 23% within 2 hours, indicating that the system has a certain mineralization ability for pollutants. Under the attack of active species, SDZ produces intermediate products with low molecular weight, which are then further converted into CO2 and H2O.

[0195] 8. Performance test of CuFe2O4 catalyst synergistically with PMS for SDZ degradation under different ball milling conditions.

[0196] Using CFO-2, the effect of heat changes during ball milling on pollutant degradation was investigated at different rotation speeds (100, 200, 300, and 400 rpm, i.e., Examples 3, 18-20). Figure 8 (a) The results show that the study found the system to be unaffected by temperature, implying that the catalytic conditions are strongly insensitive to temperature changes and that it is highly operable in practice. Furthermore, temperature does not affect the generation of free radicals in the peroxymonosulfate system, suggesting that free radicals are not important reactive species in this system.

[0197] Figure 8 (b) shows the effect of different concentrations of PMS (0.25, 0.5, and 1 mM, i.e., Examples 3, 21, and 22) on the degradation of pollutant SDZ. Figure 8 (c) shows the effect of different dosages of catalyst (5, 10, 20, 30 mg, i.e., Examples 3, 23-25) on the degradation of pollutant SDZ. Figure 8 (d) shows the effect of different pollutant concentrations (5, 10, 20 mg / L, i.e., Examples 3, 26, and 27) on the degradation of pollutant SDZ. The results show that the effect significantly increases with increasing catalyst dosage, due to the increase in active sites. However, when the catalyst dosage increases to 30 mg, the degradation effect does not significantly improve, because the active sites reach saturation for PMS activation. Therefore, from an economic perspective, a dosage of 20 mg is chosen for this system. With increasing PMS oxidant concentration, the catalytic effect significantly increases due to the increase in active species. From an environmental perspective, 0.5 mM is chosen for this system. Increasing the pollutant concentration from 5 ppm to 10 ppm does not significantly hinder the degradation ability of the system. When the pollutant concentration increases to 20 ppm, the degradation effect is somewhat hindered. Therefore, 10 ppm is used as the target concentration for the pollutant control group. Thus, the optimal reaction conditions for this system are 0.5 mM PMS, 20 mg catalyst, and 10 ppm pollutant, ensuring efficient degradation of pollutants under the most economical conditions and providing an experimental basis for its practical application.

[0198] IX. Stability test of CuFe2O4 catalyst synergistically with PMS for SDZ degradation.

[0199] A 50 mL solution of SDZ (10 mg / L) to be degraded was placed in a 50 mL zirconia ball mill jar. 20 mg of dried catalyst, thoroughly mixed with 0.5 mM PMS, was added and dispersed in the solution. 3 mm zirconia grinding beads (powder-to-ball ratio 1:500) were added, and the mixture was placed in a planetary ball mill for degradation experiments (400 rpm) for 5 minutes, achieving the triboelectric electrocatalytic degradation of the antibiotic. The reacted solution was centrifuged, washed, and the catalyst was recovered and dried for reuse. This process was repeated 7 times.

[0200] like Figure 9 As shown, after the seventh cycle, the degradation rate of SDZ decreased from nearly 100% to 78%, indicating that the catalyst maintained high stability after seven cycles. The results demonstrate that the CuFe2O4 catalyst is an environmentally friendly functional material with great potential for practical applications.

[0201] 10. Experiment to determine the active species of CuFe2O4 catalyst in synergistic PMS degradation of SDZ.

[0202] The identification of the main active species was accomplished through a series of capture experiments.

[0203] like Figure 10 As shown in (a), MeOH is used as SO4. ·- Even with the MeOH concentration increased to 2M, the degradation of SDZ was not hindered, and 100% degradation was still achieved within 5 minutes. This indicates that SO42- ·- It is not the main active species in the CFO-2 / PMS system (Examples 28-30). For example... Figure 10 As shown in (b), TBA is used as the HO. · Even with the TBA concentration increased to 1M, the degradation of SDZ was not hindered, and 100% degradation was still achieved within 5 minutes. This indicates that HO... · It is not the main active species in the CFO-2 / PMS system (Examples 31-33). For example... Figure 10 As shown in (c), the degradation efficiency of SDZ was hindered by the increase of L-his dosage concentration. When the L-his concentration reached 5mM, the SDZ degradation inhibition rate reached 60% within 5min, indicating that singlet oxygen is the main active species of the CFO-2 / PMS system (Examples 33-36).

[0204] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A method for the degradation of antibiotics by peroxymonosulfate using a transition bimetallic catalyst via triboelectric activation, characterized in that, The antibiotic solution to be degraded was placed in a ball mill jar, and a transition bimetallic catalyst, milling beads, and PMS were added before ball milling to achieve the triboelectric electrocatalytic degradation of the antibiotic. The antibiotic solution includes electron-rich sulfonamides, β-lactam antibiotics, diaminopyrimidine antibiotics, and tetracycline antibiotics; The chemical formula of the transition bimetallic catalyst is AB₂O₄, where A is Cu and B is Fe.

2. The method for degrading antibiotics with peroxymonosulfate by triboelectric activation of a transition bimetallic catalyst according to claim 1, characterized in that, The electron-rich sulfonamide antibiotics include sulfadiazine and sulfamethoxazole; The β-lactam antibiotics mentioned include 6-aminopenicillanic acid; The aforementioned diaminopyrimidine antibiotics include methoxypyrimidine; The tetracycline antibiotics mentioned include p-chlorophenol.

3. The method for degrading antibiotics with peroxymonosulfate by triboelectric activation using a transition bimetallic catalyst according to claim 1, characterized in that, The antibiotic solution comprises water, inorganic anions, metal cations, and natural organic compounds; the pH of the antibiotic solution is 4-10.

4. The method for degrading antibiotics with peroxymonosulfate by triboelectric activation of a transition bimetallic catalyst according to claim 1, characterized in that, The antibiotic solution with added transition bimetallic catalyst is a transition bimetallic catalyst dispersion, and the ratio of the transition bimetallic catalyst dispersion to PMS is 100 mL: 0.2~16 mg. The concentration of the antibiotic solution is 5-30 mg / L, and the concentration of PMS is 0.25-1 mM.

5. The method for degrading antibiotics with peroxymonosulfate by triboelectric activation of a transition bimetallic catalyst according to claim 1, characterized in that, The preparation process of the transition bimetallic catalyst is as follows: A salt solution and B salt solution are ultrasonically mixed, and an alkaline solution is added dropwise to form a dark brown solution. The dark brown solution is subjected to a hydrothermal reaction, and the precipitated product obtained is the transition bimetallic catalyst.

6. The method for degrading antibiotics with peroxymonosulfate by triboelectric activation using a transition bimetallic catalyst according to claim 5, characterized in that, Salt A is a Cu salt solution, salt B is a Fe salt solution, and the alkaline solution includes NaOH solution or KOH solution; The molar ratio of A to B in the A salt solution and B salt solution is 1:1 to 4, the concentration of the alkali solution is 1 to 10 mol / L, and the volume ratio of the A salt solution to the alkali solution is 1.5 to 10:

1. The temperature of the hydrothermal reaction is 160~200℃.

7. The method for degrading antibiotics with peroxymonosulfate by triboelectric activation of a transition bimetallic catalyst according to claim 1, characterized in that, The grinding jar includes a zirconia grinding jar, the grinding beads include zirconia grinding beads, the particle size of the grinding beads is 1~10mm, and the powder-to-ball ratio is 1:300~800.

8. The application of the method for degrading antibiotics by friction activation of a transition bimetallic catalyst as described in any one of claims 1 to 7 in the field of antibiotic wastewater treatment.

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