Method for degrading antibiotics by friction activation of peroxymonosulfate with transition bimetallic catalyst and application

Abstract

The invention relates to a method for degrading antibiotics by friction activation of peroxymonosulfate with a transition bimetallic catalyst and application of the method, an antibiotic solution to be degraded is placed in a ball milling tank, the transition bimetallic catalyst, ball milling beads and PMS are added for ball milling, and friction contact electrocatalytic degradation of the antibiotics is realized. Compared with the prior art, the method has a better degradation effect on antibiotics, has the advantages of promoting the generation of multipath < 1 > O2, realizing non-free radical dominated selective degradation of electron-rich antibiotics and the like, and has great potential in the aspect of practical application of antibiotic wastewater treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of antibiotic degradation, in particular to a method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst and application thereof. Background Art

[0002] The widespread use of antibiotics in many fields has led to their ubiquitous presence in water bodies, posing a potential threat to ecosystems and human health. By efficiently degrading antibiotics in water bodies, their toxicity to aquatic organisms and their potential impact on humans can be reduced.

[0003] Conventional wastewater treatment plants and biological treatment processes are inefficient in removing antibiotics. In recent decades, SO4 generated by peroxymonosulfate activation has been ·- It has a stronger oxidizing ability and has attracted much attention. In order to improve the removal efficiency of antibiotics, photo / electrochemical coupling technologies are also being studied, but they are limited by the high requirements for catalysts. At the same time, in recent years, researchers and our team have also found that SO4 ·- It is not the main active species, but other active species such as singlet oxygen ( 1 O2) or direct electron transfer, this non-free radical-dominated degradation pathway has completely different new insights in water treatment technology, in which 1 O2, as an electrophilic reactive excited oxygen, has an efficient and highly selective electrophilic attack capability on electron-rich antibiotics. 1 The non-radical process of O2 is more conducive to practical applications because it exhibits strong anti-interference and wider pH adaptability.

[0004] Patent publication number CN114713228A discloses a preparation method and application of a new material CNTs-TiO2@CuFe2O4, constructing a new advanced oxidation system of CNTsTiO2@CuFe2O4 / light / PMS, which produces sulfate radicals and hydroxyl radicals with long life and stronger oxidizing properties through photocatalytic synergistic activation of PMS, thereby achieving complete mineralization of antibiotics. This patent uses composite materials and photosensitive catalysts to cooperate with photocatalysis, which increases the preparation cost and process of the catalyst. In addition, the patent shows that under light-assisted conditions, PMS is activated and SO4 is in situ coupled. ·- and HO · , to achieve the removal of difficult-to-degrade organic pollutants. Although the composite catalyst has certain adsorption properties, the degradation efficiency of ciprofloxacin is over 95% within 30 minutes. Although photocatalytic wastewater degradation is a promising and environmentally friendly technology, currently, problems such as low catalyst light utilization efficiency and low energy conversion efficiency still prevent the large-scale application of light energy in wastewater treatment.

[0005] CuFe2O4, a dual-active-site catalyst, has been studied as a dual-transition-metal ferroelectric material, but SO4 ·- or HO · It is considered to be the main active species in the CuFe2O4 / PMS system, or 1 O2 is a coexisting substance. Many researchers have manipulated the electronic structure of catalysts by adjusting the surface or interface engineering to break through the generation path of free radicals and achieve 100% production. 1 O2, but the coordination environment of the catalyst and precise control to ensure uniform distribution of atoms require complex synthesis conditions, which greatly increases the cost and time of catalyst preparation. However, in 2019, friction technology was first used for dye degradation, becoming a new direction for the use of mechanical energy in sewage treatment. In particular, temporary polarized surfaces with opposite charges can be generated during ball milling, which means that friction catalysis can adjust the local electronic structure and enhance electron transfer. This is expected to be used to regulate the CuFe2O4 / PMS system. 1 Production of O2. Summary of the Invention

[0006] The purpose of the present invention is to overcome the defects of the above-mentioned prior art, especially the problem of the degradation pathway dominated by free radicals and the need for additional photosensitive catalysts for synergistic photocatalysis, and to provide a simpler and lower-energy transition bimetallic catalyst friction activation peroxymonosulfate degradation method and application, which has a better degradation effect on antibiotics and promotes multi-path 1 The 100% production of O2 realizes the non-free radical-dominated selective degradation of electron-rich antibiotics. In addition, its good acid-base resistance, stability in organic and inorganic ions and other characteristics have great potential in the practical application of antibiotic wastewater treatment.

[0007] The purpose of the present invention can be achieved by the following technical solutions:

[0008] In one aspect, the present invention provides a method for degrading antibiotics by frictionally activating peroxymonosulfate using a transition bimetallic catalyst. The method comprises placing an antibiotic solution to be degraded in a ball mill, adding a transition bimetallic catalyst, ball milling beads, and PMS, and then performing ball milling to achieve frictional contact electrocatalytic degradation of the 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 include 6-aminopenicillanic acid (6-APA);

[0012] The diaminopyrimidine antibiotics include trimethoprim (TMP);

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

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

[0015] Furthermore, the inorganic anion includes NO3 - 、HCO3 - 、Cl - ; Metal cations include Ca 2+ Mg 2 ; Natural organic matter includes 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 transition bimetallic catalyst has a chemical formula of AB2O4. AB2O4 spinel has a unique cubic crystal structure with outstanding redox ability 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 transition bimetallic catalyst is AFe2O4. The magnetic AFe2O4 nanoparticles are spinel structures, wherein Fe 3+ Ions occupy the octahedral B site, and divalent ions are located at the tetrahedral A site. Spinel structure materials are generally widely used in optics, catalysts and other fields, such as magnetic storage media, magnetic nanoparticles, photocatalytic materials, etc.

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

[0022] Furthermore, the preparation process of the transition bimetallic catalyst is: ultrasonically mixing salt solution A and salt solution B, adding alkali solution to form a dark brown solution, and subjecting the dark brown solution to a hydrothermal reaction to obtain a precipitated product which is the transition bimetallic catalyst.

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

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

[0025] The temperature of the hydrothermal reaction is 160-200° C., and the time is 12-48 hours.

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

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

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

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

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

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

[0032] Furthermore, the degradation time is 0.01 to 180 minutes, preferably 5 to 180 minutes.

[0033] On the other hand, the present invention also provides an application of a method for degrading antibiotics by frictionally activating peroxymonosulfate using a transition bimetallic catalyst 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, the present invention uses heterogeneous friction catalysis to synergize PMS activation to form non-radical intermediates to dominate oxidation; through transition bimetallic catalysts, the contact electrification effect under ball milling is used to synergize PMS activation to promote multi-path 1 The generation of O2 realizes the non-free radical-dominated selective degradation of the electron-rich sulfonamide antibiotic SDZ.

[0036] (2) The surface of the transition bimetallic catalyst of the present invention is easily polarized under ball milling conditions, and the redox potential of the catalyst is reduced under bimetallic synergy. In addition, the introduction of PMS into the transition bimetallic catalyst friction system fully utilizes the excellent potential and electron transfer properties of the transition bimetallic catalyst, effectively activates the PMS, and further enhances the catalytic activity of the entire reaction system.

[0037] (3) The transition bimetallic catalyst AB2O4 of the present invention forms A-PMS* (especially Cu-PMS*) and B-PMS* (especially Fe-PMS*) with PMS. 1 The key to O2 production is that even if HO is unavoidable, it can be induced to generate a single nearly 100% 1 O2, which is the key to the efficient and selective removal of antibiotics in a short period of time. Mass transfer may often be overlooked in the study of antibiotic degradation, but it has a great influence on the reaction rate. Currently, most of the research on improving mass transfer efficiency is focused on the interface regulation of materials, and ball milling can minimize the mass transfer loss between catalysts, PMS and antibiotics. In addition, friction contact electrocatalysis is an emerging antibiotic degradation technology. Compared with piezoelectric catalysis, it does not have great restrictions on materials, especially the contact electrification effect produced under ball milling. There are currently no reports on the use of ball milling in the exploration of transition metal activated PMS to degrade organic pollutants. This provides a new research idea for the development of more environmentally friendly wastewater treatment technologies and the effective and efficient removal of antibiotics.

[0038] (4) The A(III) / A(II) and B(III) / B(II) redox reactions on the surface of the transition bimetallic catalyst AB2O4 of the present invention make a significant contribution to the decomposition of PMS. Combined with the friction contact electrocatalytic degradation technology, compared with piezoelectric catalysis, there is no great restriction on the material. The catalyst produces a contact electrification effect under ball milling, and the catalyst surface undergoes short-term polarization, generating holes (h +) and electrons (e - ), thereby further promoting the activation of PMS.

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

[0040] (6) The material preparation and pollution control of the present invention have broken through the bottleneck of the existing technology. First, a simple one-step hydrothermal method is used to prepare a spinel-structured double transition metal catalyst. Second, an external mechanical ball milling environment is used to improve the electronic structure of the catalyst surface, thereby inducing multipath 1 The generation of O2 overcomes the problem of other active free radicals being generated during the current transition metal activation of PMS. 1 The problem of low O2 production efficiency. Finally, the mechanical ball milling environment system has high mass transfer, high 1 The method has high O2 production rate and high antibiotic removal efficiency. It is easy to operate and low in cost, and is expected to be used in large-scale polluted wastewater treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The XRD patterns of the CuFe2O4 catalysts in Examples 1-4 of the present invention are as follows;

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

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

[0044] Figure 4 is the BET spectrum of the CuFe2O4 catalyst in Examples 1-4 of the present invention;

[0045] Figure 5 Figures 1-4 show the friction-synergistic PMS ball milling degradation performance of the CuFe2O4 catalysts in Examples 1-4 of the present invention, wherein (a) shows the friction-synergistic PMS ball milling degradation of SDZ experiments of CuFe2O4, Fe2O3, CuO, and Fe2O3 / CuO synthesized with different molar ratios of raw materials, and (b) shows the friction-synergistic PMS ball milling degradation of SDZ experiments of CuFe2O4 under different conditions;

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

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

[0048] Figure 8 The optimal reaction conditions of the CFO-2 synergistic PMS ball milling system of the present invention were tested, where (a) is the experiment on the effect of different ball milling speeds, (b) is the experiment on the effect of different PMS concentrations, (c) is the experiment on the effect of different catalyst dosages, and (d) is the experiment on the effect of different pollutant concentrations.

[0049] Figure 9 This is the CFO-2 reaction stability spectrum.

[0050] Figure 10 The effect of different quenchers on SDZ degradation. DETAILED DESCRIPTION

[0051] Below in conjunction with accompanying drawing and specific embodiment, the present invention is described in detail.This embodiment is implemented on the premise of technical solution of the present invention, provides detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiment.Based on the embodiment provided, all other embodiments obtained by those of ordinary skill in the art without making creative work premise all fall within the scope of protection of this application.Unless otherwise specified, the reagent, method, instrument and equipment adopted in the present invention are conventional reagents, methods, instrument and equipment in this area.

[0052] Example 1

[0053] A method for degrading antibiotics by frictionally activating peroxymonosulfate using a transition bimetallic catalyst comprises 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) (both analytical grade, purchased from Adamas Reagent Co., Ltd.) were dissolved in 30 mL of deionized water and sonicated for 5 minutes to form homogeneous FeCl₃ and CuCl₂ solutions. The FeCl₃ solution was then added dropwise to the CuCl₂ solution under stirring. 20 mL of KOH (1.4 mol / L) (analytical grade, purchased from Adamas Reagent Co., Ltd.) was then added dropwise under stirring and stirred for 60 minutes. The resulting solution was placed in a polytetrafluoroethylene-lined autoclave and reacted at 200°C for 3 hours. After cooling the autoclave to room temperature, the precipitate was collected. The precipitate was washed three times with deionized water and three times with ethanol, then dried at 60°C for 12 hours to obtain the CuFe₂O₄ catalyst, designated CFO-1.

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

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

[0058] Example 2

[0059] A method for degrading antibiotics by frictionally activating peroxymonosulfate using a transition bimetallic catalyst comprises 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 of 1.5:1) (both analytical grade reagents, purchased from Adamas Reagent Co., Ltd.) were dissolved in 30 mL of deionized water and sonicated for 5 minutes to form homogeneous FeCl₃ and CuCl₂ solutions. The FeCl₃ solution was then added dropwise to the CuCl₂ solution under stirring. 20 mL of KOH (1.4 mol / L) (analytical grade reagent, purchased from Adamas Reagent Co., Ltd.) was then added dropwise under stirring and stirred for 60 minutes. The resulting solution was then placed in a polytetrafluoroethylene-lined autoclave and reacted at 200°C for 3 hours. After the autoclave cooled to room temperature, the precipitate was collected. The precipitate was washed three times with deionized water and three times with ethanol, then dried at 60°C for 12 hours to obtain the CuFe₂O₄ catalyst, designated CFO-1.5.

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

[0063] A 50 mL SDZ (10 mg / L) solution to be degraded (the reagent is of high purity and purchased from Adamas Reagent Co., Ltd.) was placed in a 50 mL zirconia ball mill jar, 20 mg 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, and PMS (0.5 mM) (reagent purity of 98%+, purchased from Adamas Reagent Co., Ltd.) was added, and then placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), the degradation time was 5 min, to achieve friction contact electrocatalytic degradation of antibiotics.

[0064] Example 3

[0065] A method for degrading antibiotics by frictionally activating peroxymonosulfate using a transition bimetallic catalyst comprises 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) (both analytical grade, purchased from Adamas Reagent Co., Ltd.) were dissolved in 30 mL of deionized water and sonicated for 5 minutes to form homogeneous FeCl₃ and CuCl₂ solutions. The FeCl₃ solution was then added dropwise to the CuCl₂ solution under stirring. 20 mL of KOH (1.4 mol / L) (analytical grade, purchased from Adamas Reagent Co., Ltd.) was then added dropwise under stirring and stirred for 60 minutes. The resulting solution was then placed in a polytetrafluoroethylene-lined autoclave and reacted at 200°C for 3 hours. After the autoclave cooled to room temperature, the precipitate was collected. The precipitate was washed three times with deionized water and three times with ethanol, then dried at 60°C for 12 hours to obtain the CuFe₂O₄ catalyst, designated CFO-2.

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

[0069] A 50 mL solution of SDZ (10 mg / L) to be degraded (the reagent is of high purity, 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 were added (powder-to-ball ratio of 1:500), and PMS (0.5 mM) (reagent purity of 98%+, purchased from Adamas Reagent Co., Ltd.) was added, and then placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), the degradation time was 5 min, to achieve friction contact electrocatalytic degradation of antibiotics.

[0070] Example 4

[0071] A method for degrading antibiotics by frictionally activating peroxymonosulfate using a transition bimetallic catalyst comprises 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) (both reagents were analytical grade and purchased from Adamas Reagent Co., Ltd.) were dissolved in 30 mL of deionized water and sonicated for 5 minutes to form homogeneous FeCl₃ and CuCl₂ solutions. The FeCl₃ solution was then added dropwise to the CuCl₂ solution under stirring. 20 mL of KOH (1.4 mol / L) (analytical grade, purchased from Adamas Reagent Co., Ltd.) was then added dropwise under stirring and stirred for 60 minutes. The resulting solution was then placed in a polytetrafluoroethylene-lined autoclave and reacted at 200°C for 3 hours. After the autoclave cooled to room temperature, the precipitate was collected. The precipitate was washed three times with deionized water and three times with ethanol, then dried at 60°C for 12 hours to obtain the CuFe₂O₄ catalyst, designated CFO-4.

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

[0075] A 50 mL solution of SDZ (10 mg / L) to be degraded (the reagent is of high purity, 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 were added (powder-to-ball ratio of 1:500), and PMS (0.5 mM) (reagent purity of 98%+, purchased from Adamas Reagent Co., Ltd.) was added, and then placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), the degradation time was 5 min, to achieve friction contact electrocatalytic degradation of antibiotics.

[0076] Example 5

[0077] Compared with Example 3, most of the methods are the same, except that the antibiotic to be degraded is SMX (the reagent is of high purity and purchased from Adamas Reagent Co., Ltd.). In step (2), friction activation of peroxymonosulfate to degrade the 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 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 friction contact electrocatalytic degradation of the antibiotic.

[0078] Example 6

[0079] Compared with Example 3, most of the methods are the same, except that the antibiotic to be degraded is TMP (the reagent is analytical grade and purchased from Adamas Reagent Co., Ltd.). In step (2), friction activation of peroxymonosulfate to degrade the antibiotic: 50 mL of TMP (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 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 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 friction contact electrocatalytic degradation of the antibiotic.

[0080] Example 7

[0081] Compared with Example 3, most of the methods are the same, except that the antibiotic to be degraded is 4-CP (the reagent is of high purity and purchased from Adamas Reagent Co., Ltd.). In step (2), friction activation of peroxymonosulfate to degrade the antibiotic: 50 mL of 4-CP (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 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 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 friction contact electrocatalytic degradation of the antibiotic.

[0082] Example 8

[0083] Compared with Example 3, most of the above are the same, except that 5mM Cl is added to the degradation solution. - Step (2) friction activation of peroxymonosulfate to degrade 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 of KCl (the reagent was of high purity, purchased from Adamas Reagent Co., Ltd.) was added, 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, and after adding PMS (0.5 mM), the ball milling degradation experiment was carried out in a planetary ball mill (rotation speed of 400 rpm) for a degradation time of 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0084] Example 9

[0085] Compared with Example 3, most of the above are the same, except that 5mM HCO3 is added to the degradation solution. –Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 25 mg of KHCO3 (the reagent was analytical grade and purchased from Adamas Reagent Co., Ltd.) was added, 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, and PMS (0.5 mM) was added. The ball milling degradation experiment was carried out in a planetary ball mill (rotation speed of 400 rpm) for a degradation time of 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0086] Example 10

[0087] Compared with Example 3, most of the above are the same, except that 5mM NO3 is added to the degradation solution. – Step (2) friction activation of peroxymonosulfate to degrade 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 of KNO3 (the reagent was analytical grade and purchased from Sinopharm Chemical Reagent Co., Ltd.) was added, 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, and PMS (0.5 mM) was added. The ball milling degradation experiment was carried out in a planetary ball mill (rotation speed of 400 rpm) for a degradation time of 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0088] Example 11

[0089] Compared with Example 3, most of the above are the same, except that 5mM Ca is added to the degradation solution. 2+ Step (2) friction activation of peroxymonosulfate to degrade 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 of CaCl2·2H2O (analytical grade, purchased from Adamas Reagent Co., Ltd.) was added, 20 mg of CFO-2 was 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 the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time was 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0090] Example 12

[0091] Compared with Example 3, most of the above are the same, except that 5mM Mg is added to the degradation solution. 2+Step (2) friction activation of peroxymonosulfate to degrade 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 of MgCl2·6H2O (analytical grade, purchased from Adamas Reagent Co., Ltd.) was added, 20 mg of CFO-2 was 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 the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time was 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0092] Example 13

[0093] Compared with Example 3, most of the contents are the same, except that 5 ppm of humic acid (HA) (the reagent is analytical grade and purchased from Macklin Biochemical Technology Co., Ltd.) is added to the degradation solution. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 2.5 mL of a pre-prepared 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), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0094] Example 14

[0095] Compared with Example 3, most of the contents are the same, except that 10 ppm of humic acid (HA) (the reagent is analytical grade and purchased from Macklin Biochemical Technology Co., Ltd.) is added to the degradation solution. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 5 mL of a 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), and the degradation time is 5 min, thereby achieving 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.) is used to adjust the initial pH value of the solution to 4. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, HCl solution is added dropwise until the solution pH is 4, 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction 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.) is used to adjust the initial pH value of the solution to 8. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, NaOH solution is added dropwise until the solution pH is 8, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball mill beads (powder-to-ball ratio of 1:500) are added, PMS (0.5 mM) is added, and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction 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.) is used to adjust the initial pH value of the solution to 10. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, NaOH solution is added dropwise until the solution pH is 10, 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction 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 in step (2) is adjusted to 100 rpm: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (powder-to-ball 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 100 rpm), and the degradation time is 5 min, thereby realizing friction contact 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 in step (2) is adjusted to 200 rpm: 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 are added (powder-to-ball 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 200 rpm), and the degradation time is 5 min, thereby realizing friction 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 in step (2) is adjusted to 300 rpm: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 20 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads are added (powder-to-ball 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 300 rpm), and the degradation time is 5 min, thereby realizing friction contact 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 0.25 mM: 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 are added (powder-to-ball ratio is 1:500), PMS (0.25 mM) is added, and then the ball milling degradation experiment is carried out in a planetary ball mill (rotation speed is 400 rpm), and the degradation time is 5 min, thereby realizing friction 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 1 mM: 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 are added (powder-to-ball ratio is 1:500), PMS (1 mM) is added, and 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 realizing friction 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), and the degradation time is 5 min, thereby achieving friction 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), and the degradation time is 5 min, thereby achieving friction contact 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), and the degradation time is 5 min, thereby achieving friction 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 mL / 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), and the degradation time is 5 min, thereby realizing friction 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 mL / 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 are added (powder-to-ball 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 realizing friction contact electrocatalytic degradation of antibiotics.

[0122] Example 28

[0123] Compared with Example 3, most of the methods are the same, except that methanol (MeOH) (reagent purity is 99.9%, purchased from Adamas Reagent Co., Ltd.) is used and the dosage is adjusted to 0.2 M. 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, 99.9% methanol is added to a concentration of 0.2 M, 2 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio is 1:500) are added, PMS (0.5 mM) is added, and 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 friction contact electrocatalytic degradation of antibiotics.

[0124] Example 29

[0125] Compared with Example 3, most of the contents are the same, except that methanol (MeOH) (reagent purity is 99.9%, purchased from Adamas Reagent Co., Ltd.) is used and the dosage 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, 99.9% methanol is added to a concentration of 0.5 M, 2 mg of CFO-2 is added and dispersed in the solution, 3 mm zirconia ball milling beads (powder-to-ball ratio is 1:500) are added, PMS (0.5 mM) is added, and 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 friction contact electrocatalytic degradation of antibiotics.

[0126] Example 30

[0127] Compared with Example 3, most of the contents are the same, except that methanol (MeOH) (reagent purity is 99.9%, purchased from Adamas Reagent Co., Ltd.) is used and the dosage is adjusted to 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 its concentration of 2M, 2mg CFO-2 is added and dispersed in the solution, 3mm zirconia ball milling beads (powder-to-ball ratio is 1:500) are added, PMS (0.5mM) is added, and the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed is 400rpm), and the degradation time is 5min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0128] Example 31

[0129] Compared with Example 3, most of the contents are the same, except that tert-butyl alcohol (TBA) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the dosage 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, TBA is added to a concentration of 0.2 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0130] Example 32

[0131] Compared with Example 3, most of the contents are the same, except that tert-butyl alcohol (TBA) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the dosage 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, tert-butyl alcohol 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0132] Example 33

[0133] Compared with Example 3, most of the contents are the same, except that tert-butyl alcohol (TBA) (analytical grade, purchased from Adamas Reagent Co., Ltd.) is used and the dosage is adjusted to 1 M. 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, tert-butyl alcohol is added to a concentration of 1 M, 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0134] Example 34

[0135] Compared with Example 3, most of the contents are the same, except that L-histidine (L-his) (analytical grade reagent, purchased from Adamas Reagent Co., Ltd.) is used and the dosage is adjusted to 1 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, L-histidine is added to a concentration of 1 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0136] Example 35

[0137] Compared with Example 3, most of the contents are the same, except that L-histidine (L-his) (the reagent is analytical grade and purchased from Adamas Reagent Co., Ltd.) is used and the dosage is adjusted to 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, L-histidine is added to a concentration of 2 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0138] Example 36

[0139] Compared with Example 3, most of the contents are the same, except that L-histidine (L-his) (analytical grade reagent, purchased from Adamas Reagent Co., Ltd.) is used and the dosage is adjusted to 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, L-histidine is added to a concentration of 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 the mixture is placed in a planetary ball mill for ball milling degradation experiment (rotation speed of 400 rpm), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0140] Comparative Example 1

[0141] A method for degrading antibiotics by frictionally activating peroxymonosulfate using Fe2O3 comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball milling jar, adding 20 mg of Fe2O3 (analytical grade, purchased from Adamas Reagent Co., Ltd.) and dispersing it in the solution, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), adding PMS (0.5 mM), and then placing the jar in a planetary ball mill for a ball milling degradation experiment (rotating speed of 400 rpm) for 5 minutes, thereby achieving frictional contact electrocatalytic degradation of the antibiotics.

[0142] Comparative Example 2

[0143] A method for degrading antibiotics by using CuO friction-activated peroxymonosulfate comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball milling jar, adding 20 mg of CuO (analytical grade reagent purchased from Adamas Reagent Co., Ltd.) and dispersing it in the solution, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), adding PMS (0.5 mM), and then placing the jar in a planetary ball mill for a ball milling degradation experiment (rotation speed of 400 rpm) for 5 minutes, thereby achieving frictional contact electrocatalytic degradation of the antibiotics.

[0144] Comparative Example 3

[0145] A method for degrading antibiotics by frictionally activating peroxymonosulfate using Fe2O3 / CuO comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball milling jar, adding 20 mg of a mixture of Fe2O3 and CuO (molar ratio 1:1) (all reagents are analytically pure and purchased from Adamas Reagent Co., Ltd.) and dispersing the mixture in the solution, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), adding PMS (0.5 mM), and then placing the mixture in a planetary ball milling apparatus for a ball milling degradation experiment (rotating speed 400 rpm) for 5 minutes, thereby achieving frictional contact electrocatalytic degradation of the antibiotics.

[0146] Comparative Example 4

[0147] A method for degrading antibiotics using peroxymonosulfate comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball milling jar, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), adding PMS (0.5 mM), and then placing the jar in a planetary ball mill for a ball milling degradation experiment (at a rotation speed of 400 rpm) for 5 minutes, thereby achieving frictional contact electrocatalytic degradation of the antibiotics.

[0148] Comparative Example 5

[0149] A method for frictionally degrading antibiotics using CFO-2 comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball milling jar, adding 20 mg of CFO-2 and dispersing it in the solution, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), and placing the jar in a planetary ball mill for a ball milling degradation experiment (at a rotation speed of 400 rpm) for 5 minutes, thereby achieving frictional contact electrocatalytic degradation of the antibiotics.

[0150] Comparative Example 6

[0151] A Fe 3+ The method for degrading antibiotics by friction-activated peroxymonosulfate comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball mill jar, adding 20 mg of FeCl3·6H2O (analytical grade reagent purchased from Adamas Reagent Co., Ltd.) and dispersing it in the solution, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), adding PMS (0.5 mM), and then placing the jar in a planetary ball mill for a ball milling degradation experiment (rotation speed of 400 rpm) for 5 minutes, thereby achieving friction-contact electrocatalytic degradation of the antibiotics.

[0152] Comparative Example 7

[0153] A Cu 2+ The method for degrading antibiotics by friction-activated peroxymonosulfate comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball mill jar, adding 20 mg of CuCl2·2H2O (analytical grade reagent purchased from Adamas Reagent Co., Ltd.) and dispersing it in the solution, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), adding PMS (0.5 mM), and then placing the jar in a planetary ball mill for a ball milling degradation experiment (rotation speed of 400 rpm) for 5 minutes, thereby achieving friction-contact electrocatalytic degradation of the antibiotics.

[0154] Comparative Example 8

[0155] A method for degrading antibiotics by frictionally activating peroxymonosulfate using CFO-2 comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball milling jar, adding 0.2 mM EDTA (analytical grade, purchased from Adamas Reagent Co., Ltd.) and dispersing it in the solution, adding 20 mg of CFO-2 and dispersing it in the solution, adding 3 mm zirconia ball milling beads (the mass ratio of catalyst to ball milling beads is 1:500), adding PMS (0.5 mM), and then placing the jar in a planetary ball mill for a ball milling degradation experiment (rotating speed of 400 rpm) for 5 minutes, thereby achieving frictional contact electrocatalytic degradation of the antibiotics.

[0156] Comparative Example 9

[0157] A method for degrading antibiotics by frictionally activating peroxymonosulfate using preoxidation CFO-2 (preoxidation-CFO) comprises the following steps: placing 50 mL of a 10 mg / L SDZ solution to be degraded in a 50 mL zirconia ball milling jar, adding 20 mg of CFO-2 and PMS (0.5 mM), thoroughly mixing, drying, and dispersing the mixture in the solution, adding 3 mm zirconia ball milling beads (with a mass ratio of catalyst to ball milling beads of 1:500), and placing the mixture in a planetary ball mill for a ball milling degradation experiment (at a rotation speed of 400 rpm) for 5 minutes, thereby achieving frictional contact electrocatalytic degradation of the antibiotics.

[0158] Comparative Example 10

[0159] Compared with Example 3, most of the contents are the same, except that the degraded antibiotic is CAP (the reagent is analytical grade and purchased from Adamas Reagent Co., Ltd.). In step (2), friction activation of peroxymonosulfate to degrade the antibiotic: 50 mL of CAP (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 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 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 friction contact electrocatalytic degradation of the antibiotic.

[0160] Comparative Example 11

[0161] Compared with Example 3, most of the above are the same, except that 5mM CO3 is added to the degradation solution. 2– Step (2) friction activation of peroxymonosulfate to degrade 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 of K2CO3 (the reagent was analytical grade and purchased from Adamas Co., Ltd.) was added, 20 mg of CFO-2 was 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 the ball milling degradation experiment was carried out in a planetary ball mill (the speed was 400 rpm), and the degradation time was 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0162] Comparative Example 12

[0163] Compared with Example 3, most of the above are the same, except that 5mM PO4 is added to the degradation solution. 3–Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill, 41 mg of Na3PO4 (analytical grade reagent purchased from Adamas Co., 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 the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed was 400 rpm), the degradation time was 5 min, and the friction contact electrocatalytic degradation of antibiotics was achieved.

[0164] Comparative Example 13

[0165] Compared with Example 3, most of the above are the same, except that 5mM H2PO4 is added to the degradation solution. – Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill jar, 34 mg of KH2PO4 (analytical grade reagent purchased from Adamas Co., 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 the mixture was placed in a planetary ball mill for ball milling degradation experiment (rotation speed was 400 rpm), and the degradation time was 5 min to achieve friction contact electrocatalytic degradation of antibiotics.

[0166] Comparative Example 14

[0167] Compared with Example 3, most of the contents are the same, except that 20 ppm humic acid (HA) (the reagent is analytical grade and purchased from Macklin Biochemical Technology Co., Ltd.) is added to the degradation solution. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, 5 mL of a pre-prepared 100 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), and the degradation time is 5 min, thereby achieving friction contact electrocatalytic degradation of antibiotics.

[0168] Comparative Example 15

[0169] Compared with Example 3, most of the contents are the same, except that 0.1 mol / L HCl (the reagent is analytical grade and purchased from Sinopharm Chemical Reagent Co., Ltd.) is used to adjust the initial pH value of the solution to 2. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, HCl solution is added dropwise until the solution pH is 2, 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, thereby achieving friction 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.) is used to adjust the initial pH value of the solution to 12. Step (2) friction activation of peroxymonosulfate to degrade antibiotics: 50 mL of SDZ (10 mg / L) solution to be degraded is placed in a 50 mL zirconia ball mill, NaOH solution is added dropwise until the solution pH is 12, 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 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 friction contact electrocatalytic degradation of antibiotics.

[0172] Performance testing:

[0173] 1. XRD characterization of the CuFe2O4 catalysts in Examples 1-4 is as follows:

[0174] The crystals of the samples were measured using a Rigaku Ultimate IV X-ray diffractometer with a Bruker D8 advanced Cu-Kα (λ = 0.15406 nm) as the diffraction target. Data collection was performed in 2theta scanning mode with continuous scanning from 10° to 80° at a scanning speed of 6° / min. Figure 1The XRD patterns of CuFe2O4 catalysts and Fe2O3 and CuO samples synthesized with different molar ratios of raw materials are shown. XRD comparison of CuFe2O4 (PDF#77-0010), CuO, and Fe2O3 revealed that they all contained varying degrees of CuO and Fe2O3 doping. However, we found that only the CFO-2 sample had 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, in order to better explore the heterogeneous catalytic mechanism of CuFe2O4, CFO-2 was used as the main catalyst model.

[0175] 2. 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 with different molar ratios of raw materials and synthesis times is shown, clearly showing that CuFe2O4 is composed of uniform and regular round particles stacked together, and that the particle size tends to decrease as the raw material molar ratio increases. However, when the molar ratio of the raw materials FeCl3·6H2O and CuCl2·2H2O is 4:1, the particle size increases instead. The particle size of the CFO-1 sample is mainly distributed in the range of 20nm-70nm, the particle size of the CFO-1.5 sample is mainly distributed in the range of 20nm-60nm, the particle size of the CFO-2 sample is mainly distributed in the range of 15nm-40nm, and the particle size of the CFO-4 sample is mainly distributed in the range of 60nm-140nm. It can be seen that the particle size of the CFO sample obtained when the molar ratio of FeCl3·6H2O and CuCl2·2H2O is 2:1 (Example 3) is relatively small and uniformly distributed.

[0178] 3. TEM test was performed on the CuFe2O4 catalyst in Example 3, as follows:

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

[0180] 4. The BET test of the CuFe2O4 catalyst in Examples 1-4 was performed as follows:

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

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

[0183]

[0184] 5. Test on the effect of CuFe2O4 catalyst synergistically with PMS friction degradation of SDZ.

[0185] Figure 5 The degradation performance of SDZ by friction with CuFe2O4 catalyst synergistically using PMS is shown. A certain volume of reaction solution was taken every 1 min at a fixed time interval. During the degradation reaction with a total reaction time of 5 min, 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 the next analysis.

[0186] in, Figure 5(a) shows that within 5 minutes, a comparison of Fe2O3 (Comparative Example 1), CuO (Comparative Example 2), a mixture of Fe2O3 and CuO (Comparative Example 3), and CuFe2O4 catalysts with different molar ratios of raw materials (Examples 1-4) shows that the CuFe2O4 catalysts with different molar ratios of raw materials can all achieve 100% degradation of the SDZ solution. The degradation effects of the catalysts Fe2O3, CuO, and Fe2O3 / CuO (1:1) on the SDZ solution within 5 minutes were 50%, 98%, and 90%, respectively. In addition, combined with the characterization results, the CuFe2O4 catalyst in Example 3 is more active, so CFO-2 was used as a model for further study.

[0187] Figure 5 (b) shows that there is almost no degradation of SDZ in the oxidation process of PMS alone (Comparative Example 4), which means that PMS can only be activated in the presence of CFO-2 with Cu as the main active site in conjunction with the Fe site. Only under the conditions of CFO-2 catalyst (Comparative Example 5), desorption occurred after adsorption, which has almost no effect on the removal of pollutants. Under the same conditions, the degradation results of the filtrate containing excess PMS and SDZ after adding PMS show that the degradation of SDZ by the CFO-2 / PMS system (Example 3) follows a heterogeneous catalytic reaction. EDTA is used as an ion coupling agent, and EDTA / PMS (Comparative Example 8) has no obvious inhibitory effect in 5 minutes, further illustrating that the system is non-Fe 3+ / PMS (Comparative Example 6) and Cu 2+ / PMS (Comparative Example 7) is a homogeneous system. This system is a heterogeneous solution that reflects the availability of the catalyst for further recycling and reuse. The filtrate after the reaction was used for further reaction. SDZ was almost not degraded, indicating that there was almost no leached ions or excess PMS in the solution for further reaction. Using pre-oxidized CFO-2 (Comparative Example 9), that is, mixing the same concentration of PMS with the CFO-2 catalyst and then drying it for ball milling reaction, and no PMS solution was added during the process. The results showed that SDZ contained 50% degradation, indicating that in the process of CFO / PMS degrading SDZ, PMS will first form a PMS* complex with the catalyst, and then further degrade SDZ.

[0188] 6. Effects of different antibiotics and common aqueous matrices on the degradation of SDZ by CuFe2O4 catalyst and PMS. At fixed time intervals during the degradation reaction, 1.5 mL of the suspension was filtered through a 0.22 μm MCE filter and quenched with 40 μL of sodium thiosulfate for further analysis.

[0189] Figure 6(a) shows the degradation of different antibiotics by CFO-2 in conjunction with PMS during ball milling, 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 and PMS have 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 shows that the CuFe2O4 catalyst has certain universal applicability, especially its high selective removal ability for electron-rich pollutants. This is because singlet oxygen is an electron-deficient free radical that easily attacks pollutants with electron-rich structures.

[0190] Figure 6 (b) shows the metal cations (Ca 2+ Mg 2+ ), anionic salt (Cl - 、HCO3 - 、NO3 - 、CO3 2- PO4 3- 、H2PO4 - ) on the effect of friction synergistic PMS degradation of SDZ by CuFe2O4 catalyst (Examples 3, 8-12, Comparative Examples 11-13). The concentration of organic pollutant SDZ was determined using a high performance liquid chromatograph (UHPLC, Ultimate 3000, Thermo Scientific USA) equipped with a UV-visible detector and a C18 reverse phase chromatography 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 that compared with the control (Example 3), SDZ degradation was almost unaffected by Cl - 、HCO3 - 、NO3 - The impact of CO3 2- PO4 3- 、H2PO4 - The reason for the influence on SDZ degradation is that these anions will compete with reactive free radicals to varying degrees. 2+ Mg 2+ There was no effect on SDZ degradation, which demonstrated the strong anti-interference ability of the CFO-2 / PMS ball milling system.

[0191] Figure 6(c) shows the effect of natural organic matter (5, 10, and 20 ppm hyaluronic acid (HA)) on the tribo-synergistic degradation of SDZ by PMS over a CuFe2O4 catalyst (Examples 3, 13, and 14, and Comparative Example 14). The concentration of the organic contaminant SDZ was determined using a high-performance liquid chromatograph (UHPLC, Ultimate 3000, Thermo Scientific USA) equipped with a UV-visible detector and a C18 reverse-phase column. The mobile phase consisted of 70% 0.1% phosphoric acid solution and 30% acetonitrile, with a detection wavelength of 270 nm and a flow rate of 1 mL / min. The results show the effect of 5-20 ppm HA on SDZ degradation, compared to the control (Example 3). HA concentrations below 10 ppm showed no significant inhibitory effect on SDZ degradation. Only at a high concentration of 20 ppm did HA exhibit a moderate inhibitory effect, with the SDZ degradation rate decreasing from 100% to 75% within 5 minutes. This is because high concentrations of humic acid increase the consumption of the PMS oxidant, but at low concentrations, there was almost no effect, demonstrating the system's strong tolerance to natural organic matter background environments.

[0192] Figure 6 (d) shows the effect of initial pH on the friction-synergistic PMS degradation of SDZ over a CuFe2O4 catalyst (Examples 3, 15-17, and Comparative Examples 15 and 16). In Example 3, the pH was 6. The results show that initial pH values ​​of 4-10 have little effect on SDZ degradation. However, under strongly acidic conditions (pH = 2) and strongly alkaline conditions (pH = 12), SDZ degradation is somewhat inhibited, with SDZ degradation rates of approximately 70% and 60%, respectively. This indicates that the reaction can proceed over a wide pH range without affecting SDZ degradation.

[0193] 7. TOC removal rate of SDZ by friction degradation under ball milling with CuFe2O4 catalyst and PMS.

[0194] During the degradation reaction process at fixed time intervals (Example 3, CFO-2), samples were taken every 60 min, and 20 mL of the solution was filtered through a 0.22 μm MCE filter head 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 intermediates with lower molecular weight, which are then further converted into CO2 and H2O.

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

[0196] Using CFO-2, different rotation speeds (100, 200, 300, 400 rpm, i.e., Examples 3, 18-20) were used to explore the effect of heat changes during ball milling on pollutant degradation. Figure 8 (a) The results show that the system is not affected by temperature, which means that the catalytic conditions of this system are strongly insensitive to temperature changes and have high operability in practice. In addition, in the peroxymonosulfate system, temperature affects the generation of free radicals, which means that free radicals are not important active species in this system.

[0197] Figure 8 (b) shows the effect of different concentrations of PMS (0.25, 0.5, 1 mM, i.e., Examples 3, 21, and 22) on the degradation of the 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 is significantly enhanced as the catalyst dosage increases, which is due to the increase in active sites. However, when the amount of catalyst is increased to 30 mg, the degradation effect is not significantly improved, which is due to the saturation of active sites to PMS activation. Therefore, from an economic perspective, the system selects a 20 mg dosage. As the concentration of PMS oxidant increases, the catalytic effect is significantly enhanced due to the increase in active species. From an environmental perspective, the system selects 0.5 mM. When the pollutant concentration increases from 5 ppm to 10 ppm, the system does not receive a significant hindrance to its degradation ability. When the pollutant concentration increases to 20 ppm, the degradation effect receives a certain hindrance, so the pollutant is taken as the control group target concentration of 10 ppm. The optimal reaction conditions obtained under the system are 0.5 mM PMS, 20 mg catalyst, and 10 ppm pollutants, ensuring efficient degradation of pollutants under the most economical conditions, providing an experimental basis for its practical application.

[0198] 9. Stability test of CuFe2O4 catalyst synergistically with PMS to degrade SDZ.

[0199] A 50 mL SDZ (10 mg / L) solution to be degraded was placed in a 50 mL zirconia ball mill. 20 mg CFO-2 and PMS (0.5 mM) were added and thoroughly mixed. The dried catalyst was dispersed in the solution. 3 mm zirconia beads (powder-to-ball ratio of 1:500) were then added. The solution was then milled in a planetary ball mill at 400 rpm for 5 minutes to achieve frictional electrocatalytic degradation of the antibiotic. The reaction solution was centrifuged, washed, and the catalyst recovered and dried for reuse. This was repeated seven times.

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

[0201] 10. Experiment on determining active species of SDZ degradation by CuFe2O4 catalyst in collaboration with PMS.

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

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

[0204] Although the present invention has been described in detail above using general explanations, specific embodiments, and experiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst, characterized in that: The antibiotic solution to be degraded is placed in a ball milling jar, and a transition bimetallic catalyst, ball milling beads, and PMS are added thereto for ball milling to achieve frictional contact electrocatalytic degradation of the antibiotic.

2. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 1, characterized in that: The antibiotic solution includes electron-rich sulfonamides, beta-lactam antibiotics, diaminopyrimidine antibiotics, and tetracycline antibiotics.

3. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 2, characterized in that: The electron-rich sulfonamide antibiotics include sulfadiazine and sulfamethoxazole; The β-lactam antibiotics include 6-aminopenicillanic acid; The diaminopyrimidine antibiotics include trimethoprim; The tetracycline antibiotics include p-chlorophenol.

4. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 1, characterized in that: The solvent in the antibiotic solution includes aqueous solution, inorganic anions, metal cations and natural organic aqueous solution; the pH value of the antibiotic solution is 4-10.

5. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 1, characterized in that: 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.

6. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 1, characterized in that: The chemical formula of the transition bimetallic catalyst is AB2O4, wherein A is Mn, Co, Ni, Zn or Cu, and B is Fe, Ti, Cr or Mo.

7. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 6, characterized in that: The preparation process of the transition bimetallic catalyst is as follows: ultrasonically mixing salt solution A and salt solution B, dropwise adding alkali solution to form a dark brown solution, and subjecting the dark brown solution to a hydrothermal reaction to obtain a precipitated product which is the transition bimetallic catalyst.

8. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 7, characterized in that: The salt solution A includes a Mn salt solution, a Co salt solution, a Ni salt solution, a Zn salt solution or a Cu salt solution, the salt solution B includes a Fe salt solution, a Ti salt solution, a Cr salt solution or a Mo salt solution, and the alkali solution includes a NaOH solution or a KOH solution; The molar ratio of A to B in the salt solution A and the salt solution B is 1:1-4, the concentration of the alkali solution is 1-10 mol / L, and the volume ratio of the salt solution A to the alkali solution is 1.5-10:1; The temperature of the hydrothermal reaction is 160-200°C.

9. The method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst according to claim 1, characterized in that: The ball milling jar comprises a zirconia ball milling jar, the ball milling beads comprise zirconia ball milling beads, the particle size of the ball milling beads is 1 to 10 mm, and the powder-to-ball ratio is 1:300 to 800.

10. Use of the method for degrading antibiotics by friction-activating peroxymonosulfate using a transition bimetallic catalyst as claimed in any one of claims 1 to 9 in the field of antibiotic wastewater treatment.

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