A method for degrading antibiotics using electric field-activated monopersulfate

Abstract

The application discloses a method for degrading antibiotics by using electric field activated monopersulfate, characterized in that carbonyl functionalized carbon particles and monopersulfate are added into a water body to be degraded to make them uniformly dispersed, then a micro electrolysis unit is formed by polarization of the carbonyl functionalized carbon particles through application of an electric field, and the monopersulfate is activated by the carbonyl active sites on the carbonyl functionalized carbon particles in cooperation with the electric field, so that the degradation of antibiotics in the water body is realized. The application has the advantages of good degradation effect, no secondary pollution of metal, strong cycle stability, wide application range, low energy consumption and the like.

Description

Technical Field

[0001] This invention relates to the field of environmental protection technology for removing antibiotics from water, specifically to a method for degrading antibiotics by activating peroxymonosulfate using an electric field. Background Technology

[0002] Antibiotics, widely used in medicine and animal husbandry, are increasingly prevalent in modern society. However, their poor natural degradation, widespread overuse, and inadequate regulation have led to their frequent detection in natural water bodies. Sulfonamide antibiotics (such as sulfamethoxazole) and fluoroquinolone antibiotics (such as ofloxacin) exhibit high chemical stability and ecotoxicity; even low concentrations can induce antibiotic resistance genes in bacteria, which can then spread through the water cycle, threatening human health and ecological safety. Therefore, taking effective measures to remove these pollutants from water bodies is of significant environmental importance.

[0003] Advanced oxidation techniques based on persulfate activation Sulfate radicals can be generated by activating persulfate. hydroxyl radicals Various reactive oxygen species This achieves efficient degradation and even mineralization of organic pollutants. Compared with traditional advanced oxidation technologies such as Fenton, The technology has a longer free radical half-life, It offers advantages such as wider applicability and better selectivity. Currently, the activation methods for persulfates mainly include thermal activation, ultraviolet light activation, transition metal activation, and electroactivation. Among these, electroactivation... The method is simple to operate and requires mild conditions, and has good application prospects.

[0004] However, the performance of the electrode material is a key limiting factor in the electroactivation process. Traditional electrode materials generally suffer from low utilization of active sites and slow electron transfer rates, which restrict the activation efficiency of persulfate. To improve electroactivation performance, researchers have attempted to load transition metals onto the electrode, but metal leaching can easily cause secondary pollution.

[0005] In recent years, metal-free carbon materials have attracted widespread attention due to their environmental friendliness, tunable structure, and good electrical conductivity. Studies have shown that oxygen-containing functional groups on the surface of carbon materials, especially carbonyl groups... The carbonyl group possesses the ability to regulate electronic structure and promote interfacial electron transfer. Therefore, the applicant considers using carbon materials as electrode materials for advanced oxidation techniques to activate persulfate. This utilizes the local polarization effect induced by the carbonyl group to lower the electron transfer energy barrier, which is beneficial for the adsorption and activation of persulfate. However, the mechanism by which carbonyl-functionalized carbon materials activate persulfate under synergistic electric field conditions is currently unclear, and the existing carbonyl carbon material preparation processes are complex and have insufficient active site density, limiting their practical application.

[0006] Therefore, how to utilize the efficient electronic regulation capabilities of carbonyl functionalized carbon materials, combined with the synergistic effect of electric fields, to achieve efficient activation of persulfate and deep degradation of antibiotics, while improving the degradation effect and avoiding secondary metal pollution, has become a technical problem to be solved by those skilled in the art. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is: how to provide a method for degrading antibiotics by activating peroxymonosulfate with an electric field, which has good degradation effect, no secondary metal pollution, strong cycle stability, wide applicability and low energy consumption.

[0008] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0009] A method for degrading antibiotics using peroxymonosulfate activated by an electric field is characterized by adding carbonyl functionalized carbon particles and peroxymonosulfate to the water to be degraded and dispersing them evenly. Then, an electric field is applied to polarize the carbonyl functionalized carbon particles to form micro-electrolysis units. The carbonyl active sites on the carbonyl functionalized carbon particles, in conjunction with the electric field, activate the peroxymonosulfate to achieve the degradation of antibiotics in the water.

[0010] Thus, the carbon particulate material used in this method forms an electrode surface rich in carbonyl groups under an electric field. The active sites, after activation, possess a high specific surface area and abundant hierarchical porous structure, which is conducive to the full exposure of active sites and the interfacial enrichment of target pollutants. Carbonyl-rich carbon particles undergo polarization under the action of an external electric field (the carbonyl sites further enrich electrons under the electric field, with electrons accumulating at one end and electrons lacking at the other, thus enhancing polarization). Some particles form microcathodes, while others form microanodes; some particles themselves are half cathode and half anode, thereby constructing a large number of micro-electrolysis units. In this way, the carbonyl characteristic polarization effect is significantly amplified under the action of the electric field, reducing the interfacial electron transport energy barrier and achieving efficient activation of peroxymonosulfate PMS. Characterization results show that carbonyl-functionalized carbon particles have a high carbonyl content. Larger specific surface area ( Compared to before activation Significant improvement) and Composite multi-level porous structure (average pore size) ), there is an advantage The activated localized polarized microdomains and oxygen vacancies further accelerate the reaction rate of antibiotic degradation.

[0011] Furthermore, the water body to be degraded The range is Preferred It is 5.

[0012] Studies have shown that in hour Mainly based on high activity The existence of form is most advantageous and The formation of [something]; under strongly acidic conditions. Excessive will with Formation of strong hydrogen bonds, making Protonation into less active Under alkaline conditions Down, Dissociate into less active ,and It is easily converted into something with weaker oxidizing power. ,at the same time Electrostatic repulsion generated by surface negative charging also hinders interfacial reactions. Therefore, this method is preferably used in... Under specific conditions, the catalytic activation effect can be obtained.

[0013] Furthermore, during degradation, the prepared carbonyl functionalized carbon particles and peroxymonosulfate are first added to the water to be degraded and thoroughly mixed, and then an electric field is applied to complete the degradation reaction.

[0014] This is because the carbon particle electrode itself is a porous adsorbent material with strong adsorption properties. Adding this material to the water to be degraded and mixing it thoroughly allows some antibiotics to be adsorbed into the pores of the carbon material, achieving pre-enrichment of pollutants around the active sites. Studies have shown that... right The adsorption removal rate is approximately ,and Only ,illustrate Activation significantly enhanced the adsorption performance of the material. Simultaneously, the addition of peroxymonosulfate and the application of an electric field induced an increase in the electron density on the carbon particle surface, promoting adsorption. Electrostatic migration and chemisorption onto the electrode surface, while simultaneously the carbonyl active sites are activated under the influence of an electric field, achieve the desired effect. This method efficiently cleaves and activates the antibiotic, thus achieving efficient degradation. Furthermore, it requires no initial pH adjustment and maintains good degradation performance over a wide pH range.

[0015] Furthermore, the carbonyl functionalized carbon particles and the electric field are applied by means of an electric field purification device (i.e., this method is achieved by the electric field purification device). The electric field purification device includes a purification cage, which is surrounded by a filter screen to form a cage shape. The filter screen has a pore size smaller than the carbonyl functionalized carbon particles. The purification cage contains a portion of the carbonyl functionalized carbon particles. Two electrodes are arranged at intervals inside the purification cage. The mounting ends of the two electrodes are fixed to the mounting plate at the upper end of the purification cage. An electric stirring device is also provided inside the lower end of the purification cage.

[0016] Thus, when using the above-mentioned electric field purification device, peroxymonosulfate is first added to the water to be degraded and mixed thoroughly. Then, the electric field purification device is immersed in the water to be degraded, and the electrodes and electric stirring device are energized. The electric stirring device drives the water in the purification cage to agitate, realizing the exchange of water inside and outside the purification cage. At the same time, the carbonyl functionalized carbon particles in the purification cage are stirred and dispersed into the electric field formed by the two electrodes. The carbonyl functionalized carbon particles are polarized under the action of the electric field, forming a large number of micro electrolysis units, which promotes the degradation of peroxymonosulfate. Its high efficiency activation can quickly achieve antibiotic degradation.

[0017] Parallel, opposing plate electrodes are placed in the water body to be degraded, creating a uniform electric field within the water. This method allows for a more effective and uniform formation of the electric field, ensuring consistent treatment results across all locations within the water body.

[0018] Furthermore, during degradation, the amount of the carbonyl-functionalized carbon particles added is: (Preferred) The dosage of peroxymonosulfate is (Preferred) The current density of the electric field is (Preferred) ), electrode spacing is The reaction temperature is (Preferred) ), stirring rate is .

[0019] The above data represents the range within which the degradation effect is optimal, as verified by the experiment.

[0020] Furthermore, the carbonyl-functionalized carbon particles (hereinafter referred to as...) ), is a porous carbon material with carbonyl active sites on its surface, prepared by high-temperature carbonization of glucose and activation pyrolysis by mixing with potassium hydroxide.

[0021] Thus, this method uses glucose as a carbon source precursor, after... Carbonyl-functionalized carbon particles obtained by activated pyrolysis. During pyrolysis, glucose forms a highly conjugated carbon skeleton through dehydration condensation. The activation process chemically etches the carbon framework and simultaneously drives the reconstruction of oxygen-containing functional groups on the surface, resulting in partial... The group is converted into a more stable form through a dehydrogenation reaction. The bond is partially formed through dehydration condensation. This structure allows for the surface enrichment of carbonyl groups. Photoelectron spectroscopy Analysis shows that, Surface carbonyl carbon The proportion reached Compared to before activation Significant improvement. The carbon materials produced retain a weakly graphitized amorphous carbon structure. It has a high degree of defect, good electrical conductivity, and abundant structural defects. Nitrogen gas. Analysis shows that, The specific surface area reached Total capacity is Significantly higher than . Analysis shows that, exist and The broadened diffraction peaks at these locations correspond to... and The crystal planes confirmed that it maintained an amorphous carbon structure with a low degree of graphitization. Raman spectroscopy further confirmed this. Etching primarily increased the defect concentration without significantly altering the degree of graphitization. Analysis shows that, exist Characteristic absorption peaks are observed at this location, among which Peak intensity Significantly enhanced, and The weakening of the peak confirms the directional reconstruction of the oxygen-containing functional groups. Simultaneously, the carbonyl group exhibits high polarization. The structure can form locally charged polarized microdomains, and its reversible electron capture and release properties enable it to serve as a key "relay station" for interfacial electron transfer, exhibiting superior electronic regulation capabilities compared to hydroxyl, carboxyl, and ether groups.

[0022] From the perspective of the chemical reaction process, the reason this method achieves the degradation of antibiotics by activated peroxymonosulfate lies in the fact that peroxymonosulfate has a relatively limited ability to oxidize and degrade antibiotics. However, the carbonyl-functionalized carbon particles prepared by this method have... Both antibiotics and [these substances] exhibit interfacial enrichment effects. Under the synergistic effect of an electric field, the carbonyl active site accepts electrons and undergoes directional transfer to [the target site]. Molecules, promote of Bond breakage generates sulfate free radicals. hydroxyl radicals superoxide radicals and singlet oxygen These reactive oxygen species work together to degrade adsorbed and free antibiotics. Among them, the carbonyl-mediated electron transfer pathway preferentially drives... and The generation, Further through disproportionation reaction Coupling reaction with free radicals Transform into This resulted in an oxidation system dominated by non-radical pathways. Quenching experiments and probe analysis showed that... The contribution rates to degradation reached respectively The combined contribution of the two reached ; Contribution rate , Contribution rate was only This indicates that the non-radical pathway is one of the core features that distinguishes the system described in this invention from traditional radical-dominated systems.

[0023] The catalytic activation process of the method of the present invention includes the following reaction:

[0024] ;

[0025] ;

[0026] ;

[0027] ;

[0028] ;

[0029] ;

[0030] ;

[0031] ;

[0032] Furthermore, the antibiotic is a sulfonamide antibiotic (such as sulfamethoxazole, It may be any one of the following: sulfadiazine; sulfadiazine; or fluoroquinolone antibiotics (such as ofloxacin, ciprofloxacin, norfloxacin).

[0033] In practical applications, this method can also be used to remove tricyclic antiepileptic drugs (such as carbamazepine). ), phenolic endocrine disruptors ( ) and phenol Recalcitrant organic pollutants. Experiments show that under the above optimal conditions, ciprofloxacin... Removal rate Carbamazepine Removal rate , Removal rate , Removal rate All reached The above demonstrates that the method described in this invention has a broad-spectrum ability to degrade organic pollutants.

[0034] Further, the carbonyl-functionalized carbon particles are prepared according to the following steps:

[0035] a. Glucose is placed in a tube furnace under an inert atmosphere. The following Heating rate to Pyrolysis temperature, heat preservation pyrolysis After naturally cooling to room temperature, the mixture is ground and passed through a 100-mesh sieve to obtain glucose-derived carbon. ;

[0036] b. Reconstitute the glucose-derived carbon obtained in step a with potassium hydroxide. By mass ratio range Mix and disperse in an appropriate amount of deionized water, stirring continuously. The above makes Fully impregnate into the carbon skeleton;

[0037] c. The mixture obtained in step b is separated by centrifugation. Collect solid products, at Vacuum drying ;

[0038] d. Place the dried mixture obtained in step c in a tube furnace and heat it under an inert atmosphere. Heat down to Thermal insulation and pyrolysis ;

[0039] The product obtained in step e, d, is washed with acid (dilute hydrochloric acid) and then repeatedly washed with deionized water until neutral. ,At Carbonyl-functionalized carbon particles were obtained by vacuum drying for 12 hours. .

[0040] In the above preparation process, The activation process chemically etches the carbon framework, while Decomposition and release Gas-assisted pore formation creates abundant pores. Composite structure. The chemical reactions involved in activation are as follows:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] This hierarchical porous structure not only fully exposes active sites but also significantly enhances interfacial mass transfer and diffusion kinetics. Orthogonal experimental optimization results show that when… mass ratio The pyrolysis temperature is Activation temperature is At that time, the material properties are optimal. Material yield Too low This leads to insufficient activation and a low degradation rate. Excessively high Proportion Excessive etching damages the carbon framework, causing the degradation rate to drop to [a certain percentage]. Yield dropped to This indicates that a suitable activation intensity is one of the key features of the present invention.

[0047] Furthermore, the heating rate in step a is The pyrolysis temperature is The pyrolysis time is Single-factor experiments showed that, in Within the specified range, the degradation rate initially increases and then stabilizes with increasing pyrolysis temperature. The degradation rate is only It gradually increases with rising temperature. Peak time , The degradation rate did not continue to increase, therefore, [the following was selected] The optimal pyrolysis temperature is achieved while balancing catalytic performance and energy consumption control.

[0048] Furthermore, in step b, the mass ratio of glucose-derived carbon to potassium hydroxide is... The stirring time is This better ensures that KOH is fully impregnated into the carbon skeleton.

[0049] Furthermore, the pyrolysis temperature in step d is The pyrolysis time is This ensures sufficient activation and a stable carbon skeleton structure.

[0050] Furthermore, after the degradation reaction is completed, the used carbonyl-functionalized carbon particles are regenerated. The regeneration process involves washing the used carbonyl-functionalized carbon particles three times with deionized water. Drying in an oven This allows for recycling and reuse.

[0051] This is because, with increasing reaction cycles, the degradation rate and reaction rate constant of the carbon particle electrode for antibiotics decrease, but remain at a high level. Most of the activity can be restored through simple cleaning and drying. Subsequent experiments showed that after 5 cycles, System The degradation efficiency from The rate constant is from And electric field of The system degradation rate from The rate constant is from Down to The significant difference between the two indicates that the applied electric field, by continuously supplying an electron supply, is used for... Activation effectively prevents The irreversible oxidation of surface carbonyl groups is consumed, and the shielding effect caused by intermediate product deposition is mitigated. Characterization confirms that, After one reaction in the system, Peak area from Slightly decreased and from In a system without an electric field, the voltage drops significantly. After 5 cycles, Removal rate only from Down to This indicates that the carbonyl functionalized carbon particles prepared by this invention are easy to regenerate and have excellent cycle stability under electric field protection.

[0052] In practical applications, the method described in this invention also has good applicability in actual water bodies. In tap water... middle Removal rate In surface water The removal rate is This demonstrates strong potential for practical applications. Anti-interference experiments with common coexisting substances show that: It has almost no effect on degradation. This may be related to The reaction produces It is also related to its oxidizing ability; It can significantly promote Degradation (from) ), attributed to chlorine-active species The generation of; It has a certain inhibitory effect on the reaction (reduced to a certain extent). This is attributed to its quenching of reactive oxygen species and competitive occupation of active sites; humic acid Reduce the removal rate to This is attributed to its consumption of reactive oxygen species and occupation of active sites. Overall, the method described in this invention exhibits good resistance to interference from common coexisting substances in water.

[0053] Therefore, compared with the prior art, the advantages of this invention are: less metal leaching, better catalytic performance, and lower energy consumption. Activation and high-temperature pyrolysis construct numerous carbonyl active sites on the surface of carbon materials. Combined with the synergistic effect of the electric field and in-situ protection, this significantly improves... Activation efficiency and antibiotic degradation reaction rate. This invention utilizes the pyrolysis of biomass carbon sources to obtain carbon carriers, which is low-cost, environmentally friendly, and has advantages such as simple material preparation methods, low cost, convenient implementation, good catalytic degradation effect, recyclability, and wide applicability to a wide range of water qualities.

[0054] In summary, this invention has the advantages of good degradation effect, no secondary metal pollution, strong cycle stability, wide applicability, and low energy consumption. Attached Figure Description

[0055] Figure 1 For different pyrolysis temperatures on A diagram illustrating the impact on performance.

[0056] Figure 2 for Comparison of different quality levels Schematic diagram illustrating the effect of degradation rate.

[0057] Figure 3 Scanning electron microscope images and elemental distribution diagrams before and after the preparation of degradation catalytic materials.

[0058] Figure 4 Before and after the preparation process of degradation catalytic materials Diffraction pattern.

[0059] Figure 5 Infrared spectra before and after the reaction were used to degrade the catalytic material. Schematic diagram.

[0060] Figure 6 Nitrogen adsorption-desorption isotherms for degradation catalyst materials Schematic diagram.

[0061] Figure 7 For different systems A schematic diagram comparing the degradation rate and the degradation reaction rate constant.

[0062] Figure 8 For degradation catalytic materials System degradation A schematic diagram of a cyclic experiment.

[0063] Figure 9 This is a schematic diagram of the electric field purification device used in the implementation of this method. Detailed Implementation

[0064] The present invention will now be described in further detail with reference to specific embodiments and accompanying drawings.

[0065] Optimal Implementation: A method for degrading antibiotics using peroxymonosulfate activated by an electric field, characterized in that carbonyl functionalized carbon particles and peroxymonosulfate are added to the water to be degraded and dispersed evenly. Then, an electric field is applied to polarize the carbonyl functionalized carbon particles to form micro-electrolysis units. The carbonyl active sites on the carbonyl functionalized carbon particles, in conjunction with the electric field, activate the peroxymonosulfate to achieve the degradation of antibiotics in the water.

[0066] Thus, the carbon particulate material used in this method forms an electrode surface rich in carbonyl groups under an electric field. The active sites, after activation, possess a high specific surface area and abundant hierarchical porous structure, which is conducive to the full exposure of active sites and the interfacial enrichment of target pollutants. Carbonyl-rich carbon particles undergo polarization under the action of an external electric field (the carbonyl sites further enrich electrons under the electric field, with electrons accumulating at one end and electrons lacking at the other, thus enhancing polarization). Part of the particle forms a microcathode, and the other part forms a microanode; some particles are even half cathode and half anode, thus constructing a large number of micro-electrolysis units. In this way, under the action of the electric field, the polarization effect of the carbonyl characteristic is significantly amplified, reducing the interfacial electron transport energy barrier and realizing peroxymonosulfate. Highly efficient activation. Characterization results show that carbonyl-functionalized carbon particles have a high carbonyl content. Larger specific surface area ( Compared to before activation Significant improvement) and Composite multi-level porous structure (average pore size) ), there is an advantage The activated localized polarized microdomains and oxygen vacancies further accelerate the reaction rate of antibiotic degradation.

[0067] In practice, this method is applied to the water body to be degraded. The range is Preferred .

[0068] Studies have shown that in hour Mainly based on high activity The existence of form is most advantageous The formation of [something]; under strongly acidic conditions. Excessive Formation of strong hydrogen bonds, making Protonation into less active Under alkaline conditions Down, Dissociate into less active ,and It is easily converted into something with weaker oxidizing power. ,at the same time Electrostatic repulsion generated by surface negative charging also hinders interfacial reactions. Therefore, this method is preferably used in... Under specific conditions, the catalytic activation effect can be obtained.

[0069] In this method, the carbonyl functionalized carbon particles and peroxymonosulfate are first added to the water to be degraded and mixed thoroughly, and then an electric field is applied to complete the degradation reaction.

[0070] This is because the carbon particle electrode itself is a porous adsorbent material with strong adsorption properties. Adding this material to the water to be degraded and mixing it thoroughly allows some antibiotics to be adsorbed into the pores of the carbon material, achieving pre-enrichment of pollutants around the active sites. Studies have shown that... The adsorption removal rate is approximately ,and ,illustrate Activation significantly enhanced the adsorption performance of the material. Simultaneously, the addition of peroxymonosulfate and the application of an electric field induced an increase in the electron density on the carbon particle surface, promoting adsorption. Electrostatic migration and chemisorption onto the electrode surface, while simultaneously the carbonyl active sites are activated under the influence of an electric field, achieve the desired effect. This method achieves efficient cleavage and activation, thereby efficiently degrading antibiotics. Furthermore, it eliminates the need for initial adjustment. In wide It maintains good degradation performance within the entire range.

[0071] In specific implementation, the carbonyl functionalized carbon particles and the electric field are applied via an electric field purification device (i.e., this method is achieved through this electric field purification device), see [link to relevant documentation]. Figure 9 As shown, the electric field purification device includes a purification cage 1, which is surrounded by a filter screen 2 to form a cage shape. The filter screen pore size is smaller than the carbonyl functionalized carbon particles. The purification cage 1 contains some carbonyl functionalized carbon particles. Two electrodes 3 are arranged at intervals inside the purification cage 1. The mounting ends of the two electrodes 3 are fixed on the mounting plate 4 at the upper end of the purification cage. An electric stirring device 5 is also provided inside the lower end of the purification cage.

[0072] In this way, when using the above-mentioned electric field purification device, peroxymonosulfate (PMS) is first added to the water to be degraded and mixed thoroughly. Then, the electric field purification device is immersed in the water to be degraded, and the electrodes and electric stirring device are energized. The electric stirring device drives the water in the purification cage to agitate, realizing the exchange of water inside and outside the purification cage. At the same time, the carbonyl functionalized carbon particles in the purification cage are stirred and dispersed into the electric field formed by the two electrodes. The carbonyl functionalized carbon particles are polarized under the action of the electric field, forming a large number of micro-electrolysis units, which promotes the efficient activation of peroxymonosulfate PMS, thus rapidly achieving the degradation of antibiotics. It also has the advantages of simple device structure, convenient implementation, reliable treatment, and convenient carbon particle recovery and replacement. As another possible implementation method, carbonyl functionalized carbon particles can be directly dispersed and embedded in porous water filter materials (such as porous sponges). Then, an electric field is applied to both sides of the porous water filter material, allowing the water to be degraded with added peroxymonosulfate to flow through the porous water filter material to achieve the electric field treatment. Alternatively, the water to be treated can be directly placed into a treatment container, electrodes can be directly set up inside the container to form an electric field, carbonyl functionalized carbon particles and peroxymonosulfate can be added, and then a stirring device can be used to stir and disperse them evenly to achieve the application of the electric field for treatment.

[0073] During degradation using this method, the amount of carbonyl-functionalized carbon particles added is: (Calculated based on the internal volume of the electric field purification device during implementation), the dosage of peroxymonosulfate is: (Calculated based on the volume of water to be purified during implementation), the current density of the electric field is The electrode spacing is The reaction temperature is The stirring rate is .

[0074] The above data represents the range within which the degradation effect is optimal, as verified by experiments. Specifically, the applicant determined the optimal operating parameters through preliminary experiments. During the preliminary experiments, [the following data was used]. Sulfamethoxazole The solution is the target pollutant, at room temperature The degradation process is carried out under the specified conditions without adjusting the initial conditions. The results show that:

[0075] (1) Concentration optimization: when from At that time, the degradation rate from Upgraded to The reaction rate constant is from Continue to increase to The degradation rate decreased to The rate constant decreased to This is due to excessive It can quench reactive oxygen species ,therefore This is the optimal dosage.

[0076] (2) KGDC dosage optimization: when The degradation rate was significantly increased to The rate constant reaches When the dosage is further increased, the particulate electrodes are prone to agglomeration, shielding active sites. Furthermore, the increased contact between particles easily leads to short-circuit currents, weakening the electric field effect and causing a decline in degradation performance. This is the optimal dosage.

[0077] (3) Current density optimization: Current density from At this time, the electrocatalytic driving force is enhanced, the electron transfer and repolarization processes are accelerated, and the degradation rate and rate constant reach their optimal values. Continue to increase to At this time, side reactions such as hydrogen evolution and oxygen evolution are intensified, and with Activating competitive electron transfer channels reduces degradation rate to Energy consumption analysis shows that the current density from At that time, the power consumption per unit mass of organic matter degrading Therefore, considering both degradation kinetics and energy consumption, This represents the optimal current density.

[0078] (4) Energy consumption assessment: under optimal conditions , System The value is only Significantly lower than that of a standalone electrolysis system , and system ,show The introduction of [a specific technology / method] effectively promoted interface electron transfer and significantly improved [the efficiency / performance]. The activation efficiency and utilization efficiency are compared with those reported in the literature for electrocatalysis. system In comparison, the system described in this invention The value is at a low level, demonstrating excellent energy utilization efficiency.

[0079] In practice, the carbonyl functionalized carbon particles (hereinafter referred to as...) ), is a porous carbon material with carbonyl active sites on its surface, prepared by high-temperature carbonization of glucose and activation pyrolysis by mixing with potassium hydroxide.

[0080] Thus, this method uses glucose as a carbon source precursor, after... Carbonyl-functionalized carbon particles obtained by activated pyrolysis. During pyrolysis, glucose forms a highly conjugated carbon skeleton through dehydration condensation. The activation process chemically etches the carbon framework and simultaneously drives the reconstruction of oxygen-containing functional groups on the surface, resulting in partial... The group is converted into a more stable form through a dehydrogenation reaction. The bond is partially formed through dehydration condensation. This structure allows for the surface enrichment of carbonyl groups. Photoelectron spectroscopy Analysis shows that, Surface carbonyl carbon The proportion reached Compared to before activation Significant improvement. The carbon materials produced retain a weakly graphitized amorphous carbon structure. It has a high degree of defect, good electrical conductivity, and abundant structural defects. Nitrogen gas. Analysis shows that, The specific surface area reached Total capacity is Significantly higher than . Analysis shows that, The broadened diffraction peaks at these locations correspond to... The crystal planes confirmed that it maintained an amorphous carbon structure with a low degree of graphitization. Raman spectroscopy further confirmed this. Etching primarily increased defect concentration without significantly altering the degree of graphitization. FTIR analysis showed that... exist Characteristic absorption peaks are observed at this location, among which Peak intensity Significantly enhanced, and The weakening of the peak confirms the directional reconstruction of the oxygen-containing functional groups. Simultaneously, the carbonyl group exhibits high polarization. The structure can form locally charged polarized microdomains, and its reversible electron capture and release properties enable it to serve as a key "relay station" for interfacial electron transfer, exhibiting superior electronic regulation capabilities compared to hydroxyl, carboxyl, and ether groups.

[0081] From the perspective of the chemical reaction process, the reason this method achieves the degradation of antibiotics by activated peroxymonosulfate lies in the fact that peroxymonosulfate has a relatively limited ability to oxidize and degrade antibiotics. However, the carbonyl-functionalized carbon particles prepared by this method have... Both antibiotics and [these substances] exhibit interfacial enrichment effects. Under the synergistic effect of an electric field, the carbonyl active site accepts electrons and undergoes directional transfer to [the target site]. Molecules, promote Breakdown, producing sulfate free radicals hydroxyl radicals superoxide radicals and singlet oxygen These reactive oxygen species work together to degrade adsorbed and free antibiotics. Among them, the carbonyl-mediated electron transfer pathway preferentially drives... The generation, Further through disproportionation reaction Coupling reaction with free radicals Transform into This resulted in an oxidation system dominated by non-radical pathways. Quenching experiments and probe analysis showed that... The contribution rates to degradation reached respectively The combined contribution of the two reached ; , This indicates that the non-radical pathway is one of the core features that distinguishes the system described in this invention from traditional radical-dominated systems.

[0082] The catalytic activation process of the method of the present invention includes the following reaction:

[0083] ;

[0084] ;

[0085] ;

[0086] ;

[0087] ;

[0088] ;

[0089] ;

[0090] ;

[0091] The antibiotics targeted by this method are sulfonamide antibiotics (such as sulfamethoxazole, It may be any one of the following: sulfadiazine; sulfadiazine; or fluoroquinolone antibiotics (such as ofloxacin, ciprofloxacin, norfloxacin).

[0092] In practical applications, this method can also be used to remove tricyclic antiepileptic drugs (such as carbamazepine). ), phenolic endocrine disruptors and phenol Recalcitrant organic pollutants. Experiments show that under the above optimal conditions, ciprofloxacin... Removal rate Carbamazepine Removal rate Bisphenol Removal rate ,phenol All reached The above demonstrates that the method described in this invention has a broad-spectrum ability to degrade organic pollutants.

[0093] In specific implementation, the carbonyl functionalized carbon particles are prepared according to the following steps:

[0094] a. Glucose is placed in a tube furnace under an inert atmosphere. Heating rate to Pyrolysis temperature, heat preservation pyrolysis After naturally cooling to room temperature, the mixture is ground and passed through a 100-mesh sieve to obtain glucose-derived carbon. ;

[0095] b. Reconstitute the glucose-derived carbon obtained in step a with potassium hydroxide. By mass ratio range Mix and disperse in an appropriate amount of deionized water, stirring continuously. The above makes Fully impregnate into the carbon skeleton;

[0096] c. The mixture obtained in step b is separated by centrifugation. Collect solid products, at ;

[0097] d. Place the dried mixture obtained in step c in a tube furnace and heat it under an inert atmosphere. Heat down to Thermal insulation and pyrolysis ;

[0098] The product obtained in step e, d, is washed with acid (dilute hydrochloric acid) and then repeatedly washed with deionized water until neutral. ,At Vacuum drying Thus, carbonyl-functionalized carbon particles are obtained. .

[0099] In the above preparation process, the KOH activation process chemically etches the carbon framework, while... Decomposition Gas-assisted pore formation creates abundant pores. Composite structure. The chemical reactions involved in activation are as follows:

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] This hierarchical porous structure not only fully exposes active sites but also significantly enhances interfacial mass transfer and diffusion kinetics. Orthogonal experimental optimization results show that when… The pyrolysis temperature is Activation temperature is At that time, the material properties are optimal. Material yield Too low This leads to insufficient activation and a low degradation rate. Excessively high Proportion (e.g.) Excessive etching damages the carbon framework, causing the degradation rate to drop to [a lower percentage]. Yield dropped to This indicates that a suitable activation intensity is one of the key features of the present invention.

[0106] During implementation, the applicant optimized the parameter range through experiments. A better parameter selection is that the heating rate in step a is... The pyrolysis temperature is The pyrolysis time is Single-factor experiments showed that, in Within the specified range, the degradation rate initially increases and then stabilizes with increasing pyrolysis temperature. The degradation rate is only It gradually increases with rising temperature. Peak time , The degradation rate did not continue to increase, therefore, [the following was selected] The optimal pyrolysis temperature is achieved while balancing catalytic performance and energy consumption control.

[0107] In practice, a better parameter selection is that the mass ratio of glucose-derived carbon to potassium hydroxide in step b is [missing value]. The stirring time is To better guarantee Fully impregnate the carbon skeleton.

[0108] In practice, a better parameter selection is to set the pyrolysis temperature in step d as follows: The pyrolysis time is This ensures sufficient activation and a stable carbon skeleton structure.

[0109] During implementation, after the degradation reaction is complete, the used carbonyl-functionalized carbon particles undergo regeneration. The regeneration process involves washing the used carbonyl-functionalized carbon particles three times with deionized water. Drying in an oven This allows for recycling and reuse.

[0110] This is because, with increasing reaction cycles, the degradation rate and reaction rate constant of the carbon particle electrode for antibiotics decrease, but remain at a high level. Most of the activity can be restored through simple cleaning and drying. Subsequent experiments showed that after 5 cycles, The degradation efficiency from The rate constant is from ;and of The system degradation rate from The rate constant is from The significant difference between the two indicates that the applied electric field, by continuously supplying an electron supply, is used for... Activation effectively prevents The irreversible oxidation of surface carbonyl groups is consumed, and the shielding effect caused by intermediate product deposition is mitigated. Characterization confirms that, After one reaction in the system, Peak area from Slightly decreased and from In a system without an electric field, the voltage drops significantly. After 5 cycles, Removal rate only from This indicates that the carbonyl functionalized carbon particles prepared by this invention are easy to regenerate and have excellent cycle stability under electric field protection.

[0111] In practical applications, the method described in this invention also has good applicability in actual water bodies. In tap water... middle Removal rate In surface water The removal rate is This demonstrates strong potential for practical applications. Anti-interference experiments with common coexisting substances show that: It has almost no effect on degradation. This may be related to The reaction produces It is also related to its oxidizing ability; It can significantly promote degradation Attributable to chlorine-active species The generation of; It has a certain inhibitory effect on the reaction (reduced to a certain extent). This is attributed to its quenching of reactive oxygen species and competitive occupation of active sites; humic acid Reduce the removal rate to This is attributed to its consumption of reactive oxygen species and occupation of active sites. Overall, the method described in this invention exhibits good resistance to interference from common coexisting substances in water.

[0112] To further study and verify the process, principle, parameter selection, and performance of this method, the applicant conducted the following specific experimental studies. The steps not specifically mentioned in the experiments were consistent with the steps in the above specific implementation methods.

[0113] The applicant first conducted experimental research on the pyrolysis temperature during material preparation in the aforementioned specific implementation process. (See...) Figure 1 As shown, the applicant set the pyrolysis temperature to... , , , and ,by For the target pollutant, in , , The catalytic performance of samples prepared at different temperatures was evaluated under the given conditions. The results showed that... The degradation rate is only As the pyrolysis temperature increases, the degradation rate gradually increases. , ; The degradation rate reaches its peak at that time. ; The degradation rate is ,and Basically the same, only in the front It exhibits a slight kinetic advantage. Considering both catalytic performance and energy consumption, the optimal pyrolysis temperature is determined to be... .

[0114] Figure 2 for Comparison of different quality levels A graph showing the impact of degradation rate. The applicant will... The mass ratios are respectively set as follows: A comparative experiment was conducted. The results showed that... The proportion from hour, Degradation rate from , Meanwhile, the material yield increased from Continue to improve Ratio to At that time, the degradation rate dropped back to Material yield further decreased This indicates Insufficient dosage results in incomplete activation and limited exposure of active sites. Excessive dosage can lead to over-etching, damaging the carbon framework structure and reducing material yield. Therefore, determining the optimal dosage is crucial. mass ratio .

[0115] Figure 3 The images show scanning electron microscope (SEM) images and elemental distributions of the degradation catalytic material before and after the preparation process. The SEM image of GDC shows a smooth, dense blocky structure; The images show SEM images of KGDC at different magnifications, revealing that after activation by KOH, it transforms into loose, rough, and porous layered aggregates with well-developed pores, indicating that KOH etching successfully constructed a porous structure that facilitates the exposure of active sites and the transport of substances. The image shows the overall elemental distribution of KGDC's EDS, indicating that C and O are uniformly distributed in the material, with no other impurity elements. The individual distribution images of each element further confirm the purity of the material.

[0116] Figure 4 Before and after the preparation process of degradation catalytic materials Diffraction patterns. The figure shows a comparison of the XRD patterns of GDC and KGDC; both materials show diffraction patterns. The diffraction peaks at the points shown correspond to the (002) and (100) crystal planes, respectively. This result confirms that KGDC retains an amorphous carbon structure with a low degree of graphitization after activation by KOH. KOH etching does not significantly change the crystal phase structure of the carbon skeleton, and the overall degree of graphitization of the material remains basically unchanged.

[0117] Figure 5 Schematic diagram of the Fourier Transform Infrared (FTIR) spectra of the degradation catalyst material before and after the reaction. The FTIR spectra show GDC and KGDC at... , and It exhibits a characteristic absorption peak at [location missing]. Compared to GDC, KGDC [is more pronounced / is less ...]. The absorption peak intensity is significantly enhanced at this point. The weakening of the absorption peak indicates that KOH activation drove the reconstruction of oxygen-containing functional groups, partially The group is converted into a more stable form through dehydrogenation. The bond is partially formed through dehydration condensation. The structure achieved surface enrichment of carbonyl groups. The positions of the characteristic peaks of KGDC remained largely unchanged after the reaction, indicating that the material structure exhibits good chemical stability during use.

[0118] Figure 6 This is a schematic diagram of the nitrogen adsorption-desorption isotherm (BET) curve for the degradation catalyst material. The isotherms show that both GDC and KGDC are Isotherm characteristics and The branches largely overlap, indicating that micropores are dominant; the pore size distribution shows that the pore size is concentrated in... Present Composite structure. Specific surface area of ​​KGDC He Zong Kongrong All significantly higher than This indicates that KOH activation effectively increased the specific surface area and pore volume, constructing a multi-level porous network that facilitates full exposure of active sites and improved interfacial mass transfer efficiency.

[0119] Figure 7 This diagram illustrates the comparison of SMX degradation rates and degradation reaction rate constants in different systems. Figure 7 (a) Degradation rate curves of SMX in each system, set up for PMS alone, KGDC alone, E alone, Seven comparative systems were used. The results showed that the degradation rates of each system at 60 min were as follows: , , , , , , . Figure 7 (b) represents the reaction rate constants of each system. Comparison chart, , respectively and The system's synergy index is 3.90 times and 4.21 times that of the previous system. The synergy index calculation shows that... , , ,and The value was significantly higher than that of each binary system, confirming a strong synergistic effect among the electric field, carbonyl site, and PMS.

[0120] Figure 8 For degradation catalytic materials A schematic diagram of the cyclic experiment for the degradation of SMX in the system. The figure shows... After 5 cycles, the SMX degradation rate of the system decreased from , from ; and without electric field The system degradation rate from , from The significant difference between the two indicates that the applied electric field, by continuously providing electrons for PMS activation, effectively prevents the irreversible oxidation and consumption of carbonyl groups on the KGDC surface and mitigates the shielding effect caused by intermediate product deposition. After 5 cycles, the TOC removal rate only increased from [previous value]. This indicates that the carbonyl-functionalized carbon particles prepared by this invention are easily regenerated and exhibit excellent cycle stability under electric field protection. In summary, the method described in this invention first prepares a porous carbon particle electrode (KGDC) with abundant carbonyl active sites. This material possesses high specific surface area, a hierarchical porous structure, and excellent conductivity, enabling efficient activation of PMS and exhibiting a significant synergistic effect with an electric field. Combining KGDC with PMS and applying an electric field allows for the degradation of antibiotic-like pollutants. The process has advantages such as high efficiency, no secondary metal pollution, recyclability, strong adaptability, and low energy consumption in degrading antibiotics, and has good prospects for practical application.

Claims

1. A method for degrading antibiotics using peroxymonosulfate activated by an electric field, characterized in that, Carbonyl-functionalized carbon particles and peroxymonosulfate are added to the water to be degraded and dispersed evenly. Then, an electric field is applied to polarize the carbonyl-functionalized carbon particles to form micro-electrolysis units. The carbonyl active sites on the carbonyl-functionalized carbon particles are used to activate the peroxymonosulfate in conjunction with the electric field, thereby achieving the degradation of antibiotics in the water.

2. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 1, characterized in that, The pH range of the water to be degraded is 3-11.

3. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 1, characterized in that, During degradation, the carbonyl functionalized carbon particles and peroxymonosulfate are first added to the water to be degraded and mixed thoroughly, and then an electric field is applied to complete the degradation reaction.

4. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 1, characterized in that, The carbonyl functionalized carbon particles and the electric field are applied by an electric field purification device. The electric field purification device includes a purification cage, which is surrounded by a filter screen to form a cage shape. The filter screen has a pore size smaller than the carbonyl functionalized carbon particles. The purification cage contains a portion of the carbonyl functionalized carbon particles. Two electrodes are arranged at intervals inside the purification cage. The mounting ends of the two electrodes are fixed to a mounting plate at the upper end of the purification cage. An electric stirring device is also provided inside the lower end of the purification cage.

5. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 1, characterized in that, During degradation, the amount of carbonyl functionalized carbon particles added is 0.02-0.2 g / L, the amount of peroxymonosulfate added is 1-5 mM, the current density of the electric field is 5-20 mA / cm², the electrode spacing is 2 cm, the reaction temperature is 15-35℃, and the stirring rate is 500 rpm.

6. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 1, characterized in that, The carbonyl-functionalized carbon particles are porous carbon materials with carbonyl active sites on their surface, obtained by carbonizing glucose at high temperature and then activating and pyrolyzing it with potassium hydroxide.

7. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 6, characterized in that, The antibiotic is at least one of sulfonamide antibiotics or fluoroquinolone antibiotics.

8. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 6, characterized in that, The carbonyl-functionalized carbon particles are prepared according to the following steps: a. Place glucose in a tube furnace and heat it to a pyrolysis temperature of 700-1100℃ at a heating rate of 4-6℃ / min under an inert atmosphere. Hold the temperature for pyrolysis for 1.5-2.5h, and after naturally cooling to room temperature, grind and pass through a 100-mesh sieve to obtain glucose-derived carbon. b. Mix the glucose-derived carbon obtained in step a with potassium hydroxide in a mass ratio of 1 / 4 to 3 / 4, disperse in an appropriate amount of deionized water, and stir continuously for 23-25 ​​hours or more to allow potassium hydroxide to fully impregnate the carbon skeleton. c. The mixture obtained in step b is centrifuged to separate the solid product, which is then vacuum dried at 80°C for 12 hours. d. Place the dried mixture obtained in step c in a tube furnace and heat it to 700-900℃ under an inert atmosphere, and keep it at that temperature for 1.5-2.5 hours for pyrolysis. The product obtained in step e, d, is acid-washed, then repeatedly washed with deionized water until neutral, and finally vacuum-dried at 80°C for 12 hours to obtain carbonyl-functionalized carbon particles.

9. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 8, characterized in that, In step a, the heating rate is 5℃ / min, the pyrolysis temperature is 1000℃, and the pyrolysis time is 2h. In step b, the mass ratio of glucose-derived carbon to potassium hydroxide is 1:2, and the stirring time is 24 hours. In step d, the pyrolysis temperature is 800℃ and the pyrolysis time is 2h.

10. The method for degrading antibiotics using peroxymonosulfate activated by an electric field as described in claim 8, characterized in that, After the degradation reaction is completed, the used carbonyl functionalized carbon particles are regenerated. The regeneration process is as follows: the used carbonyl functionalized carbon particles are washed three times with deionized water and dried in an oven at 60℃ for 12 hours to achieve recycling.

Images