CN114628707A - Modified carbon brush cathode material for microbial electro-Fenton fuel cell and preparation method and application thereof - Google Patents
Modified carbon brush cathode material for microbial electro-Fenton fuel cell and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
Abstract
The invention belongs to the technical field of water treatment processes, and particularly relates to a modified carbon brush cathode material for a microbial electro-Fenton fuel cell, and a preparation method and application thereof. The invention is sequentially subjected to heat activation and H2O2The modified carbon brush cathode material for the microbial electro-Fenton fuel cell is prepared by modification and used in the microbial electro-Fenton fuel cell, and tests prove that the modified carbon brush cathode material not only has higher degradation rate on antibiotic ciprofloxacin hydrochloride, but also can be used for degrading organic dyes such as methyl orange and the like. Therefore, the modified carbon brush cathode material and the microbial fuel cell-electro-Fenton system have wide application prospects in the fields of water body improvement, biological recovery resistance and the like. The cathode material synthesis process disclosed by the invention is easy to operate, does not contain an adhesive, does not contain toxic chemical substances, and has the characteristics of economy, high efficiency, safety, environmental friendliness and contribution to popularization.
Description
Technical Field
The invention belongs to the technical field of water treatment processes, and particularly relates to a modified carbon brush cathode material for a microbial electro-Fenton fuel cell, and a preparation method and application thereof.
Background
In recent years, a large amount of refractory organic pollutants and drug residues enter the environmental water body, so that the problem of serious water pollution is caused. As the most widely used medicine, the use of antibiotics in large quantities (perhaps 10 to 20 ten thousand tons per year) causes the continuous increase of antibiotic residues in water, which not only causes continuous pollution to the water area and land ecosystem, but also influences the supply of drinking water, thus threatening human health.
Ciprofloxacin (CIP) is a synthetic third-generation fluoroquinolone antibiotic and is widely used for the treatment of human bacterial infections due to its broad-spectrum antibacterial activity and good oral absorption effect. As carboxybenzoic acid nucleus on Ciprofloxacin (CIP) has stronger chemical stability, most of CIP can not be completely metabolized in vivo, and according to statistics, 70 percent of unmetabolized CIP is discharged out of a body based on CIP ingested by a human body, and finally enters a sewage treatment link.
The removal of antibiotics such as ciprofloxacin in sewage by using the traditional biological method obviously shows the problem of insufficient removal capability, which also leads to the frequent detection of CIP in surface water and secondary effluent of sewage treatment plants. If antibiotics such as ciprofloxacin are not completely removed or remain, even in a trace concentration, CIP can cause the generation and the transmission of antibiotic resistance, thereby threatening the health of human beings.
Therefore, there is an urgent need to develop an effective method for treating wastewater containing various antibiotics such as CIP to eliminate the potential adverse effects on the water environment.
Currently, Advanced Oxidation Processes (AOPs), such as photocatalytic, photo-fenton, ozone, and electro-fenton processes, are widely used as an effective removal means for removing antibiotic residues and other recalcitrant contaminants. Among them, the E-Fenton method (Electro-Fenton, EF) is one of the most common electrochemical advanced oxidation methods (EAOP), and its high degradation capability has attracted much attention. The electro-Fenton system generates H in situ by electrochemical reaction on a cathode2O2To avoid adding H2O2For example, chinese patent publication No. CN109052578A discloses a method for preparing a modified electrode and a method for treating wastewater in a continuous flow bioelectricity fenton system, which improves the conductivity of the composite material and the catalytic oxygen electron reduction capability of the system by using the modified electrode for wastewater treatment, but still has the problems of insufficient degradation efficiency and high operation cost due to the high energy input required in practical application.
The Microbial Fuel Cell (MFC) is used as a newly developed bioelectrochemical system, and is used for oxidizing organic matters and inorganic matters by using microbes to generate electric power, so that the microbial fuel cell system can be selected as an energy source to provide power for the electro-Fenton reaction, and the continuous in-situ production of H is realized2O2Meanwhile, pollutants such as antibiotics and the like can be effectively degraded.
However, in the prior art, the effect of using the MFC-based in-situ dual-chamber cathode electro-fenton system to degrade antibiotics still does not work well, and compared with the traditional electrochemical method, the cathode electrode material used needs to be modified to improve the degradation performance of the electro-fenton system on pollutants.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a modified carbon brush cathode which has the advantages of excellent catalytic activity, low price and the like, and the preparation process is easy to operate, relatively safe and environment-friendly.
The invention also provides a preparation method of the modified carbon brush cathode material.
The modified carbon brush cathode is applied to an electro-Fenton system based on a microbial fuel cell, and antibiotics or organic dyes are used as target pollutants to degrade the target pollutants.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a modified carbon brush cathode material for a microbial electro-Fenton fuel cell comprises the following steps:
(1) carrying out thermal activation pretreatment on a Carbon Brush (CB):
immersing the Carbon Brush (CB) in pure acetone overnight (18-24 h), then centrifuging to remove the acetone, and calcining at the temperature of 400-500 ℃ for 30-60 minutes to complete the pretreatment;
(2) by means of H2O2Modifying CB by an oxidation method:
immersing pretreated carbon brush in H2O2And heating the carbon brush in the solution in a water bath to 60-120 ℃, keeping the temperature for 1-3 hours for modification treatment, washing the treated carbon brush with deionized water, and then drying the carbon brush in vacuum to obtain the carbon brush.
Specifically, step (2) is H2O2The mass fraction of the solution is 10 percent, H2O2The total volume of the solution is 80-100 mL.
The above process is successively subjected to heat activation and H2O2And modifying to obtain the modified carbon brush cathode material for the microbial electro-Fenton fuel cell.
Furthermore, the invention also provides application of the modified carbon brush cathode material in a microbial fuel cell-electro-Fenton system.
Furthermore, the invention also provides a microbial electro-Fenton fuel cell prepared by using the modified carbon brush cathode material.
Specifically, the microbial electro-Fenton fuel cell takes the modified carbon brush cathode material as a cathode, so that the problem that metal is easily leached out by taking an inorganic metal catalyst as the cathode in the prior art is solved, and meanwhile, the microbial electro-Fenton fuel cell provides bioelectricity as power supply of an electro-Fenton system.
Specifically, the microbial electro-Fenton fuel cell can generate 0.6-0.7V bioelectricity.
Specifically, the microbial electro-fenton fuel cell is a two-chamber microbial fuel cell with a cathode chamber and an anode chamber, and during preparation, the modified carbon brush cathode material is used as an electrode and is placed in the cathode chamber of the microbial fuel cell, the electrolyte in the cathode chamber is an anhydrous sodium sulfate solution with the concentration of 0.05M, and the initial pH of the electrolyte is 3.
Furthermore, the invention also provides application of the microbial electro-Fenton fuel cell in degrading water pollutants.
Specifically, the water pollutant is an antibiotic or an organic dye.
Preferably, the antibiotic is ciprofloxacin hydrochloride; the organic dye is methyl orange.
Compared with the prior art, the invention has the advantages that:
the invention does not adopt a metal catalyst as the cathode of the microbial fuel cell-electro-Fenton system, can overcome the problem that the electro-Fenton system in the prior art is easy to cause metal leaching, and avoids the inherent defect of secondary pollution.
The cathode material synthesis process disclosed by the invention is easy to operate, does not contain an adhesive, does not contain toxic chemical substances, and has the characteristics of economy, high efficiency, safety, environmental friendliness and contribution to popularization.
The invention combines the microbial fuel cell and electro-Fenton into a system, and has the characteristics of good treatment effect, low system energy consumption and simple and convenient operation when degrading the wastewater containing ciprofloxacin hydrochloride and other antibiotics.
Drawings
FIG. 1 is a graph showing the degradation effect of ciprofloxacin hydrochloride (CIP, initial concentration 40 mg/L) of modified carbon brush cathode materials prepared in examples 1 to 4 at different oxidation temperatures (70 ℃, 80 ℃, 90 ℃, 100 ℃) and a control Original CB;
FIG. 2 is a Raman spectrum of a modified carbon brush cathode material prepared at different oxidation temperatures (70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C) and a control Original CB of examples 1-4;
fig. 3 is a cycle test chart of the modified carbon brush cathode material prepared in example 2 for degradation of CIP in a bioelectrical fenton system;
FIG. 4 is a graph showing the degradation effect of methyl orange (initial concentration 40 mg/L) on modified carbon brush cathode materials prepared in examples 1-4 at different oxidation temperatures (70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C) and control Original CB;
fig. 5 is a graph showing performance tests of the modified CB material prepared in example 2 in degrading ciprofloxacin hydrochloride (initial concentration 40 mg/L) at different initial phs in a microbial electro-fenton fuel cell.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. The raw materials and reagents used in the following examples are commercially available or self-made.
Commercial Carbon Brushes (CB) used in the examples were purchased from material of great novelty, inc. The carbon brush electrode material is composed of carbon fibers and high-purity titanium wires, wherein the carbon fibers are cylinders with the diameter of 3 cm and the height of 3 cm, and the high-purity titanium wires are 12 cm long.
Methods for the culture and acclimation of microbial fuel cells are described in the documents J. Zhang, l.l. Chu, z.w. Wang, w. Guo, x. Zhang, r.y. Chen, s.y. Dong, j.h. Sun, Dynamic evaluation of electrochemical and biological services in microbial fuels up to bacterial interaction with aerobic biochemical approach [ J ]. Bioelectrochemistry (136), 107623.
The method for establishing the bioelectricity Fenton system is described in Sathe, S.M., Chakraborty, I., Cheela, V.R.S., Shamik, C., Dubey, B.K., Ghangrekar, M.M., 2021. A novel bio-electro-Fenton process for electrically stimulating a sodium node free water using dual chamber microbial fuel cell, BioResource. Technol. 341.
Example 1
A preparation method of a modified carbon brush cathode material for a microbial electro-Fenton fuel cell comprises the following specific steps:
(1) carrying out thermal activation pretreatment on a Carbon Brush (CB):
immersing a Carbon Brush (CB) with the specification of 3 multiplied by 12 cm into pure acetone overnight, then centrifuging to remove the acetone, and then placing the carbon brush in a muffle furnace to calcine for 30 minutes at 450 ℃ to finish pretreatment;
(2) by means of H2O2Modifying CB by an oxidation method:
immersing the pretreated carbon brush into H with the mass fraction of 10%2O2In solution of H2O2And heating the solution to 70 ℃ in a water bath with the total volume of 90 mL, keeping the temperature for 2 hours for modification treatment, washing the treated carbon brush by using continuously flowing deionized water, and drying the carbon brush in a vacuum drying oven to obtain the carbon brush.
Application example 1
Placing the CB material obtained by modification at the temperature of 70 ℃ in the embodiment 1 in a microbial fuel cell-electro-Fenton system to prepare a microbial electro-Fenton fuel cell, performing degradation performance test, wherein a reaction is performed on ciprofloxacin hydrochloride as a pollutant, and performing test by using a double-chamber microbial fuel cell with a cathode chamber and an anode chamber, wherein the double-chamber microbial fuel cell can generate 0.6-0.7V bioelectricity, and the specific steps are as follows:
the modified carbon brush cathode material prepared in example 1 was placed in a cathode chamber of a microbial fuel cell as an electrode, and an electrolyte in the cathode chamber was 130 mL of an anhydrous sodium sulfate solution having a concentration of 0.05M, and 2.6 mL of ciprofloxacin hydrochloride (CIP) solution having an initial concentration of 2 g/L was added to prepare CIP-Na having a concentration of 40 mg/L and a pH =32SO4A solution; continuously supplying compressed air to the catholyte at a constant flow rate of 0.4L/min, carrying out electro-Fenton reaction, degrading the ciprofloxacin hydrochloride, and measuring the concentration of the ciprofloxacin hydrochloride by adopting a spectrophotometry method.
Sampling time is 0 h, 0.5 h, 1 h, 2 h, 3 h, 6 h, 9 h, 12 h, 24h, 36 h and 48 h respectively, and the concentration of ciprofloxacin hydrochloride is measured by using a spectrophotometer at a maximum wavelength of 272 nm.
The detection result is shown in figure 1, and the test shows that the degradation rate reaches 86.86% after the reaction is carried out for 48 hours.
Example 2
A preparation method of a modified carbon brush cathode material for a microbial electro-Fenton fuel cell comprises the following specific steps:
(1) carrying out thermal activation pretreatment on a Carbon Brush (CB):
immersing a Carbon Brush (CB) with the specification of 3 multiplied by 12 cm into pure acetone overnight, then centrifuging to remove the acetone, and then calcining in a muffle furnace at 450 ℃ for 30 minutes to complete pretreatment;
(2) by means of H2O2Modifying CB by an oxidation method:
immersing the pretreated carbon brush into H with the mass fraction of 10%2O2In solution of H2O2And heating the carbon brush to 80 ℃ in a water bath with the total volume of 90 mL, keeping the temperature for 2 hours for modification treatment, washing the treated carbon brush with continuously flowing deionized water, and drying the carbon brush in a vacuum drying oven to obtain the carbon brush.
Application example 2
Placing the CB material obtained by modification at the temperature of 80 ℃ in the embodiment 2 in a microbial fuel cell-electro-Fenton system to prepare a microbial electro-Fenton fuel cell, performing degradation performance test, wherein a reaction is carried out on ciprofloxacin hydrochloride as a pollutant, and performing test by adopting a double-chamber microbial fuel cell with a cathode chamber and an anode chamber, wherein the double-chamber microbial fuel cell can generate 0.6-0.7V bioelectricity, and the specific steps are as follows:
the modified carbon brush cathode material prepared in example 2 was placed in a cathode chamber of a microbial fuel cell as an electrode, and an electrolyte in the cathode chamber was 130 mL of an anhydrous sodium sulfate solution with a concentration of 0.05M, and 2.6 mL of ciprofloxacin hydrochloride (CIP) solution with an initial concentration of 2 g/L was added to prepare CIP-Na with a concentration of 40 mg/L and a pH =32SO4A solution; continuously supplying compressed air to the catholyte at a constant flow rate of 0.4L/min, carrying out electro-Fenton reaction, degrading the ciprofloxacin hydrochloride, and measuring the concentration of the ciprofloxacin hydrochloride by adopting a spectrophotometry method.
Sampling time is 0 h, 0.5 h, 1 h, 2 h, 3 h, 6 h, 9 h, 12 h, 24h, 36 h and 48 h respectively, and the concentration of ciprofloxacin hydrochloride is measured by using a spectrophotometer at a maximum wavelength of 272 nm.
The detection result is shown in figure 1, and the test shows that the degradation rate reaches 94.05% after the reaction is carried out for 48 hours.
Example 3
A preparation method of a modified carbon brush cathode material for a microbial electro-Fenton fuel cell comprises the following specific steps:
(1) carrying out thermal activation pretreatment on a Carbon Brush (CB):
immersing a Carbon Brush (CB) with the specification of 3 multiplied by 12 cm into pure acetone overnight, then centrifuging to remove the acetone, and then calcining in a muffle furnace at 450 ℃ for 30 minutes to complete pretreatment;
(2) by means of H2O2Modifying CB by an oxidation method:
immersing the pretreated carbon brush into H with the mass fraction of 10%2O2In solution of H2O2The total volume of the solution is 90 mL, the solution is heated to 90 ℃ in a water bath and is kept for 2 hours for modification treatment, and the treated carbon brush is subjected to continuous flowWashing with dynamic deionized water, and drying in a vacuum drying oven.
Application example 3
Placing the CB material obtained by modification at the temperature of 90 ℃ in the embodiment 3 in a microbial fuel cell-electro-Fenton system to prepare a microbial electro-Fenton fuel cell, performing degradation performance test, wherein a reaction is performed on ciprofloxacin hydrochloride as a pollutant, and performing test by using a double-chamber microbial fuel cell with a cathode chamber and an anode chamber, wherein the double-chamber microbial fuel cell can generate 0.6-0.7V bioelectricity, and the specific steps are as follows:
the modified carbon brush cathode material prepared in example 3 was placed in a cathode chamber of a microbial fuel cell as an electrode, and an electrolyte in the cathode chamber was 130 mL of an anhydrous sodium sulfate solution having a concentration of 0.05M, and 2.6 mL of ciprofloxacin hydrochloride (CIP) solution having an initial concentration of 2 g/L was added to prepare CIP-Na having a concentration of 40 mg/L and a pH =32SO4A solution; continuously supplying compressed air to the catholyte at a constant flow rate of 0.4L/min, carrying out electro-Fenton reaction, degrading the ciprofloxacin hydrochloride, and measuring the concentration of the ciprofloxacin hydrochloride by adopting a spectrophotometry method.
The sampling time is 0 h, 0.5 h, 1 h, 2 h, 3 h, 6 h, 9 h, 12 h, 24h, 36 h and 48 h respectively, and the concentration of ciprofloxacin hydrochloride is measured by using a spectrophotometer at a maximum wavelength of 272 nm.
The detection result is shown in figure 1, and the test shows that the degradation rate reaches 85.31% after the reaction is carried out for 48 hours.
Example 4
A preparation method of a modified carbon brush cathode material for a microbial electro-Fenton fuel cell comprises the following specific steps:
(1) carrying out thermal activation pretreatment on a Carbon Brush (CB):
immersing a Carbon Brush (CB) with the specification of 3 multiplied by 12 cm into pure acetone overnight, then centrifuging to remove the acetone, and then calcining in a muffle furnace at 450 ℃ for 30 minutes to complete pretreatment;
(2) by means of H2O2Modifying CB by an oxidation method:
pretreating carbonBrush immersion H10% by mass2O2In solution, H2O2And (3) heating the solution to 100 ℃ in a water bath with the total volume of 90 mL, keeping the temperature for 2 hours for modification treatment, washing the treated carbon brush by using continuously flowing deionized water, and drying the carbon brush in a vacuum drying oven to obtain the carbon brush.
Application example 4
Placing the CB material obtained by modification at the temperature of 100 ℃ in the embodiment 4 in a microbial fuel cell-electro-Fenton system to prepare a microbial electro-Fenton fuel cell, performing degradation performance test, wherein a reaction is performed on ciprofloxacin hydrochloride as a pollutant, and performing test by using a double-chamber microbial fuel cell with a cathode chamber and an anode chamber, wherein the double-chamber microbial fuel cell can generate 0.6-0.7V bioelectricity, and the specific steps are as follows:
the modified carbon brush cathode material prepared in example 4 was placed in a cathode chamber of a microbial fuel cell as an electrode, and an electrolyte in the cathode chamber was 130 mL of an anhydrous sodium sulfate solution having a concentration of 0.05M, and 2.6 mL of ciprofloxacin hydrochloride (CIP) solution having an initial concentration of 2 g/L was added to prepare CIP-Na having a concentration of 40 mg/L and a pH =32SO4A solution; continuously supplying compressed air to the catholyte at a constant flow rate of 0.4L/min, carrying out electro-Fenton reaction, degrading the ciprofloxacin hydrochloride, and measuring the concentration of the ciprofloxacin hydrochloride by adopting a spectrophotometry method.
Sampling time is 0 h, 0.5 h, 1 h, 2 h, 3 h, 6 h, 9 h, 12 h, 24h, 36 h and 48 h respectively, and the concentration of ciprofloxacin hydrochloride is measured by using a spectrophotometer at a maximum wavelength of 272 nm.
The detection result is shown in figure 1, and the test shows that the degradation rate reaches 90.36% after the reaction is carried out for 48 hours.
Comparative example 1
The method for degrading the ciprofloxacin hydrochloride in the microbial electro-Fenton fuel cell directly uses a carbon brush (origin CB) subjected to thermal activation pretreatment without modification treatment, wherein the method for thermally activating the carbon brush is the same as that of example 1, and the performance test for degrading the ciprofloxacin hydrochloride comprises the following specific steps:
placing an unmodified carbon brush cathode material serving as an electrode in a cathode chamber of a microbial fuel cell, wherein an electrolyte in the cathode chamber is an anhydrous sodium sulfate solution containing 0.05M, and a ciprofloxacin hydrochloride solution with the initial concentration of 40 mg/L and the initial pH of 3 is added; continuously supplying compressed air to the catholyte at a constant flow rate of 0.4L/min, carrying out electro-Fenton reaction, degrading the ciprofloxacin hydrochloride, and measuring the concentration of the ciprofloxacin hydrochloride by adopting a spectrophotometry method.
Sampling time is 0 h, 0.5 h, 1 h, 2 h, 3 h, 6 h, 9 h, 12 h, 24h, 36 h and 48 h respectively, and the concentration of ciprofloxacin hydrochloride is measured by using a spectrophotometer at a maximum wavelength of 272 nm.
The detection result is shown in figure 1, and the test shows that the degradation rate reaches 48.38% after the reaction is carried out for 48 hours.
Fig. 2 is a raman spectrum of the modified carbon brush cathode materials of examples 1, 2, 3 and 4 and the unmodified carbon brush cathode material of comparative example 1, and it can be seen from fig. 2 that the intensity ratio of the D and G peaks of the activated product is slightly increased, indicating that some defects are generated on the surface of the CB electrode by the activation process.
Test example 1
Further, the invention also provides a cycle test of the modified carbon brush cathode material prepared in the example 2 for degrading CIP in a bioelectricity Fenton system, and specifically, a new cycle test period can be started only by replacing the catholyte again during the test.
The determination result is shown in fig. 3, after five cycles of continuous operation, the degradation efficiency of CIP is not obviously reduced, and the degradation rate can still reach 91% after 48 hours. The system is stable and efficient in the long-term operation process, and the modified carbon brush electrode material can be repeatedly used in multiple cycles.
Test example 2
Further, the present invention also measured the performance test of the modified CB materials of examples 1, 2, 3, and 4 and the carbon brush (Original CB) of comparative example 1 for degrading methyl orange in microbial electro-fenton fuel cell, and the specific steps and measuring method are the same as those of application example 1, wherein the difference from application example 1 is that the initial concentration of Methyl Orange (MO) is 40 mg/L and the initial pH is 3.
The measurement result is shown in fig. 4, which shows that the CB material obtained by modifying the material in example 2 at 80 ℃ has the best degradation performance of MO, and can reach a removal rate of 99.4%.
Test example 3
Furthermore, the invention also measures the performance test of the CB material obtained by modification in the example 2 in degrading ciprofloxacin hydrochloride with different initial pH values in a microbial electro-Fenton fuel cell, and the specific steps and the measuring method are the same as the application example 2, wherein the differences from the application example 2 are that the initial pH values of the ciprofloxacin hydrochloride are 1, 3, 5 and 7 respectively.
The results are shown in FIG. 5, and it can be seen from FIG. 5 that the optimum catholyte pH for CIP degradation in the present system is 3.
In summary, the carbon brush is sequentially subjected to heat activation and H2O2The modified carbon brush cathode material prepared by modification is used in a microbial electro-Fenton fuel cell, and tests prove that the modified carbon brush cathode material not only has higher degradation rate on antibiotic ciprofloxacin hydrochloride, but also can be used for degrading organic dyes such as methyl orange and the like. Therefore, the modified carbon brush cathode material and the microbial fuel cell-electro-Fenton system have wide application prospects in the fields of water body improvement, biological recovery resistance and the like.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of a modified carbon brush cathode material for a microbial electro-Fenton fuel cell is characterized by comprising the following steps:
(1) carrying out thermal activation pretreatment on the carbon brush:
immersing the carbon brush into pure acetone for treatment for 18-24h, then centrifuging to remove the acetone, and then calcining at the temperature of 400-500 ℃ for 30-60 min to complete pretreatment;
(2) by means of H2O2Modifying CB by an oxidation method:
immersing pretreated carbon brush in H2O2Heating the solution to 60-120 ℃ and keeping the temperature for 1-3 hours for modification treatment, washing and drying to obtain the catalyst.
2. The method according to claim 1, wherein H in the step (2)2O2The mass fraction of the solution is 10 percent, H2O2The total volume of the solution is 80-100 mL.
3. A modified carbon brush cathode material prepared by the method of any one of claims 1 or 2.
4. The use of the modified carbon brush cathode material of claim 3 in a microbial fuel cell-electro-fenton system.
5. A microbial electro-Fenton fuel cell prepared by using the modified carbon brush cathode material of claim 3.
6. The microbial electro-fenton fuel cell according to claim 5, wherein the microbial electro-fenton fuel cell is manufactured by using the modified carbon brush cathode material as a cathode and using a two-chamber microbial fuel cell as an electric power supply, and the modified carbon brush cathode material is placed as an electrode in a cathode chamber of the microbial fuel cell, and an electrolyte in the cathode chamber is an anhydrous sodium sulfate solution having a concentration of 0.05M, and the initial pH of the electrolyte is 3.
7. Use of the microbial electro-fenton fuel cell of claim 5 for degrading water pollutants.
8. The use of claim 7, wherein the water body contaminant is an antibiotic or an organic dye.
9. The use of claim 8, wherein the antibiotic is ciprofloxacin hydrochloride; the organic dye is methyl orange.
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