CN113270602B - Carbon-based biological anode, preparation method thereof and microbial fuel cell - Google Patents

Carbon-based biological anode, preparation method thereof and microbial fuel cell Download PDF

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CN113270602B
CN113270602B CN202110541203.1A CN202110541203A CN113270602B CN 113270602 B CN113270602 B CN 113270602B CN 202110541203 A CN202110541203 A CN 202110541203A CN 113270602 B CN113270602 B CN 113270602B
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carbon
anode
sisal fibers
based biological
microbial fuel
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CN113270602A (en
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杜锐
石张延
余传柏
饶文辉
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Guilin University of Technology
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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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a carbon-based biological anode, a preparation method thereof and a microbial fuel cell, and belongs to the technical field of microbial fuel cells. The preparation method comprises the following steps: 1) cleaning and shearing sisal fibers into small sections, and acidizing the small sections of the sisal fibers; 2) mixing the acidified sisal fibers with an iron source catalyst, grinding and carbonizing to obtain a fibrous carbon material; 3) dissolving the obtained fibrous carbon material with hydrochloric acid solution to remove iron-containing substances, cleaning, and performing ball milling to obtain a black powdery sample; 4) and dissolving the obtained black powdery sample in distilled water, uniformly stirring, transferring to a high-pressure reaction kettle, and carrying out hydrothermal reaction to obtain the carbon-based biological anode. The carbon-based biological anode has good biocompatibility, larger specific surface area and abundant pore structures, has good electrical conductivity, and can provide an ideal carrier for the attachment of microorganisms and the transfer of electrons.

Description

Carbon-based biological anode, preparation method thereof and microbial fuel cell
Technical Field
The invention relates to the technical field of microbial fuel cells, in particular to a carbon-based biological anode, a preparation method thereof and a microbial fuel cell.
Background
A Microbial Fuel Cell (MFC) is a device that degrades organic substances using microorganisms, thereby directly converting chemical energy stored in the organic substances into electrical energy. Therefore, the microbial fuel cell is a novel electrochemical device which combines the solution of environmental pollution with the production of new energy, and can treat sewage and convert organic matters in the sewage into electric energy by degrading the organic matters in the sewage in the process of treating the sewage. The characteristics and catalytic activity of the electrochemically active microorganisms of the anode are one of the key factors influencing the electricity generation efficiency of the microbial fuel cell.
Although the traditional carbon electrode material (anode material) of the microbial fuel cell has better conductivity and chemical stability, the material can provide few attachment sites for microorganisms, and has limited effect on improving the electrochemical activity of the surface of the electrode material.
Disclosure of Invention
The invention provides a carbon-based biological anode, a preparation method thereof and a microbial fuel cell, aiming at the problems, the carbon-based biological anode has good biocompatibility, larger specific surface area and abundant pore structures, is suitable for the attachment and growth of microorganisms, has good electrical conductivity, can provide an ideal carrier for the attachment and electron transfer of the microorganisms, and provides a better environment for the growth of the microorganisms.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a carbon-based biological anode comprises the following steps:
(1) rubbing and cleaning the sisal fibers, cutting the sisal fibers into small sections with the length of 1-2cm, acidizing the small sections of the cut sisal fibers by using a hydrochloric acid solution, washing the acidized sisal fibers, and drying the washed sisal fibers for later use;
(2) mixing the acidified sisal fibers with a certain mass of iron source catalyst, and grinding for 1-2h by using a ball mill; after washing and drying the mixture after grinding treatment, putting the mixture into a tube furnace for carbonization for 2-2.5h under inert atmosphere, wherein the carbonization temperature is 700-;
(3) dissolving the fibrous carbon material obtained in the step (2) by using 3-5wt% hydrochloric acid solution to remove iron-containing substances, and repeatedly washing the fibrous carbon material by using deionized water and ethanol in sequence until the fibrous carbon material is neutral; putting the neutral fiber carbon material into a ball mill for ball milling and crushing for 5-6h, and sieving to obtain a black powder sample;
(4) and (3) dissolving the black powdery sample obtained in the step (3) in a proper amount of distilled water, uniformly stirring, transferring to a polytetrafluoroethylene lining of a high-pressure reaction kettle, transferring the reaction kettle to a blast drying box, carrying out hydrothermal treatment at the temperature of 120-160 ℃ for 5-6h, filtering, cleaning and drying the sample obtained after the reaction is finished to obtain a sisal fiber activated carbon black powder sample, namely the carbon-based biological anode.
Preferably, the concentration of the hydrochloric acid solution during the acidification treatment in step (1) is 5 to 10 wt%. The acid solution with the concentration is adopted for acid treatment, and the main effect is to treat inorganic residues in the sisal fibers by using strong acid, and simultaneously, the sisal fibers before carbonization can be pretreated, so that the pore forming rate of the sisal fiber activated carbon in the carbonization process is improved, and further more attachment sites are provided for microorganisms.
Preferably, the iron source catalyst in the step (2) is one or more than two of ferrous oxide, ferric oxide and ferroferric oxide. The main effect of mixing the acidified sisal fibers with a certain mass of iron source catalyst and then grinding the mixture by using a ball mill is to reduce the graphitization temperature required by the carbonization of the sisal fibers by using the iron source catalyst so as to improve the graphitization degree of the obtained sisal fiber activated carbon, so that a porous sisal fiber activated carbon biological anode with perfectly balanced graphitization degree and porosity is obtained after carbonization, the conductivity of the biological anode is further improved, and the subsequent electron transfer in the electrochemical reaction process is facilitated.
Preferably, the mass of the iron-source catalyst in the step (2) accounts for 15-18wt% of the mass of the sisal fibers, and the optimized mass ratio enables the acidified sisal fibers and the iron-source catalyst to be fully ground and mixed, so that the iron-source catalyst can be more fully contacted with the sisal fibers, and the required graphitization temperature for carbonization of the sisal fibers is further reduced.
Preferably, the specific process of step (4) is as follows: and (3) putting 70mL of distilled water into a beaker, adding 1g of black powder sample, transferring the sample into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into an air-blowing drying box, carrying out hydrothermal treatment at the temperature of 120-160 ℃ for 5-6h, filtering and washing the reaction kettle with absolute ethyl alcohol after the reaction kettle is naturally cooled to room temperature, and drying the reaction kettle in the air-blowing drying box at the temperature of 80 ℃ for 12h to obtain the carbon-based biological anode.
The invention also provides the carbon-based biological anode prepared by the preparation method.
The invention also provides a microbial fuel cell which comprises the carbon-based biological anode, and the preparation method of the microbial fuel cell comprises the following steps:
dissolving the carbon-based biological anode in deionized water, mixing the carbon-based biological anode with an anode catalyst, and transferring the mixture into an anode reaction tank; cleaning the cathode, placing the cathode into a cathode reaction tank, adding a proton exchange membrane at the contact position of the cathode and anode reaction tanks, respectively sealing the cathode chamber and the anode chamber, leading out anode electrons from the anode chamber by using a lead, connecting the anode electrons in series with an external resistor and then connecting the anode electrons into the cathode chamber.
Preferably, the preparation method of the anode catalyst comprises the following steps:
(1) weighing a certain amount of glucose, ammonium sulfate and potassium dihydrogen phosphate, adding into sewage, stirring under a sealed condition until the glucose, the ammonium sulfate and the potassium dihydrogen phosphate are completely dissolved to obtain an anaerobic bacteria domestication nutrient solution;
(2) mixing the anaerobic bacteria domestication nutrient solution with anaerobic sludge in a sewage treatment plant to obtain slurry, sealing and storing for 20 days, and screening out anaerobic bacteria which are the needed anode catalyst.
The anode catalyst is simple and easy to obtain, and has higher catalytic activity on the carbon-based biological anode obtained after sisal fiber treatment, so that the energy conversion efficiency in the electrochemical reaction process is further improved.
Preferably, the molar ratio of the glucose to the ammonium sulfate to the potassium dihydrogen phosphate to the sewage is 8-15:10-16:12-18:100, so as to improve the biological activity of anaerobic bacteria; the concentration of suspended solids in the slurry is 5-8 g/L.
Preferably, the wire is one of a titanium wire, a molybdenum wire and a copper wire, and the cathode is one of a carbon felt, a carbon brush, carbon paper and carbon fiber cloth.
By adopting the technical scheme, the invention has the beneficial effects that:
the carbon-based biological anode is prepared by using the sisal fiber activated carbon obtained after the treatment of the sisal fibers, so that the preparation method of the carbon-based biological anode is environment-friendly and economical in cost, the biological anode prepared by the method has good biocompatibility, large specific surface area and rich pore structures, and is suitable for the attachment growth of microorganisms, the biological anode has good electrical conductivity, an ideal carrier can be provided for the attachment of the microorganisms and the transmission of electrons, and a better environment is provided for the growth of the microorganisms. Electrochemical tests on the microbial fuel cell prepared by the carbon-based biological anode show that the electricity-generating microbes on the anode material have better adaptability to the environment in the reaction process, and can effectively convert organic matters in wastewater into electric energy.
Drawings
FIG. 1 is a scanning electron microscope image of a carbon-based bioanode of the present invention at a low magnification;
FIG. 2 is a scanning electron microscope image of a carbon-based bioanode of the present invention at high magnification;
FIG. 3 is a graph showing the change of voltage with time in one cycle of Microbial Fuel Cells (MFCs) of example 1 of the present invention and a comparative example;
fig. 4 is a graph showing the change of the COD concentration of the bioanode over time in one complete cycle of electricity generation for Microbial Fuel Cells (MFCs) of example 1 of the present invention and comparative example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 invention.
Example 1
A preparation method of a carbon-based biological anode comprises the following steps:
(1) rubbing and cleaning the sisal fibers, cutting the sisal fibers into small sections with the length of 1-2cm, carrying out acidification treatment on the small sections of the cut sisal fibers by using a hydrochloric acid solution with the concentration of 10wt%, and then washing and drying the sisal fibers after the acidification treatment for later use;
(2) mixing the acidified sisal fibers with a certain mass of ferric oxide, and grinding for 1h by using a ball mill, wherein the mass of the ferric oxide accounts for 15wt% of the mass of the sisal fibers; after washing and drying the mixture after grinding, putting the mixture into a tubular furnace for carbonization for 2 hours in an inert atmosphere, wherein the carbonization temperature is 900 ℃, the heating rate is 3 ℃/min, and after the furnace temperature is cooled to room temperature, sieving the mixture by a 200-mesh sieve to obtain a fibrous carbon material;
(3) dissolving the fibrous carbon material obtained in the step (2) by using 5wt% hydrochloric acid solution to remove iron-containing substances, and repeatedly washing the fibrous carbon material by using deionized water and ethanol in sequence until the fibrous carbon material is neutral; putting the neutral fiber carbon material into a planetary ball mill, and ball-milling and crushing for 5 hours at the rotating speed of 35r/s to prepare a black powder sample;
(4) putting 70mL of distilled water into a beaker, adding 1g of black powder sample, transferring the sample into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into an air-blast drying oven, carrying out hydrothermal treatment for 6h at 140 ℃, filtering and washing the product with absolute ethyl alcohol after the product is naturally cooled to room temperature, and drying the product for 12h at 80 ℃ in the air-blast drying oven to obtain a sisal fiber activated carbon black powder sample, namely the carbon-based biological anode.
The microbial fuel cell of the embodiment includes the carbon-based bioanode obtained by the preparation method, and the preparation method of the microbial fuel cell includes:
dissolving the carbon-based biological anode in deionized water, mixing the carbon-based biological anode with an anode catalyst, and transferring the mixture into an anode reaction tank; cleaning a carbon fiber cloth cathode, putting the carbon fiber cloth cathode into a cathode reaction tank, adding a proton exchange membrane at the contact position of the cathode reaction tank and the anode reaction tank, respectively sealing a cathode chamber and an anode chamber, leading out anode electrons from the anode chamber by using a titanium wire, connecting the anode electrons in series with an external resistor of 1000 omega, and then connecting the anode chamber and the anode chamber. Then the reaction device is placed in a constant temperature incubator, in order to ensure that the anode is fully and uniformly mixed and the anode catalyst is better dispersed, the invention also continuously stirs the anolyte in the reaction process, and the temperature during the stirring is 50 ℃.
The preparation method of the anode catalyst comprises the following steps:
(1) weighing a certain amount of glucose, ammonium sulfate and potassium dihydrogen phosphate, adding into sewage, stirring under a sealed condition until the glucose, the ammonium sulfate and the potassium dihydrogen phosphate are completely dissolved to obtain an anaerobic bacteria domestication nutrient solution; in this embodiment, the molar ratio of the glucose, the ammonium sulfate, the potassium dihydrogen phosphate and the sewage is 15:16:18: 100;
(2) mixing the anaerobic bacteria domestication nutrient solution with anaerobic sludge in a sewage treatment plant to obtain slurry with the suspended solid concentration of 6-7g/L, and sealing and storing for about 20 days to screen out anaerobic bacteria which are the required anode catalyst.
Applicants also analyzed the microscopic morphology of the carbon-based bioanode prepared in this example (fig. 1 and 2), and performed electrochemical testing of the microbial fuel cell prepared using the carbon-based bioanode (fig. 3 and 4).
Example 2
A preparation method of a carbon-based biological anode comprises the following steps:
(1) rubbing and cleaning the sisal fibers, cutting the sisal fibers into small sections with the length of 1-2cm, carrying out acidification treatment on the small sections of the cut sisal fibers by using a hydrochloric acid solution with the concentration of 5wt%, and then washing and drying the sisal fibers after the acidification treatment for later use;
(2) mixing the acidified sisal fibers with a certain mass of ferrous oxide, and grinding for 1h by using a ball mill, wherein the mass of the ferrous oxide accounts for 18wt% of the mass of the sisal fibers; after washing and drying the mixture after grinding, putting the mixture into a tubular furnace for carbonization for 2 hours in an inert atmosphere, wherein the carbonization temperature is 1200 ℃, the heating rate is 4 ℃/min, and after the furnace temperature is cooled to room temperature, sieving the mixture by a 200-mesh sieve to obtain a fibrous carbon material;
(3) dissolving the fibrous carbon material obtained in the step (2) by using 3wt% hydrochloric acid solution to remove iron-containing substances, and repeatedly washing the fibrous carbon material by using deionized water and ethanol in sequence until the fibrous carbon material is neutral; putting the neutral fiber carbon material into a planetary ball mill, and ball-milling and crushing for 5 hours at the rotating speed of 35r/s to prepare a black powder sample;
(4) putting 70mL of distilled water into a beaker, adding 1g of black powder sample, transferring the sample into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into an air-blast drying oven, carrying out hydrothermal treatment for 6h at 150 ℃, filtering and washing the product with absolute ethyl alcohol after the product is naturally cooled to room temperature, and drying the product for 12h at 80 ℃ in the air-blast drying oven to obtain a sisal fiber activated carbon black powder sample, namely the carbon-based biological anode.
The microbial fuel cell of the embodiment includes the carbon-based bioanode obtained by the preparation method, and the preparation method of the microbial fuel cell includes:
dissolving the carbon-based biological anode in deionized water, mixing the carbon-based biological anode with an anode catalyst, and transferring the mixture into an anode reaction tank; cleaning a carbon fiber cloth cathode, putting the carbon fiber cloth cathode into a cathode reaction tank, adding a proton exchange membrane at the contact position of the cathode reaction tank and the anode reaction tank, respectively sealing a cathode chamber and an anode chamber, leading out anode electrons from the anode chamber by using a titanium wire, connecting the anode electrons in series with an external resistor of 1000 omega, and then connecting the anode chamber and the anode chamber. And then placing the reaction device in a constant-temperature incubator, and continuously stirring the anolyte during the reaction, wherein the stirring temperature is 30 ℃.
The preparation method of the anode catalyst comprises the following steps:
(1) weighing a certain amount of glucose, ammonium sulfate and potassium dihydrogen phosphate, adding into sewage, stirring under a sealed condition until the glucose, the ammonium sulfate and the potassium dihydrogen phosphate are completely dissolved to obtain an anaerobic bacteria domestication nutrient solution; in the embodiment, the molar ratio of the glucose, the ammonium sulfate, the potassium dihydrogen phosphate and the sewage is 10:14:16: 100;
(2) mixing the anaerobic bacteria domestication nutrient solution with anaerobic sludge in a sewage treatment plant to obtain slurry with the suspended solid concentration of 7-8g/L, and sealing and storing for about 20 days to screen out anaerobic bacteria which are the required anode catalyst.
The results of the topographic analysis and electrochemical testing of this example are the same as example 1.
Example 3
A preparation method of a carbon-based biological anode comprises the following steps:
(1) rubbing and cleaning the sisal fibers, cutting the sisal fibers into small sections with the length of 1-2cm, carrying out acidification treatment on the small sections of the cut sisal fibers by using a hydrochloric acid solution with the concentration of 5wt%, and then washing and drying the sisal fibers after the acidification treatment for later use;
(2) mixing the acidified sisal fibers with ferroferric oxide with a certain mass, and grinding the mixture for 2 hours by using a ball mill, wherein the ferroferric oxide accounts for 18wt% of the sisal fibers; after washing and drying the mixture after grinding, putting the mixture into a tube furnace for carbonization for 2.5 hours under inert atmosphere, wherein the carbonization temperature is 700 ℃, the heating rate is 3 ℃/min, and after the furnace temperature is cooled to room temperature, sieving the mixture through a 200-mesh sieve to obtain a fibrous carbon material;
(3) dissolving the fibrous carbon material obtained in the step (2) by using 3wt% hydrochloric acid solution to remove iron-containing substances, and repeatedly washing the fibrous carbon material by using deionized water and ethanol in sequence until the fibrous carbon material is neutral; putting the neutral fiber carbon material into a planetary ball mill, and ball-milling and crushing for 6 hours at the rotating speed of 35r/s to prepare a black powder sample;
(4) putting 70mL of distilled water into a beaker, adding 1g of black powder sample, transferring the sample into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into an air-blast drying oven, carrying out hydrothermal treatment for 6h at 160 ℃, filtering and washing the product with absolute ethyl alcohol after the product is naturally cooled to room temperature, and drying the product for 12h at 80 ℃ in the air-blast drying oven to obtain a sisal fiber activated carbon black powder sample, namely the carbon-based biological anode.
The microbial fuel cell of the embodiment includes the carbon-based bioanode obtained by the preparation method, and the preparation method of the microbial fuel cell includes:
dissolving the carbon-based biological anode in deionized water, mixing the carbon-based biological anode with an anode catalyst, and transferring the mixture into an anode reaction tank; cleaning a carbon fiber cloth cathode, putting the carbon fiber cloth cathode into a cathode reaction tank, adding a proton exchange membrane at the contact position of the cathode reaction tank and the anode reaction tank, respectively sealing a cathode chamber and an anode chamber, leading out anode electrons from the anode chamber by using a titanium wire, connecting the anode electrons in series with an external resistor of 1000 omega, and then connecting the anode chamber and the anode chamber. And then placing the reaction device in a constant-temperature incubator, and continuously stirring the anolyte during the reaction process, wherein the stirring temperature is 60 ℃.
The preparation method of the anode catalyst comprises the following steps:
(1) weighing a certain amount of glucose, ammonium sulfate and potassium dihydrogen phosphate, adding into sewage, stirring under a sealed condition until the glucose, the ammonium sulfate and the potassium dihydrogen phosphate are completely dissolved to obtain an anaerobic bacteria domestication nutrient solution; in this embodiment, the molar ratio of the glucose, the ammonium sulfate, the potassium dihydrogen phosphate and the sewage is 8:10:12: 100;
(2) mixing the anaerobic bacteria domestication nutrient solution with anaerobic sludge in a sewage treatment plant to obtain slurry with the suspended solid concentration of 5-6g/L, and sealing and storing for about 20 days to screen out anaerobic bacteria which are the required anode catalyst.
The results of the topographic analysis and electrochemical testing of this example are the same as example 1.
Comparative example
In this comparative example, the procedure was the same as in example 1 except that the carbon-based bioanode was prepared in a different manner from example 1.
In the comparative example, the chopped segments of sisal fibers in the preparation method of the carbon-based bioanode are not acidified by using a hydrochloric acid solution, and are not ground after being mixed with an iron source catalyst with a certain mass. Specifically, the preparation method of the carbon-based bioanode of the comparative example comprises the following steps:
(1) rubbing and cleaning sisal fiber, cutting into small sections with the length of 1cm, and placing the small sections in a crucible; carbonizing in a tube furnace under inert atmosphere for 2h at 900 deg.C at a heating rate of 3 deg.C/min, cooling to room temperature, and ball milling the obtained fibrous carbon material in a planetary ball mill at a rotation speed of 35r/s for 5h to obtain black powder sample;
(2) dissolving the black powdery sample obtained in the step (1) in a proper amount of distilled water, uniformly stirring, transferring to a polytetrafluoroethylene lining of a high-pressure reaction kettle, transferring the reaction kettle to a blast drying oven, carrying out hydrothermal treatment for 6 hours at 140 ℃, filtering, cleaning and drying the sample obtained after the reaction is finished to obtain a black powdery sample, namely the carbon-based electrode.
The electrochemical data of the comparative example are shown in fig. 3 and 4, and it can be seen from the comparison between the comparative example and the data of example 1 in fig. 3 and 4 that the carbon-based bioanode prepared by the present invention has more excellent conductivity and biocompatibility, and simultaneously has a larger specific surface area, which is beneficial to the growth and propagation of microorganisms in the electrochemical reaction process, and improves the electron transfer rate. This allows the Microbial Fuel Cell (MFC) output voltage after startup to reach a maximum value in a short time and to be maintained for a certain period of time. Meanwhile, in a complete electrogenesis period, the anode COD concentration is obviously reduced along with the lengthening of the retention time, which shows that the electrogenesis microorganisms on the anode material have better adaptability to the environment in the reaction process and can effectively convert the organic matters in the wastewater into electric energy. Therefore, the method has great significance for the prepared carbon-based biological anode by treating the sisal fibers with strong acid, mixing the acidified sisal fibers with a certain mass of iron source catalyst and then grinding the mixture with a ball mill.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.

Claims (10)

1. A preparation method of a carbon-based biological anode is characterized by comprising the following steps:
(1) rubbing and cleaning the sisal fibers, cutting the sisal fibers into small sections with the length of 1-2cm, acidizing the small sections of the cut sisal fibers by using a hydrochloric acid solution, washing the acidized sisal fibers, and drying the washed sisal fibers for later use;
(2) mixing the acidified sisal fibers with a certain mass of iron source catalyst, and grinding for 1-2h by using a ball mill; after washing and drying the mixture after grinding treatment, putting the mixture into a tube furnace for carbonization for 2-2.5h under inert atmosphere, wherein the carbonization temperature is 700-;
(3) dissolving the fibrous carbon material obtained in the step (2) by using 3-5wt% hydrochloric acid solution to remove iron-containing substances, and repeatedly washing the fibrous carbon material by using deionized water and ethanol in sequence until the fibrous carbon material is neutral; putting the neutral fiber carbon material into a ball mill for ball milling and crushing for 5-6h to prepare a black powder sample;
(4) and (3) dissolving the black powdery sample obtained in the step (3) in a proper amount of distilled water, uniformly stirring, transferring to a polytetrafluoroethylene lining of a high-pressure reaction kettle, transferring the reaction kettle to a blast drying box, carrying out hydrothermal treatment at the temperature of 120-160 ℃ for 5-6h, filtering, cleaning and drying the sample obtained after the reaction is finished to obtain a sisal fiber activated carbon black powder sample, namely the carbon-based biological anode.
2. The method as claimed in claim 1, wherein the concentration of the hydrochloric acid solution during the acidification step (1) is 5-10 wt%.
3. The method for preparing the carbon-based bioanode as claimed in claim 1, wherein the iron source catalyst in the step (2) is one or more than two of ferrous oxide, ferric oxide and ferroferric oxide.
4. The method for preparing the carbon-based bioanode as claimed in claim 1, wherein the mass of the iron source catalyst in the step (2) accounts for 15-18wt% of the mass of the sisal fibers.
5. The preparation method of the carbon-based bioanode as defined in claim 1, wherein the step (4) comprises the following steps: and (3) putting 70mL of distilled water into a beaker, adding 1g of black powder sample, transferring the sample into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into an air-blowing drying box, carrying out hydrothermal treatment at the temperature of 120-160 ℃ for 5-6h, filtering and washing the reaction kettle with absolute ethyl alcohol after the reaction kettle is naturally cooled to room temperature, and drying the reaction kettle in the air-blowing drying box at the temperature of 80 ℃ for 12h to obtain the carbon-based biological anode.
6. A carbon-based bioanode obtainable by the method of any one of claims 1 to 5.
7. A microbial fuel cell comprising the carbon-based bioanode of claim 6, prepared by:
dissolving the carbon-based biological anode in deionized water, mixing the carbon-based biological anode with an anode catalyst, and transferring the mixture into an anode reaction tank; cleaning the cathode, placing the cathode into a cathode reaction tank, adding a proton exchange membrane at the contact position of the cathode and anode reaction tanks, respectively sealing the cathode chamber and the anode chamber, leading out anode electrons from the anode chamber by using a lead, connecting the anode electrons in series with an external resistor and then connecting the anode electrons into the cathode chamber.
8. The microbial fuel cell according to claim 7, wherein the anode catalyst is prepared by:
(1) weighing a certain amount of glucose, ammonium sulfate and potassium dihydrogen phosphate, adding into sewage, stirring under a sealed condition until the glucose, the ammonium sulfate and the potassium dihydrogen phosphate are completely dissolved to obtain an anaerobic bacteria domestication nutrient solution;
(2) mixing the anaerobic bacteria domestication nutrient solution with anaerobic sludge in a sewage treatment plant to obtain slurry, sealing and storing for 20 days, and screening out anaerobic bacteria which are the needed anode catalyst.
9. The microbial fuel cell of claim 8, wherein the molar ratio of glucose, ammonium sulfate, potassium dihydrogen phosphate, and wastewater is 8-15:10-16:12-18: 100; the concentration of suspended solids in the slurry is 5-8 g/L.
10. The microbial fuel cell of claim 7, wherein the wire is one of titanium wire, molybdenum wire and copper wire, and the cathode is one of carbon felt, carbon brush, carbon paper and carbon fiber cloth.
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