CN115172769A - Self-supporting microbial fuel cell anode and preparation method and application thereof - Google Patents

Self-supporting microbial fuel cell anode and preparation method and application thereof Download PDF

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CN115172769A
CN115172769A CN202210905643.5A CN202210905643A CN115172769A CN 115172769 A CN115172769 A CN 115172769A CN 202210905643 A CN202210905643 A CN 202210905643A CN 115172769 A CN115172769 A CN 115172769A
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anode
fuel cell
microbial fuel
self
transition metal
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邓洪
胡美华
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South China University of Technology SCUT
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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
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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 self-supporting microbial fuel cell anode and a preparation method and application thereof. The method comprises the following steps: and (3) immersing the anode carrier into a mixed solution of transition metal ion salt and nitrogenous organic matter, carrying out thermal adsorption modification, and then calcining to obtain the microbial fuel cell anode. The preparation method is simple and controllable, and the prepared microbial fuel cell anode has a rough anode surface, a large specific surface area, good biocompatibility and excellent conductivity, is beneficial to the attachment of microorganisms on the anode surface, effectively promotes the rapid formation of the anode biomembrane of the microbial fuel cell, and can greatly improve the power density of the microbial fuel cell.

Description

Self-supporting microbial fuel cell anode and preparation method and application thereof
Technical Field
The invention belongs to the field of microbial fuel cells, and particularly relates to a self-supporting microbial fuel cell anode and a preparation method and application thereof.
Background
Microbial Fuel Cells (MFCs) are considered to be a cost-effective energy technology that converts organic energy in a substrate into electrical energy by using electrochemically active microorganisms. When organic matters in the wastewater are used as substrates, the MFCs have double capabilities of generating electricity and treating the wastewater, become research hotspots for environmental management and energy development, and have attracted great interest worldwide. The treatment of wastewater by MFCs is performed in the anode compartment, and various types of wastewater include: urban wastewater, livestock and poultry manure, industrial wastewater, printing and dyeing wastewater, garbage leachate and the like are all applied to MFCs, the commonly reported actual wastewater COD removal rate is over 80 percent, and the method has strong practical applicability.
Although MFCs are considered as important advanced technologies to solve energy crisis and environmental problems, there is still a large gap in power density of MFCs compared to other fuel cells. The large-scale application of MFCs still requires a lower power density. The anode acts as an attachment site for microorganisms and a wastewater treatment site, directly affecting the adhesion of the electrogenic microorganisms and the extracellular electron transfer of electrons from the microorganisms to the anode, and thus having a decisive influence on the electrogenic properties of the MFCs. The ideal anode has the advantages of large specific surface area, strong biocompatibility, good conductivity, chemical stability and the like. The existing studies on MFCs anodes are mainly directed to increasing the specific surface area of MFCs anodes and the attachment points of electrogenic microorganisms, and studies on the interaction between microorganisms and anode composition are still very lacking.
Particularly, a three-dimensional porous nitrogen-rich graphitized carbon scaffold prepared by a direct calcination method is taken as an anode of the MFCs (you.et al. Adv. Energy mater.2017,7, 1601364), shows excellent biocompatibility, but the power of the MFCs loading the anode is still low, and the barrier of large-scale application of the MFCs cannot be effectively broken through. Hu et al reported that iron carbide nanoparticles were dispersed in two-dimensional porous graphitized carbon to produce Nano-Fe 3 C @2D-NC @ CC is used as an anode material of a microbial fuel cell (Hu. Et al. Electrochimica Acta 2022,404, 139618), and although the power of MFCs is improved to a certain extent, the anode still has the problem of complicated preparation process. Therefore, the design and research of the anode of the microbial fuel cell with the potential have important theoretical significance and application value in analyzing the influence of the anode surface on the performance of the MFCs anode and improving the power generation capacity of the microbial fuel cell.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a self-supporting microbial fuel cell anode.
The invention also aims to provide a self-supporting microbial fuel cell anode prepared by the method.
The anode of the microbial fuel cell has the characteristics of good conductivity, high biocompatibility, large specific surface area, rough surface and the like, is favorable for attachment of microorganisms, and has the characteristics of promoting quick formation of a biological membrane and effectively improving the power output of the microbial fuel cell due to special chemical composition and surface morphology.
It is a further object of the present invention to provide a use of a self-supporting microbial fuel cell anode as described above in a microbial fuel cell.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a self-supporting microbial fuel cell anode comprises the following steps:
immersing an anode carrier into a mixed solution of a transition metal ion salt and an organic matter, carrying out thermal adsorption modification, and calcining in a nitrogen or inert gas atmosphere to obtain a microbial fuel cell anode;
the organic matter is at least one of nitrogen-containing organic matter and glucose.
Preferably, the anode carrier is one of carbon cloth, carbon felt and melamine sponge.
Preferably, in the mixed solution of the transition metal ion salt and the organic matter, the transition metal ion salt is at least one of iron acetate, ferroferric citrate, ferric nitrate, manganese acetate and cobalt acetate; more preferably at least one of iron acetate, triiron citrate and iron nitrate.
Preferably, the nitrogen-containing organic matter is at least one of amino acid, urea and 4- (2-aminoethyl) -1, 2-benzenediol hydrochloride; the amino acid is at least one of glycine, alanine and glutamic acid.
Preferably, in the mixed solution of the transition metal ion salt and the organic matter, the concentration of the transition metal ion salt is 0.25-1.0 mol/L; more preferably 0.52mol/L; the concentration of the organic matters is 0.2-8.3 mol/L; more preferably 8.3mol/L.
Preferably, the solvent of the mixed solution of the transition metal ion salt and the organic substance is water.
Preferably, the temperature of the thermal adsorption modification is 60-90 ℃; the time is 1 to 5 hours.
Preferably, the temperature of the calcination is 650-850 ℃; the time is 2 to 6 hours.
Preferably, the thermal adsorption is modified and then freeze-dried or vacuum-dried, wherein the temperature of vacuum drying is 60-80 ℃ and the time is 24-36 hours.
The self-supporting microbial fuel cell anode prepared by the method.
The self-supporting microbial fuel cell anode obtained by the invention contains a carbon material, a nitrogen-doped carbon material and at least one nano material of iron nitride, iron carbide, cobalt oxide and manganese carbide.
The self-supporting microbial fuel cell anode is applied to a microbial fuel cell.
A microbial fuel cell comprises the self-supporting microbial fuel cell anode, a cathode, an electrolyte, an organic substrate, a proton exchange membrane and a cell model.
Preferably, the cathode is 20% Pt/C by mass, the electrolyte is phosphate buffer solution, and the organic substrate is acetate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a self-supporting microbial fuel cell anode, which consists of a transition metal compound nano material (one or more of iron nitride, iron carbide, cobalt oxide and manganese carbide) and a carbon nano material (a carbon material) loaded on an anode carrier (one of carbon cloth, carbon felt and melamine sponge), wherein the anode carrier is an anode main body frame, the carbon nano material formed on the carbon fiber and the surface provides a conductive network, and the nano material forms an array type porous nano tube on the surface of the carrier to provide a transmission channel of electrolyte and gas. The existence of the transition metal compound nano particles can improve the conductivity of the electrode, provide rich catalytic reaction active points for the anode and ensure the rapid transfer of electrons generated by the anode. The serial microbial fuel cell anodes of the invention have the characteristics of good activity, high catalytic efficiency, simple operation, economy, environmental protection, high benefit and the like.
2. According to the invention, an adsorption deposition method is effectively utilized to add a modified material as a precursor to an anode carrier, and the self-supporting microbial fuel cell anode with a special morphology is controllably prepared by regulating and controlling the composition of a modified solvent, the adsorption modification temperature and time, the calcination time and temperature and the like; the use of a self-supporting microbial fuel cell anode may reduce the use of binders compared to powdered microbial fuel cell anode catalysts. Typically these binders are high molecular weight polymers that can degrade the active sites of the anode material. The method is beneficial to exploring the influence of the surface morphology and the composition of the anode on the oxidative decomposition of the organic matters of the anode and the electron transmission process of the anode, and further promotes the reasonable design and the controllable preparation of the anode catalyst.
3. The microbial fuel cell anode mainly contains elements such as carbon, nitrogen, iron and the like which are abundant in the nature, and has abundant resources and low price. The synthesis process adopts an adsorption method and a high-temperature calcination method, the synthesis method is easy to control, the product is a carbon/nitrogen/transition metal material self-supported by an anode carrier, no harmful substance is generated in the preparation process, and the preparation method is green and environment-friendly.
4. Compared with a blank carbon carrier, the nano particles attached to the surface of the anode carrier have better biocompatibility, larger specific surface area and special surface morphology, and the array-type porous nano tubes formed on the surface can promote the attachment of microorganisms, so that bacteria can quickly form a biological membrane on the surface of the anode, and the method has important significance for improving the output power of the microbial fuel cell.
Drawings
FIG. 1 is a scanning electron micrograph of the anode of the microbial fuel cell according to example 1, example 2, example 3, example 4 and comparative example 1.
FIG. 2 is an X-ray diffraction pattern of example 1, example 2, example 3, example 4 and comparative example 1 of the present invention.
Fig. 3 is a cyclic voltammogram of the anode of the microbial fuel cell prepared in example 1, example 2, example 3, example 4, and comparative example 1 of the present invention.
FIG. 4 is a graph of current versus time at constant potential for anodes of microbial fuel cells prepared in examples 1,2, 3, 4 and 1 of the present invention.
FIG. 5 is a graph showing voltage output curves of the microbial fuel cells of different anodes in example 1, example 2 and comparative example 1 of the present invention.
Fig. 6 is a polarization curve diagram of microbial fuel cells of different anodes in example 1, example 2 and comparative example 1 of the present invention.
FIG. 7 is a graph showing power density curves of microbial fuel cells of different anodes in example 1, example 2 and comparative example 1 of the present invention.
FIG. 8 is a bar graph of biomass of different anodes after cycling through microbial fuel cells in inventive example 1, example 2, and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
The embodiment provides a preparation method of a self-supporting microbial fuel cell anode, which comprises the following specific preparation steps:
(1) Cutting the melamine sponge into proper size, soaking and cleaning the melamine sponge with deionized water for 1 hour, and then putting the melamine sponge into an oven for drying to obtain the treated melamine sponge;
(2) Adding 10g of urea and 2.4g of iron acetate into 20mL of deionized water, and stirring for 30 minutes until the urea and the iron acetate are dissolved to obtain a mixed solution;
(3) Adding the melamine sponge treated in the step (1) into the mixed solution obtained in the step (2), and stirring and heating for 1 hour at 75 ℃ to fully adsorb urea and iron ions on the surface of the melamine sponge;
(4) Freeze-drying the melamine sponge obtained in the step (3) for 24 hours to obtain the adsorbed melamine sponge;
(5) Placing the adsorbed sponge obtained in the step (4) in a tubular furnace, and calcining for 2 hours at 650 ℃ in an argon atmosphere to obtain a self-supporting microbial fuel cell anode;
(6) Cutting the anode of the microbial fuel cell obtained in the step (5) into 2 x 2cm 2 And assembling the battery.
Example 2
The embodiment provides a preparation method of a self-supporting microbial fuel cell anode, which comprises the following specific preparation steps:
(1) Cutting melamine sponge into proper size, soaking and cleaning the melamine sponge in deionized water for 1 hour, and then putting the melamine sponge into an oven for drying to obtain the treated melamine sponge;
(2) Adding 15g of glucose and 2.4g of iron acetate into 20mL of deionized water, and stirring for 30 minutes until the glucose and the iron acetate are dissolved to obtain a mixed solution;
(3) Adding the melamine sponge treated in the step (1) into the mixed solution obtained in the step (2), and stirring and heating for 1 hour at 75 ℃ to enable the surface of the melamine sponge to be fully adsorbed with glucose and iron ions;
(4) Freeze-drying the melamine sponge obtained in the step (3) for 24 hours to obtain the adsorbed melamine sponge;
(5) Placing the adsorbed sponge obtained in the step (4) in a tubular furnace, and calcining for 2 hours at 650 ℃ in an argon atmosphere to obtain a self-supporting microbial fuel cell anode;
(6) Cutting the anode of the microbial fuel cell obtained in the step (5) into 2 x 2cm 2 And assembling the battery.
Example 3
The embodiment provides a preparation method of a self-supporting microbial fuel cell anode, which comprises the following specific preparation steps:
(1) Cutting the carbon cloth into proper size, soaking and cleaning the carbon cloth for 1 hour by using deionized water, and then putting the carbon cloth into an oven for drying to obtain the treated carbon cloth;
(2) Adding 1g of 4- (2-aminoethyl) -1, 2-benzenediol hydrochloride, 3g of glutamic acid and 3.5g of cobalt acetate into 20mL of deionized water, and stirring for 30 minutes until the mixture is dissolved to obtain a mixed solution;
(3) Adding the carbon cloth treated in the step (1) into the mixed solution, stirring and heating at 90 ℃ for 3 hours to enable a layer of 4- (2-aminoethyl) -1, 2-benzenediol hydrochloride, glutamic acid and cobalt ions to be adsorbed on the surface of the carbon felt;
(4) Placing the carbon cloth obtained in the step (3) at 60 ℃ for vacuum drying for 36 hours to obtain the carbon cloth after adsorption;
(5) Placing the carbon cloth obtained in the step (4) after adsorption in a tube furnace, and calcining for 6 hours at 750 ℃ in an argon atmosphere to obtain a self-supporting microbial fuel cell anode;
(6) Cutting the anode of the microbial fuel cell obtained in the step (5) into 2 x 2cm 2 And assembling to form the battery.
Example 4
The embodiment provides a preparation method of a self-supporting microbial fuel cell anode, which comprises the following specific preparation steps:
(1) Cutting a commercial carbon felt into a proper size, soaking and cleaning the commercial carbon felt for 1 hour by using deionized water, and then putting the commercial carbon felt into an oven for drying to obtain a treated carbon felt;
(2) Adding 5g of urea, 2g of glycine, 2g of alanine and 0.86g of manganese acetate into 20mL of deionized water, and stirring for 30 minutes until the materials are dissolved to obtain a mixed solution;
(3) Adding a carbon felt treated in the step (1) into the mixed solution, stirring and heating at 60 ℃ for 5 hours to enable the surface of the carbon felt to adsorb a layer of urea, glycine, alanine and manganese ions;
(4) Placing the carbon felt obtained in the step (3) at 80 ℃ for vacuum drying for 30 hours to obtain an adsorbed carbon felt;
(5) Placing the carbon felt dried in the step (4) in a tubular furnace, and calcining for 4 hours at 850 ℃ in an argon atmosphere to obtain a self-supporting microbial fuel cell anode;
(6) Cutting the anode of the microbial fuel cell obtained in the step (5) into 2 x 2cm 2 And assembling to form the battery.
Comparative example 1
Using 2X 2cm 2 Commercial carbon cloth anodes were assembled into batteries.
Testing method and result analysis:
the anodes prepared in example 1, example 2, example 3, example 4 and comparative example 1 were subjected to a scanning electron microscope test, and the results are shown in fig. 1. In fig. 1, SEM pictures of the anode obtained in example 1, example 2, example 3, and example 4 and the carbon cloth anode (comparative example 1) are shown. By comparing fig. 1, it can be seen that, compared with carbon cloth (comparative example 1), in examples 1,2, 3 and 4, a plurality of nanoparticles are attached to the surface of the anode support, and this particular morphology effectively increases the specific surface area of the material, which is beneficial to the attachment of microorganisms.
The anode for microbial fuel cells prepared in example 1, example 2, example 3, example 4, and comparative example 1 was subjected to X-ray diffraction, and the results are shown in fig. 2. It can be found that the carbon cloth (comparative example 1) has the composition of amorphous carbon, while the nano-material-loaded melamine carbide sponge anode of example 1 presents XRD diffraction peaks of iron nitride, iron carbide and carbon; example 2 shows XRD diffraction peaks of iron carbide and carbon; the anode of the embodiment 3 shows XRD diffraction peaks of cobalt oxide and carbon; the anode of example 4 showed XRD diffraction peaks for manganese carbide and carbon.
The resulting anodes were assembled into cells and subjected to electrochemical testing under the following conditions:
the electrochemical tests used in this experiment were all performed on Chenghua electrochemical workstation (CHI-1040C). Electrochemical tests such as cyclic voltammetry and alternating current impedance method were performed using a three-electrode system, in which the anodes prepared in example 1, example 2, example 3, example 4 and comparative example 1 were used as working electrodes, a titanium wire electrode was used as an auxiliary electrode, and a saturated calomel electrode (Hg/Hg) was used as a saturated calomel electrode 2 Cl 2 satured with KCl) as reference electrode.
The electrochemical test results are shown in fig. 3 and fig. 4, wherein fig. 3 is a cyclic voltammogram of different anodes before microorganism inoculation, and fig. 4 is a time-current curve of different anodes under constant potential after microorganism inoculation. Before inoculation with the microorganisms, all anodes showed a capacitive behavior in the cyclic voltammetry test (FIG. 3), i.e.the capacitance density of all electrodes was positively correlated with the electrode current. When the capacitance comes from the double layer of an electrode, it is proportional to the specific surface area (or electrochemically active surface area) of the electrode. That is, the larger the electrochemically active surface area of the anode, the greater the current generated. Self-supporting nanomaterial-loaded microbial fuel cell anodes (example 1, example 2, example 3, example 4) were able to produce higher currents than commercial carbon cloth anodes (comparative example 1), confirming that the anodes of the examples have a much larger electrochemically active surface area; the highest current is shown in example 1 containing iron nitride, which indicates that the special morphology and the composition of the iron nitride nanoparticles can effectively improve the electrochemical active surface area of the anode and promote the electron transfer among microorganisms.
As can be seen from fig. 4, the nanomaterial-loaded microbial fuel cell anodes (examples 1,2, 3, and 4) that were self-supporting at a constant potential after inoculation of the microorganisms had a higher current response than the commercial carbon cloth anodes (comparative example 1), where the anodes of example 1 produced the highest current response, confirming that the composition of the nano iron nitride was effective in promoting electron transfer between the microorganisms and the anodes, and had excellent electrocatalytic activity.
The microbial fuel cell test conditions were as follows:
the electrochemical tests used for the microbial fuel cell tests were performed on Chenghua electrochemical workstation (CHI-1040C) and data acquisition unit. Electrochemical tests such as a voltage output curve, a polarization curve, a power density curve and the like of the microbial fuel cell adopt an air cathode single-chamber microbial fuel cell as a model. Examples 1,2 and 1 are taken as examples, examples 1,2 and 1 are taken as anode electrodes, and Pt/C air cathodes are taken as cathode electrodes.
The electrochemical test results are shown in fig. 5-7, fig. 5 is a graph of voltage output of microbial fuel cells loaded with different anodes; FIG. 6 is a polarization diagram of a microbial fuel cell loaded with different anodes; fig. 7 is a graph of power density of microbial fuel cells loaded with different anodes. As can be seen in fig. 5, with self-supporting nanomaterial-loaded anodeThe microbial fuel cell outputs higher voltage than that of the microbial fuel cell with the carbon cloth anode, wherein the microbial fuel cell with the anode containing iron nitride (example 1) produces the highest voltage output, and the effect of the iron nitride nanoparticles on improving the electricity generation performance of the microbial fuel cell is verified. In the polarization curve (fig. 6), the microbial fuel cell loaded with nanomaterial anode has smaller polarization; the microbial fuel cell in which the anode (example 1) contained iron nitride produced the least polarization. The nanomaterial anode loaded microbial fuel cell produced higher power output in the power density test, where the anode containing iron nitride (example 1) produced a maximum power density of 2.03W m -2 In comparison with an anode not containing iron nitride (example 2,1.39W m) -2 ) And commercial carbon cloth (comparative example 1,0.84W m -2 ) The maximum power density is improved by 46% and 141% respectively. The conductivity of the electrode is enhanced by the iron nitride and other nano particles, and meanwhile, the nano particles on the surface of the melamine sponge frame are carbonized, so that the specific surface area of the anode is effectively increased, a large number of sites are provided for the attachment of microorganisms, the formation of a biological membrane is promoted, and the output power of the microbial fuel cell is improved.
FIG. 8 is a comparison of biomass loading for different anode loads after cycling through a microbial fuel cell in example 1, example 2, and comparative example 1. As can be seen from fig. 8, the anode containing iron nitride (example 1) attached more biomass than the anode without iron nitride (example 2) and the anode without nanoparticles (comparative example 1), and the difference in biomass indicates that the anode containing iron nitride (example 1) was more favorable for microbial attachment, ensuring bacterial biofilm growth and resulting in better biocompatibility.
In conclusion, the invention effectively utilizes cheap materials such as melamine sponge and the like as the substrate, and controllably prepares the self-supporting anode loaded with the nano-material, which has multiple active sites, high conductivity and high biocompatibility, by an adsorption-calcination method. The catalyst has simple preparation process, no secondary pollution and good environmental protection benefit. The specific surface area, the conductivity and the bioelectrochemical activity of the anode can be effectively improved, the preparation process is simple and convenient to operate, and the environment is protected without generating secondary pollution. The invention has important significance for developing high-efficiency anode catalysts of microbial fuel cells.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a self-supporting microbial fuel cell anode is characterized by comprising the following steps:
immersing an anode carrier into a mixed solution of a transition metal ion salt and an organic matter, carrying out thermal adsorption modification, and calcining in a nitrogen or inert gas atmosphere to obtain a microbial fuel cell anode;
the organic matter is at least one of nitrogen-containing organic matter and glucose.
2. The method for preparing the anode of the self-supporting microbial fuel cell according to claim 1, wherein in the mixed solution of the transition metal ion salt and the organic matter, the transition metal ion salt is at least one of iron acetate, ferroferric citrate, iron nitrate, manganese acetate and cobalt acetate; the nitrogen-containing organic matter is at least one of amino acid, urea and 4- (2-aminoethyl) -1, 2-benzenediol hydrochloride; the amino acid is at least one of glycine, alanine and glutamic acid.
3. The method for preparing the anode of the self-supporting microbial fuel cell according to claim 1, wherein in the mixed solution of the transition metal ion salt and the organic matter, the concentration of the transition metal ion salt is 0.25 to 1.0mol/L; the concentration of the organic matters is 0.2 to 8.3mol/L.
4. The method for preparing the anode of the self-supporting microbial fuel cell according to claim 1, wherein in the mixed solution of the transition metal ion salt and the organic matter, the transition metal ion salt is at least one of iron acetate, iron citrate and iron nitrate.
5. The method of claim 1, wherein the temperature of the thermal adsorption modification is 60-90 ℃; the time is 1 to 5 hours.
6. The method of claim 1, wherein the calcining is at a temperature of 650 to 850 ℃; the time is 2 to 6 hours.
7. The method of claim 1, wherein the anode support is one of carbon cloth, carbon felt, and melamine sponge.
8. The method for preparing the anode of the self-supporting microbial fuel cell according to claim 1, wherein in the mixed solution of the transition metal ion salt and the organic matter, the concentration of the transition metal ion salt is 0.52mol/L; the concentration of the organic matter was 8.3mol/L.
9. A self-supporting microbial fuel cell anode produced by the production method according to any one of claims 1 to 8.
10. Use of a self-supporting microbial fuel cell anode of claim 9 in a microbial fuel cell.
CN202210905643.5A 2022-07-29 2022-07-29 Self-supporting microbial fuel cell anode and preparation method and application thereof Pending CN115172769A (en)

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