CN107342428B - Method for enhancing microbial extracellular electron transfer in microbial electrochemical system - Google Patents
Method for enhancing microbial extracellular electron transfer in microbial electrochemical system Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention provides a method for enhancing microbial extracellular electron transfer in a microbial electrochemical system, wherein graphene or aza-graphene is loaded to a carbon electrode as an anode, wherein the graphene or aza-graphene is directly loaded to the carbon electrode through electrophoretic deposition. The invention also provides a modified carbon electrode for use as an anode in a microbial electrochemical system, a method of making the carbon electrode, and a microbial electrochemical system comprising the carbon electrode. The system and the method provided by the invention are simple to operate, low in operation cost, good in electricity generation effect and convenient for large-scale use.
Description
Technical Field
The invention relates to the field of microbial electrochemistry, in particular to a method for enhancing microbial extracellular electron transfer.
Background
Environmental pollution and energy shortage are two major problems facing human beings today. The microbial electrochemical system is a bioreactor which utilizes microbe to drive oxidation or reduction reaction, can generate electric energy while degrading pollutants, can relieve energy crisis by being used as a renewable energy technology, and is beneficial to sustainable development of human beings.
Currently, the practical application of this technology is mainly limited by its weak power generation capacity, mainly due to the low electron transfer capacity between the microorganisms and the anode. The traditional anode material in the microbial electrochemical system needs to have the following characteristics: high conductivity, good biocompatibility, large specific surface area, good chemical stability, high mechanical strength and low cost.
In microbial electrochemical systems, the electrode material which is most widely applied at present is a carbon material, and the carbon material generally has the advantages of good biocompatibility, corrosion resistance, low cost and the like. Among the carbon materials commonly found in microbial electrochemical systems are: carbon paper, carbon felt, carbon cloth, carbon brush, carbon fiber and the like, but the pure utilization of the carbon material as the anode of the microbial electrochemical system has lower electricity generation performance and cannot meet the expected requirements of people.
Disclosure of Invention
In view of this, in some embodiments, the present invention is a method of enhancing microbial extracellular electron transfer, wherein graphene or aza-graphene is loaded to a carbon electrode as an anode, wherein the graphene or aza-graphene is loaded directly to the carbon electrode by electrophoretic deposition.
In some embodiments, anodes useful in the present invention can have a planar shape, a cylindrical shape, a spiral shape, a curved shape, including but not limited to a sheet, a plurality of sheets, a wire mesh, a porous tube, and a sponge shape, in some embodiments. In some embodiments, the anodes of the present invention have a large surface area to volume ratio. In some embodiments, the anode is removable from the microbial fuel cell. In some embodiments, the anode material comprises a conductive material such as carbon, carbon nanotubes, carbon nanofibers, carbon cloth, carbon paper, and the like. In some embodiments, the anode preferably has a high surface area, low electrical resistance, high electrical conductivity, or a combination thereof. In some embodiments, the anode allows for a high bacterial growth density. In some embodiments, carbon electrodes that may be used in the present invention include carbon paper, carbon cloth, carbon fiber, carbon brush, carbon felt.
In some embodiments, the graphene or aza-graphene is directly loaded to the carbon electrode by electrophoretic deposition, such as cathodic electrophoretic deposition, as an anode load to the carbon electrode. In some embodiments, the electrophoretic deposition methods that may be used in the present invention are not particularly limited. In some embodiments, the deposition dispersion that may be used in the present invention includes acetone, isopropanol, or ethanol.
In some embodiments, the electrogenic bacteria that may be used in the present invention include Pseudomonas (Pseudomonas), Geobacter (Geobacter), Shewanella (Shewanella), and rhodobacter (Rhodoferax). In some embodiments, the electrogenic bacteria that can be used in the present invention include, for example, Pseudomonas aeruginosa (Pseudomonas aeruginosa), Pseudomonas putida, Shewanella bacteria such as Shewanella oneidensis MR-1, Shewanella putrefaciens (Shewanella oneidensis) IR-1, Shewanella shikaensis DSP10, Geobacillus thioredolus (Geobacillus thioredoccus), Geobacillus metallobacterium (Geobacillus metalloidus), Geobacillus caldus (Peletomaculum thermophilus), Thermomyces autotrophicus (Methanobacterium thermonatrotrophic), human Xanthium californicum (Ochrotrum anthropi), Clostridium butyricum (Clostridium butyricum) EG3, Pseudomonas acetobutylicum (Pseudomonas aeruginosa), Escherichia coli (Escherichia coli), Escherichia coli (Desulfuricus A thiobacillus thiocola), Rhodococcus rhodobacter coli (Desulfuricus) S, Escherichia coli (Desulfuricus A thiobacillus thiocola, Clostridium thiocola (Desulfuricus) 3, Clostridium thiobacillus subtilis, Clostridium thiobacillus subtilis A, Clostridium thiobacillus subtilis (Desulfuricus) and Escherichia coli (Desulfuricus) s, Clostridium thiobacillus acidicum (Pseudomonas aeruginosa, Clostridium thiobacillus acidus, Clostridium thiobacillus acidus, Pseudomonas aeruginosa, Escherichia coli (Pseudomonas aeruginosa, Escherichia coli (Escherichia, Acidiphilium species (Acidiphilium sp.), Klebsiella pneumoniae (Klebsiella pneumoniae) L17. In some embodiments, Shewanella bacteria, such as MR-1, are used as the electrogenic bacteria. In some embodiments, the culture medium in the reaction chamber of the microbial electrochemical system is formulated to be non-toxic to bacteria with which it comes into contact. In some embodiments, the culture medium or solvent may be adjusted to be compatible with the metabolism of the bacteria. In some embodiments, the pH may be adjusted to a range of about pH3-9, for example about 5-8.5. In some embodiments, it has been found that the present invention can be practiced without a neutral pH without significantly adversely affecting the electricity generating capability. Thus, in some embodiments, the pH of the culture medium of the invention can be adjusted, for example, to about 3-6.5, 4-6, 4.5-5.5, 7.5-8, and the like. If necessary, a buffer may be added to the medium or the solvent, and the concentration of the medium or the solvent may be adjusted by diluting or adding an osmotic pressure activating substance. In some embodiments, a salt may be added to adjust the ionic strength. In addition, nutrients, cofactors, vitamins and other similar additives may be included to maintain a healthy bacterial population, if desired. In some embodiments, fluids with low conductivity can be used in the systems and methods of the invention without the need for buffers. In some embodiments, the systems and methods of the present invention can efficiently produce energy from a fluid containing biodegradable materials, and efficiently remove biodegradable materials from the fluid. The system and method of the present invention can avoid significant acidification of the fluid. In some embodiments, the systems and methods of the present invention have high current densities. In some embodiments, the present invention achieves high current densities using starting materials with low or no buffering. In some embodiments, the systems and methods of the present invention reduce losses, e.g., due to ion transport.
In some embodiments, the present invention provides a modified carbon electrode for use as an anode in a microbial electrochemical system, wherein the modified carbon electrode is a graphene-or aza-graphene-loaded carbon electrode, wherein the graphene or aza-graphene is loaded directly to the carbon electrode by electrophoretic deposition.
In some embodiments, the carbon electrode comprises carbon paper, carbon cloth, carbon fiber, carbon brush, carbon felt.
In some embodiments, the present invention provides a microbial electrochemical system comprising the modified carbon electrode of the present invention as an anode.
In some embodiments, the microbial electrochemical system comprises a microbial fuel cell and a microbial electrolysis cell.
In some embodiments, the microbial fuel cell comprises the modified carbon electrode of the invention as an anode, a cathode, and a conductor connecting the anode and the cathode.
In some embodiments, as described above, anodes useful in the present invention can have various suitable shapes. In some embodiments, the anode may be connected to the cathode by a wire, such as copper. In some embodiments, the cathode of the microbial fuel cell of the invention comprises the following electrically conductive materials: metal, carbon nanotubes, carbon nanofibers, carbon cloth, carbon paper, platinum, graphite rods, graphite felt, graphite particles, or other conductive materials. In some embodiments, the anode and cathode compartments may be separated by a spacer, such as a separator or membrane. In some embodiments, a spacer separating the anode and cathode compartments slows, reduces, or prevents electrons from moving directly from the anode to the cathode, while the electrons flow through the leads of the circuit. In some embodiments, the spacer can be, for example, a biofilm, a fabric, a barrier, an ion exchange membrane.
In some embodiments, the present invention provides systems, such as microbial fuel cells, comprising: the modified carbon electrode of the invention as an anode, an electrogenic microorganism in contact with said anode, a cathode comprising one or more electrically conductive materials, an ion exchange membrane between said anode and said cathode, an electrical conductor, which is in contact with said anode and said cathode. In some embodiments, the methods and systems of the present invention may include a means for directing the fluid species to the anode. In some embodiments, the anode and/or the cathode are located in a sealed chamber. In some embodiments, the anode chamber has an inlet adapted to introduce a fluid containing biodegradable material and an outlet for removing the fluid from the chamber. In some embodiments, there is an inlet in the cathode compartment suitable for introducing an oxygen-containing gas. In some embodiments, the cathode chamber is open to air. In some embodiments, the anode chamber and/or cathode chamber is removable.
In some embodiments, the invention provides an apparatus comprising a microbial fuel cell and a microbial electrolysis cell, wherein the microbial fuel cell may be a cell as described above, wherein the microbial electrolysis cell may comprise the modified carbon electrode of the invention as an anode and a cathode such as a platinum wire electrode. In some embodiments, the cathode compartment of the cell has a gas outlet. In some embodiments, the anode compartment of the cell may be in communication with the cathode compartment of the cell via a conduit. In some embodiments, the fuel cell anode electrode is connected to the electrolysis cell cathode electrode, and the fuel cell cathode electrode is connected to the electrolysis cell anode electrode. In some embodiments, the anode compartment of the electrolytic cell has an inlet for a carbon source. In the device, the microbial fuel cell can provide power for the microbial electrolysis cell. In some embodiments, the apparatus may be used for wastewater treatment and the like.
In some embodiments, the present invention provides a method of preparing the modified carbon electrode, comprising the step of loading graphene or aza-graphene to a carbon electrode as an anode, wherein the graphene or aza-graphene is directly loaded to the carbon electrode by electrophoretic deposition.
According to the invention, a cathode electrophoretic deposition method is firstly utilized to load graphene and aza-graphene on the surface of a carbon paper electrode, and then the carbon paper electrode is used as an anode of a microbial electrochemical system to promote electricity generation. In the present invention, the microorganism serves as a catalyst for oxidation/reduction reaction, and generates electrons while consuming a substrate, lactic acid, and transfers the electrons to the anode by means of extracellular electron transfer to generate electric energy.
The method adopts a cathode electrophoretic deposition method, and the graphene and the aza-graphene are loaded on the surface of the carbon paper electrode to be used as a biological anode to promote the electricity generation of BESs. According to the invention, the anode modified by graphene and aza-graphene is adopted, so that the electricity generating capacity of BESs can be improved by 6-8 times. The invention also finds that the electricity generating capacity of the BESs when the graphene is used as the anode modifier is about 1.3 times of the electricity generating capacity of the BESs after the aza-graphene modified anode, which is attributed to the better biocompatibility, higher conductivity and better response to riboflavin of the graphene. The method is simple to operate, low in operation cost, good in effect of promoting the BESs to generate electricity, simple in experimental equipment requirement and convenient for large-scale use.
Drawings
FIG. 1: fig. 1a, 1b, and 1c are scanning electron micrographs of a carbon-paper electrode, a graphene-carbon paper electrode, and an aza-graphene-carbon paper electrode used in example 1 of the present invention;
FIG. 2: fig. 2a and 2b are transmission electron micrographs of graphene and aza-graphene used in example 1 of the present invention;
FIG. 3 is an XPS characterization spectrum of graphene and aza-graphene used in example 1 of the present invention;
fig. 4 is a histogram of the specific surface area of graphene, aza-graphene, carbon-paper, graphene-carbon-paper and aza-graphene-carbon-paper electrodes used in example 1 of the present invention;
FIG. 5: fig. 5a, 5b, and 5c are water contact angle characterization pictures of a carbon paper electrode, a graphene-carbon paper electrode, and an aza-graphene-carbon paper electrode used in example 1 of the present invention;
fig. 6 is an EIS impedance spectrum of a carbon paper electrode, a graphene-carbon paper electrode, and an aza-graphene-carbon paper electrode used in example 1 of the present invention;
FIG. 7 is an electrogenesis diagram of a microbial electrochemical system employing a carbon paper electrode, a graphene-carbon paper electrode and an aza-graphene-carbon paper electrode mounting in example 2 of the present invention;
FIG. 8: FIGS. 8a, 8b and 8c are SEM images of microorganisms on the surface of the anode after the reactor installed in example 2 of the present invention is operated;
FIG. 9 is a bar graph of protein assay by BCA method for microorganisms on the surface of the anode after the reactor installed in example 2 of the present invention is operated.
FIG. 10 is a plot of cyclic voltammetric scans at the peak of power generation during operation of a reactor installed in accordance with example 2 of the present invention;
fig. 11 is a cyclic voltammogram scan of a carbon paper electrode, a graphene-carbon paper electrode, and an aza-graphene-carbon paper electrode used in example 3 of the present invention in a riboflavin system.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of 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.
Experimental materials:
the following experimental materials were used herein:
graphene and aza-graphene: chinese academy of sciences Chengdu organic chemistry Co., Ltd
Shewanella MR-1 bacteria: provided by professor k.h.nealson of university of southern california
LB culture medium: 10g/L peptone; 5g/L NaCl; 5g/L yeast extract. Wherein, peptone and yeast extract are purchased from: oxoid ltd. wad road. foundation stoke. hants. rg248pw. uk. made in the United Kingdom, NaCl from: chemical agents of the national drug group, ltd.
Aerobic culture medium: 10mL/L macroelements, 10mL/L microelements,10mL/LMgSO4·7H2O, 2.788mL/LL sodium lactate (60%), 11.91g/L HEPES, 1L medium/2 mL Casa mini Acid concentrate, 1L medium/500. mu. LVitamin
Anaerobic culture medium: 10mL/L macroelement, 10mL/L microelement, 10mL/LMgSO4·7H2O, 2.788mL/LL sodium lactate (60%), 6.4g/L fumaric Acid 11.91g/L HEPES, 1L medium/2 mL Casa mini Acid concentrate, 1L medium/500. mu.L Vitamin
The macroelement composition and specific sources are as follows:
NH4chemical reagent of Cl national drug group Co Ltd
(NH4)2SO4Chemical reagents of national drug group Co Ltd
K2HPO4Chemical reagents of national drug group Co Ltd
KH2PO4Chemical reagents of national drug group Co Ltd
The composition and specific sources of the trace elements are as follows:
chemical reagents of NTA national drug group Co., Ltd
MnCl2·4H2Chemical reagent of O national drug group Co Ltd
FeSO4·7H2Chemical reagent of O national drug group Co Ltd
CoCl2·6H2Chemical reagent of O national drug group Co Ltd
ZnCl2Chemical reagents of national drug group Co Ltd
CuSO4·4H2Chemical reagent of O national drug group Co Ltd
AlK(SO4)2·12H2Chemical reagent of O national drug group Co Ltd
H3BO3Chemical reagents of national drug group Co Ltd
NaMoO4·2H2Chemical reagent of O national drug group Co Ltd
NiCl2·6H2Chemical reagent of O national drug group Co Ltd
NaWO4·2H2Chemical reagent of O national drug group Co Ltd
NaSeO4Chemical reagents of national drug group Co Ltd
Concentrated solution of Casa mini Acid: 20g of Casa micro Acid powder dissolved in 100mL of distilled water, Bio-engineering (Shanghai) Co., Ltd
Specific sources of Vitamin and various drugs:
chemical reagent of national drug group of pyridoxine hydrochloride of 10mg/L
National chemical group chemical reagent Co., Ltd, 5mg/L riboflavin
5mg/L vitamin B1 national drug group chemical reagent Co., Ltd
5mg/L Niacin national drug group chemical reagent Co., Ltd
5mg/L calcium D-pantothenate chemical reagents of national drug group Co., Ltd
5mg/L P-aminobenzoic acid national chemical group chemical reagent Co., Ltd
5mg/L lipoic acid national drug group chemical reagent Co., Ltd
2mg/L Biotin national drug group chemical reagent Co., Ltd
2mg/L Folic acid national drug group chemical reagent Co., Ltd
0.1mg/L vitamin B12 national drug group chemical reagent Co., Ltd
MgSO4·7H2Chemical reagent of O national drug group Co Ltd
L-sodium lactate (60%) Biotech (Shanghai) Ltd
HEPES Biotechnology engineering (Shanghai) Co., Ltd
Fumaric acid aladine reagent
Chemical reagent of acetone solution national drug group Co., Ltd
Chemical reagent of iodine simple substance national medicine group Limited
Carbon paper: shanghai Hesen electric appliances, Inc.: dongli 090.
The experimental scheme is as follows:
in one embodiment, the present invention may comprise the steps of:
loading graphene and aza-graphene on the surface of a carbon paper electrode;
culturing Shewanella MR-1 bacteria in LB culture medium, aerobic culture medium and anaerobic culture medium in sequence;
installation of microbial electrochemical systems (BESs) in the ultra-clean bench;
BESs were run under the control of Shanghai Chenghua electrochemical workstation (CHI1030C) to monitor the data.
In the present invention, the electrode modification method may be electrophoretic deposition, such as cathodic electrophoretic deposition.
In the present invention, the dc voltage value of the cathodic electrophoretic deposition may be 10V to 20V, such as 15V.
In the present invention, the time of the cathodic electrophoretic deposition can be 5min to 15min, such as 10 min.
In the present invention, when the autoclave is sterilized, the parameters thereof may be set as follows: temperature: 121 ℃, sterilization time: and 20 min.
In the present invention, the microbial electrochemical system may be operated at a room temperature of 30 ℃.
In the present invention, a Chenghua electrochemical workstation such as Amperometric i-t curve may be employed.
In the invention, when the microbial electrochemical system is in operation, the anode potential of the microbial electrochemical system can be controlled to be +0.1 V.s.Ag/AgCl reference electrode.
In the invention, the microorganism can be a pure bacterium S.Oneidensis MR-1, and the bacterium liquid of the BESs system can be prepared by the following method:
firstly, culturing S.Oneidensis MR-112h in an LB culture medium by a monoclonal method; then culturing the S.Oneidensis MR-124 h in an aerobic mineral salt culture medium; and finally, culturing the S.Oneidensis MR-16-8 h, for example 7h, in an anaerobic mineral salt culture medium.
The sources of the acetone solution, the carbon paper, the graphene, the aza-graphene, the electrogenic bacteria and the iodine simple substance are not particularly limited, and the raw materials used in the invention are all commercially available unless otherwise specified.
The invention has no special limitation on the DC power supply used for the cathodic electrophoretic deposition, as long as the performance is reliable and can meet the relevant experimental requirements.
The method adopts a cathode electrophoretic deposition method, and the graphene and the aza-graphene are loaded on the surface of the carbon paper electrode to be used as a biological anode to promote the electricity generation of BESs. According to the invention, the anode modified by graphene and aza-graphene is adopted, so that the electricity generating capacity of BESs can be improved by 6-8 times. The invention also finds that the electricity generating capacity of the BESs when the graphene is used as the anode modifier is about 1.3 times of the electricity generating capacity of the BESs after the aza-graphene modified anode, which is attributed to the better biocompatibility, higher conductivity and better response to riboflavin of the graphene. The method is simple to operate, low in operation cost, good in effect of promoting the BESs to generate electricity, simple in experimental equipment requirement and convenient for large-scale use.
In order to further illustrate the present invention, the following examples are provided to describe the method for enhancing the extracellular electron transfer of microorganisms in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Ultrasonically dispersing 20mg of graphene or aza-graphene in 50ml of acetone solution for 30min, then adding 1 iodine simple substance, ultrasonically treating for 15min to obtain cathode electrophoretic deposition dispersion liquid, and then controlling the direct-current voltage to be as follows by using a cathode electrophoretic deposition method: 15V, deposition time: and (3) wrapping the graphene and the aza-graphene on the surface of the carbon paper fiber in an electrostatic combination manner for 10min to obtain the modified anode material.
The modified anode material is analyzed by a scanning electron microscope, and is shown in fig. 1, and fig. 1 is a scanning electron microscope image of graphene and aza-graphene used in example 1 of the present invention. The surface morphology of the modified electrode can be seen in fig. 1.
The transmission electron microscope analysis of the graphene and aza-graphene used in example 1 is performed, and fig. 2 shows the transmission electron microscope images of the graphene and aza-graphene used in example 1 of the present invention. The surface morphology of the graphene and aza-graphene materials themselves can be seen in fig. 2.
The XPS analysis of the graphene and aza-graphene used in example 1 is shown in fig. 3, and the chemical element types contained in the commercially available graphene and aza-graphene used in the present invention can be seen from fig. 3.
According to the present invention, BET specific surface area measurements were performed on the graphene, aza-graphene, graphene-carbon paper, aza-graphene-carbon paper, and carbon paper used in example 1, and the results are shown in fig. 4, as can be seen from fig. 4, the specific surface area of graphene is about 7 times that of aza-graphene, the specific surface areas of graphene-carbon paper and aza-graphene-carbon paper are similar, and the specific surface areas of both are about 4 times that of carbon paper, which indicates that after loading of graphene and aza-graphene, the specific surface area of carbon paper is increased, and attachment of microorganisms is facilitated.
The carbon paper electrode, the graphene-carbon paper electrode and the aza-graphene-carbon paper electrode used in example 1 are characterized by water contact angles, the result is shown in fig. 5, the experimental result of fig. 5 shows that the aza-graphene-carbon paper electrode has the largest water contact angle and the contact angle is larger than 150 degrees, the aza-graphene-carbon paper electrode belongs to a super-hydrophobic material, the graphene-carbon paper electrode is the second lowest, and the smallest aza-graphene-carbon paper electrode belongs to a carbon paper electrode, so that the hydrophobicity of the anode material is improved after the graphene or aza-graphene modification.
The carbon paper electrode, the graphene-carbon paper electrode and the aza-graphene-carbon paper electrode used in example 1 are characterized by impedance spectra, the result is shown in fig. 6, and the experimental result of fig. 6 shows that after the graphene or aza-graphene is modified, the charge transfer impedance of the carbon paper electrode is greatly reduced, and the extracellular electron transfer of microorganisms is facilitated.
Example 2
The method comprises the following steps of sterilizing reactor accessories such as a reactor, a magnetic stirring rotor, a butyl rubber plug and the like at high temperature, sterilizing a working electrode, a platinum wire counter electrode and an Ag/AgCl reference electrode by an ultraviolet lamp, and assembling the battery in a super clean bench. The system uses a single chamber MEC, wherein after the completion of the anaerobic culture process of Shewanella MR-1 bacteria, the anaerobic culture medium is directly distributed into 6 reactors, the volume of the culture medium in each reactor is 130mL, and H + ion reduction is carried out on a platinum wire electrodeProduce H2The anode is oxidized to generate acetic acid, and electrons are released in the process. After the batteries are installed, the Chenghua electrochemical workstation is utilized to monitor the electricity generation performance of the BESs system. Referring to fig. 7, it can be seen from fig. 7 that the reactor assembled by different anode materials has the following electricity generating capacity: graphene-carbon paper > aza-graphene carbon paper > carbon paper.
The present invention performs scanning electron microscope analysis on the anode surface microorganisms after the reactor operation is finished, see fig. 8, and fig. 8 is a scanning electron microscope image of the anode material surface microorganisms used in example 2 of the present invention. The morphology of the microorganisms and the modifying material on the electrode surface after the end of the reactor run can be seen in fig. 8.
The BCA method protein assay method is used for measuring the content of microorganisms on the surface of the electrode after the operation of the reactor is finished, as shown in figure 9, the content of the microorganisms on the surface of different anode materials is as follows from large to small as shown in figure 9: graphene-carbon paper > aza-graphene carbon paper > carbon paper.
According to the invention, CV scanning is carried out on the anode of the reactor in the running process of the reactor, as shown in FIG. 10, CV scanning is carried out on each reactor at the power generation peak value, as can be seen from FIG. 10, the oxidation/reduction peak currents of different anode materials are different, and the oxidation/reduction peak currents are ranked from large to small as follows: graphene-carbon paper > aza-graphene carbon paper > carbon paper.
Example 3
The method comprises the steps of preparing a solution with riboflavin concentration of 5mM by using a mineral salt culture medium as an electrolyte for CV scanning, respectively using a graphene-carbon paper electrode, an aza-graphene-carbon paper electrode and a carbon paper electrode as working electrodes, using a counter electrode as a platinum wire electrode and using a reference electrode as an Ag/AgCl reference electrode, and then performing CV scanning on different working electrodes by using a Chenghua electrochemical workstation, wherein the result can be shown in FIG. 11, and the results of FIG. 11 show that in a riboflavin system, different working electrodes have large difference in oxidation/reduction peak current of CV scanning curves, and the oxidation/reduction peak currents are sequentially ordered from large to small: the graphene-carbon paper electrode is more than the aza-graphene-carbon paper electrode is more than the carbon paper electrode, so that the graphene-carbon paper electrode has the strongest response to riboflavin, the process of obtaining and losing electrons of the riboflavin is most facilitated, the aza-graphene-carbon paper electrode is next time, and the carbon paper electrode has the weakest response to the riboflavin.
Claims (7)
1. A method for enhancing microbial extracellular electron transfer uses a riboflavin system, wherein graphene or aza-graphene is loaded to a carbon electrode as an anode, the graphene or aza-graphene is directly loaded to the carbon electrode through electrophoretic deposition, the graphene or aza-graphene is subjected to ultrasonic dispersion in an acetone solution, then an iodine simple substance is added, ultrasonic treatment is carried out to obtain a cathode electrophoretic deposition dispersion liquid, and then the graphene or aza-graphene is wrapped on the surface of the carbon electrode through a cathode electrophoretic deposition method in an electrostatic combination mode to obtain a modified anode material.
2. The method of claim 1, wherein the carbon electrode comprises carbon paper, carbon cloth, carbon fiber, carbon brush, carbon felt.
3. The process as claimed in any of claims 1 to 2, wherein the electrogenic bacteria used comprise Pseudomonas (Pseudomonas), Geobacter (Geobacter), Shewanella (Shewanella) and Rhodococcus (Rhodoferax).
4. A microbial electrochemical system uses a riboflavin system and comprises a modified carbon electrode as an anode, wherein the modified carbon electrode is a carbon electrode loaded with graphene or aza-graphene, the graphene or aza-graphene is directly loaded to the carbon electrode through electrophoretic deposition, the graphene or aza-graphene is subjected to ultrasonic dispersion in an acetone solution, an iodine simple substance is added, ultrasonic treatment is carried out to obtain a cathode electrophoretic deposition dispersion liquid, and the graphene or aza-graphene is wrapped on the surface of the carbon electrode in an electrostatic combination mode by using a cathode electrophoretic deposition method to obtain a modified anode material.
5. The microbial electrochemical system of claim 4, wherein the carbon electrode comprises carbon paper, carbon cloth, carbon fiber, carbon brush, carbon felt.
6. The microbial electrochemical system of claim 4 comprising a microbial fuel cell and a microbial electrolysis cell.
7. The microbial electrochemical system of claim 6, wherein the microbial fuel cell comprises the modified carbon electrode as an anode, a cathode, and a conductor connecting the anode and the cathode.
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| CN110343602A (en) * | 2019-06-28 | 2019-10-18 | 浙江大学 | The pure bacterium Geobacter microorganism belonging to genus electro-chemical systems that can simply start in aerobic environment |
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