CN108400363A - A kind of electrode material and its preparation method and application - Google Patents
A kind of electrode material and its preparation method and application Download PDFInfo
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- CN108400363A CN108400363A CN201810194287.4A CN201810194287A CN108400363A CN 108400363 A CN108400363 A CN 108400363A CN 201810194287 A CN201810194287 A CN 201810194287A CN 108400363 A CN108400363 A CN 108400363A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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Abstract
The invention belongs to microorganism electrochemical fields more particularly to a kind of electrode material and its preparation method and application.Electrode material provided by the invention includes electrode matrix and is deposited on the biological carbon materials on the electrode matrix surface；The biological carbon materials after poultry feather and alkali metal hydroxide mixing through pyrolysis by being made.Electrode material provided by the invention uses the charcoal modified electrode matrix that poultry feather is pyrolyzed, it applies it in microorganism electrochemical system (BESs), the electricity generation ability of BESs can be allow to improve nearly 2 times, this, which is mainly due to the charcoal that poultry feather is pyrolyzed, has good biocompatibility, excellent conductivity, big specific surface area and be known as better response to core yellow.Simultaneously because the recycling of poultry feather waste may be implemented as the raw materials for production of electrode material using poultry feather, environmental problem caused by poultry feather waste is effectively solved, is had a good application prospect.
Description
Technical field
The invention belongs to microorganism electrochemical fields more particularly to a kind of electrode material and its preparation method and application.
Background technology
Nowadays environmental pollution and energy shortage are the two large problems of facing mankind.Poultry feather is a kind of abundant, cheap
And reproducible resource.But at present due to lacking cost-effective administering method, a large amount of poultry feather solid waste is logical
The mode of landfill is crossed to handle.If poultry feather can be converted to valuable material to be used for various production applications, so
, can also greatly alleviate environmental problem while generating great economic benefit.
Microorganism electrochemical system (BESs) is to drive one kind biology of oxidation or reduction reaction progress anti-using microorganism
Device is answered, can be produced electricl energy while degradation of contaminant, microorganism electrochemical system can have as a kind of renewable energy technologies
Effect ground alleviating energy crisis, contributes to the sustainable development of the mankind.But the practical application of this current technology is primarily limited to it
It is relatively low to be mainly due to electron transmission ability between microorganism and anode for weaker electricity generation ability.
Invention content
In view of this, the purpose of the present invention is to provide a kind of electrode material and its preparation method and application, the present invention carries
The electrode material of confession is modified using the charcoal that poultry feather is pyrolyzed, and the resource of poultry feather waste may be implemented
Change and utilize, while the electrode material has excellent chemical property, applies it in microorganism electrochemical system, it can be notable
Promote the electricity generation ability of microorganism electrochemical system.
The present invention provides a kind of electrode materials, including electrode matrix and the charcoal for being deposited on the electrode matrix surface
Material；The biological carbon materials after poultry feather and alkali metal hydroxide mixing through pyrolysis by being made.
Preferably, the holding temperature of the pyrolysis is 600~700 DEG C；The soaking time of the pyrolysis is 2~5h.
Preferably, the temperature curve of the pyrolysis is that the heating rate first with 5~10 DEG C/min is warming up to the heat preservation temperature
Degree, heat preservation, is cooled to 80~120 DEG C with the rate of temperature fall of 5~10 DEG C/min again later, finally naturally cools to 15~35 DEG C.
Preferably, the poultry feather includes one or more in chicken feather, drake feather and goose feather.
Preferably, the mass ratio of the poultry feather and alkali metal hydroxide is 1：(1.5~5).
Preferably, the electrode matrix is carbon paper electrode, other applicable electrodes have:, carbon felt electrode, carbon cloth electrode, carbon
Brush electrode, stainless (steel) wire electrode or graphite felt electrode.
The present invention provides a kind of preparation methods of electrode material described in above-mentioned technical proposal, include the following steps：
A) poultry feather and alkali metal hydroxide mixing, pyrolysis obtain biological carbon materials；
B) biological carbon materials are deposited into electrode matrix surface, obtains electrode material.
Preferably, the step b) is specifically included：
B1 the biological carbon materials, elemental iodine and acetone) are mixed into ultrasound, obtain electrophoretic deposition dispersion liquid；
B2) electrode matrix is placed in as cathode in the capacitance deposition dispersion liquid and carries out electrophoretic deposition, obtains electrode material
Material.
The present invention provides a kind of microorganism electrochemical system, the working electrode of the microorganism electrochemical system is above-mentioned
Electrode material described in technical solution；The electrolyte of the microorganism electrochemical system is electricity-producing microorganism solution.
Preferably, the electricity-producing microorganism in the electricity-producing microorganism solution includes Shewanella MR-1, ground bacillus, desulfurization arc
It is one or more in bacterium and Escherichia coli and mixed bacterium.
Compared with prior art, the present invention provides a kind of electrode materials and its preparation method and application.The present invention provides
Electrode material include electrode matrix and be deposited on the biological carbon materials on the electrode matrix surface；The biological carbon materials are by fowl
It is made through pyrolysis after class feather and alkali metal hydroxide mixing.Electrode material provided by the invention is pyrolyzed to obtain using poultry feather
The charcoal modified electrode matrix arrived, applies it in microorganism electrochemical system (BESs), can make the electricity generation ability of BESs
Nearly 2 times can be improved, this, which is mainly due to charcoal that poultry feather is pyrolyzed, has good biocompatibility, excellent
Conductivity, big specific surface area and better response is known as to core yellow.Simultaneously because using poultry feather as electrode material
The recycling of poultry feather waste may be implemented in raw materials for production, effectively solves environment caused by poultry feather waste
Problem has a good application prospect.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the 10000x scanning electron microscope (SEM) photographs for the GFC- carbon paper electrodes that the embodiment of the present invention 1 provides；
Fig. 2 is the 5000x scanning electron microscope (SEM) photographs for the GFC- carbon paper electrodes that the embodiment of the present invention 1 provides；
Fig. 3 is the scanning electron microscope (SEM) photograph for the carbon paper electrode that the embodiment of the present invention 1 provides；
Fig. 4 is the Raman characterization collection of illustrative plates for the charcoal that the embodiment of the present invention 1 uses；
Fig. 5 is the XPS characterization collection of illustrative plates for the charcoal that the embodiment of the present invention 1 uses；
Fig. 6 is the EIS impedance spectras that the embodiment of the present invention 1 provides；
Fig. 7 is the CV scanning figures that the embodiment of the present invention 1 provides；
Fig. 8 is the electricity production figure for the microorganism electrochemical system that the embodiment of the present invention 2 provides；
Fig. 9 is the scanning electron microscope of unmodified carbon paper electrode after the BESs end of runs that the embodiment of the present invention 2 provides
Figure；
Figure 10 be the embodiment of the present invention 2 provide BESs end of runs after GFC modify carbon paper electrode scanning electron microscope
Figure；
Figure 11 is the BCA method eggs of working electrode surface microorganism after the BESs end of runs that the embodiment of the present invention 2 provides
It is white to measure block diagram；
Figure 12 is the cyclic voltammetry scan figure at electricity production peak value that the embodiment of the present invention 2 provides；
Figure 13 is the EIS impedance spectras at electricity production peak value that the embodiment of the present invention 2 provides；
Figure 14 is the fitting circuit for the GFC-CP electrode EIS impedance spectrums that the present invention applies the offer of example 1；
Figure 15 is the fitting circuit for the CP electrode EIS impedance spectrums that the present invention applies the offer of example 1；
Figure 16 is the cyclic voltammetry scan figure that the embodiment of the present invention 3 provides.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of electrode materials, including electrode matrix and the charcoal for being deposited on the electrode matrix surface
Material；The biological carbon materials after poultry feather and alkali metal hydroxide mixing through pyrolysis by being made.
Electrode material provided by the invention includes electrode base material and biological carbon materials, wherein the electrode base material include but
It is not limited to carbon paper electrode, carbon felt electrode, carbon cloth electrode, carbon brush electrode, stainless (steel) wire electrode or graphite felt electrode.
In the present invention, it is made through pyrolysis after the biological carbon materials are mixed by poultry feather and alkali metal hydroxide,
It is deposited on the electrode matrix surface.In the present invention, the poultry feather includes but not limited in chicken feather, drake feather and goose feather
It is one or more；The alkali metal hydroxide includes but not limited to sodium hydroxide and/or potassium hydroxide；The poultry feather
Mass ratio with alkali metal hydroxide is preferably 1：(1.5~5), concretely 1:1.5、1:2、1:2.5、1:3、1:3.5、1:
4、1:4.5 or 1:5.In the present invention, the holding temperature of the pyrolysis is preferably 600~700 DEG C, concretely 600 DEG C, 620
DEG C, 640 DEG C, 650 DEG C, 660 DEG C, 680 DEG C or 700 DEG C；The soaking time of the pyrolysis is preferably 2~5h, concretely 2h,
2.5h, 3h, 3.5h, 4h, 4.5h or 5h.In the present invention, the pyrolysis is preferably heated up according to following temperature curve, is kept the temperature
And cooling：The holding temperature is first warming up to the heating rate of 5~10 DEG C/min, is kept the temperature, later again with 5~10 DEG C/min's
Rate of temperature fall is cooled to 80~120 DEG C, finally naturally cools to 15~35 DEG C.In above-mentioned temperature curve provided by the invention,
The heating rate concretely 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min；The drop
Warm rate concretely 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min；The cooling temperature
Concretely 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C or 120 DEG C；Temperature after the natural cooling
Spend concretely room temperature.
In the present invention, the biological carbon material is deposited on the electrode matrix surface, and the biological carbon materials are in electrode
The deposition of substrate surface is preferably 0.2~1mg/cm2, concretely 0.67mg/cm2。
The present invention also provides a kind of preparation methods of electrode material described in above-mentioned technical proposal, include the following steps：
A) poultry feather and alkali metal hydroxide mixing, pyrolysis obtain biological carbon materials；
B) biological carbon materials are deposited into electrode matrix surface, obtains electrode material.
In preparation method provided by the invention, poultry feather and alkali metal hydroxide are mixed first, wherein described
The specific type of poultry feather and alkali metal hydroxide, usage ratio hereinbefore by the agency of, details are not described herein.Mixing
It after uniformly, is pyrolyzed, the device of the pyrolysis is preferably tube furnace, and the detailed process of the pyrolysis, condition are hereinbefore
By the agency of, details are not described herein.After pyrolysis, biological carbon materials are obtained.
After obtaining biological carbon materials, the biological carbon materials are deposited into electrode matrix surface, obtain the electrode material.
In the present invention, it is preferred to carry out the deposition of biological carbon materials in the following way：
B1 the biological carbon materials, elemental iodine and acetone) are mixed into ultrasound, obtain electrophoretic deposition dispersion liquid；
B2) electrode matrix is placed in as cathode in the capacitance deposition dispersion liquid and carries out electrophoretic deposition, obtains electrode material
Material.
In above-mentioned depositional mode provided by the invention, biological carbon materials, elemental iodine and acetone are mixed into ultrasound first.Its
In, the amount ratio of the biological carbon materials, elemental iodine and acetone is preferably 20mg：(40~80) mg：(20~100) mL, it is more excellent
It is selected as 20mg：(50~60) mg：(40~60) mL, concretely 20mg：60mg：50mL；The frequency of the ultrasound is preferably 20
~60kHz, concretely 40kHz；The power of the ultrasound is preferably 200~300W, concretely 250W；It is described ultrasound when
Between preferably 20~60min, concretely 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or
60min.In the present invention, it is preferred to biological carbon materials and acetone are first mixed ultrasound, time of the ultrasound is preferably 15~
50min, concretely 15min, 20min, 25min, 30min, 35min, 40min, 45min or 50min；Later again by charcoal
The mixed system of material and acetone mixes ultrasound with elemental iodine, and the time of the ultrasound is preferably 5~30min, concretely
5min, 10min, 15min, 20min, 25min or 30min.After ultrasound, electrophoretic deposition dispersion liquid is obtained.It is heavy to obtain electrophoresis
After integrating dispersion liquid, electrode matrix is placed in as cathode in the capacitance deposition dispersion liquid and carries out electrophoretic deposition.Wherein, the electricity
The DC voltage of swimming deposition is preferably 10~30V, concretely 10V, 15V, 20V, 25V or 30V；The electrophoretic deposition when
Between preferably 5~20min, concretely 5min, 10min, 15min or 20min.After electrophoretic deposition, the electrode is obtained
Material.
Electrode material provided by the invention uses the charcoal modified electrode matrix that poultry feather is pyrolyzed, and is applied
Into microorganism electrochemical system (BESs), the electricity generation ability of BESs can be allow to improve nearly 2 times, this is mainly due to birds plumage
The charcoal that hair pyrolysis obtains has good biocompatibility, excellent conductivity, big specific surface area and is known as to core yellow
Preferably response.Simultaneously because poultry feather waste may be implemented as the raw materials for production of electrode material using poultry feather
Recycling, effectively solve poultry feather waste caused by environmental problem, have a good application prospect.
The present invention provides a kind of microorganism electrochemical system (BESs), the working electrodes of the microorganism electrochemical system
For the electrode material described in above-mentioned technical proposal；The electrolyte of the microorganism electrochemical system is electricity-producing microorganism solution.
Microorganism electrochemical system provided by the invention includes working electrode, to electrode, reference electrode and electrolyte.Its
In, the working electrode is the electrode material described in above-mentioned technical proposal；Described includes but not limited to platinum filament to electrode；The ginseng
Include but not limited to Ag/AgCl reference electrodes than electrode；The electrolyte is electricity-producing microorganism solution；The electricity-producing microorganism is molten
Electricity-producing microorganism in liquid includes one or more in Shewanella MR-1, ground bacillus, desulfovibrio and Escherichia coli.
In the present invention, the source of the electricity-producing microorganism solution is not particularly limited, is preferably obtained in the following manner
：Electricity-producing microorganism is cultivated in the medium, obtains electricity-producing microorganism solution.In the present invention, the electricity-producing microorganism is preferred
It is cultivated in LB (Luria-Bertani) culture medium, aerobic culture medium and anaerobic culture medium successively.Wherein, the LB culture mediums
In contain peptone, NaCl, yeast extract and water, the peptone, NaCl, yeast extract and water amount ratio concretely 1g：
0.5g：0.5g：100mL；When being cultivated in LB culture mediums, an independent electricity-producing microorganism bacterium point is preferably inoculated into 0.2
In~1mL LB culture mediums, can specifically it be inoculated into 0.5mL LB culture mediums；The temperature of the culture is preferably 25~35 DEG C, more
Preferably 30 DEG C；The time of the culture is preferably 6~18h, more preferably 12h；The culture preferably carries out in the incubator,
The rotating speed of incubator is preferably 100~250rpm/min, concretely 180rpm/min.In the present invention, the aerobic culture
Base is preferably aerobic mineral salts medium, in the aerobic mineral salts medium containing 4- hydroxyethyl piperazineethanesulfonic acids (Hepes),
NH4Cl、K2HPO4、KH2PO4、MgSO4、(NH4)2SO4, sodium lactate and water；The aerobic mineral salts medium is preferably according to following
Mode is prepared to obtain：By 11.91g Hepes, 0.46g NH4Cl、0.225g K2HPO4、0.225g KH2PO4、0.117g
MgSO4·7H2O、0.225g(NH4)2SO4With 2.788mL 60wt%- sodium lactate solutions with water dissolution is distilled, use is a concentration of
PH value is adjusted to 7.2 by the NaOH solution of 1mol/L, then uses 1L volumetric flask constant volumes, high-temperature sterilization.It is carried out in aerobic culture medium
When culture, the volume ratio of the bacterium solution and the aerobic culture medium that are obtained through LB medium cultures is preferably 1：(500~2000), more
Preferably 1:1000；The temperature of the culture is preferably 25~35 DEG C, more preferably 30 DEG C；The time of the culture is preferably 12
~48h, more preferably for 24 hours；The culture preferably carries out in the incubator, and the rotating speed of incubator is preferably 100~250rpm/
Min, concretely 180rpm/min.In the present invention, the anaerobic culture medium is preferably anaerobism mineral salts medium, described to detest
Contain 4- hydroxyethyl piperazineethanesulfonic acids (Hepes), NH in oxygen mineral salts medium4Cl、K2HPO4、KH2PO4、MgSO4、(NH4)2SO4, sodium lactate and water；The aerobic mineral salts medium is preferably prepared and is obtained in the following way：By 11.91g Hepes,
0.46g NH4Cl、0.225g K2HPO4、0.225g KH2PO4、0.117g MgSO4·7H2O、0.225g(NH4)2SO4、
2.788mL 60wt%- sodium lactate solutions, 4.64g fumaric acids and 1.6gNaOH distillation water dissolution, with a concentration of 1mol/L
NaOH solution pH value is adjusted to 7.2, then use 1L volumetric flask constant volumes, high-temperature sterilization.When being cultivated in anaerobic culture medium,
The bacterium solution obtained through aerobic culture medium culture and the volume ratio of the anaerobic culture medium are preferably 1：(5~15), more preferably 1:
9；The temperature of the culture is preferably 25~35 DEG C, more preferably 30 DEG C；The time of the culture is preferably 4~16h, more preferably
For 8h；The culture preferably carries out in the incubator, and the rotating speed of incubator is preferably 100~250rpm/min, concretely
180rpm/min。
The working electrode surface deposition of microorganism electrochemical system provided by the invention has poultry feather to be pyrolyzed charcoal, phase
Than not depositing the microorganism electrochemical system that poultry feather is pyrolyzed charcoal in working electrode surface, electricity generation ability can increase
Nearly 2 times.Simultaneously because using poultry feather as the raw material for preparing charcoal, the recycling of poultry feather waste may be implemented
It utilizes, effectively solves environmental problem caused by poultry feather waste, have a good application prospect.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
The biological carbon materials (GFC) that the following embodiments of the present invention use are prepared in the following way：By 1g goose feather and
3gKOH is added in tube furnace and is pyrolyzed, and tube furnace initial temperature is room temperature：20 DEG C, later with the heating rate liter of 8 DEG C/min
To 650 DEG C, 3h is kept the temperature, then 100 DEG C are down to the rate of temperature fall of 8 DEG C/min, then cooled to room temperature, obtains biological raw material of wood-charcoal
Expect (GFC).
Embodiment 1
The preparation of electrode material
First by 20mg GFC, ultrasonic disperse 30min, supersonic frequency 40kHz, ultrasonic power are in 50ml acetone solns
1 elemental iodine (about 60mg), then ultrasound 15min is then added in 250W, and supersonic frequency 40kHz, ultrasonic power 250W are obtained
Dispersion liquid is deposited to ability cathode electrophoresis.
By two panels carbon paper (producer：Upper Haihe River is gloomy, model：East beautiful 090, surface area：4.5cm2) deposited as ability cathode electrophoresis
Positive and negative electrode, and be immersed in ability cathode electrophoresis deposition dispersion liquid in, the positive and negative polarities of DC power supply are separately connected two panels carbon paper, beat
DC power supply is opened, voltage value is adjusted to 20V, after energization, GFC constantly deposits to carbon paper fiber table by way of electrostatical binding
Power supply after deposition process continues 15min, is closed in face, the anode material of the GFC modifications prepared, anode material surface GFC
Deposition be about 3mg.
Electron microscope analysis is scanned to unmodified carbon paper electrode and anode material manufactured in the present embodiment respectively, sees Fig. 1
~3, Fig. 1 are the 10000x scanning electron microscope (SEM) photographs for the GFC- carbon paper electrodes that the embodiment of the present invention 1 provides, and Fig. 2 is the embodiment of the present invention 1
The 5000x scanning electron microscope (SEM) photographs of the GFC- carbon paper electrodes of offer, Fig. 3 are the scanning electricity for the carbon paper electrode that the embodiment of the present invention 1 provides
Mirror figure.Comparison diagram 1~3 can be seen that the configuration of surface of the anode material of GFC modifications.
Raman spectrum analysis is carried out to the charcoal that the present embodiment uses, as a result sees that Fig. 4, Fig. 4 are the embodiment of the present invention 1 and make
The Raman characterization collection of illustrative plates of charcoal, as seen from Figure 4 carbon key different included in the charcoal that uses of the present invention
And the size of charcoal defect level obtained.
Raman spectrum analysis is carried out to the charcoal that the present embodiment uses, as a result sees that Fig. 5, Fig. 5 are the embodiment of the present invention 1 and make
The XPS of charcoal characterizes collection of illustrative plates, the chemical element type that the charcoal that the present invention uses as seen from Figure 5 is included.
The table of electrochemical impedance collection of illustrative plates is carried out to unmodified carbon paper electrode and anode material manufactured in the present embodiment respectively
As a result sign is shown in that Fig. 6, Fig. 6 are the EIS impedance spectras that the embodiment of the present invention 1 provides, CP indicates carbon paper electrode, GFC-CP tables in figure
Show the carbon paper electrode of GFC modifications, i.e., anode material manufactured in the present embodiment.By Fig. 6's it can be seen that after GFC modifications,
The load transfer impedance for greatly reducing carbon paper electrode is conducive to the extracellular electron transmission of microorganism.
CV scannings are carried out to unmodified carbon paper electrode and anode material manufactured in the present embodiment respectively, as a result see Fig. 7, are schemed
7 be the CV scanning figures that the embodiment of the present invention 1 provides, and CP indicates that carbon paper electrode, GFC-CP indicate the carbon paper electricity of GFC modifications in figure
Pole, i.e., anode material manufactured in the present embodiment.Pass through as seen from Figure 7 after GFC modifications, considerably increases carbon paper surface
Electrochemical surface area is conducive to the extracellular electron transmission of microorganism.
Embodiment 2
The preparation of LB culture mediums：1g peptones, 0.5g NaCl, 0.5g yeast extracts is weighed to be dissolved in 100mL distilled water, it is high
Temperature sterilizing, it is spare.
The preparation of aerobic culture medium：11.91g Hepes、0.46g NH4Cl、0.225g K2HPO4、0.225g KH2PO4、
0.117g MgSO4·7H2O、0.225g(NH4)2SO4With 2.788mL 60wt%- sodium lactate solutions with water dissolution is distilled, use is dense
Degree is that pH value is adjusted to 7.2 by the NaOH solution of 1mol/L, then uses 1L volumetric flask constant volumes, high-temperature sterilization spare.
The preparation of anaerobic culture medium：11.91g Hepes、0.46g NH4Cl、0.225g K2HPO4、0.225g KH2PO4、
0.117g MgSO4·7H2O、0.225g(NH4)2SO4, 2.788mL 60wt%- sodium lactate solutions, 4.64g fumaric acids and
1.6gNaOH distillation water dissolutions, 7.2 are adjusted to the NaOH solution of a concentration of 1mol/L by pH value, then use 1L volumetric flasks fixed
Hold, high-temperature sterilization is spare.
The culture of bacterium solution：
A) 200 microlitres of the yellow pipette tips picking on the bacterium plate of Shewanella MR-1 (S.Oneidensis MR-1) is utilized
One independent bacterium point, is seeded in the sterilized LB culture mediums of 0.5mL, is then cultivated in 30 DEG C of constant incubator
12h, incubator rotating speed：180rpm/min.
B) 40 μ L LB bacterium solutions are seeded in 40mL aerobic culture mediums, are cultivated in 30 DEG C of constant incubator for 24 hours, culture
Case rotating speed：180rpm/min.
C) the aerobic culture bacterium solutions of 40mL are seeded in 360mL anaerobic culture mediums, 8h are cultivated in 30 DEG C of constant incubator,
Incubator rotating speed：180rpm/min.
The assembling and operation of microorganism electrochemical system (BESs)：
The reactors accessories such as reactor, magnetic agitation rotor, butyl rubber bung are first passed through into high-temperature sterilization, working electrode
(anode material or unmodified carbon paper electrode prepared by embodiment 1), platinum filament pass through electrode and Ag/AgCl reference electrodes
Ultraviolet lamp sterilizes；Then using the bacterium solution of step c) culture acquisitions as electrolyte, by working electrode, to electrode, reference electrode, electricity
Solution liquid and reactor are assembled into microorganism electrochemical system (BESs) in super-clean bench.After BESs is assembled, BESs, BESs are run
Running temperature be 30 DEG C, anode potential control when operation is+0.2V v.s.Ag/AgCl reference electrodes.
It is monitored respectively using anode material prepared by embodiment 1 as the BESs of working electrode using occasion China electrochemical workstation
With electricity generation performance (the one group of parallel reality of setting of the BESs using unmodified carbon paper electrode as working electrode in the process of running
Test), see that Fig. 8, Fig. 8 are the electricity production figures for the microorganism electrochemical system that the embodiment of the present invention 2 provides, in figure, CP is indicated with carbon paper
The electrode BESs as working electrode, GFC-CP expression is using anode material prepared by embodiment 1 as the BESs of working electrode.By
Fig. 8 can be seen that the reactor being assembled by different anode materials, and the size of electricity generation ability is：Sun prepared by embodiment 1
Pole material (GFC- carbon paper electrodes) ＞ carbon paper electrodes.
Using anode material prepared by embodiment 1 as the BESs of working electrode and using unmodified carbon paper electrode as
After the BESs end of runs of working electrode, scanning electron microscope point has been carried out to the working electrode surface microorganism of two BESs respectively
Analysis is shown in that Fig. 9~10, Fig. 9 are the scanning of unmodified carbon paper electrode after the BESs end of runs that the embodiment of the present invention 2 provides
Electron microscope, Figure 10 be the embodiment of the present invention 2 provide BESs end of runs after GFC modify carbon paper electrode scanning electron microscope
Figure.Comparison diagram 9~10 can be seen that the microorganism of electrode surface and the form of decorative material after reactor end of run.
Using BCA methods albuminometry to the anode material prepared using embodiment 1 as the BESs of working electrode and with not
Modified carbon paper electrode is carried out as the content of the working electrode surface microorganism after the BESs end of runs of working electrode
It measures, sees that Figure 11, Figure 11 are working electrode surface microorganisms after the BESs end of runs that the embodiment of the present invention 2 provides
BCA method protein determination block diagrams, CP indicates the BESs using carbon paper electrode as working electrode in figure, and GFC-CP expressions are with embodiment
BESs of 1 anode material prepared as working electrode.Anode material (the GFC- carbon that as seen from Figure 11 prepared by embodiment 1
Paper electrode) content of surface microorganism is about 3 times of carbon paper electrode.
Anode material prepared by embodiment 1 is as the BESs of working electrode and using unmodified carbon paper electrode as work
In the BESs operational process of electrode, CV scannings are carried out at electricity production peak value, see that Figure 12, Figure 12 are that the embodiment of the present invention 2 provides
Cyclic voltammetry scan figure at electricity production peak value, CP indicates the BESs using carbon paper electrode as working electrode, GFC-CP tables in figure
Show the BESs using anode material prepared by embodiment 1 as working electrode, the small figure in figure is that CP homologous threads are put in big figure
Big figure.As seen from Figure 12, the size of different anode material, oxidation/reduction peak current has differences, oxidation/reduction
Peak current be ranked up from big to small for：Anode material (GFC- carbon paper electrodes) ＞ carbon paper electrodes prepared by embodiment 1.
Anode material prepared by embodiment 1 is as the BESs of working electrode and using unmodified carbon paper electrode as work
In the BESs operational process of electrode, EIS analyses are carried out to its working electrode at electricity production peak value, see that Figure 13~15, Figure 13 are these
The EIS impedance spectras at electricity production peak value that inventive embodiments 2 provide, CP is indicated using carbon paper electrode as working electrode in figure
BESs, GFC-CP indicate that the small figure in figure is in big figure using anode material prepared by embodiment 1 as the BESs of working electrode
The partial enlarged view of GFC-CP homologous threads, Figure 14 are the fitting circuits of GFC-CP electrode EIS impedance spectrums, and Figure 15 is CP electrodes
The fitting circuit of EIS impedance spectrums, R1Represent solution resistance, R2Represent interface load transfer impedance, Q2Constant phase element is represented, Mg3, which is represented, to be expanded
Impedance is dissipated, the size of the different electrode material it can be seen from Figure 13~15, load transfer impedance has very big difference, load transfer resistance
Anti- size be ranked up from big to small for：Anode material (GFC- carbon paper electrodes) ＞ carbon paper electrodes prepared by embodiment 1.
Embodiment 3
0.0038g riboflavin powder is weighed, is dissolved using the aerobic culture medium that embodiment 2 is prepared, it is then fixed with volumetric flask
Hold to 100mL, obtains the riboflavin solution of a concentration of 100 μm of ol/L, be then diluted to 5 μM/L again.
The electrolyte scanned as CV using the riboflavin solution of above-mentioned 5 μm of ol/L, GFC- carbon paper electrodes (make by embodiment 1
Standby anode material) and carbon paper electrode respectively as working electrode, be platinum electrode to electrode, reference electrode is Ag/AgCl ginsengs
Than electrode, microorganism electrochemical system (BESs) is assembled into super-clean bench.Then utilize occasion China electrochemical workstation to difference
Working electrode do CV scannings, as a result visible Figure 16, Figure 16 are the cyclic voltammetry scan figures that the embodiment of the present invention 3 provides, in figure
CP indicates that the BESs using carbon paper electrode as working electrode, GFC-CP are indicated using anode material prepared by embodiment 1 as work
The BESs of electrode, the small figure in figure are the enlarged drawing of CP homologous threads in big figure.In riboflavin it can be seen from the result of Figure 16
In system, there are larger difference, oxidation/reduction peaks for the oxidation/reduction peak current of its CV scanning curve of different working electrodes
Electric current sorts be followed successively by from big to small：Anode material GFC- carbon paper electrode ＞ carbon paper electrodes prepared by embodiment 1, illustrate process
Electrode after GFC modifications, is more advantageous to the progress of riboflavin receiving and losing electrons process, is more conducive to S.Oneidensis MR-1
The progress of the extracellular indirect electron transmittance process of bacterium, ground bacillus, desulfovibrio, Escherichia coli, mixed bacterium etc..
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of electrode material, including electrode matrix and the biological carbon materials for being deposited on the electrode matrix surface；The biology
Carbon Materials after poultry feather and alkali metal hydroxide mixing through pyrolysis by being made.
2. electrode material according to claim 1, which is characterized in that the holding temperature of the pyrolysis is 600~700 DEG C；
The soaking time of the pyrolysis is 2~5h.
3. electrode material according to claim 2, which is characterized in that the temperature curve of the pyrolysis be first with 5~10 DEG C/
The heating rate of min is warming up to the holding temperature, heat preservation, 80 are cooled to the rate of temperature fall of 5~10 DEG C/min again later~
120 DEG C, finally naturally cool to 15~35 DEG C.
4. electrode material according to claim 1, which is characterized in that the poultry feather includes chicken feather, drake feather and goose feather
In it is one or more.
5. electrode material according to claim 1, which is characterized in that the matter of the poultry feather and alkali metal hydroxide
Amount is than being 1：(1.5~5).
6. electrode material according to claim 1, which is characterized in that the electrode matrix be carbon paper electrode, carbon felt electrode,
Carbon cloth electrode, carbon brush electrode, stainless (steel) wire electrode or graphite felt electrode.
7. the preparation method of electrode material, includes the following steps described in a kind of claim 1：
A) poultry feather and alkali metal hydroxide mixing, pyrolysis obtain biological carbon materials；
B) biological carbon materials are deposited into electrode matrix surface, obtains electrode material.
8. preparation method according to claim 7, which is characterized in that the step b) is specifically included：
B1 the biological carbon materials, elemental iodine and acetone) are mixed into ultrasound, obtain electrophoretic deposition dispersion liquid；
B2) electrode matrix is placed in as cathode in the capacitance deposition dispersion liquid and carries out electrophoretic deposition, obtains electrode material.
9. a kind of microorganism electrochemical system, which is characterized in that the working electrode of the microorganism electrochemical system is wanted for right
Seek 1~6 any one of them electrode material；The electrolyte of the microorganism electrochemical system is electricity-producing microorganism solution.
10. electro-chemical systems according to claim 9, which is characterized in that the electricity production in the electricity-producing microorganism solution is micro-
Biology includes one or more in Shewanella MR-1, ground bacillus, desulfovibrio and Escherichia coli.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830698A (en) * | 2019-02-18 | 2019-05-31 | 湖南农业大学 | A kind of preparation method of the electrode with hollow pleated structure |
| CN109873171A (en) * | 2019-03-04 | 2019-06-11 | 中国科学技术大学 | A kind of microorganism electrochemical system combination electrode and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979530A (en) * | 2014-06-11 | 2014-08-13 | 安徽工业大学 | Method for preparing porous carbon for electrochemical capacitor from egg white used as raw material |
| CN104003371A (en) * | 2014-06-11 | 2014-08-27 | 安徽工业大学 | Method for preparing porous carbon material used for super capacitor through using cashmere wool as raw material |
| CN104386685A (en) * | 2014-10-22 | 2015-03-04 | 北京化工大学 | Method for preparing nitrogen-doped active carbon from nitrogen-enriched biomass raw material |
| CN105489908A (en) * | 2016-01-13 | 2016-04-13 | 中国科学院广州能源研究所 | Application of humic acid composite biochar in microbial fuel cell and preparation method of humic acid composite biochar |
| CN105565497A (en) * | 2015-12-15 | 2016-05-11 | 东华大学 | Air cathode microbial fuel cell constructed wetland device of biological carbon matrix anode |
| CN106920972A (en) * | 2017-04-11 | 2017-07-04 | 大连理工大学 | The preparation method and microbiological fuel cell of the novel composite anode of a kind of N doping charcoal based on sludge and porous volcanic rock |
-
2018
- 2018-03-09 CN CN201810194287.4A patent/CN108400363A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979530A (en) * | 2014-06-11 | 2014-08-13 | 安徽工业大学 | Method for preparing porous carbon for electrochemical capacitor from egg white used as raw material |
| CN104003371A (en) * | 2014-06-11 | 2014-08-27 | 安徽工业大学 | Method for preparing porous carbon material used for super capacitor through using cashmere wool as raw material |
| CN104386685A (en) * | 2014-10-22 | 2015-03-04 | 北京化工大学 | Method for preparing nitrogen-doped active carbon from nitrogen-enriched biomass raw material |
| CN105565497A (en) * | 2015-12-15 | 2016-05-11 | 东华大学 | Air cathode microbial fuel cell constructed wetland device of biological carbon matrix anode |
| CN105489908A (en) * | 2016-01-13 | 2016-04-13 | 中国科学院广州能源研究所 | Application of humic acid composite biochar in microbial fuel cell and preparation method of humic acid composite biochar |
| CN106920972A (en) * | 2017-04-11 | 2017-07-04 | 大连理工大学 | The preparation method and microbiological fuel cell of the novel composite anode of a kind of N doping charcoal based on sludge and porous volcanic rock |
Non-Patent Citations (1)
| Title |
|---|
| HONG-YANG TANG ECT.: "In-suit Mg(OH)2 template synthesis of nitrogen-doped porous carbon materials from glutinous rice for supercapacitors with excellent electrochemical performance", 《COMPOSITES PART A: APPLIED SCIENCE AND MANUFACTURING》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830698A (en) * | 2019-02-18 | 2019-05-31 | 湖南农业大学 | A kind of preparation method of the electrode with hollow pleated structure |
| CN109830698B (en) * | 2019-02-18 | 2022-02-08 | 湖南农业大学 | Preparation method of electrode with hollow fold structure |
| CN109873171A (en) * | 2019-03-04 | 2019-06-11 | 中国科学技术大学 | A kind of microorganism electrochemical system combination electrode and preparation method thereof |
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