CN105355938B - A kind of method that peptide nanotube embeds riboflavin modified microorganism anode of fuel cell - Google Patents
A kind of method that peptide nanotube embeds riboflavin modified microorganism anode of fuel cell Download PDFInfo
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- CN105355938B CN105355938B CN201510742327.0A CN201510742327A CN105355938B CN 105355938 B CN105355938 B CN 105355938B CN 201510742327 A CN201510742327 A CN 201510742327A CN 105355938 B CN105355938 B CN 105355938B
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- riboflavin
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—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
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- 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 provides a kind of method that riboflavin progress anode of microbial fuel cell modification is embedded using self-assembling peptides nanotube, key step includes：First carbon-based electrode material is pre-processed to remove surface organic matter with acetone, then polyethyleneimine electrolyte coating is coated on carbon-based electrode surface, make positive charge in electrode surface load, then the mixed liquor of phenylalanine dipeptide and electron mediator riboflavin is added dropwise in the electrode surface, riboflavin is embedded in its nanostructured being self-assembly of during peptide nanotube by phenylalanine dipeptide, so as to form three-dimensional structure combination electrode.Peptide nanotube adds the electric conductivity of electrode, and riboflavin enhances extracellular electron transmission.The riboflavin of peptide nanotube embedding has lasting slowly releasing effect, and the anode that this mode is modified reduces microbiological fuel cell reactor internal resistance, improves electricity generation performance.
Description
Art
The invention belongs to microbiological fuel cell field, and in particular to be carried out using self-assembling peptides nanotube embedding riboflavin
The modification of anode of microbial fuel cell.
Background technology
Microbiological fuel cell (Microbial fuel cells, MFCs) be one kind by the use of microorganism as catalyst,
The technology of electric energy is produced by oxidative degradation organic or inorganic thing.MFC is so that its operating condition is simple, available substrate extensively,
The advantage that degradation of contaminant is produced electricity simultaneously, by people's extensive concern.But, so far, the output of microbiological fuel cell
Electric energy is still relatively low, it is difficult to realize large-scale application, limits the further development of microbiological fuel cell.
The anode of microbiological fuel cell is the important place of attached growth of microorganisms, and anode performance directly influences electronics
The efficiency of electrode is delivered to out of microbial cell.Therefore, the electric conductivity of anode, biocompatibility, extracellular electricity are improved
Sub- transfer performance is extremely important.Chemical mediator or electron medium are added into microbiological fuel cell, electronics can be accelerated
From intracellular to extracellular electron transmission, electronics is improved in microorganism and interelectrode transfer rate.These external source mediators include
Riboflavin, dimethyl diaminophenazine chloride, 2,6- anthraquinone disulfonic acids (AQS), thionine, the potassium ferricyanide and methyl viologen etc..Into anode chamber's electrolyte
It is directly added into redox electron mediator, although extracellular electron transmission performance can be improved, but electron mediator is easily with electrolysis
Fluid exchange and be lost in.Therefore, electron mediator is fixed on anode surface often through polymer embedding.But because some polymer are led
It is electrically poor, the effect that electron medium transmits electronics can be reduced.
In recent years, studies have found that phenylalanine dipeptide nano material has good electric conductivity and biocompatibility, with
It is past to be used for the fields such as nano material synthesis, sensing analysis, drug delivery and tissue repair.If Gazit et al. is by phenylalanine
Dipeptides nanosphere Modified graphite electrode is used for Electrochemical Detection, it is found that its detection sensitivity is doubled.Therefore, this patent is carried
Go out a kind of utilization phenylalanine dipeptide and be self-assembly of peptide nanotube (peptide nanotube, PNT), and it is hollow using its
Nanostructured embeds electron mediator riboflavin, and carbon-based material electrode surface is successively assembled into by self assembly mode, so as to reach
To modified microorganism anode of fuel cell, the purpose of system production capacity is improved.This method for being self-assembly of peptide nanotube has
Simple to operate, material is easy to get, fixed electron medium activity is damaged the advantages of small, slowly releasing effect is lasting, is held so as to reach
Continue stable anode of microbial fuel cell modification effect.
The content of the invention
The embedding riboflavin modified microorganism anode of fuel cell modification of self-chambering peptide nanotube is utilized the invention provides one kind
Method.Riboflavin is a kind of electron shuttle amboceptor, can promote electronics out of cell to extracellular transfer.In order that riboflavin can
Electrode material surface is stably fixed at, present invention employs phenylalanine dipeptide self assembly in electrode surface formation peptide nanotube mistake
Riboflavin is embedded in its nano tube structure in journey, peptide nanotube enhances electrode surface electric conductivity and biocompatibility, and
The riboflavin of embedding accelerates extracellular electron transmission to anode, so as to reduce reactor internal resistance, improves microbiological fuel cell
Electricity generation performance.The key step of the present invention includes：Make its smooth carbon-based electrode surface preparation and remove surface organic matter,
Then the polyethyleneimine amine layer coating of positive charge will be carried on pretreated electrode load, band then is added dropwise to the coating surface
There are the phenylalanine dipeptide of negative electrical charge and the mixed solution of riboflavin, phenylalanine dipeptide is self-assembly of during peptide nanotube
By in riboflavin empty nanostructured embedded therein, and by electrostatic interaction absorption in electrode surface, by LBL self-assembly,
Anode electrode surface forms the electrode layer of peptide nanotube-riboflavin modification, enhances the electric conductivity and extracellular electronics of electrode
Transfer performance.
The present invention is proposed one kind and repaiied using self-assembling peptides nanotube embedding riboflavin progress anode of microbial fuel cell
The method of decorations, it is characterised in that comprise the following steps：
(1) carbon-based electrode (carbon cloth or carbon paper) is immersed in acetone soln and pre-processed, dip time is 8~24h, is taken out
Rinsed repeatedly with deionized water after electrode 3~5 times, then electrode is placed in 105 DEG C of baking ovens and dries 2-8h, horse is then placed into
Not continue to dry 20~40min at 350~450 DEG C in stove, obtain pretreated electrode；
(2) pretreated electrode is impregnated in polyethyleneimine (PEI) solution that concentration is 2~5g/L, during dipping
Between be 5~20min, take out after under condition of nitrogen gas dry, then electrode is impregnated in again in above-mentioned PEI solution, so weight
It is multiple 2~4 times, make the upper positively charged polyethyleneimine amine layer of electrode surface load；
(3) by concentration for 4~10mg/mL the phenylalanine dipeptide aqueous solution and 5~15mM the riboflavin aqueous solution according to
Certain proportion is mixed, and is made into phenylalanine dipeptide and riboflavin mixed liquor, and it is 2 to control phenylalanine dipeptide concentration in the mixed liquor
~5mg/mL, riboflavin concentration is 3~7mM；Uniformly it is applied to after phenylalanine dipeptide is sufficiently mixed with riboflavin mixed liquor
Electrode surface, phenylalanine dipeptide is self-assembly of peptide nanotube (PNTs) process and embeds riboflavin and be fixed on electrode table
PNTs amounts are 0.10~0.50mgPNTs/cm on face, final electrode2, riboflavin amount is 0.05~0.50mg/cm2, then by electricity
At least 24h is dried under air in pole, you can the composite anode that peptide nanotube embeds riboflavin is made.
Advantages of the present invention and beneficial effect are：
The composite anode is using carbon-based electrode as anode, using riboflavin as electron mediator, will by self-assembling peptides nanotube
Riboflavin is fixed to electrode material surface, and peptide nanotube has good electric conductivity and biocompatibility, passes through its hollow tubular
Riboflavin is effectively embedded and fixed by structure, so as to accelerate the transmission of anode extracellular microbial exoelectron, reduces Microbial fuel electricity
Pond internal resistance, improves the electricity generation performance of microbiological fuel cell.The inventive method is simple, easy to operate, without using noxious material
And material, it is with a wide range of applications.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph of the peptide nanotube morphologies of carbon paper surface.
Fig. 2 is X-ray single crystal diffraction figure of the peptide nanotube in carbon paper surface.
Fig. 3 is the riboflavin/work(of peptide nanotube electrode and plain carbon cloth electrode after microbiological fuel cell is stable
Rate density map.
Fig. 4 is AC impedance figure of the riboflavin/peptide nanotube electrode and plain carbon cloth electrode in microbiological fuel cell.
Embodiment：
Below in conjunction with the accompanying drawings and the present invention is further described in embodiment, its object is to more fully understand the present invention
Content, but present disclosure not limited to this.
Embodiment 1
(1) using carbon paper as electrode material, 2.5cm × 2.5cm sizes is cut into, carbon paper is immersed in acetone soln
Row pretreatment, dip time is 12h, is rinsed repeatedly with deionized water 3 times after taking-up, is positioned over 3h after being dried in 105 DEG C of baking ovens,
370 DEG C of dry 30min in Muffle furnace are moved into again, obtain pretreated carbon paper；
(2) pretreated carbon paper is impregnated in the aq. polyethyleneimine that concentration is 3g/L, dipping 10min is rearmounted
In being dried under condition of nitrogen gas, so it is repeated 3 times, carbon paper surface is enclosed positively charged polyethyleneimine amine layer；
(3) by concentration for 4mg/mL the phenylalanine dipeptide aqueous solution and 10mM the riboflavin aqueous solution according to 1:1 body
Product is than mixing, and mixed phenylalanine dipeptide concentration is 2mg/mL, after the concentration of riboflavin is 5mM, vortex 5min, takes every time
200 μ L-Phes dipeptides and riboflavin mixed solution are added drop-wise on the carbon paper handled by step (2), mixed by being repeatedly added dropwise
It is 0.128mgPNTs/cm to close the PNTs amounts loaded on liquid, final electrode2, riboflavin amount is 0.12mg/cm2, by the electrode in sky
24h is dried under the conditions of gas, you can the composite anode (riboflavin/peptide nanometer tube anode of the fixed riboflavin of peptide nanotube embedding is made
A).The electrode surface structures prepared with scanning electron microscopic observation, as a result as shown in Figure 1.As can be seen from the figure the carbon after modifying
Paper material (Figure 1A) is compared with unmodified carbon paper material (Figure 1B), and a large amount of fibrous peptide nanotubes are contained on its surface, mutually hand over
Mistake forms tridimensional network, and the diameter of nanotube is between 50~150nm.X-ray single crystal diffraction (Fig. 2) result shows,
The material of one layer of six times of corner structure is formd in carbon paper surface, is coincide with the mono-crystalline structures of phenylalanine dipeptide assembly.
Embodiment 2
(1) using carbon cloth as electrode material, carbon cloth (5cm × 5cm) is immersed in acetone soln and handles 24h, remove surface
Organic matter, rinsed repeatedly with deionized water 3 times after taking-up, be positioned in 105 DEG C of baking ovens dry after move into again 370 in Muffle furnace
DEG C dry 30min, obtain pretreated carbon cloth；
(2) pretreated carbon cloth is impregnated in the polyethylenimine solution that concentration is 5g/L, be placed in after dipping 10min
Dried under condition of nitrogen gas, be repeated 4 times, carbon cloth surfaces is enclosed positively charged polyethyleneimine amine layer；
(3) by concentration for 9mg/mL the phenylalanine dipeptide aqueous solution and 9mM the riboflavin aqueous solution according to volume ratio 1:2
Mixing, mixed phenylalanine dipeptide concentration is 3mg/mL, and the concentration of riboflavin is 6mM, takes 200 μ L mixed solutions to be added drop-wise to
On the carbon cloth that step (2) is handled well, PNTs amounts are 0.144mgPNTs/cm on final electrode2, riboflavin amount is 0.072mg/cm2,
24h is dried under air, you can the composite anode (riboflavin/peptide nanometer tube anode B) of the fixed riboflavin of peptide nanotube embedding is made.
The composite anode of fixed riboflavin is embedded as the anode of microbiological fuel cell using peptide nanotube, inoculation sewage treatment plant is detested
Oxygen sludge is used as inoculation bacterium source, to simulate biochemical sewage (COD about 1000mg/L) as anolyte, the microbiological fuel cell
Maximum power density reaches 767mW m-2, and unmodified plain carbon cloth is close for the peak power of the microbiological fuel cell of anode
Degree is only 258mW m-2.In addition, the total internal resistance of anode of the Microbial fuel for anode of peptide nanotube embedding riboflavin modification is
88 Ω, far below with reactor internal resistance of the unmodified carbon cloth (212 Ω) for anode.
Embodiment 3
(1) using carbon cloth as electrode material, carbon cloth (5cm × 5cm) is immersed in acetone soln and handles 24h, remove surface
Organic matter, rinsed repeatedly with deionized water 3 times after taking-up, be positioned in 105 DEG C of baking ovens dry after move into again 370 in Muffle furnace
DEG C dry 30min, obtain pretreated carbon cloth；
(2) pretreated carbon cloth is impregnated in the polyethylenimine solution that concentration is 5g/L, be placed in after dipping 10min
Dried under condition of nitrogen gas, be repeated 4 times, carbon cloth surfaces is enclosed positively charged polyethyleneimine amine layer；
(3) by concentration for 6mg/mL the phenylalanine dipeptide aqueous solution and 6mM the riboflavin aqueous solution according to volume ratio 1:2
Mixing, mixed phenylalanine dipeptide concentration is 3mg/mL, and the concentration of riboflavin is 3mM, and carbon cloth is impregnated in into phenylalanine
In the mixed liquor of dipeptides and riboflavin, taken out after 30 seconds, 24h is dried under air, you can the fixed core of peptide nanotube embedding is made
The composite anode (riboflavin/peptide nanometer tube anode B) of flavine.
Claims (2)
1. a kind of embed the method that riboflavin carries out anode of microbial fuel cell modification, its feature using self-assembling peptides nanotube
It is to comprise the following steps：
(1) carbon-based electrode is immersed in acetone soln and pre-processed, dip time be 8~24h, take out electrode after spend from
Sub- water is rinsed 3~5 times repeatedly, and then electrode is placed in 105 DEG C of baking ovens and dried, is then placed into Muffle furnace 350~450
DEG C continue dry 20~40min, obtain pretreated electrode；
(2) pretreated electrode is impregnated in polyethyleneimine (PEI) solution that concentration is 2~5g/L, dip time is 5
~20min, takes out after being dried under condition of nitrogen gas, is then impregnated in electrode again in above-mentioned PEI solution, and so repeatedly 2~4
It is secondary, electrode surface is loaded the polyethyleneimine amine layer that positive charge is presented；
(3) by concentration for 4~10mg/mL the phenylalanine dipeptide aqueous solution and 5~15mM the riboflavin aqueous solution according to certain
Ratio is mixed, and is made into phenylalanine dipeptide and riboflavin mixed liquor, control in the mixed liquor phenylalanine dipeptide concentration for 2~
5mg/mL, riboflavin concentration is 3~7mM；It is repeatedly uniform after phenylalanine dipeptide and riboflavin mixed liquor are sufficiently mixed to smear
To electrode surface, PNTs is set to embed riboflavin by self assembly mode and be fixed on electrode surface, PNTs amounts on final electrode
For 0.10~0.50mgPNTs/cm2, riboflavin amount is 0.05~0.50mg/cm2, then electrode is dried at least in atmosphere
24h, you can the composite anode that peptide nanotube embeds riboflavin is made.
2. one kind according to claim 1 utilizes self-assembling peptides nanotube embedding riboflavin to carry out microbiological fuel cell sun
The method of pole modification, it is characterised in that the carbon-based electrode described in step (1) is carbon cloth or carbon paper.
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| CN110911655B (en) * | 2018-09-18 | 2021-04-13 | 天津荣盛盟固利新能源科技有限公司 | Self-assembled super-fast-charging positive electrode material and lithium ion battery thereof |
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| CN101924220B (en) * | 2010-08-27 | 2012-11-28 | 东南大学 | Modification method for electrode of microbial fuel cell |
| CN102368559B (en) * | 2011-11-01 | 2013-10-30 | 浙江大学 | Alkaline microbial fuel cell |
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