CN101924220B - Modification method for electrode of microbial fuel cell - Google Patents

Modification method for electrode of microbial fuel cell Download PDF

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CN101924220B
CN101924220B CN2010102646655A CN201010264665A CN101924220B CN 101924220 B CN101924220 B CN 101924220B CN 2010102646655 A CN2010102646655 A CN 2010102646655A CN 201010264665 A CN201010264665 A CN 201010264665A CN 101924220 B CN101924220 B CN 101924220B
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conductive glass
solution
ito
fuel cell
conductive
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CN101924220A (en
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葛丽芹
嵇剑宇
贾永军
吴文果
柏林玲
顾忠泽
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Southeast University
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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
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    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a modification method for an electrode of a microbial fuel cell. The method is characterized in that ITO conductive glass is taken as a template, and chitosan with positive and negative charges and nano-conductive particles are alternatively adsorbed on the surface of the ITO conductive glass through a layer-by-layer self-assembling method based on electrostatic interaction of the positive and negative charges, thus forming the modified electrode of the microbial fuel cell. The ITO conductive glass modified by the method can be used as the anode of the microbial fuel cell, thus greatly improving the electrogenesis output of the microbial fuel cell, the method is simple and effective, the operation is simple and convenient, the required time is shorter, the transportation is convenient and the application range is wide.

Description

The method of modifying of electrode of microbial fuel cell
Technical field
The invention belongs to electrode of microbial fuel cell developing material technical field, be specifically related to a kind of preparation method of microbiological fuel cell modified electrode.
Background technology
Chemically modified electrode is to carry out MOLECULE DESIGN at electrode surface, and molecule, ion, the polymer design that will have excellent chemical character are fixed on electrode surface, makes electrode have certain specific chemistry and electrochemical properties.Chemically modified electrode has been expanded electrochemical research field, has been applied to many aspects such as life, environment, the energy, analysis, electronics and materialogy at present.Generally comprise absorbent-type modified electrode and covalent bond mould assembly modified electrode; Said absorbent-type modified electrode with particular functional group's Molecular Adsorption to electrode surface, and covalent bond mould assembly modified electrode through chemical reaction keyed jointing particular functional group's molecule or polymer to electrode surface.
Layer-by-layer (Layer-by-Layer self assembly) is the method for preparing order thin film that development in recent years is got up; The Electrostatic Absorption characteristic of this techniques make use organic or inorganic zwitterion is through the alternately molecule deposition formation film of counter ion system.Human layer-by-layers such as D.Decher had carried out pionerring research to the structure order thin film in 1991.Its method is alternately to adsorb the preparation multilayer film with amphipathic organic cation-anion (perhaps polyelectrolyte) at the ionization substrate surface.
Up to the present, a variety of materials all are used for constructing the multilayer order film with specific composition, thickness and character by success such as CNT, protein, nucleic acid, phosphatide and organic/inorganic particle.The method of utilizing self assembly layer by layer like people such as B.Aoki is with the phospholipid modified electrode surface that arrives, to improve the sensitivity of electrode.Recently; J.J.Sun etc. utilize the method for self assembly layer by layer that multilayer carbon nanotube and PEI are modified on the carbon cloth; With anode, make the power density ratio of microbiological fuel cell not carry out layer by layer the battery of self-assembling electrode and mentioned 20% as microbe fuel electromagnetism.People such as Ryuhei Nakamura have worked out α-Fe 2O 3The light that can utilize wavelength to surpass 420nm carries out photocatalysis and produces electronics, and this electron-like is the same with the electronics that generation is transmitted in the extracellular of the cytochrome c mediation of Shewanella.The method of self assembly layer by layer has very desirable application prospect at raising microbiological fuel cell electrogenesis output facet, and the present invention researchs and develops on this basis.
Summary of the invention
The object of the invention is to provide a kind of method of modifying of electrode of microbial fuel cell, and its purpose is to improve microbiological fuel cell electrogenesis output, for the exploitation of electrode of microbial fuel cell provides a kind of new thinking.
Technical scheme provided by the invention is:
A kind of method of modifying of electrode of microbial fuel cell; It is characterized in that said method comprises that with the ITO electro-conductive glass be template; Make the shitosan and the conductive nano particle that have positive and negative electric charge alternately be adsorbed on the ITO conductive glass surface, form the microbiological fuel cell modified electrode through self-assembling method layer by layer based on the positive and negative charge electrostatic interaction.
Preferably, said conductive nano particle is selected from α-Fe 2O 3Particle, SiO 2Particle and Al 2O 3Particle.
Preferably, said method specifically may further comprise the steps:
(1) with water is solvent, respectively preparation of nano conductive particle solution and low-molecular weight chitoglycan solution;
(2) the ITO electro-conductive glass is carried out clean preliminary treatment;
(3) the ITO electro-conductive glass is alternately immersed in chitosan solution and the conductive nano particle solution successively, assemble repeatedly repeatedly, thereby form the multi-layer polyelectrolyte film at the ITO conductive glass surface.
Preferably, shitosan is selected from molecular weight at 1-5 ten thousand daltonian shitosans in the said method step (1), and said chitosan solution is a saturated solution.
Preferably, the conductive nano particle is α-Fe described in the said method step (1) 2O 3Particle, said α-Fe 2O 3The concentration of solution is at 0.08～0.12mmol/ml.
Preferably; Clean pretreated method comprises ITO electro-conductive glass substrate is immersed 3.95% potassium hydroxide-ethanol solution sonic oscillation in the said method step (2); Immerse sonic oscillation in the ethanol liquid after the flushing again; Immerse in the ultra-pure water ultrasonicly at last, dry up and obtain clean pretreated blank ITO electro-conductive glass substrate.
Preferably,, uses by the ITO electro-conductive glass distilled water flushing ITO electro-conductive glass before switching immersion chitosan solution or conductive nano particle solution repeatedly in the said method step (3).
The modification that is used as electrode of microbial fuel cell in the technical scheme of the present invention is that a kind of ITO of utilization electro-conductive glass is template, in conjunction with layer-by-layer with α-Fe 2O 3With chitosan-modified method to the ITO conductive glass surface.The ITO electro-conductive glass that this modification is good is used as electrode of microbial fuel cell, can improve the electrogenesis output of microbiological fuel cell.The preparation method is to be template with the ITO electro-conductive glass, will have the shitosan and the α-Fe of positive and negative electric charge 2O 3Alternately be adsorbed on the ITO conductive glass surface, wherein shitosan is a saturated solution, α-Fe 2O 3Concentration is 0.1mmol/ml.Compare with traditional ITO electrode that does not have to modify, the ITO electrode of modified can make the electrogenesis output of microbiological fuel cell increase substantially.
Principle of the present invention is can make electrode surface form multilayer space network structure through self-assembling method layer by layer; Thereby increase electrode effective specific area of working region in microbiological fuel cell, and increase the contact area of electronics in contact area or increase electrode and the solution of electrode and bacterium.With α-Fe 2O 3The modified microorganism fuel cell electrode can improve the electronics output of battery.
The concrete method step of the present invention can be as follows:
1) water is cooked solvent and is disposed α-Fe respectively 2O 3Solution and low-molecular-weight chitosan solution;
When 2) the ITO electro-conductive glass is substrate; It is immersed 3.95% potassium hydroxide-ethanol solution sonic oscillation 5min; Immerse sonic oscillation 5min in the ethanol liquid after the flushing again, immerse ultrasonic 5min in the ultra-pure water at last, dry up the blank ITO electro-conductive glass substrate that obtains cleaning up;
3) the ITO electro-conductive glass is immersed in earlier in the chitosan solution with its oppositely charged, distilled water flushing repeatedly; And then be immersed in α-Fe 2O 3In the solution, repeated multiple times is assembled multi-layer polyelectrolyte at the ITO conductive glass surface, thereby obtains (α-Fe 2O 3/ CTS) n/ ITO electrode, wherein n is the natural number of 1-12.
Water soluble chitosan is positively charged in the technical scheme of the present invention, α-Fe 2O 3Be with electronegative.α-Fe wherein 2O 3Can be other conductive nano particles, like SiO 2, Al 2O 3Deng.
With respect to scheme of the prior art, advantage of the present invention is:
1. the ITO electro-conductive glass of the inventive method modified can improve the electrogenesis output of microbiological fuel cell greatly as the anode of microbiological fuel cell.This method is simply effective, and is easy and simple to handle, and required time is shorter.
2. the preparation facilities that technical scheme of the present invention need adopt is simple, does not need what special devices, and common culture dish just can meet the demands.Store transportation easily: if with the ITO electro-conductive glass of the modified that obtains as for just can be subsequent use in the culture dish.Also can pass through long-distance transport and not need special protection.
3, the inventive method applied range: the ITO electro-conductive glass of the modified of acquisition all will have purposes very widely in biology and microbiological fuel cell system and area of solar cell.And material non-toxic is harmless.The material of selecting for use all is a bio-compatible or degradable, thus all as safe as a house to bacterium and environment, be extraordinary ecological environment material nd.
In sum, the method that the present invention modifies about electrode of microbial fuel cell is by the α-Fe of oppositely charged 2O 3Accomplish with low-molecular-weight shitosan (CTS).The preparation method is the α-Fe with oppositely charged 2O 3Be dissolved in the water with low-molecular-weight shitosan, successively be assembled into the ITO conductive glass surface then.The electrode of this method modified can improve the electrogenesis output of microbiological fuel cell.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Fig. 1 is the embodiment of the invention 1 usefulness (α-Fe 2O 3/ CTS) 4/ ITO is as the microbiological fuel cell of anode and with the electric current-time plot of blank ITO as the microbiological fuel cell of electrode.
Embodiment
Below in conjunction with specific embodiment such scheme is further specified.Should be understood that these embodiment are used to the present invention is described and are not limited to limit scope of the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Embodiment 1 anode of microbial fuel cell (α-Fe 2O 3/ CTS) 4The preparation of/ITO
The preparation method is following:
1) water is cooked solvent and is disposed α-Fe respectively 2O 3Solution and low-molecular-weight chitosan solution, α-Fe 2O 3Solution concentration is 0.1mmol/ml, and chitosan solution is a saturated solution;
When 2) the ITO electro-conductive glass is substrate; It is immersed 3.95% potassium hydroxide-ethanol solution sonic oscillation 5min; Immerse sonic oscillation 5min in the ethanol liquid after the flushing again, immerse ultrasonic 5min in the ultra-pure water at last, dry up the blank ITO electro-conductive glass substrate that obtains cleaning up;
3) the ITO electro-conductive glass is immersed in earlier in the chitosan solution with its oppositely charged, distilled water flushing repeatedly; And then be immersed in α-Fe 2O 3In the solution, repeated multiple times is at ITO conductive glass surface assembling multi-layer polyelectrolyte (α-Fe 2O 3/ CTS) 4/ ITO structure.
(α-the Fe of preparation 2O 3/ CTS) 4/ ITO structure as the microbiological fuel cell of anode with as shown in Figure 1 as the electric current-time plot of the microbiological fuel cell of electrode, by scheming to know (α-Fe with blank ITO 2O 3/ CTS) 4/ ITO structure has improved 20% as the electrogenesis output of the microbiological fuel cell of anode.
Embodiment 2 anode of microbial fuel cell (α-Fe 2O 3/ CTS) 6The preparation of/ITO
The preparation method is following:
1) water is cooked solvent and is disposed α-Fe respectively 2O 3Solution and low-molecular-weight chitosan solution, α-Fe 2O 3Solution concentration is 0.1mmol/ml, and chitosan solution is a saturated solution;
When 2) the ITO electro-conductive glass is substrate; It is immersed 3.95% potassium hydroxide-ethanol solution sonic oscillation 5min; Immerse sonic oscillation 5min in the ethanol liquid after the flushing again, immerse ultrasonic 5min in the ultra-pure water at last, dry up the blank ITO electro-conductive glass substrate that obtains cleaning up;
3) the ITO electro-conductive glass is immersed in earlier in the chitosan solution with its oppositely charged, distilled water flushing repeatedly; And then be immersed in α-Fe 2O 3In the solution, repeated multiple times is at ITO conductive glass surface assembling multi-layer polyelectrolyte (α-Fe 2O 3/ CTS) 6/ ITO structure.
Embodiment 3 anode of microbial fuel cell (SiO 2/ CTS) 5The preparation of/ITO
Concrete preparation method is following:
1) water is cooked solvent and is disposed SiO respectively 2Solution and low-molecular-weight chitosan solution;
When 2) the ITO electro-conductive glass is substrate; It is immersed 3.95% potassium hydroxide-ethanol solution sonic oscillation 5min; Immerse sonic oscillation 5min in the ethanol liquid after the flushing again, immerse ultrasonic 5min in the ultra-pure water at last, dry up the blank ITO electro-conductive glass substrate that obtains cleaning up;
3) the ITO electro-conductive glass is immersed in earlier in the chitosan solution with its oppositely charged, distilled water flushing repeatedly; And then be immersed in SiO 2In the solution, repeated multiple times is assembled multi-layer polyelectrolyte at the ITO conductive glass surface, thereby obtains (SiO 2/ CTS) 5/ ITO electrode.
Embodiment 4 anode of microbial fuel cell (Al 2O 3/ CTS) 7The preparation of/ITO
Concrete preparation method is following:
1) water is cooked solvent and is disposed Al respectively 2O 3Solution and low-molecular-weight chitosan solution;
When 2) the ITO electro-conductive glass is substrate; It is immersed 3.95% potassium hydroxide-ethanol solution sonic oscillation 5min; Immerse sonic oscillation 5min in the ethanol liquid after the flushing again, immerse ultrasonic 5min in the ultra-pure water at last, dry up the blank ITO electro-conductive glass substrate that obtains cleaning up;
3) the ITO electro-conductive glass is immersed in earlier in the chitosan solution with its oppositely charged, distilled water flushing repeatedly; And then be immersed in Al 2O 3In the solution, repeated multiple times is assembled multi-layer polyelectrolyte at the ITO conductive glass surface, thereby obtains (Al 2O 3/ CTS) 7/ ITO electrode.
Above-mentioned instance only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.

Claims (6)

1. the method for modifying of an electrode of microbial fuel cell; It is characterized in that said method comprises that with the ITO electro-conductive glass be template; Make the shitosan and the conductive nano particle that have positive and negative electric charge alternately be adsorbed on the ITO conductive glass surface, form the microbiological fuel cell modified electrode through self-assembling method layer by layer based on the positive and negative charge electrostatic interaction; Said method specifically may further comprise the steps:
(1) with water is solvent, respectively preparation of nano conductive particle solution and low-molecular weight chitoglycan solution;
(2) the ITO electro-conductive glass is carried out clean preliminary treatment;
(3) the ITO electro-conductive glass is alternately immersed in chitosan solution and the conductive nano particle solution successively, assemble repeatedly repeatedly, thereby form the multi-layer polyelectrolyte film at the ITO conductive glass surface.
2. method according to claim 1 is characterized in that said conductive nano particle is selected from α-Fe 2O 3Particle, SiO 2Particle and Al 2O 3Particle.
3. method according to claim 1 is characterized in that shitosan is selected from molecular weight at 1-5 ten thousand daltonian shitosans in the said method step (1), and said chitosan solution is a saturated solution.
4. method according to claim 1 is characterized in that the conductive nano particle is α-Fe described in the said method step (1) 2O 3Particle, said α-Fe 2O 3The concentration of solution is at 0.08～0.12mmol/ml.
5. method according to claim 1; It is characterized in that clean pretreated method comprises in the said method step (2) immerses 3.95% potassium hydroxide-ethanol solution sonic oscillation with ITO electro-conductive glass substrate; Immerse sonic oscillation in the ethanol liquid after the flushing again; Immerse in the ultra-pure water ultrasonicly at last, dry up and obtain clean pretreated blank ITO electro-conductive glass substrate.
6. method according to claim 1 is characterized in that before the ITO electro-conductive glass switches immersion chitosan solution or conductive nano particle solution, using distilled water flushing ITO electro-conductive glass repeatedly in the said method step (3).
CN2010102646655A 2010-08-27 2010-08-27 Modification method for electrode of microbial fuel cell Expired - Fee Related CN101924220B (en)

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Publication number Priority date Publication date Assignee Title
CN102136581B (en) * 2011-02-22 2013-07-10 东南大学 Method for modifying cathode of microbial fuel cell
DE102011075202B4 (en) 2011-05-04 2021-09-02 Robert Bosch Gmbh Layer arrangement
CN103401008B (en) * 2013-07-31 2016-10-05 华南理工大学 Utilize the method and apparatus that capacitive character anode stores biological power
CN105047955A (en) * 2015-05-28 2015-11-11 东南大学 Preparation method of carbon paper coating for fuel cell based on layer-by-layer self-assembly technique
CN105140549A (en) * 2015-07-08 2015-12-09 沈阳化工大学 Technique for treating fermentation wastewater by microbial fuel cell
CN105355938B (en) * 2015-11-05 2017-07-21 北京师范大学 A kind of method that peptide nanotube embeds riboflavin modified microorganism anode of fuel cell
CN107271524B (en) * 2017-06-29 2020-04-03 华侨大学 Method for applying (CNTs/PANI) n-ITO anode-based MFC biosensor to drug sensitivity test

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