WO2013065581A1 - バイオ燃料電池、バイオ燃料電池の製造方法、電子機器、酵素固定化電極、酵素固定化電極の製造方法、酵素固定化電極製造用電極、酵素固定化電極製造用電極の製造方法および酵素反応利用装置 - Google Patents
バイオ燃料電池、バイオ燃料電池の製造方法、電子機器、酵素固定化電極、酵素固定化電極の製造方法、酵素固定化電極製造用電極、酵素固定化電極製造用電極の製造方法および酵素反応利用装置 Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
- C12N11/082—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
- C12N11/082—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C12N11/087—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
- C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
- C12N11/12—Cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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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
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
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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
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/30—Fuel cells in portable systems, e.g. mobile phone, laptop
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present disclosure includes a biofuel cell, a biofuel cell manufacturing method, an electronic device, an enzyme-immobilized electrode, an enzyme-immobilized electrode manufacturing method, an enzyme-immobilized electrode manufacturing electrode, an enzyme-immobilized electrode manufacturing method, and
- the present invention relates to an enzyme reaction utilization apparatus. More specifically, the present disclosure uses, for example, biofuel cells, biosensors, bioreactors, etc., their production methods, enzyme-immobilized electrodes suitable for them and their production methods, or biofuel cells as a power source. It is suitable for application to various electronic devices.
- a carbon fiber electrode or carbon paper which is a porous electrode
- MEA membrane electrode assembly
- a membrane electrode assembly is formed by mixing a fluorine resin such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), or Nafion into carbon powder as a binder.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- Nafion Nafion
- the electrode obtained is also water repellent because the fluorine resin is water repellent. Therefore, when this electrode is applied to a biofuel cell, the enzyme solution is not soaked into the electrode when the enzyme is immobilized on the electrode using the enzyme solution, so that the enzyme is hardly immobilized or the enzyme is lost. There was a problem of being used.
- an enzyme-immobilized electrode capable of easily immobilizing an enzyme while maintaining activity, a method for producing the same, and an enzyme immobilization suitable for use in the production of the enzyme-immobilized electrode It is providing the electrode for manufacturing electrode, and its manufacturing method.
- Another problem to be solved by the present disclosure is to provide a high-performance biofuel cell using the excellent enzyme-immobilized electrode and a method for producing the same.
- Still another problem to be solved by the present disclosure is to provide a high-performance electronic device using the above-described excellent biofuel cell.
- Still another problem to be solved by the present disclosure is to provide a high-performance enzyme reaction utilization device using the above-described excellent enzyme-immobilized electrode.
- the present disclosure provides: A positive electrode; A negative electrode, A proton conductor provided between the positive electrode and the negative electrode, At least one of the positive electrode and the negative electrode is a biofuel cell that is an electrode in which an enzyme is immobilized, which is made of a mixture containing carbon particles and a hydrophilic binder insoluble in water.
- At least one fuel cell A positive electrode; A negative electrode, A proton conductor provided between the positive electrode and the negative electrode, At least one of the positive electrode and the negative electrode is an electronic device that is a biofuel cell that is an electrode in which an enzyme is immobilized, which is made of a mixture containing carbon particles and a hydrophilic binder insoluble in water.
- the carbon particles include, for example, at least one selected from the group consisting of carbon black, biocarbon, and vapor grown carbon fiber, but other than these, for example, activated carbon may be used.
- carbon black include furnace black, acetylene black, channel black, thermal black, ketjen black, and the like. Among these, ketjen black is preferable.
- Biocarbon is made from a plant-derived material with a silicon (silicon) content of 5% by weight or more.
- the specific surface area by nitrogen BET method is 10 m 2 / g or more, and the silicon content is 1% by weight or less.
- a porous carbon material having a pore volume of 0.1 cm 3 / g or more by the BJH method and the MP method (see Patent Document 13).
- biocarbon is produced as follows, for example. That is, first, the crushed rice husk (produced in Kagoshima Prefecture, Isehikari rice husk) was carbonized by heating in a nitrogen stream at 500 ° C. for 5 hours to obtain a carbide. Thereafter, 10 g of this carbide was placed in an alumina crucible and heated to 1000 ° C. at a rate of 5 ° C./min in a nitrogen stream (10 liters / min).
- porous carbon material precursor After carbonizing at 1000 degreeC for 5 hours and converting into a carbonaceous substance (porous carbon material precursor), it cooled to room temperature. In addition, nitrogen gas was kept flowing during carbonization and cooling. Next, this porous carbon material precursor was subjected to an acid treatment by immersing it overnight in a 46% by volume hydrofluoric acid aqueous solution, and then washed with water and ethyl alcohol until the pH reached 7. And the porous carbon material, ie, biocarbon, is obtained by making it dry at the end.
- the vapor grown carbon fiber is, for example, VGDF (registered trademark of Showa Denko KK).
- the activated carbon examples include wood charcoal such as oak charcoal, kunugi charcoal, cedar charcoal, oak charcoal, hinoki charcoal, rubber charcoal, bamboo charcoal, oga charcoal, and coconut shell charcoal.
- the hydrophilic binder that is insoluble in water is selected from various conventionally known binders as required, and is preferably selected from the group consisting of ethyl cellulose, polyvinyl butyral, acrylic resin, and epoxy resin, for example. There is at least one kind.
- the mixture containing carbon particles and a water-insoluble hydrophilic binder may contain one or more other components in addition to the carbon particles and water-insoluble hydrophilic binder, if necessary.
- the ratio of the weight (weight) of the hydrophilic binder insoluble in water to the weight (weight) of the carbon particles in this mixture is not less than 0.01 and not more than 1. Absent.
- a paste containing carbon particles and a hydrophilic binder insoluble in water is prepared. After applying the paste on the substrate, the paste is solidified.
- a solvent for preparing this paste for example, an organic solvent such as methyl isobutyl ketone (MIBK), terpineol or 2-propanol can be used.
- MIBK methyl isobutyl ketone
- 2-propanol terpineol
- various solvents used for ink used in printing for example, organic solvents such as butyl carbitol acetate, butyl carbitol, and methyl ethyl ketone can be used as the solvent.
- the substrate on which the paste is applied may basically be any substrate, and is appropriately selected from substrates made of conventionally known materials.
- the electrode integrated with the substrate the mechanical strength of the electrode can be improved. As needed, after forming an electrode on a board
- the positive electrode and the negative electrode when a separator is provided between the positive electrode and the negative electrode, proton transfer between the positive electrode and the negative electrode is further performed from the viewpoint of simplifying the manufacturing process or improving the mechanical strength of the positive electrode or the negative electrode.
- at least one of the positive electrode and the negative electrode is preferably formed integrally with the separator.
- the positive electrode and the negative electrode are formed integrally with the separator, one of the positive electrode and the negative electrode is formed on one surface of the separator, and the other of the positive electrode and the negative electrode is formed on the other surface.
- a separator when a separator is provided between the positive electrode and the negative electrode, a paste containing carbon particles and a hydrophilic binder insoluble in water is preferably applied on the separator. Then, by solidifying this paste, at least one of the positive electrode and the negative electrode is formed integrally with the separator. In this case, this separator corresponds to the substrate.
- a separator conventionally well-known various things can be used, and it selects as needed.
- the enzyme immobilized on the negative electrode includes an oxidase that promotes and decomposes the monosaccharide and is usually reduced by the oxidase.
- NAD + -dependent glucose dehydrogenase GDH
- NAD + nicotinamide adenine dinucleotide
- diaphorase is used as the coenzyme oxidase.
- the hydrolysis of the polysaccharide is promoted to decompose and monosaccharides such as glucose Is also immobilized.
- the polysaccharide is a polysaccharide in a broad sense and refers to all carbohydrates that generate two or more monosaccharides by hydrolysis, and includes oligosaccharides such as disaccharides, trisaccharides, and tetrasaccharides.
- polysaccharide examples include starch, amylose, amylopectin, glycogen, cellulose, maltose, sucrose, and lactose. These are a combination of two or more monosaccharides, and any polysaccharide contains glucose as a monosaccharide of the binding unit. Note that amylose and amylopectin are components contained in starch, and starch is a mixture of amylose and amylopectin.
- glucoamylase When glucoamylase is used as the polysaccharide degrading enzyme and glucose dehydrogenase is used as the oxidase degrading monosaccharide, if it contains a polysaccharide that can be degraded to glucose by glucoamylase, It is possible to generate electricity as fuel.
- polysaccharides are specifically starch, amylose, amylopectin, glycogen, maltose and the like.
- Glucoamylase is a degrading enzyme that hydrolyzes ⁇ -glucan such as starch to produce glucose
- glucose dehydrogenase is an oxidase that oxidizes ⁇ -D-glucose to D-glucono- ⁇ -lactone.
- the degradation enzyme that decomposes the polysaccharide is also immobilized on the negative electrode, and the polysaccharide that will eventually become the fuel is also immobilized on the negative electrode.
- starch when starch is used as fuel, it is possible to use a gelatinized fuel obtained by gelatinizing starch.
- the starch concentration on the negative electrode surface can be kept higher than when starch dissolved in a solution is used, and the enzymatic decomposition reaction becomes faster.
- the output of the biofuel cell is improved and the fuel handling is easier than in the case of a solution, so that the fuel supply system can be simplified and the biofuel cell does not need to be used upside down. For example, it is very advantageous when used in a mobile device.
- Alcohol dehydrogenase that acts on methanol as a catalyst to oxidize to formaldehyde
- formaldehyde dehydrogenase FalDH
- formaldehyde dehydrogenase FateDH
- NADH formate dehydrogenase
- ethanol When ethanol is used as a fuel, a two-step oxidation process is performed using alcohol dehydrogenase (ADH) that acts on ethanol as a catalyst to oxidize to acetaldehyde and aldehyde dehydrogenase (AlDH) that acts on acetaldehyde and oxidizes to acetic acid. Then it is decomposed to acetic acid. That is, a total of 4 electrons are generated by two-stage oxidation reaction per molecule of ethanol.
- ADH alcohol dehydrogenase
- AlDH aldehyde dehydrogenase
- ethanol can be decomposed to CO 2 in the same manner as methanol.
- acetaldehyde dehydrogenase AalDH
- AlDH acetaldehyde dehydrogenase
- These fuels are typically used in the form of a fuel solution obtained by dissolving these fuels in a conventionally known buffer solution such as a phosphate buffer solution or a Tris buffer solution.
- any type of electron mediator may be basically used, but a compound having a quinone skeleton, particularly, a compound having a naphthoquinone skeleton is preferably used.
- a compound having a naphthoquinone skeleton various naphthoquinone derivatives can be used.
- Specific examples of the naphthoquinone derivatives include 2-amino-1,4-naphthoquinone (ANQ), 2-amino-3-methyl-1,4-naphthoquinone (AMNQ), 2-methyl-1,4- Naphthoquinone (VK3), 2-amino-3-carboxy-1,4-naphthoquinone (ACNQ) and the like.
- anthraquinone or a derivative thereof can be used in addition to a compound having a naphthoquinone skeleton.
- the electron mediator may contain one or two or more other compounds that function as an electron mediator, if necessary.
- acetone is preferably used as a solvent used when a compound having a quinone skeleton, particularly a compound having a naphthoquinone skeleton, is immobilized on the negative electrode.
- the solubility of the compound having a quinone skeleton can be increased, and the compound having a quinone skeleton can be efficiently immobilized on the negative electrode.
- the solvent may contain one or two or more other solvents other than acetone.
- this enzyme when an enzyme is immobilized on the positive electrode, this enzyme typically contains an oxygen reductase.
- this oxygen reductase for example, bilirubin oxidase, laccase, ascorbate oxidase and the like can be used.
- an electron mediator is preferably immobilized on the positive electrode in addition to the enzyme.
- the electron mediator for example, potassium hexacyanoferrate or potassium octacyanotungstate is used.
- the electron mediator is preferably immobilized at a sufficiently high concentration, for example, 0.64 ⁇ 10 ⁇ 6 mol / mm 2 or more on average.
- Various proton conductors can be used and are selected as necessary.
- cellophane, perfluorocarbon sulfonic acid (PFS) -based resin film, and trifluorostyrene derivative can be used together.
- an ion exchange resin having a fluorine-containing carbon sulfonic acid group Nafion (trade name, DuPont, USA), etc.
- the concentration of the buffer substance contained in the electrolyte is 0.2 M or more and 2.5 M or less, preferably 0.2 M or more and 2 M or less, more preferably 0.4 M or more and 2 M or less, More preferably, it is 0.8M or more and 1.2M or less.
- Buffer substances in general, as long as a pK a of 6 to 9, may it be used What Specific examples and, dihydrogen phosphate ion (H 2 PO 4 - ), 2-amino-2-hydroxymethyl-1,3-propanediol (abbreviated Tris), 2- (N-morpholino) ethanesulfonic acid (MES), cacodylic acid, carbonic acid (H 2 CO 3 ), hydrogen citrate Ions, N- (2-acetamido) iminodiacetic acid (ADA), piperazine-N, N′-bis (2-ethanesulfonic acid) (PIPES), N- (2-acetamido) -2-aminoethanesulfonic acid ( ACES), 3- (N-morpholino) propanesulfonic acid (MOPS), N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid (HEPES), N-2-hydroxyethylpiperazine- '-3-prop
- Examples of the substance that generates dihydrogen phosphate ions include sodium dihydrogen phosphate (NaH 2 PO 4 ) and potassium dihydrogen phosphate (KH 2 PO 4 ).
- As the buffer substance a compound containing an imidazole ring is also preferable.
- compounds containing an imidazole ring include imidazole, triazole, pyridine derivatives, bipyridine derivatives, imidazole derivatives (histidine, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, imidazole-2 -Ethyl carboxylate, imidazole-2-carboxaldehyde, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazol-1-yl-acetic acid, 2-acetylbenzimidazole, 1-acetylimidazole, N-acetyl Imidazole, 2-aminobenzimidazole, N- (3-aminopropyl) imidazole, 5-amino-2- (trifluoromethyl) benzimidazole, 4-azabenzimidazole, 4-aza-2-mercapto Benzimidazole, benzimidazole, 1-benzyl
- buffer substances for example, selected from the group consisting of hydrochloric acid (HCl), acetic acid (CH 3 COOH), phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 )
- HCl hydrochloric acid
- CH 3 COOH acetic acid
- H 3 PO 4 phosphoric acid
- SO 4 sulfuric acid
- At least one acid may be added as a neutralizing agent. By doing so, the activity of the enzyme can be maintained higher.
- the pH of the electrolyte containing the buffer substance is preferably around 7, but may be any of 1 to 14 in general.
- This biofuel cell can be used for almost anything that requires electric power, and can be of any size.
- electronic devices mobile objects (automobiles, motorcycles, aircraft, rockets, spacecrafts, ships, etc.), power units It can be used for construction machines, machine tools, power generation systems, cogeneration systems, etc., and the output, size, shape, type of fuel, etc. are determined depending on the application.
- Electronic devices may be basically any type, and include both portable and stationary devices. Specific examples include cell phones, mobile devices (portable information terminals). (PDA, etc.), robots, personal computers (including both desktop and notebook computers), game machines, camera-integrated VTRs (video tape recorders), in-vehicle devices, home appliances, industrial products, and the like.
- PDA portable information terminals
- PDA portable information terminals
- robots personal computers (including both desktop and notebook computers), game machines, camera-integrated VTRs (video tape recorders), in-vehicle devices, home appliances, industrial products, and the like.
- VTRs video tape recorders
- in-vehicle devices home appliances, industrial products, and the like.
- the present disclosure is an enzyme-immobilized electrode in which an enzyme is immobilized on an electrode composed of a mixture containing carbon particles and a water-insoluble hydrophilic binder.
- this disclosure Forming an electrode comprising a mixture comprising carbon particles and a hydrophilic binder insoluble in water; Immobilizing an enzyme on the electrode; Is a method for producing an enzyme-immobilized electrode.
- the enzyme-immobilized electrode When the enzyme-immobilized electrode is used for a biofuel cell, the enzyme-immobilized electrode is integrally formed on the separator as necessary. Similarly, in the method for producing the enzyme-immobilized electrode, if necessary, a paste containing carbon particles and a hydrophilic binder insoluble in water is applied onto the separator, and then the paste is solidified. An electrode made of a mixture containing carbon particles and a hydrophilic binder insoluble in water is formed integrally with the separator.
- the present disclosure is also an electrode for producing an enzyme-immobilized electrode comprising a mixture containing carbon particles and a hydrophilic binder insoluble in water.
- the present disclosure also relates to an enzyme-immobilized electrode for producing an electrode for producing an enzyme-immobilized electrode by applying a paste containing carbon particles and a hydrophilic binder insoluble in water on a substrate and then solidifying the paste. It is a manufacturing method of the electrode for manufacture.
- An enzyme-immobilized electrode can be obtained by immobilizing an enzyme on the enzyme-immobilized electrode manufacturing electrode.
- the present disclosure is an enzyme reaction utilization apparatus having an enzyme-immobilized electrode made of a mixture containing carbon particles and a hydrophilic binder insoluble in water and having an enzyme immobilized thereon.
- This enzyme reaction utilization apparatus is, for example, a biofuel cell, a biosensor, or a bioreactor.
- the electrode for immobilizing the enzyme is composed of a mixture containing carbon particles and a hydrophilic binder insoluble in water, so that the enzyme solution is immobilized when the enzyme is immobilized on the electrode. It is easy to soak into the electrode and can prevent inactivation of the enzyme.
- an enzyme-immobilized electrode that can be easily immobilized while maintaining the activity of the enzyme can be obtained.
- An excellent biofuel cell can be realized by using this enzyme-immobilized electrode for at least one of the positive electrode and the negative electrode of the biofuel cell.
- a high-performance electronic device can be realized.
- an excellent enzyme reaction utilization device can be realized.
- FIG. 1A and 1B are schematic diagrams illustrating an electrode for producing an enzyme-immobilized electrode according to a first embodiment.
- 2A, 2B, and 2C are cross-sectional views for explaining a method for producing an electrode for producing an enzyme-immobilized electrode according to the first embodiment.
- 3A and 3B are cross-sectional views for explaining a method for producing an electrode for producing an enzyme-immobilized electrode according to Examples 1 to 8.
- 4A, FIG. 4B, FIG. 4C, FIG. 4D and FIG. 4E are schematic diagrams showing the contact angle of the enzyme solution with respect to the electrode for producing an enzyme-immobilized electrode of Examples 3, 5, 7 and Comparative Examples 1, 2. .
- FIG. 5 is a schematic diagram showing the results of cyclic voltammetry measurement performed using the enzyme-immobilized electrode production electrode of Example 1.
- FIG. 6 is a schematic diagram in which the peak current density obtained from the results shown in FIG. 5 is plotted against the 1/2 power of the potential sweep speed.
- 7 is a schematic diagram showing the results of cyclic voltammetry measurement performed using the enzyme-immobilized electrode production electrode of Example 8.
- FIG. 8 is a schematic diagram showing the results of cyclic voltammetry measurement performed using the enzyme-immobilized electrode production electrode of Example 8.
- FIG. 9 is a drawing-substituting photograph showing the results of evaluating the solubility and hydrophilicity of various binders in water.
- FIG. 9 is a drawing-substituting photograph showing the results of evaluating the solubility and hydrophilicity of various binders in water.
- FIG. 10 is a schematic diagram showing the results of cyclic voltammetry measurement performed using the enzyme-immobilized electrode of Example 9.
- FIG. 11 is a schematic diagram showing a biofuel cell according to the third embodiment.
- FIG. 12 schematically shows the details of the configuration of the negative electrode of the biofuel cell according to the third embodiment, an example of an enzyme group and a coenzyme immobilized on the negative electrode, and an electron transfer reaction by the enzyme group and the coenzyme. It is a basic diagram shown in FIG.
- FIG. 13 is a schematic diagram illustrating a specific configuration example of the biofuel cell according to the third embodiment.
- FIG. 14 shows the measurement results of the relative output after 1 hour has passed since the biofuel cell using the electrodes for producing an enzyme-immobilized electrode of Examples 5 and 7 and Comparative Examples 1 and 2 was operated as the positive electrode and the negative electrode. It is a basic diagram.
- FIG. 1A shows an electrode 10 for producing an enzyme-immobilized electrode according to the first embodiment.
- the enzyme-immobilized electrode manufacturing electrode 10 is composed of a mixture containing carbon particles and a hydrophilic binder insoluble in water.
- This mixture typically includes at least carbon particles and a water-insoluble hydrophilic binder as main components, and preferably includes carbon particles and a water-insoluble hydrophilic binder.
- the ratio of the mass of the hydrophilic binder insoluble in water to the mass of the carbon particles in this mixture is, for example, 0.01 or more and 1 or less.
- the carbon particles are, for example, carbon black (Ketjen black, etc.), biocarbon, vapor grown carbon fiber, and the like.
- the water-insoluble hydrophilic binder include ethyl cellulose, polyvinyl butyral, acrylic resin, and epoxy resin.
- the enzyme-immobilized electrode manufacturing electrode 10 may be used alone, or an enzyme-immobilized electrode manufacturing electrode 10 formed on a substrate 11 as shown in FIG. 1B may be used. In this case, since the enzyme-immobilized electrode manufacturing electrode 10 is supported by the substrate 11, the mechanical strength of the enzyme-immobilized electrode manufacturing electrode 10 can be improved.
- the enzyme-immobilized electrode manufacturing electrode 10 can be manufactured, for example, as follows.
- carbon particles and water-insoluble hydrophilic binder are mixed.
- the ratio of the mass of the hydrophilic binder insoluble in water to the mass of the carbon particles in this mixture is, for example, 0.01 or more and 1 or less.
- a solvent is added to this mixture and a paste is prepared by stirring.
- a solvent for example, a solvent appropriately selected from organic solvents such as methyl isobutyl ketone (MIBK), terpineol, 2-propanol, butyl carbitol acetate, butyl carbitol, and methyl ethyl ketone is used.
- MIBK methyl isobutyl ketone
- terpineol 2-propanol
- butyl carbitol acetate butyl carbitol
- methyl ethyl ketone methyl ethyl ketone
- a substrate 11 is prepared.
- the paste 12 prepared as described above is applied or printed on one main surface of the substrate 11 to a predetermined thickness.
- a non-woven fabric can be preferably used.
- various organic polymer compounds such as polyolefin, polyester, cellulose, polyacrylamide and the like can be used, but the material is not limited thereto.
- coating or printing of the paste 12 A conventionally well-known method can be used.
- a coating method for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or the like can be used.
- a printing method a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method, etc. can be used.
- the substrate 11 coated with the paste 12 is heated or kept at room temperature to dry and remove the solvent in the paste 12 and solidify.
- an electrode 10 for producing an enzyme-immobilized electrode comprising carbon particles and a hydrophilic binder insoluble in water is obtained on the substrate 11.
- both surfaces of the substrate 11 on which the enzyme-immobilized electrode manufacturing electrode 10 is formed are cleaned by ozone treatment or the like.
- the paste 12 may penetrate into the substrate 11 depending on the material of the substrate 11.
- the enzyme-immobilized electrode manufacturing electrode 10 is formed with its lower part embedded in the substrate 11.
- the enzyme-immobilized electrode manufacturing electrode 10 was formed using ketjen black as carbon particles and ethyl cellulose as a hydrophilic binder insoluble in water.
- a nonwoven fabric 14 is used as the substrate 11. Then, as shown in FIG. 3B, the paste 12 was applied to the nonwoven fabric 14 with a thickness of 50 ⁇ m using a coater, and then heated on a hot plate at 75 ° C. for 2 hours to remove and remove terpineol.
- the enzyme-immobilized electrode manufacturing electrode 10 made of ketjen black and ethyl cellulose was formed on the nonwoven fabric 14.
- the electrode 10 for producing an enzyme-immobilized electrode was formed with its lower part embedded in the nonwoven fabric 14.
- both surfaces of the nonwoven fabric 14 on which the enzyme-immobilized electrode manufacturing electrode 10 was formed that is, the upper surface of the enzyme-immobilized electrode manufacturing electrode 10 and the back surface of the nonwoven fabric 14 were subjected to ozone treatment for 20 minutes for cleaning.
- the enzyme-immobilized electrode manufacturing electrode 10 was formed using ketjen black and biocarbon as carbon particles and ethyl cellulose as a hydrophilic binder insoluble in water.
- Ketjen Black 0.5g, Biocarbon 1g and Ethylcellulose 0.4g were mixed, and Terpineol 7.5g was added to this mixture, followed by stirring for 10 minutes twice to prepare Paste 12.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode 10 made of ketjen black, biocarbon, and ethyl cellulose on the nonwoven fabric 14.
- the enzyme-immobilized electrode manufacturing electrode 10 was formed using Ketjen Black and VGCF (registered trademark) as carbon particles and ethyl cellulose as a hydrophilic binder insoluble in water.
- Ketjen Black 0.5g, VGCF 0.5g and ethyl cellulose 0.4g were mixed, and after adding Terpineol 7.5g to this mixture, 10 minutes of stirring was performed twice to prepare Paste 12.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode 10 made of ketjen black, VGCF, and ethyl cellulose on the nonwoven fabric 14.
- an electrode 10 for producing an enzyme-immobilized electrode was formed using VGCF (registered trademark) as carbon particles and ethyl cellulose as a hydrophilic binder insoluble in water.
- VGCF registered trademark
- VGCF (1 g) and ethyl cellulose (0.4 g) were mixed, terpineol (7.5 g) was added to the mixture, and then the mixture was stirred twice for 10 minutes to prepare paste 12.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode 10 made of VGCF and ethyl cellulose on the nonwoven fabric 14.
- the enzyme-immobilized electrode manufacturing electrode 10 was formed using Ketjen Black and VGCF (registered trademark) as carbon particles and ethyl cellulose as a hydrophilic binder insoluble in water.
- Ketjen Black 0.5g, VGCF 0.5g and ethyl cellulose 0.6g were mixed, and after adding 8ml of methyl isobutyl ketone to this mixture, stirring for 10 minutes was performed twice to prepare paste 12.
- the paste 12 was applied to the nonwoven fabric 14 with a thickness of 50 ⁇ m using a coater, and then methyl isobutyl ketone was removed by drying at room temperature.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode 10 made of ketjen black, VGCF, and ethyl cellulose on the nonwoven fabric 14.
- the enzyme-immobilized electrode manufacturing electrode 10 was formed using Ketjen Black and VGCF (registered trademark) as carbon particles and ethyl cellulose as a hydrophilic binder insoluble in water.
- Ketjen Black 0.5g, VGCF 0.5g, and ethylcellulose 0.6g were mixed, 8 ml of 2-propanol was added to the mixture, and then the mixture was stirred twice for 10 minutes to prepare paste 12.
- the paste 12 was applied to the nonwoven fabric 14 with a thickness of 50 ⁇ m by a coater, and then 2-propanol was removed by drying at room temperature.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode 10 made of ketjen black, VGCF, and ethyl cellulose on the nonwoven fabric 14.
- the enzyme-immobilized electrode manufacturing electrode 10 was formed using Ketjen Black and VGCF (registered trademark) as carbon particles and polyvinyl butyral as a hydrophilic binder insoluble in water.
- Ketjen Black 0.5g, VGCF 0.5g and polyvinyl butyral (degree of polymerization 1000) 0.2g were mixed, 8 ml of methyl isobutyl ketone was added to this mixture, and then the mixture was stirred twice for 10 minutes. Prepared.
- the paste 12 was applied to the nonwoven fabric 14 with a thickness of 50 ⁇ m using a coater, and then methyl isobutyl ketone was removed by drying at room temperature.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode 10 made of ketjen black, VGCF, and polyvinyl butyral on the nonwoven fabric 14.
- the electrode 10 for producing an enzyme-immobilized electrode was formed using biocarbon as carbon particles and ethyl cellulose as a hydrophilic binder insoluble in water.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode 10 made of biocarbon and ethyl cellulose on the nonwoven fabric 14.
- an electrode for producing an enzyme-immobilized electrode was formed using ketjen black and VGCF (registered trademark) as carbon particles and carboxymethyl cellulose as a binder.
- Ketjen Black 0.5g, VGCF 0.5g, and carboxymethylcellulose 0.2g were mixed, 8 ml of water was added to this mixture, and then stirred for 10 minutes twice to prepare a paste.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode production electrode made of ketjen black, VGCF and carboxymethylcellulose on the nonwoven fabric 14.
- an electrode for producing an enzyme-immobilized electrode was formed using ketjen black and VGCF (registered trademark) as carbon particles and polyvinylidene fluoride (PVDF) as a binder.
- VGCF registered trademark
- PVDF polyvinylidene fluoride
- Ketjen Black 0.5g, VGCF 0.5g, and polyvinylidene fluoride (PVDF) 0.1g were mixed. After adding 8ml of N-methylpyrrolidone (NMP) to this mixture, stirring for 10 minutes was performed twice, A paste was prepared.
- NMP N-methylpyrrolidone
- the paste was applied to the nonwoven fabric 14 with a thickness of 50 ⁇ m by a coater, and then fired at 120 ° C.
- Example 2 Thereafter, the same treatment as in Example 1 was performed to form an enzyme-immobilized electrode manufacturing electrode composed of ketjen black, VGCF, and polyvinylidene fluoride (PVDF) on the nonwoven fabric 14.
- an enzyme-immobilized electrode manufacturing electrode composed of ketjen black, VGCF, and polyvinylidene fluoride (PVDF) on the nonwoven fabric 14.
- PVDF polyvinylidene fluoride
- the contact angle ⁇ with respect to the enzyme-immobilized electrode production electrode of Comparative Example 1 shown in FIG. 4D was 24 °, and the enzyme solution soaked easily. However, after a few minutes, peeling of the carbon particles was confirmed. It was confirmed that the electrode for producing an enzyme-immobilized electrode does not function as an electrode. Further, the contact angle ⁇ with respect to the enzyme-immobilized electrode production electrode of Comparative Example 2 shown in FIG. 4E was as large as 122 °. As a result, the enzyme solution did not soak into the electrode for producing an enzyme-immobilized electrode of Comparative Examples 1 and 2, and was dried on the electrode surface.
- FIG. 7 shows AQ2S (anthraquinone-2-sulfonic acid) which is a quinone derivative as an electron mediator in a 10 mM phosphate buffer solution (pH 7) using an electrode 10 for producing an enzyme-immobilized electrode comprising biocarbon and ethyl cellulose.
- AQ2S anthraquinone-2-sulfonic acid
- FIG. 7 shows that the electrochemical characteristics are maintained even when the potential sweep is performed for 10 cycles.
- FIG. 8 shows the results of cyclic voltammetry measurement when the fuel solution is replaced. It can be seen that the electrochemical characteristics are maintained even when the fuel solution is replaced.
- FIG. 9 shows the results of experiments using five types of binders. From FIG. 9, polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) are insoluble and hydrophobic in water, and carboxymethylcellulose (CMC) is soluble in water.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- polyacrylic acid is also soluble in water like carboxymethylcellulose.
- a water-soluble binder is not suitable as a binder because the carbon powder cannot be maintained in an electrode shape.
- ethyl cellulose and polyvinyl butyral are both insoluble in water and hydrophilic, and float or settle in water.
- the structural formulas of these binders are as follows. ⁇ Ethylcellulose ⁇ Polyvinyl butyral (PVB) ⁇ Polyvinylidene fluoride (PVDF) ⁇ Polytetrafluoroethylene (PTFE) ⁇ Carboxymethylcellulose (CMC)
- the enzyme-immobilized electrode manufacturing electrode 10 is composed of carbon particles and a hydrophilic binder insoluble in water, so that the enzyme solution can easily permeate. Can be easily immobilized, and the activity of the enzyme can be maintained.
- the enzyme-immobilized electrode according to the second embodiment is obtained by immobilizing one or more kinds of enzymes on the enzyme-immobilized electrode manufacturing electrode 10 according to the first embodiment. These enzymes are appropriately selected according to the use of the enzyme-immobilized electrode.
- the enzyme-immobilized electrode is obtained by applying or dropping an enzyme solution to the enzyme-immobilized electrode manufacturing electrode 10 according to the first embodiment, or immersing the enzyme-immobilized electrode manufacturing electrode 10 in the enzyme solution. Can be manufactured.
- a water-repellent separator as the substrate 14, for example, a non-woven fabric that has been made water-repellent by a silicon-based water repellent, this carbon is applied by applying a carbon paint to a predetermined region on the surface of the separator.
- the enzyme solution can be selectively applied only to the place where the paint is applied.
- this enzyme-immobilized electrode for the positive electrode or the negative electrode of a biofuel cell, it is possible to prevent the fuel from spreading to other than the power generation unit, thereby preventing the loss of fuel or the addition or injection of fuel.
- the body can be prevented from getting dirty.
- Example 9 An enzyme solution in which bilirubin oxidase (BOD), which is an oxygen reductase, is dissolved in 10 mM phosphate buffer (pH 7) is dropped into the electrode 10 for producing an enzyme-immobilized electrode of Example 5 composed of ketjen black, VGCF, and ethyl cellulose. By doing so, bilirubin oxidase was immobilized and the positive electrode of the biofuel cell was formed.
- BOD bilirubin oxidase
- an enzyme-immobilized electrode that can be easily immobilized while maintaining the activity of the enzyme can be obtained.
- FIG. 11 schematically shows this biofuel cell.
- glucose is used as a fuel.
- FIG. 12 schematically shows details of the configuration of the negative electrode of this biofuel cell, an example of an enzyme group and a coenzyme immobilized on the negative electrode, and an electron transfer reaction by the enzyme group and the coenzyme.
- this biofuel cell has a structure in which a negative electrode 21 and a positive electrode 22 face each other with an electrolyte layer 23 interposed therebetween.
- the negative electrode 21 decomposes glucose supplied as fuel with an enzyme to extract electrons and generate protons (H + ).
- the positive electrode 22 generates water by protons transported from the negative electrode 21 through the electrolyte layer 23, electrons sent from the negative electrode 21 through an external circuit, and oxygen in the air, for example.
- the enzyme-immobilized electrode according to the second embodiment is used as the negative electrode 21, the enzyme-immobilized electrode according to the second embodiment. Immobilized on this enzyme-immobilized electrode are enzymes involved in the degradation of glucose, coenzymes that generate reductants during the oxidation process of glucose, and coenzyme oxidases that oxidize reductants of coenzymes. Has been. On the electrode 10 for producing an enzyme-immobilized electrode, if necessary, an electron mediator that receives electrons from the coenzyme oxidase accompanying oxidation of the coenzyme and passes it to the electrode 10 for producing an enzyme-immobilized electrode is also immobilized. .
- glucose dehydrogenase preferably NAD-dependent glucose dehydrogenase
- NAD-dependent glucose dehydrogenase preferably NAD-dependent glucose dehydrogenase
- ⁇ -D-glucose can be oxidized to D-glucono- ⁇ -lactone.
- this D-glucono- ⁇ -lactone can be decomposed into 2-keto-6-phospho-D-gluconate in the presence of two enzymes, gluconokinase and phosphogluconate dehydrogenase (PhGDH).
- D-glucono- ⁇ -lactone is hydrolyzed to D-gluconate, which in the presence of gluconokinase, adenosine triphosphate (ATP) and adenosine diphosphate (ADP) and phosphate And then phosphorylated to 6-phospho-D-gluconate.
- This 6-phospho-D-gluconate is oxidized to 2-keto-6-phospho-D-gluconate by the action of the oxidase PhGDH.
- glucose can also be decomposed to CO 2 by utilizing sugar metabolism.
- the decomposition process utilizing sugar metabolism is roughly divided into glucose decomposition and pyruvic acid generation by a glycolysis system and a TCA cycle, which are widely known reaction systems.
- the oxidation reaction in the monosaccharide decomposition process is accompanied by a coenzyme reduction reaction.
- This coenzyme is almost determined by the acting enzyme.
- NAD + is used as the coenzyme. That is, when ⁇ -D-glucose is oxidized to D-glucono- ⁇ -lactone by the action of GDH, NAD + is reduced to NADH to generate H + .
- NADH is immediately oxidized to NAD + in the presence of diaphorase (DI), generating two electrons and H + . Therefore, two electrons and two H + are generated by one-step oxidation reaction per glucose molecule. In the two-stage oxidation reaction, a total of four electrons and four H + are generated.
- DI diaphorase
- the electrons generated by the above process are transferred from diaphorase to the electrode 10 for producing an enzyme-immobilized electrode through an electron mediator, and H + is transported to the positive electrode 22 through the electrolyte layer 23.
- the above enzyme, coenzyme, and electron mediator are optimal for the enzyme by using a buffer solution such as a phosphate buffer solution or a Tris buffer solution contained in the electrolyte layer 23 so that the electrode reaction can be performed efficiently and constantly. It is preferably maintained at a low pH, for example, around pH 7.
- a buffer solution such as a phosphate buffer solution or a Tris buffer solution contained in the electrolyte layer 23 so that the electrode reaction can be performed efficiently and constantly. It is preferably maintained at a low pH, for example, around pH 7.
- phosphate buffer for example, NaH 2 PO 4 or KH 2 PO 4 is used.
- the ionic strength (IS) is too large or too small to adversely affect the enzyme activity, but considering the electrochemical response, it should be an appropriate ionic strength, for example, about 0.3. Is preferred.
- pH and ionic strength have optimum values for each enzyme used, and are not limited to the values described above.
- glucose dehydrogenase is an enzyme involved in the degradation of glucose
- NAD + is a coenzyme that generates a reductant due to an oxidation reaction in the glucose degradation process, and a reductant of coenzyme.
- the coenzyme oxidase that oxidizes certain NADH is diaphorase (DI), and the electron mediator that receives electrons generated from the coenzyme oxidase accompanying the oxidation of the coenzyme and passes it to the electrode 10 for producing an enzyme-immobilized electrode may be ACNQ It is shown in the figure.
- the enzyme-immobilized electrode As the positive electrode 22, the enzyme-immobilized electrode according to the second embodiment is used.
- an oxygen reductase such as bilirubin oxidase, laccase, or ascorbate oxidase is immobilized on the enzyme-immobilized electrode.
- an electron mediator that transfers electrons to and from the positive electrode 22 is also immobilized on the positive electrode 22.
- the electrolyte layer 23 is for transporting H + generated in the negative electrode 21 to the positive electrode 22, and is made of a material that does not have electron conductivity and can transport H + .
- Specific examples of the electrolyte layer 23 include those already mentioned, such as cellophane.
- the glucose when glucose is supplied to the negative electrode 21 side, the glucose is decomposed by a decomposing enzyme including an oxidase. Since the oxidase is involved in the monosaccharide decomposition process, electrons and H + can be generated on the negative electrode 21 side, and a current can be generated between the negative electrode 21 and the positive electrode 22.
- a decomposing enzyme including an oxidase. Since the oxidase is involved in the monosaccharide decomposition process, electrons and H + can be generated on the negative electrode 21 side, and a current can be generated between the negative electrode 21 and the positive electrode 22.
- this biofuel cell has a configuration in which a negative electrode 21 and a positive electrode 22 are opposed to each other with an electrolyte layer 23 interposed therebetween.
- Ti current collectors 41 and 42 are placed under the positive electrode 22 and the negative electrode 21, respectively, so that current collection can be performed easily.
- Reference numerals 43 and 44 denote fixed plates. The fixing plates 43 and 44 are fastened to each other by screws 45, and the positive electrode 22, the negative electrode 21, the electrolyte layer 23, and the Ti current collectors 41 and 42 are sandwiched between them.
- One surface (outer surface) of the fixing plate 43 is provided with a circular recess 43a for taking in air, and a plurality of holes 43b penetrating to the other surface are provided in the bottom surface of the recess 43a. These holes 43 b serve as air supply paths to the positive electrode 22.
- a circular recess 44a for fuel loading is provided on one surface (outer surface) of the fixing plate 44, and a number of holes 44b penetrating to the other surface are provided on the bottom surface of the recess 44a. These holes 44 b serve as a fuel supply path to the negative electrode 21.
- a spacer 46 is provided on the periphery of the other surface of the fixing plate 44, and when the fixing plates 43 and 44 are fastened to each other with screws 45, the interval between them becomes a predetermined interval. .
- a load 47 is connected between the Ti current collectors 41 and 42, and, for example, a glucose solution in which glucose is dissolved in a phosphate buffer is used as a fuel in the recess 44a of the fixed plate 44 to generate power. .
- Example 10 As the negative electrode 21, glucose dehydrogenase (GDH), diaphorase (DI) and NADH were immobilized on the enzyme-immobilized electrode production electrode 10 of Examples 5 and 7 and the enzyme-immobilized electrode production electrode of Comparative Examples 1 and 2. Was used.
- the positive electrode 22 was prepared by immobilizing bilirubin oxidase (BOD) on the enzyme-immobilized electrode production electrode 10 of Examples 5 and 7 and the enzyme-immobilized electrode production electrode of Comparative Examples 1 and 2. The output of the biofuel cell using these positive electrode 22 and negative electrode 21 was measured. A glucose solution was used as the fuel solution.
- BOD bilirubin oxidase
- FIG. 14 shows the relative output with respect to the biofuel cell using the electrode 10 for producing an enzyme-immobilized electrode of Example 5 after 1 hour has elapsed since the biofuel cell was operated. From FIG. 14, the biofuel cell using the enzyme-immobilized electrode production electrode 10 of Examples 5 and 7 for the positive electrode 22 and the negative electrode 21 was used for producing the enzyme-immobilized electrode of Comparative Examples 1 and 2 for the positive electrode 22 and the negative electrode 21. It can be seen that a higher output is obtained compared to a biofuel cell using electrodes.
- a high-power biofuel cell suitable for use as a power source for various electronic devices can be obtained.
- this technique can also take the following structures.
- a biofuel cell which is an electrode made of a mixture containing the enzyme and immobilized thereon.
- the binder includes at least one selected from the group consisting of ethyl cellulose, polyvinyl butyral, acrylic resin, and epoxy resin.
- the carbon particles include at least one selected from the group consisting of carbon black, biocarbon, vapor grown carbon fiber, and activated carbon.
- the ratio of the mass of the binder to the mass of the carbon particles in the mixture is 0.01 or more and 1 or less.
- at least one of the positive electrode and the negative electrode is formed integrally with a separator provided between the positive electrode and the negative electrode.
- a method for producing a biofuel cell comprising: forming an electrode, and forming at least one of a positive electrode and a negative electrode by immobilizing an enzyme on the electrode.
- the method for producing a biofuel cell according to [6] in which at least one of a positive electrode and a negative electrode is formed by applying a paste containing carbon particles and a binder on a substrate and then solidifying the paste.
- the paste containing carbon particles and a binder is applied on the separator, and then the paste is solidified to form at least one of the positive electrode and the negative electrode integrally with the separator.
- Manufacturing method of biofuel cell comprising: forming an electrode, and forming at least one of a positive electrode and a negative electrode by immobilizing an enzyme on the electrode.
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Abstract
Description
正極と、
負極と、
正極と負極との間に設けられたプロトン伝導体とを有し、
正極および負極のうちの少なくとも一方が、カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなり、酵素が固定化された電極であるバイオ燃料電池である。
正極と、
負極と、
正極と負極との間に設けられたプロトン伝導体とを有するバイオ燃料電池を製造する場合に、
カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる電極を形成する工程と、
電極に酵素を固定化することにより正極および負極のうちの少なくとも一方を形成する工程、
を有するバイオ燃料電池の製造方法である。
一つまたは複数の燃料電池を用い、
少なくとも一つの燃料電池が、
正極と、
負極と、
正極と負極との間に設けられたプロトン伝導体とを有し、
正極および負極のうちの少なくとも一方が、カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなり、酵素が固定化された電極であるバイオ燃料電池である電子機器である。
カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる電極を形成する工程と、
電極に酵素を固定化する工程、
とを有する酵素固定化電極の製造方法である。
1.第1の実施の形態(酵素固定化電極製造用電極およびその製造方法)
2.第2の実施の形態(酵素固定化電極およびその製造方法)
3.第3の実施の形態(バイオ燃料電池)
[酵素固定化電極製造用電極]
図1Aは第1の実施の形態による酵素固定化電極製造用電極10を示す。
この酵素固定化電極製造用電極10は、例えば、次のようにして製造することができる。
次のようにして、カーボン粒子としてケッチェンブラック、水に不溶な親水性のバインダーとしてエチルセルロースを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてケッチェンブラックおよびバイオカーボン、水に不溶な親水性のバインダーとしてエチルセルロースを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてケッチェンブラックおよびVGCF(登録商標)、水に不溶な親水性のバインダーとしてエチルセルロースを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてVGCF(登録商標)、水に不溶な親水性のバインダーとしてエチルセルロースを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてケッチェンブラックおよびVGCF(登録商標)、水に不溶な親水性のバインダーとしてエチルセルロースを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてケッチェンブラックおよびVGCF(登録商標)、水に不溶な親水性のバインダーとしてエチルセルロースを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてケッチェンブラックおよびVGCF(登録商標)、水に不溶な親水性のバインダーとしてポリビニルブチラールを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてバイオカーボン、水に不溶な親水性のバインダーとしてエチルセルロースを用いて酵素固定化電極製造用電極10を形成した。
次のようにして、カーボン粒子としてケッチェンブラックおよびVGCF(登録商標)、バインダーとしてカルボキシメチルセルロースを用いて酵素固定化電極製造用電極を形成した。
次のようにして、カーボン粒子としてケッチェンブラックおよびVGCF(登録商標)、バインダーとしてポリフッ化ビニリデン(PVDF)を用いて酵素固定化電極製造用電極を形成した。
実施例3、5、7の酵素固定化電極製造用電極10および比較例1、2の酵素固定化電極製造用電極に対する酵素溶液の接触角の測定を行った結果を、それぞれ図4A~図4Eに示す。図4Aに示す実施例3の酵素固定化電極製造用電極10に対する接触角θは10°、図4Bに示す実施例5の酵素固定化電極製造用電極10に対する接触角θは29°、図4Cに示す実施例7の酵素固定化電極製造用電極10に対する接触角θは19°と小さい。この結果、酵素溶液は、実施例3、5、7の酵素固定化電極製造用電極10に対して容易に染み込んだ。これに対し、図4Dに示す比較例1の酵素固定化電極製造用電極に対する接触角θは24°と酵素溶液は容易に染み込んだが、数分後に炭素粒子の剥離が確認され、比較例1の酵素固定化電極製造用電極は電極として機能しないことが確認された。また、図4Eに示す比較例2の酵素固定化電極製造用電極に対する接触角θは122°と大きかった。この結果、酵素溶液は、比較例1、2の酵素固定化電極製造用電極には染み込まず、電極表面上で乾燥した。
実施例1の酵素固定化電極製造用電極10を用いて電極性能の評価を行った。そのために、ヘキサシアノ鉄酸イオンを用い、サイクリックボルタンメトリー評価を行った。その結果を図5に示す。図5から明らかなように、エチルセルロースをバインダーにした実施例1の酵素固定化電極製造用電極10は非常に良い電気化学応答を示した。図6は、電位掃引速度Vの1/2乗(V1/2)を横軸に取り、縦軸にサイクリックボルタモグラムのピーク電流値をプロットしたものである。図6には、比較のために、市販されている平滑なグラッシーカーボン(GC)電極を用いた場合の同様なデータをプロットした。図6より、実施例1の酵素固定化電極製造用電極10では、一般的に電気化学評価で用いられるグラッシーカーボン電極とほぼ同じピーク電流が得られ、V1/2に比例していることから、電気化学的に可逆的な応答を示していることが分かる。
ここで、酵素固定化電極製造用電極10の製造に用いる水に不溶な親水性のバインダーの規定方法について説明する。
・エチルセルロース
・ポリビニルブチラール(PVB)
・ポリフッ化ビニリデン(PVDF)
・ポリテトラフルオロエチレン(PTFE)
・カルボキシメチルセルロース(CMC)
[酵素固定化電極]
第2の実施の形態による酵素固定化電極は、第1の実施の形態による酵素固定化電極製造用電極10に、一種類または二種類以上の酵素が固定化されたものである。これらの酵素は、酵素固定化電極の用途に応じて適宜選択される。
この酵素固定化電極は、第1の実施の形態による酵素固定化電極製造用電極10に酵素溶液を塗布あるいは滴下したり、酵素固定化電極製造用電極10を酵素溶液に浸漬したりすることにより製造することができる。この際、基板14として撥水的なセパレータ、例えばシリコン系撥水剤により撥水性とされた不織布を用いる場合には、このセパレータの表面の所定の領域にカーボン塗料を塗布することにより、このカーボン塗料が塗布された場所にのみ選択的に酵素溶液を塗布することができる。また、この酵素固定化電極をバイオ燃料電池の正極または負極に用いることにより、燃料が発電部以外に広がらないようにすることができ、それによって燃料の損失や燃料の添加あるいは注入の際に筐体などが汚れるのを防止することができる。
ケッチェンブラックとVGCFとエチルセルロースとからなる実施例5の酵素固定化電極製造用電極10に、10mMリン酸緩衝液(pH7)に酸素還元酵素であるビリルビンオキシダーゼ(BOD)を溶解した酵素溶液を滴下することにより、ビリルビンオキシダーゼを固定化し、バイオ燃料電池の正極を形成した。
[バイオ燃料電池]
次に、第3の実施の形態について説明する。この第3の実施の形態においては、バイオ燃料電池の正極および負極として、第2の実施の形態による酵素固定化電極を用いる。
負極21として、実施例5、7の酵素固定化電極製造用電極10および比較例1、2の酵素固定化電極製造用電極にグルコースデヒドロゲナーゼ(GDH)、ジアホラーゼ(DI)およびNADHを固定化したものを用いた。正極22として、実施例5、7の酵素固定化電極製造用電極10および比較例1、2の酵素固定化電極製造用電極にビリルビンオキシダーゼ(BOD)を固定化したものを用いた。これらの正極22および負極21を用いたバイオ燃料電池の出力を測定した。燃料溶液としてはグルコース溶液を用いた。図14は、バイオ燃料電池を動作させてから1時間経過後の、実施例5の酵素固定化電極製造用電極10を用いたバイオ燃料電池に対する相対出力を示す。図14より、正極22および負極21に実施例5、7の酵素固定化電極製造用電極10を用いたバイオ燃料電池は、正極22および負極21に比較例1、2の酵素固定化電極製造用電極を用いたバイオ燃料電池に比べて高い出力が得られていることが分かる。
[1]正極と、負極と、正極と負極との間に設けられたプロトン伝導体とを有し、正極および負極のうちの少なくとも一方が、カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなり、酵素が固定化された電極であるバイオ燃料電池。
[2]バインダーは、エチルセルロース、ポリビニルブチラール、アクリル樹脂およびエポキシ樹脂からなる群より選ばれた少なくとも一種類を含む[1]に記載のバイオ燃料電池。
[3]カーボン粒子は、カーボンブラック、バイオカーボン、気相法炭素繊維および活性炭からなる群より選ばれた少なくとも一種類を含む[1]または[2]に記載のバイオ燃料電池。
[4]混合物におけるカーボン粒子の質量に対するバインダーの質量の比は0.01以上1以下である[1]乃至[3]のいずれかに記載のバイオ燃料電池。
[5]正極および負極のうちの少なくとも一方が、正極と負極との間に設けられるセパレータと一体に形成されている[1]乃至[4]のいずれかに記載のバイオ燃料電池。
[6]正極と、負極と、正極と負極との間に設けられたプロトン伝導体とを有するバイオ燃料電池を製造する場合に、カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる電極を形成する工程と、電極に酵素を固定化することにより正極および負極のうちの少なくとも一方を形成する工程とを有するバイオ燃料電池の製造方法。
[7]カーボン粒子とバインダーとを含むペーストを基板上に塗布した後、このペーストを固化させることにより正極および負極のうちの少なくとも一方を形成する[6]に記載のバイオ燃料電池の製造方法。
[8]カーボン粒子とバインダーとを含むペーストをセパレータ上に塗布した後、このペーストを固化させることにより正極および負極のうちの少なくとも一方をセパレータと一体に形成する[6]または[7]に記載のバイオ燃料電池の製造方法。
11 基板
12 ペースト
14 不織布
21 負極
22 正極
23 電解質層
41、42 Ti集電体
43、44 固定板
Claims (18)
- 正極と、
負極と、
正極と負極との間に設けられたプロトン伝導体とを有し、
正極および負極のうちの少なくとも一方が、カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなり、酵素が固定化された電極であるバイオ燃料電池。 - バインダーは、エチルセルロース、ポリビニルブチラール、アクリル樹脂およびエポキシ樹脂からなる群より選ばれた少なくとも一種類を含む請求項1記載のバイオ燃料電池。
- カーボン粒子は、カーボンブラック、バイオカーボン、気相法炭素繊維および活性炭からなる群より選ばれた少なくとも一種類を含む請求項2記載のバイオ燃料電池。
- 混合物におけるカーボン粒子の質量に対するバインダーの質量の比は0.01以上1以下である請求項1記載のバイオ燃料電池。
- 正極および負極のうちの少なくとも一方が、正極と負極との間に設けられるセパレータと一体に形成されている請求項1記載のバイオ燃料電池。
- 正極と、
負極と、
正極と負極との間に設けられたプロトン伝導体とを有するバイオ燃料電池を製造する場合に、
カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる電極を形成する工程と、
電極に酵素を固定化することにより正極および負極のうちの少なくとも一方を形成する工程、
とを有するバイオ燃料電池の製造方法。 - カーボン粒子とバインダーとを含むペーストを基板上に塗布した後、このペーストを固化させることにより正極および負極のうちの少なくとも一方を形成する請求項6記載のバイオ燃料電池の製造方法。
- カーボン粒子とバインダーとを含むペーストをセパレータ上に塗布した後、このペーストを固化させることにより正極および負極のうちの少なくとも一方をセパレータと一体に形成する請求項6記載のバイオ燃料電池の製造方法。
- 一つまたは複数の燃料電池を用い、
少なくとも一つの燃料電池が、
正極と、
負極と、
正極と負極との間に設けられたプロトン伝導体とを有し、
正極および負極のうちの少なくとも一方が、カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなり、酵素が固定化された電極であるバイオ燃料電池である電子機器。 - カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる電極に酵素が固定化された酵素固定化電極。
- セパレータ上にこのセパレータと一体に形成された請求項10記載の酵素固定化電極。
- カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる電極を形成する工程と、
電極に酵素を固定化する工程、
とを有する酵素固定化電極の製造方法。 - カーボン粒子とバインダーとを含むペーストを基板上に塗布した後、このペーストを固化させることにより電極を形成する請求項12記載の酵素固定化電極の製造方法。
- カーボン粒子とバインダーとを含むペーストをセパレータ上に塗布した後、このペーストを固化させることにより電極を上記セパレータと一体に形成する請求項12記載の酵素固定化電極の製造方法。
- カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる酵素固定化電極製造用電極。
- カーボン粒子と水に不溶な親水性のバインダーとを含むペーストを基板上に塗布した後、このペーストを固化させることにより酵素固定化電極製造用電極を製造する酵素固定化電極製造用電極の製造方法。
- カーボン粒子と水に不溶な親水性のバインダーとを含む混合物からなる電極に酵素が固定化された酵素固定化電極を有する酵素反応利用装置。
- 上記酵素反応利用装置はバイオ燃料電池、バイオセンサーまたはバイオリアクターである請求項17記載の酵素反応利用装置。
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JP2019053906A (ja) * | 2017-09-15 | 2019-04-04 | 学校法人立命館 | 発電装置用の電極 |
JP7043052B2 (ja) | 2017-09-15 | 2022-03-29 | 学校法人立命館 | 発電装置用の電極及び発電装置 |
JP7043053B2 (ja) | 2017-09-15 | 2022-03-29 | 学校法人立命館 | 発電装置 |
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CN104054202A (zh) | 2014-09-17 |
JP6015665B2 (ja) | 2016-10-26 |
JPWO2013065581A1 (ja) | 2015-04-02 |
US20150280266A1 (en) | 2015-10-01 |
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