EP2176405A1 - Procédé d'obtention d'une culture microbienne productrice d'hydrogène, cathodophile, culture microbienne obtenue par ce procédé et utilisation de cette culture microbienne - Google Patents

Procédé d'obtention d'une culture microbienne productrice d'hydrogène, cathodophile, culture microbienne obtenue par ce procédé et utilisation de cette culture microbienne

Info

Publication number
EP2176405A1
EP2176405A1 EP08778996A EP08778996A EP2176405A1 EP 2176405 A1 EP2176405 A1 EP 2176405A1 EP 08778996 A EP08778996 A EP 08778996A EP 08778996 A EP08778996 A EP 08778996A EP 2176405 A1 EP2176405 A1 EP 2176405A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
cathode
microbial culture
anode
compartments
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08778996A
Other languages
German (de)
English (en)
Inventor
René Alexander ROZENDAL
Hubertus Victor Marie Hamelers
Cees Jan Nico Buisman
Adriaan Willem Jeremiasse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stichting Wetsus Centre of Excellence for Sustainable Water Technology
Original Assignee
Stichting Wetsus Centre of Excellence for Sustainable Water Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stichting Wetsus Centre of Excellence for Sustainable Water Technology filed Critical Stichting Wetsus Centre of Excellence for Sustainable Water Technology
Publication of EP2176405A1 publication Critical patent/EP2176405A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/36—Adaptation or attenuation of cells
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M25/00—Means for supporting, enclosing or fixing the microorganisms, e.g. immunocoatings
    • C12M25/06—Plates; Walls; Drawers; Multilayer plates
    • C12M25/08—Plates; Walls; Drawers; Multilayer plates electrically charged
    • 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
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • 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
    • 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
    • C12N13/00—Treatment of microorganisms or enzymes with electrical or wave energy, e.g. magnetism, sonic waves
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • 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

Definitions

  • the present invention relates to a method for obtaining a cathodophilic, hydrogen-producing microbial culture.
  • the invention relates to the cathodophilic, hydrogen- producing microbial culture and the use of this microbial culture for the production of hydrogen. Further aspects of the invention relate to a method for manufacturing a bifunctional bioelectrode in which the cathodophilic, hydrogen-producing microbial culture is applied, and the bifunctional bioelectrode obtained with this method.
  • Hydrogen-producing cathodes are typically used in water electrolysis processes. In water electrolysis water is split into hydrogen and oxygen under the influence of a potential difference applied between anode and cathode in accordance with the reaction:
  • Hydrogen-producing cathodes have recently also found application in a new type of electrolysis process, i.e. biocatalyzed electrolysis of dissolved bio-oxidizable material (e.g. in wastewater), hi biocatalyzed electrolysis bio-oxidizable material is split into carbon dioxide and hydrogen under the influence of a potential difference between anode and cathode.
  • biocatalyzed electrolysis of dissolved bio-oxidizable material e.g. in wastewater
  • hi biocatalyzed electrolysis bio-oxidizable material is split into carbon dioxide and hydrogen under the influence of a potential difference between anode and cathode.
  • This can be schematically represented as: [CH 2 O] + H 2 O ⁇ 2 H 2 + CO 2 (4)
  • biocatalyzed electrolysis is derived from the fact that the oxidation of bio- oxidizable material at the anode is catalyzed by electrochemically active micro-organisms. Conversely, the hydrogen-producing reduction reaction at the cathode is catalyzed chemically (e.g. with platinum) in its standard embodiment, just as in water electrolysis. In biocatalyzed electrolysis of dissolved bio-oxidizable material (e.g. in wastewater) the following electrode reactions take place:
  • Overpotentials generally have the property of increasing (i.e. energy loss increases) as current density increases (i.e. as reaction speed increases). This is also the case for cathode overpotentials.
  • the relation between the cathode potential and current density can be represented in a so-called E-j curve or polarization curve, which represents the cathode potential as a function of the current density (j).
  • a cathode is generally assembled from two elements, i.e. a charge distributor of an electrically conductive material and a catalyst for accelerating the cathode reaction.
  • Carbon is a frequently used charge distributor, since it has a low cost price, a high electrical conductivity and a high chemical resistance.
  • Using only a charge distributor without catalyst the electrochemical production of hydrogen at a cathode is however very slow from a kinetic viewpoint. Large overpotentials (i.e. large energy losses) can hereby already occur at relatively low current densities.
  • Use is often made of platinum as catalyst for electrochemical hydrogen production at a cathode.
  • platinum is indeed a very effective cathode catalyst which can limit the overpotential to a minimum at very high current densities (e.g. 0.025 V overpotential at 1.08 A/cm as described in the book ''''Electrochemical oxygen technology' ' ' written by Kinoshita, K; John Wiley & Sons Inc.: New York, 1992).
  • Platinum has unfortunately been found for a number of reasons to be a much less suitable cathode catalyst for biocatalyzed electrolysis. Firstly, platinum is a very expensive material, hi addition, the current densities of biocatalyzed electrolysis are typically three to five orders of magnitude lower than those in water electrolysis (i.e.
  • a (bio)fuel cell is understood to mean “an electrochemical 'device' that continuously converts chemical energy into electrical energy (and some heat) for as long as fuel and oxidant are supplied” (Hoogers, G, “Fuel Cell Technology Handbook", CRC Press 2003). The reverse takes place in an electrolysis cell: electrical energy is invested in order to cause desired chemical reactions (Bard, AJ., Faulkner, L.R., “Electrochemical Methods, Fundamentals and Applications”, Wiley 2001), or electrical energy is converted into chemical energy (and some heat).
  • Examples of electrolysis processes are water electrolysis and biocatalyzed electrolysis. Described in the international patent application WO 2004/015806 is a stainless steel electrode, the surface of which is covered with a biofilm (defined in WO 2004/015806 as "a film consisting of micro-organisms from biological water such as sea water, river water etc., which have been deposited spontaneously onto a surface"), which is intended to catalyze the reaction at the electrode of a fuel cell.
  • the biofilm is formed by immersing the electrode in a medium which enhances the growth of biofilms, and by simultaneously applying a polarization potential to the electrode (value between -0.5 and 0.0 V relative to a standard calomel electrode).
  • the electrode of a fuel cell covered with biofilm can be a cathode as well as an anode.
  • the biofilm catalyzes oxygen reduction.
  • the biofilm catalyzes an anodic fuel cell reaction.
  • the patent application does not however relate to possible biofilm applications for catalysis of electrochemical hydrogen production at a cathode in an electrolysis cell, nor does this application describe how an electrochemically active microbial culture suitable for electrochemical hydrogen production could be obtained.
  • Tatsumi et al. (Analytical Chemistry, vol. 71. p. 1753-1759, 1999), Tsujimura et al. (Phys. Chem. Chem. Phys., vol. 3, p. 1331-1335, 2001), Lojou et al. (Electroanalysis, vol. 14, p. 913-922, 2002) describe the use of electrodes with immobilized Desulfov ⁇ brio vulgaris Hildenborough (DvH) cells for the production and/or oxidation of hydrogen. The cells were immobilized by enclosing a suspension with the relevant cells between a membrane and an electrically conductive carrier material.
  • DvH Desulfov ⁇ brio vulgaris Hildenborough
  • Electrochemistry, vol. 38, p. 97-102, 2002 moreover showed that, of one of such electrodes, 50% of the original activity was retained after conserving for six months in buffer solution at 4°C.
  • Described in the patent application WO 2004/114494 is a fuel cell which makes use of immobilized hydrogenases at the anode for the purpose of catalyzing hydrogen oxidation, and immobilized oxidases at the cathode for the purpose of catalyzing oxygen reduction.
  • the immobilization can be brought about by means of sorption from an aqueous solution or by means of chemical bonding.
  • Described in US 2006/0159981 is a biological fuel cell consisting of an anode with an attached anode enzyme and a cathode with an attached cathode enzyme.
  • the enzyme on the anode catalyzes the oxidation of a reductant (not further specified), and the enzyme on the cathode catalyzes the reduction of an oxidant (not further specified).
  • the present invention has for its object to provide an alternative to the cathode systems described up to this point for electrochemical hydrogen production.
  • the invention provides for this purpose a method for obtaining a cathodophilic, hydrogen-producing microbial culture. The method comprises the steps of:
  • bioelectrode comprising an electrochemically active microbial culture on an electric conductor, this microbial culture being capable of hydrogen oxidation;
  • the bioelectrode provided in the method comprises an electrochemically active microbial culture on an electric conductor.
  • This microbial culture is capable of hydrogen oxidation.
  • electrochemically active microbial culture is understood in the context of the present invention to mean a culture of micro-organisms which can use an electrode directly, i.e. without the use of externally supplied redox mediators, as electron donor
  • the microbial culture is present on an electric conductor, i.e. a material which can conduct an electric current.
  • an electric conductor i.e. a material which can conduct an electric current.
  • Carbon for instance in the form of carbon felt or carbon paper or graphite felt or graphite paper, is particularly suitable as electric conductor. The skilled person may however select other suitable materials.
  • An electric conductor is also referred to in this description and the claims with the term charge distributor.
  • the electrochemically active microbial culture present on the bioelectrode is capable of hydrogen oxidation.
  • Hydrogen oxidation is a process in which H 2 is converted to protons and electrons in accordance with the reverse reaction of the above reaction equation (3 a and/or 3b).
  • the skilled person will appreciate that the reactions in accordance with reaction equation 3 a and 3b are similar reactions, and that reaction 3 a is obtained by deleting 2 OH " on the left and right from reaction 3b.
  • the organisms of an electrochemically active microbial culture capable of hydrogen oxidation are herein able to relinquish the formed electrons directly, i.e. without an externally supplied redox mediator, to an anode as electron acceptor.
  • the bioelectrode is placed in a medium, the culture medium, suitable for supporting the physiology of at least a part of the organisms in the microbial culture.
  • Supporting the physiology means here that the organisms can be metabolically active.
  • Metabolic activity of the organisms in the microbial culture in respect of hydrogen formation via for instance one or more of the above reactions 3 a and 3b is of particular importance in the context of the present invention.
  • Media suitable as culture medium are known to the skilled person. Such a suitable medium is for instance Postgate's medium. Other suitable media are described in examples 1 and 2. It is of further importance in hydrogen production that the culture medium has a low oxygen tension.
  • the medium is therefore preferably microaerophilic, and more preferably substantially anaerobic.
  • aqueous solution of trace elements further comprising a carbon source, for instance carbon dioxide, with a pH of 2-10, such as pH 3-9, preferably pH 5-7.
  • a carbon source for instance carbon dioxide
  • pH of 2-10 such as pH 3-9, preferably pH 5-7.
  • a low pH of below pH 5.0 such as below pH 4.0.
  • methanogenic organisms are inhibited by such a low pH value.
  • growth of methanogenic bacteria can be inhibited by minimizing the concentration of carbon dioxide once the microbial culture has grown sufficiently.
  • a PCO 2 of below 0.0003 atm, such as below 0.0002 or below 0.0001 atm, can be used for this purpose.
  • a potential is applied to the bioelectrode which is lower than the equilibrium potential in the culture medium of the H + /H 2 redox couple.
  • the equilibrium potential of the H + /H 2 redox couple in the culture medium can be determined by the skilled person on theoretical basis (on the basis of knowledge of the composition of the culture medium and the other reaction conditions).
  • the equilibrium potential can further be determined in a number of cases by determining the open-circuit voltage of a cell.
  • the potential can be applied using a potentiostat or other suitable electrical power source.
  • the changeover to a potential which is lower than the equilibrium potential of the H + /H 2 redox couple in the culture medium means a reversal of their electrochemical reaction. Because this potential lies below the equilibrium potential of the H + ZH 2 couple, the cells will be forced to catalyze the reaction in the direction of proton reduction. They will thus produce hydrogen in electroactive manner.
  • the potential applied in step (iii) of the method is for instance 5, 10, 15, 20, 25, 40, 50, 60 mV lower than the equilibrium potential of the H + ZH 2 redox couple in the culture medium, such as more than 70, 80, 90, 100, 120, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or more than 1000 mV lower than the equilibrium potential of the H 4 VH 2 redox couple in the culture medium.
  • the applied potential can be applied using a power source.
  • a potentiostat is for instance suitable as power source.
  • Such a potentiostat can be coupled to a reference electrode, for instance a standard hydrogen electrode, a calomel electrode or an Ag/ AgCl electrode, for the purpose of precisely regulating the potential of the bioelectrode relative to the equilibrium potential of the H 4 VH 2 couple in the culture medium.
  • the use of a potentiostat is not however essential, and any other electric power source which the skilled person understands to be suitable for applying a potential to the bioelectrode can be used.
  • the potential can be regulated to below the equilibrium potential of the H 4 VH 2 redox couple by shifting, such as decreasing, this equilibrium potential of the H + ZH 2 redox couple, for instance by decreasing the pH of the culture medium and/or decreasing the hydrogen pressure or by other changes in the reaction conditions such as the temperature, as known to the skilled person.
  • a potential rise of ⁇ 60 mV per pH unit can be inferred herefrom.
  • a pH reduction of the culture medium can thus also be used to give a potential present at a cathode a value below the equilibrium potential of the H + ZH 2 redox couple in the culture medium.
  • the bioelectrode is obtained by placing a bioanode, comprising an electrochemically active microbial culture on a charge distributor, this microbial culture being capable of oxidation of a biologically oxidizable carbon compound, in a culture medium which is able to support the physiology of at least a part of the microbial culture, at a potential higher than the equilibrium potential of the H-VH 2 redox couple in the culture medium.
  • the applied potential can be for instance up to 1000 mV, up to 800 mV, such as up to 500 mV, higher than the equilibrium potential of the H 1 VH 2 redox couple in the culture medium.
  • the applied potential is preferably up to 200 mV higher, such as up to 150 mV, 100 mV or 50 mV higher.
  • Suitable biologically oxidizable carbon compounds can be selected by the skilled person.
  • suitable biologically oxidizable carbon compounds are for instance short-chain (C 1 -C 6 ) organic acids, such as lactic acid, ascetic acid and dissociated forms thereof, short-chain (C 1 -C 6 ) alcohols, such as ethanol and propanol or carbohydrates such as glucose, fructose, lactose or saccharose.
  • an electrochemically active microbial culture capable of hydrogen oxidation is selected at the bioanode, for instance via a reaction which is the reverse of the reaction shown in the above stated reaction equation 3a or 3b.
  • the inventors of the present invention have found that such an electrochemically active microbial culture capable of hydrogen oxidation can produce hydrogen electrochemically at a potential lower than the equilibrium potential of the H 4 VH 2 redox couple in the culture medium in which they are present.
  • a biologically non- oxidizable carbon source such as a carbon dioxide source
  • a carbon dioxide source is present under conditions of limitation of the biologically oxidizable carbon compound.
  • a carbon dioxide source is for instance carbon dioxide or a solution containing H 2 CO 3 and/or HCO 3 " and/or CO 3 2' .
  • a further preferred embodiment comprises of inoculating the cathodophilic, hydro gen- producing microbial culture to a charge distributor. Inoculation of the cathodophilic, hydrogen-producing microbial culture makes it possible to multiply this culture in simple manner and/or to obtain a plurality of electrodes with the cathodophilic microbial culture. Inoculation can take place in any suitable manner known to the skilled person for the purpose of inoculating micro-organisms.
  • a further aspect of the invention relates to a cathodophilic, hydrogen-producing microbial culture. Such a microbial culture able to produce hydrogen in electrochemical manner without use of external redox mediators has not been described earlier.
  • the microbial culture comprises micro-organisms able to produce hydrogen by means of proton reduction and/or water reduction, as described in for instance reaction equations 3 a and 3b.
  • the microbial culture can be a monoculture or a mixed culture. According to a preferred embodiment, the microbial culture is obtainable with the method according to the invention for obtaining said microbial culture.
  • FIG. 1 Further aspects of the invention relate to the use of a microbial culture according to the invention for producing hydrogen.
  • the microbial culture is suitable for the production of hydrogen.
  • bioelectrode which is for instance suitable as biocathode, for instance for use in biocatalyzed electrolysis of water.
  • the method comprises of providing a body of an electrically conductive material and arranging a cathodophilic, hydrogen-producing microbial culture on the surface of the electrically conductive material.
  • this is a method wherein:
  • the provided body of the electrically conductive material comprises two separate surfaces; (ii) the cathodophilic, hydrogen-producing microbial culture is arranged on a first surface, the cathode surface; (iii) a catalyst for an electrochemical oxidation reaction is arranged on a second surface, the anode surface.
  • a body of an electrically conductive material, or a charge distributor is provided in the method, hi the context of this invention the term charge distributor is understood to mean a material which can conduct electrical charge.
  • Suitable charge distributors are for instance carbon, preferably carbon paper, a carbon plate, graphite paper, a graphite plate or an electrically conductive material such as copper or titanium.
  • a cathodophilic, hydrogen-producing microbial culture according to the invention is arranged on the surface of the body of the electric conductor.
  • the arranging can take place in any manner which the skilled person understands to be suitable for arranging a microbial culture.
  • the body comprises two separate surfaces. This is understood to mean that it must be possible to separate the two surfaces from each other such that one surface can serve as cathode and the other can serve as anode. This is possible for instance by selecting the body as a substantially two-dimensional body such as a plate-like body, preferably a flat plate.
  • a cathodophilic, hydrogen-producing microbial culture according to the invention is arranged on the first surface, the cathode surface.
  • a catalyst for an electrochemical oxidation reaction for instance an anaerobic oxidation reaction, is arranged on a second surface, the anode surface.
  • the catalyst can be any suitable catalyst and the arranging can take place in any manner which the skilled person understands to be suitable for arranging the type of catalyst used.
  • the catalyst can for instance be selected from the group of platinum and/or an electrochemically active microbial culture capable of electrochemical oxidation, for instance an anaerobic oxidation, of a biologically oxidizable substrate, such as a biologically oxidizable carbon compound.
  • This latter microbial culture can comprise organisms from the group of Geobacter sulfurreducens, Shewanella putrefaciens, Geobacter metallireducens and Rhodoferax ferrireducens or other organisms from the genera to which these stated species belong, or a consortium of these organisms.
  • the bifunctional bioelectrode obtained with the above described preferred embodiment of the method comprises a body of a charge distributor, which body comprises two separate surfaces, with a cathodophilic, hydrogen-producing microbial culture on the first surface, the cathode surface, and a catalyst for an electrochemical oxidation reaction on the second surface, the anode surface.
  • the present invention also relates to the bioelectrode, in particular a bifunctional bioelectrode, obtained with this method.
  • bioelectrode in particular a bifunctional bioelectrode, obtained with this method.
  • the characteristics of this bioelectrode and the bifunctional bioelectrode and those of the preferred embodiments stated in the claims will be apparent to the skilled person from the description relating to the method for manufacturing this bifunctional bioelectrode.
  • the invention relates to a device.
  • This device is suitable for use as electrolysis device.
  • the device comprises a number of compartments, with an anode and a cathode placed at a mutual distance in each of the compartments.
  • On the anode there is a catalyst for the electrochemical oxidation of an oxidizable substrate, and on the cathode there is a cathodophilic, hydrogen-producing microbial culture.
  • an ion-conducting separation which divides the number of compartments into a cathode sub-compartment on the side of the cathode and an anode sub- compartment on the side of the anode.
  • the cathode sub-compartments Present in the cathode sub-compartments is a culture medium suitable for supporting the physiology of the cathodophilic, hydrogen-producing microbial culture.
  • the device further comprises means for supplying to the anode sub- compartments a substrate medium comprising the oxidizable substrate and means for discharging hydrogen from the cathode sub-compartments.
  • the ion-conducting separation can be a cation or anion-conducting material, such as a cation-selective membrane, an anion-selective membrane or a bipolar membrane.
  • a cation-selective membrane such as a cation-selective membrane, an anion-selective membrane or a bipolar membrane.
  • (Micro)porous membranes such as microfiltration, ultrafiltration or nanofiltration membranes are also suitable. Such materials are known to the skilled person.
  • a device for electrolysis of the above stated type is per se known in the field.
  • the electrolysis device according to the invention is however distinguished from those known in the prior art by the presence of a cathodophilic, hydrogen-producing microbial culture on the cathode.
  • the term 'a number' means one or more.
  • the number of compartments is a plurality of compartments.
  • the plurality of compartments is subdivided into a first and a second terminal compartment and a number of intermediate compartments lying therebetween.
  • the number of anodes and cathodes is here present in alternating manner in the device.
  • the electrical connection between the number of anodes and the number of cathodes is further adapted as an electrical connection between the anode and cathode of adjacent intermediate compartments, an electrical connection between the cathode of the first terminal compartment and the anode of the intermediate compartment adjacent to the first terminal compartment, an electrical connection between the anode of the second terminal compartment and the cathode of the intermediate compartment adjacent to the second terminal compartment, and an electrical connection between the anode and cathode of the terminal compartments.
  • the electrolysis device according to this embodiment can be designed as a stack of electrolysis cells.
  • the electrical connection between a number of anodes and cathodes comprises a power source for the purpose of adjusting the potential of the cathode. If a power source is present, it will be accommodated for a stack in the electrical connection between the anode and cathode of the terminal compartments.
  • the catalyst for the electrochemical oxidation of an oxidizable substrate on the anodes comprises a catalyst from the group comprising platinum and/or a micro-organism selected from the group of Geobacter sulfurreducens, Shewanella putrefaciens, Geobacter metallkeducens and Rhodoferaxferrireducens or other organisms from the stated genera or a consortium of one or more organisms herefrom. It is known of these organisms that they can have an anodophilic action.
  • the anodes and cathodes of the intermediate compartments are adapted as bifunctional electrodes according to the invention. Owing to the low internal resistance of the bifunctional electrode, the internal resistance of the electrolysis device is also reduced compared to a prior art electrolysis device with a similar electrode surface area.
  • the invention relates to a method for producing hydrogen.
  • the method comprises of: (i) providing a device for electrolysis according to the invention;
  • the oxidizable substrate can be any suitable substrate as known to the skilled person.
  • the substrate medium can for instance be a wastewater flow with a high content of organic compounds.
  • the potential can alternatively be regulated to below the equilibrium potential of the H 4 VH 2 redox couple, by shifting, such as decreasing, this equilibrium potential of the H 4 VH 2 redox couple, for instance by reducing the pH of the culture medium and/or reducing the hydrogen pressure.
  • the potential applied to the cathode is preferably such that a desired quantity of H 2 is produced per unit of time.
  • This desired quantity of H 2 can be predetermined.
  • Another possible criterion for the production of H 2 is the energy invested in the form of the applied potential. A higher energy investment can cause an increase in the cost price of the produced H 2 .
  • the skilled person will be able to optimize the applied potential in respect of cost price of the hydrogen.
  • the hydrogen produced at the cathode sub-compartments can be discharged in any suitable manner for direct use and/or storage.
  • Figures IA- 1C show an overview of an embodiment of the method for obtaining the cathodophilic, hydrogen-producing microbial culture
  • FIG. 2 shows an embodiment of an electrolysis device according to the invention
  • Figure 3 shows a detail of the biocathode of the electrolysis device of figure 2;
  • Figure 4 shows a section through a bifunctional electrode according to the invention;
  • Figure 5 shows a detail of the section through the bifunctional electrode of figure 4.
  • FIG. 6 shows another embodiment of an electrolysis device according to the invention which makes use of the bifunctional electrode
  • Figure 7 shows a polarization curve of the current density as a function of the cathode potential as obtained using the cathodophilic, hydrogen-producing microbial culture, and two reference experiments;
  • Figure 8 shows the volume of hydrogen as a function of time for a test in which the cathodophilic microbial culture is used, and a reference experiment.
  • an electrochemical cell 1 as shown in figures IA, IB, 1C.
  • a cell consists for instance of two compartments 2, 3 separated by an ion-conducting separation 4 (for instance Nafion® 117).
  • a compartment 3 comprises a carbon rod electrode 5. This electrode serves as the bioelectrode (working electrode) and is connected to a potentiostat 6 functioning as power source.
  • the other compartment 2 comprises a platinum electrode 7 which is connected to the power source and which serves as counter-electrode.
  • a reference electrode (not shown in figures IA, IB, 1C) can also be placed in the bioelectrode compartment.
  • Both compartments 2, 3 are filled with a suitable medium (for instance a medium consisting of 0.74 g/L KCl, 1.36 g/L KH 2 PO 4 , 0.28 g/L NH 4 Cl, 0.84 g/L NaHCO 3 -, 0.1 g/L CaCl 2 -2H 2 O, 1 g/L MgSO 4 -7H 2 O and 1 mL/L trace elements).
  • a suitable medium for instance a medium consisting of 0.74 g/L KCl, 1.36 g/L KH 2 PO 4 , 0.28 g/L NH 4 Cl, 0.84 g/L NaHCO 3 -, 0.1 g/L CaCl 2 -2H 2 O, 1 g/L MgSO 4 -7H 2 O and 1 mL/L trace elements.
  • the bioelectrode compartment 3 of electrochemical cell 1 is inoculated with electrochemically active micro-organisms from the anode compartment of a biocatalyze
  • FIG. 2 shows an overview of a biocatalyzed electrolysis device.
  • the biocatalyzed electrolysis cell comprises components similar to the electrochemical cell of figure 1C, i.e. two compartments 2, 3 separated by an ion-conducting separation 4. Both compartments 2, 3 comprise in this case a bioelectrode.
  • Bioelectrode 5 in compartment 3 comprises a cathodophilic, hydrogen-producing microbial culture 8a according to the invention.
  • Bioelectrode 7 in compartment 2 (the anode) comprises an anodophilic microbial culture 10 which is able to convert a biologically oxidizable carbon compound into CO 2 , H + and electrons.
  • the electrons produced at anode 7 are conducted via an electrical circuit to cathode 5.
  • the electrons are used by the cathodophilic microbial culture 8 to reduce protons to H 2 .
  • a power source 6 for supplying the required energy is incorporated in the electrical circuit.
  • the protons are formed in anode compartment 2 and flow via the ion-conducting separation 4 (for instance a National membrane) to cathode compartment 3.
  • the biologically oxidizable carbon compound OM comes from wastewater which enters anode compartment 2 via an inlet 11.
  • FIG. 3 shows a schematic overview of the proton reduction reaction which is catalyzed by the cathodophilic, hydrogen-producing microbial culture in biofilm 8a on cathode 5. The schematic overview does not intend to present a stoichiometric representation of the reaction.
  • Bifunctional electrode 15 comprises an electric conductor 16, here a carbon plate.
  • a film of a cathodophilic microbial culture 8a is arranged on one surface of carbon plate 16.
  • a catalyst for an oxidation reaction is arranged on the other surface of carbon plate 16.
  • a biofilm of an anodophilic microbial culture is arranged on the other surface of carbon plate 16.
  • Figure 5 shows schematically the reactions which take place on both sides of bifunctional electrode 15. This schematic overview once again does not intend to show a stoichiometric representation of the reactions. It can be seen that on the anode side a biologically oxidizable carbon compound (OM) is converted by the anodophilic micro- organisms into electrons, CO 2 and H . The electrons flow through electric conductor 16 to the cathode side where they are used by the cathodophilic, hydrogen-producing microbial culture 8a to reduce protons to H 2 .
  • OM biologically oxidizable carbon compound
  • the bifunctional electrode can be applied in an electrolysis device according to the invention.
  • An embodiment of an electrolysis device is shown in figure 6.
  • This electrolysis device 17 comprises a plurality of bifunctional electrodes 15 according to the invention.
  • Bifunctional electrodes 15 are placed between a terminal anode 18 and a terminal cathode 19. Bifunctional electrodes 15 form compartments between the terminal anode and terminal cathode. These compartments are subdivided by an ion-conducting separation 4 into an anode sub-compartment 20 and a cathode sub-compartment 21.
  • a feed flow 22 comprising wastewater is supplied to the anode sub-compartments.
  • Biologically oxidizable carbon compounds in the wastewater are converted by the anodophile biofilm 10 into protons, CO 2 and electrons. The protons flow through the proton-conducting separation 4 to cathode sub- compartment 21.
  • CO 2 leaves the anode sub-compartment via an outlet 22, for instance together with the effluent from the wastewater.
  • the electrons generated on the anode side of a bifunctional electrode are conducted by the electrically conductive material of the bifunctional electrode directly to the cathode side of the bifunctional electrode.
  • the electrons generated at the monofunctional terminal anode are conducted via an electrical circuit to the monofunctional terminal cathode.
  • a power source 6 is arranged in this electrical circuit.
  • On the cathode side of bifunctional electrodes 15 the electrons are used by the cathodophilic hydrogen-producing microbial culture 8a to reduce protons. Hydrogen is herein produced which leaves cathode sub-compartments 21 via an outlet 23. Power source 6 supplies sufficient electrical energy for the production of hydrogen in the system. Owing to the low electrical resistance in the bifunctional electrodes the electrical resistance in this device is lower than in a prior art device with a similar electrode surface area. Examples Example 1
  • An electrochemical cell was made from glass.
  • the cell consisted of two compartments separated by a cation-selective membrane (Nafion® 117) with an area of 9.5 cm 2 .
  • One compartment (volume: IL) comprised a carbon rod electrode with an area of 10 cm 2 . This electrode served as the bioelectrode (working electrode) and was connected to a potentiostat 6 ( ⁇ Autolablll, Eco Chemie B. V., the Netherlands).
  • the other compartment (volume: 100 mL) comprised a platinum electrode 7 (1.25 cm 2 ) which was comiected to the potentiostat and which was vertically oriented relative to the bioelectrode and served as counter-electrode.
  • both electrodes to the membrane amounted to 1 cm.
  • An Ag/ AgCl, 3 M KCl reference electrode was also placed in the bioelectrode compartment. Both compartments were filled with a medium consisting of 0.74 g/L KCl, 1.36 g/L KH 2 PO 4 , 0.28 g/L NH 4 Cl,
  • the bioelectrode compartment of the electrochemical cell was inoculated with electrochemically active micro-organisms from the anode compartment of a biocatalyzed electrolysis cell, subsequently fed with acetate and hydrogen and monitored at a potential of +0.1 V (vs. standard hydrogen electrode; NHE) and pH 7. Under these conditions electrochemically active micro-organisms formed a biofilm on the bioelectrode and produced anodic current. The pH was then decreased to pH 6 and the potential to -0.1 V (vs. NHE) and, after adapting the biofilm to these conditions, the bioelectrode was fed with hydrogen and medium in which only bicarbonate was dissolved as carbon source for the purpose of selecting hydrogen oxidizing micro-organisms.
  • the potential of the bioelectrode was decreased to -0.65 V (vs. NHE, at pH 6) so that the anodic current changed into a cathodic current.
  • the cathodic current increased to a value of 1 A/m 2 bioelectrode surface area, while the potential was held constant at -0.65 V (vs. NHE).
  • the increase in the cathodic current density under unchanging conditions indicated a modification of the microbial community in the biofilm.
  • the measured cathodic current density (1 A/m 2 ) was more than twice as high as that measured with a platinum catalyzed electrode as used in a previous study (Rozendal et al., International Journal of Hydrogen Energy, vol. 31, p. 1632-1640, 2006) under similar conditions (pH 7 and a cathode potential of -0.71 V). Hydrogen was detected in the gas phase of the bioelectrode compartment (using a Shimadzu GC-2010 gas chromatograph).
  • the experiment described in example 1 was repeated in a somewhat modified setup.
  • the two inner plates formed the anode and cathode compartments, while the two outer plates served as heating jacket and reinforcement.
  • the inner plates comprised channels (channel depth: 1 cm) for liquid transport (volume: 0.25 L) and a head-space for gas accumulation (volume 0.029 L).
  • Two graphite felt electrodes (effective area: 250 cm 2 ) separated by a cation-selective membrane (Fumasep® FKE, 20 x 30 cm) were placed between the inner plates.
  • Both electrodes were connected to a potentiostat (Wenking Potentiostat/Galvanostat KP5V3A, Bank IC, Germany).
  • the bioelectrode was the working electrode.
  • the Ag/ AgCl, 3 M KCl reference electrodes (QM710X, ProSense BV, the Netherlands) were connected to Haber- Luggin capillaries.
  • the Haber-Luggin capillaries were placed a short distance from the electrodes in order to minimize the ohmic voltage loss between the reference electrode and working or counter-electrode.
  • the bioelectrode compartment was filled with medium as specified in example 1.
  • the counter-electrode compartment was filled with a solution of hexacyanoferrate(III) when the bioelectrode was operated anodically, and with a solution of hexacyanoferrate(II) when the bioelectrode was operated cathodically.
  • the bioelectrode compartment of the electrochemical cell was inoculated with electrochemically active micro-organisms from the anode compartment of a biocatalyzed electrolysis cell, subsequently fed with acetate and hydrogen and monitored at a potential of +0.1 V (vs. standard hydrogen electrode; NHE) and pH 7. Under these conditions electrochemically active micro-organisms formed a biofilm on the bioelectrode and produced anodic current. The bioelectrode was then fed with hydrogen and medium in which sodium bicarbonate was dissolved as only carbon source for the purpose of selecting hydrogen oxidizing micro-organisms. Once a constant current was being generated at a potential of -0.2 V (vs.
  • the potential of the bioelectrode was decreased to -0.7 V (vs. NHE, at pH 7) so that the anodic current changed into a cathodic current.
  • the cathodic current increased to a value of 1.1 A/m 2 bioelectrode surface area, while the potential was held constant at -0.7 V (vs. NHE).
  • the increase in the cathodic current under unchanging conditions indicated a modification of the microbial community in the biofilm.
  • the thus formed biocathode was then fed with medium which was prepared without carbon source.
  • Carbon monoxide is known as an inhibitor of hydro genases, the enzymes which catalyze hydrogen production in hydrogen-producing micro-organisms.
  • the decrease in the cathodic current is an indication that electrochemically active micro-organisms catalyze the hydrogen production at the biocathode.
  • the cathodic current recovered to 1.1 A/m 2 .
  • the control cathode was inoculated with electrochemically active micro-organisms by coupling the effluent from the biocathode to the influent of the control cathode.
  • control cathode was uncoupled from the biocathode and fed with the above specified 10 niM of bicarbonate medium.
  • current at the 'control' cathode increased from -0.3 A/m 2 to -1.0 A/m 2 .
  • Electron microscopy also indicated that a microbial film was present on the biocathode and the later inoculated 'control' cathode. This demonstrates that a biocathode for hydrogen production can also be obtained by inoculating the electrochemically active micro- organisms from an already operative biocathode for hydrogen production.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Genetics & Genomics (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Development (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
  • Molecular Biology (AREA)
  • Virology (AREA)
  • Medicinal Chemistry (AREA)
  • Immunology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Cell Biology (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Selon un premier aspect, la présente invention porte sur un procédé d'obtention d'une culture microbienne productrice d'hydrogène, cathodophile. Selon d'autres aspects, l'invention porte sur la culture microbienne productrice d'hydrogène, cathodophile, et sur l'utilisation de cette culture microbienne pour la production d'hydrogène. D'autres aspects de l'invention portent sur un procédé de fabrication d'une bioélectrode bifonctionnelle dans laquelle la culture microbienne productrice d'hydrogène, cathodophile, est appliquée, et sur la bioélectrode bifonctionnelle obtenue par ce procédé. D'autres aspects de l'invention portent sur un dispositif de production d'hydrogène dans lequel la culture microbienne productrice d'hydrogène, électrochimiquement active, est appliquée.
EP08778996A 2007-07-12 2008-07-08 Procédé d'obtention d'une culture microbienne productrice d'hydrogène, cathodophile, culture microbienne obtenue par ce procédé et utilisation de cette culture microbienne Withdrawn EP2176405A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1034123A NL1034123C2 (nl) 2007-07-12 2007-07-12 Werkwijze voor het verkrijgen van een kathodofiele, waterstof producerende microbiele cultuur, microbiele cultuur verkregen met deze werkwijze en gebruik van deze microbiele cultuur.
PCT/NL2008/000172 WO2009008709A1 (fr) 2007-07-12 2008-07-08 Procédé d'obtention d'une culture microbienne productrice d'hydrogène, cathodophile, culture microbienne obtenue par ce procédé et utilisation de cette culture microbienne

Publications (1)

Publication Number Publication Date
EP2176405A1 true EP2176405A1 (fr) 2010-04-21

Family

ID=39102947

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08778996A Withdrawn EP2176405A1 (fr) 2007-07-12 2008-07-08 Procédé d'obtention d'une culture microbienne productrice d'hydrogène, cathodophile, culture microbienne obtenue par ce procédé et utilisation de cette culture microbienne

Country Status (4)

Country Link
EP (1) EP2176405A1 (fr)
CN (1) CN101784661A (fr)
NL (1) NL1034123C2 (fr)
WO (1) WO2009008709A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0719009D0 (en) * 2007-09-28 2007-11-07 Plus Energy Ltd H Hydrogen production from a photosynthetically driven electrochemical device
CN102170667B (zh) 2010-02-25 2013-02-27 中兴通讯股份有限公司 一种实现基站间切换的方法、系统及基站装置
WO2014043690A1 (fr) * 2012-09-17 2014-03-20 Musc Foundation For Research Development Cellules d'électrosynthèse microbienne
CN102925492A (zh) * 2012-11-09 2013-02-13 中国科学院成都生物研究所 一种利用生物电化学系统还原二氧化碳生产甲烷和乙酸的方法
EP2976421B1 (fr) * 2013-03-22 2016-11-09 Danmarks Tekniske Universitet Système bio-électrochimique pour supprimer des inhibiteurs de processus de digestion anaérobie de réacteurs anaérobie
FR3026413B1 (fr) * 2014-09-30 2023-05-12 Institut National De Recherche En Sciences Et Tech Pour Lenvironnement Et Lagriculture Irstea Procede et dispositif de regulation de l'activite d'un systeme bioelectrochimique comportant a la fois une bioanode et une biocathode
DE102016109606A1 (de) 2016-05-25 2017-11-30 Clausthaler Umwelttechnikinstitut Gmbh, (Cutec-Institut) Verfahren und Vorrichtungen zur bioelektrischen Stromgewinnung aus organischen Inhaltsstoffen eines Abwassers
CN112830566B (zh) * 2020-06-11 2023-03-28 潍坊智善新能源科技有限公司 一种微生物电催化降解亚硝基二甲胺的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005005981A2 (fr) * 2003-07-10 2005-01-20 Stichting Wetsus Centre For Sustainable Water Technology Procede de production d'hydrogene
ES2322880B1 (es) * 2005-09-30 2010-04-23 Consejo Superior Investig. Cientificas Electrodo biologico con la enzima hidrogenasa, procedimiento de obtencion y sus aplicaciones.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009008709A1 *

Also Published As

Publication number Publication date
NL1034123C2 (nl) 2009-01-13
CN101784661A (zh) 2010-07-21
WO2009008709A1 (fr) 2009-01-15

Similar Documents

Publication Publication Date Title
Nawaz et al. Microbial fuel cells: Insight into simultaneous wastewater treatment and bioelectricity generation
Jung et al. Important factors influencing microbial fuel cell performance
Zhen et al. Microbial electrolysis cell platform for simultaneous waste biorefinery and clean electrofuels generation: current situation, challenges and future perspectives
Butti et al. Microbial electrochemical technologies with the perspective of harnessing bioenergy: maneuvering towards upscaling
Zhou et al. Recent advances in microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) for wastewater treatment, bioenergy and bioproducts
Lim et al. Bioanode as a limiting factor to biocathode performance in microbial electrolysis cells
US7491453B2 (en) Bio-electrochemically assisted microbial reactor that generates hydrogen gas and methods of generating hydrogen gas
Freguia et al. Sequential anode–cathode configuration improves cathodic oxygen reduction and effluent quality of microbial fuel cells
Singh et al. Microbial fuel cells: A green technology for power generation
Clauwaert et al. Methanogenesis in membraneless microbial electrolysis cells
Torres et al. Proton transport inside the biofilm limits electrical current generation by anode‐respiring bacteria
Prasad et al. Microbial fuel cell constructed with a micro-organism isolated from sugar industry effluent
Kiran et al. Microbial electroactive biofilms
WO2009008709A1 (fr) Procédé d'obtention d'une culture microbienne productrice d'hydrogène, cathodophile, culture microbienne obtenue par ce procédé et utilisation de cette culture microbienne
US20050208343A1 (en) Membraneless and mediatorless microbial fuel cell
AU2007215611C1 (en) Device comprising a new cathode system and method for generating electrical energy with use thereof
CA2923794C (fr) Module de bioreacteur electrochimique et procedes d'utilisation de celui-ci
CN103881905A (zh) 一种嵌入式生物电合成系统及方法
US9673471B2 (en) Production of a biofilm on an electrode for a biocell, electrode and biocell obtained
CN101897069A (zh) 微生物发电装置
Scott An introduction to microbial fuel cells
EP3075884A1 (fr) Système et procédé d'oxydation d'eau bio-électrochimique
US10777835B2 (en) Biological-alkali ion hybrid battery
Azuma et al. Catalyst development of microbial fuel cells for renewable-energy production
Pinto Electronic transfer within a microbial fuel cell. Better understanding of Experimental and Structural Parameters at the Interface between Electro-active Bacteria and Carbon-based Electrodes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100205

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17Q First examination report despatched

Effective date: 20100517

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1140511

Country of ref document: HK

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130201

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1140511

Country of ref document: HK