Classifications

• • 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
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
  • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
  • H01M8/1013—Other direct alcohol fuel cells [DAFC]
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
  • H01M4/92—Metals of platinum group
  • H01M4/923—Compounds thereof with non-metallic elements
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
  • H01M4/92—Metals of platinum group
  • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
  • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0202—Polynuclearity
  • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/827—Iridium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
• • 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

• Organo-metallic complexes based on iridium as oxidation catalysts Organo-metallic complexes based on iridium as oxidation catalysts
• the present invention relates to the field of fuel cells, in particular to carbohydrates. More specifically, it aims to propose a new type of catalyst for the oxidation of carbohydrates and / or oligosaccharides, in particular glucose.
• a fuel cell is a battery in which the manufacture of electricity is done through the oxidation on an electrode, called anode, of a reducing fuel (such as hydrogen or glucose for example) coupled with the reduction on the other electrode, the cathode, an oxidant, such as oxygen in the air.
• a reducing fuel such as hydrogen or glucose for example
• batteries whose fuel is based on carbohydrates and / or oligosaccharides, in particular glucose
• their operation most often requires the use of an enzymatic or the image, for example, of gold nanoparticles [1], catalysts based on iron or cobalt [2] or else catalysts based on iridium (IV) oxides and lead (II) [3] ], to stimulate the kinetics of oxidation reaction of the carbohydrate considered.
• the enzymatic catalysts interesting in that they operate at physiological pH, have, on the other hand, the disadvantage of being endowed with a very high molar mass.
• the active center that catalyzes glucose oxidation is too far away from the electron conducting medium and mediators must be added to facilitate electron transfer.
• metal catalysts they are most often not compatible with use at a physiological pH.
• gold nanoparticles are effective only at pHs well above 7.
• the subject of the present invention is the use of an organometallic complex based on iridium (II) and / or (III), as a catalyst for the oxidation of carbohydrates and / or oligosaccharides and in particular glucose.
• an organometallic complex based on iridium (II) and / or (III) as a catalyst for the oxidation of carbohydrates and / or oligosaccharides and in particular glucose.
• the radicals A 1 , A 2 , A 3 and A 4 which are identical or different, represent a halogen atom, a group chosen from unsaturated monocyclic or polycyclic hydrocarbon radicals, optionally containing one or more heteroatoms and optionally substituted , or a group chosen from the groups N0 2 , CN, COR 1 , SO 2 R 1 , CO 2 R 1 , SO 2 OR 1 , NO, CONHR 1 , CO I NRV, NR * R 2 , OR 1 and SR 1 ,
• radicals B 1 , B 2 , B 3 and B 4 which may be identical or different, represent an oxygen atom, a methylene group or a single bond between Iridium Ir and the associated radical A, and preferably a link simple,
• R 1 and R 2 which are identical or different, represent a hydrogen atom or a linear or branched C 1-6 -alkyl or C 3-7 -cycloalkyl group,
• the dashes respectively between the radicals A 1 and A 2 and between the radicals A 3 and A 4 represent a possible covalent bond between the said radicals when they represent an unsaturated monocyclic or polycyclic hydrocarbon radical
• X and X ' which may be identical or different, represent an NR 1 group or a halogen, sulfur or oxygen atom, n represents an integer equal to 0, 1, 2 or 3,
• organometallic complex means a complex having at least one sigma bond ( ⁇ ) at a metal atom of said complex, in particular with respect to a carbon atom.
• organometallic complexes based on iridium (II) and / or (III), and more preferably on formula (I) can be effectively considered as catalysts for the oxidation of carbohydrates and this under pH conditions close to neutrality.
• the complexes considered according to the invention prove to be effective at a pH ranging from 5 to 9, preferably from 6 to 8.
• organometallic complexes based on iridium (III) are already known for their electroluminescent properties. [5] [6] However, this use is on the one hand clearly different from that considered according to the invention and moreover did not prejudge the effectiveness of such complexes as carbohydrate oxidation catalysts.
• the present invention relates to a battery comprising, as anode, an electrode on which is immobilized an organometallic complex of iridium as described above.
• the present invention relates to the use of an electrode comprising an organometallic metal complex of iridium according to the invention for the oxidation of carbohydrates and / or oligosaccharides, and preferably for the oxidation of glucose.
• FIGS. 1 to 3 correspond to the performance of three glucose cells according to examples 1 to 3, measured by cyclic voltammetry (power density in mW / cm 2 as a function of the voltage applied at V, scanning speed: 2 mV / s).
• FIG. 4 illustrates a cyclic voltammetry curve between 0 and 600 mV of an electrode according to the invention with respect to a saturated calomel electrode (SCE), in 0.5 M sulfuric acid (scanning speed: 50 mV / s).
• SCE saturated calomel electrode
• organometallic metal complex of iridium is advantageously of general formula (I) below:
• the radicals A 1 , A 2 , A 3 and A 4 which are identical or different, represent a halogen atom, a group chosen from unsaturated monocyclic or polycyclic hydrocarbon radicals, optionally containing one or more heteroatoms and optionally substituted, or a group selected from the groups N0 2 , CN, COR 1 , S0 2 OR 1 , NO, CONHR 1 , CO 2 V, NR * R 2 , OR 1 and SR 1 ,
• radicals B 1 , B 2 , B 3 and B 4 which may be identical or different, represent an oxygen atom, a methylene group or a single bond between Iridium Ir and the associated radical A, and preferably a link simple, R 1 and R 2, which are identical or different, represent a hydrogen atom or a linear or branched C 1-6 -alkyl or C 3-7 -cycloalkyl group,
• the dashes respectively between the radicals A 1 and A 2 and between the radicals A 3 and A 4 represent a possible covalent bond between the said radicals when they represent an unsaturated monocyclic or polycyclic hydrocarbon radical
• X and X ' which may be identical or different, represent a group R 1 or a halogen, sulfur or oxygen atom,
• n an integer equal to 0, 1, 2 or 3
• a halogen atom denotes a fluorine, a chlorine, a bromine or an iodine
• t and z can take values from 1 to 7, designates a carbon chain which can have from t to z carbon atoms, for example a C 1-3 carbon chain which can have from 1 to 3 carbon atoms;
• alkyl denotes a saturated, linear or branched aliphatic group; for example a C 1-6 alkyl group represents a linear or branched carbon chain of 1 to 6 carbon atoms, more particularly a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl;
• cycloalkyl denotes a cyclic alkyl group, for example a C 3-7 -cycloalkyl group represents a cyclic carbon group of 3 to 7 carbon atoms, more particularly a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl;
• an unsaturated monocyclic or polycyclic hydrocarbon radical denotes a radical consisting of one to four rings, comprising from 2 to 20 carbon atoms, each ring having at least one unsaturation and comprising from 3 to 7 ring members.
• a radical may include one or more identical or different heteroatoms selected from nitrogen, oxygen and sulfur.
• each ring cycle has zero or one heteroatom.
• this radical is polycyclic, the rings can be condensed, for example the naphthalenyl, quinolinyl, anthracenyl, carbazolyl, acridinyl or indolyl radical, or linked to one another by a methine group, for example in the form of a porphinyl or chlorinyl radical.
• This radical preferably represents an aromatic or heteroaromatic radical.
• aromatic radical may be mentioned more particularly the phenyl, naphthalenyl and anthracenyl groups.
• heteroaromatic radical may be more particularly mentioned the pyridinyl, furanyl, thiophenyl, porphinyl, quinolinyl, carbazolyl, acridinyl, pyrrolyl and indolyl groups;
• substituted signifies that the radical may be substituted more particularly by a halogen atom, a phenyl and a R U R 12 group with R 11 and R 12 being as defined below;
• radicals x, y and their derivatives denotes the radicals x, y as such and the radicals x and y substituted with one or more identical or different substituents chosen from a halogen atom, a
• the radicals A 1 , A 2 , A 3 and A 4 represent unsaturated monocyclic or polycyclic hydrocarbon radicals and are preferably chosen from pyridinyl, phenyl, furanyl, benzyl, thiophenyl, porphinyl and naphthalenyl radicals. , quinolinyl, anthracenyl, carbazolyl, acridinyl, pyrrolyl, chlorinyl, indolyl and their derivatives, preferably from pyridinyl, phenyl and indolyl radicals, and their derivatives, in particular from pyridinyl and phenyl radicals and their derivatives.
• radicals X and X ' are preferably identical and advantageously represent a halogen atom, and in particular a chlorine atom.
• formula (I) preferably:
• n 3 and m is 0, or
• n 2 and m is 1.
• radicals A 1 and A 2 are advantageously substituted monocyclic or unsaturated polycyclic hydrocarbon radicals, which are linked together via a covalent bond.
• radicals A 1 , A 2 , A 3 and A 4 advantageously represent unsaturated monocyclic or polycyclic hydrocarbon radicals. optionally substituted, the radicals A 1 and A 3 being respectively linked to the radicals A 2 and A 4 via a covalent bond.
• a ⁇ A 2 is then preferably identical to A -A 4 .
• radicals A 3 and A 4 are advantageously unsaturated monocyclic or polycyclic hydrocarbon radicals which are optionally substituted and bound together via a covalent bond.
• a 1 and A 2 are preferably different, and / or
• a 3 and A 4 are preferably different.
• n is zero
• a 3 and A 4 are preferably different.
• a 1 and A 2 are preferably different.
• n and m are different from zero, A 1 and A 2 as well as A 3 and A 4 are preferably different.
• one of the radicals A 1 and A 2 may advantageously represent an optionally substituted heteroaromatic radical and the other an optionally substituted aromatic radical, and / or
• one of the radicals A 3 and A 4 can advantageously represent an optionally substituted heteroaromatic radical and the other a substituted aromatic radical,
• the organometallic iridium complex is of general formula (I), in which:
• n is equal to three and m is equal to zero
• one of the radicals A 1 and A 2 represents an optionally substituted heteroaromatic radical, and the other an optionally substituted aromatic radical, the bond established between the iridium atom and the heteroaromatic radical being an Ir bond; -NOT,
• B 1 , B 2 , B 3 and B 4 represent a single bond.
• the organometallic iridium complex is of general formula (I), in which:
• n is equal to two and m is equal to one
• one of the radicals A 1 and A 2 represents an optionally substituted heteroaromatic radical, and the other an optionally substituted aromatic radical, the bond established between the iridium atom and the heteroaromatic radical being an Ir bond; -NOT,
• one of the radicals A 3 and A 4 represents an optionally substituted heteroaromatic radical, and the other an optionally substituted aromatic radical, the bond established between the iridium atom and the heteroaromatic radical being an Ir bond; -NOT,
• a 1 and A 3 are respectively linked to the radicals A 2 and A 4 via a covalent bond
• a 1 -A 2 is identical to A -A 4 , and
• the organometallic iridium complex corresponds to the following general formula (Ia):
• R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 which may be identical or different, represent an atom chosen from hydrogen and a halogen or a group chosen from R U R 12 or phenyl and preferably represent a hydrogen atom or a halogen, in particular a hydrogen atom or a fluorine atom,
• R 11 and R 12 which may be identical or different, represent a hydrogen atom or a C 1-6 -alkyl or C 3-7 -cycloalkyl group.
• radicals X and X ' are identical, and preferably represent a halogen atom, in particular a chlorine atom.
• the organometallic metal complex of iridium is preferably chosen from the following compounds:
• the present invention relates to a battery comprising as anode an electrode on which is immobilized an organo-metallic complex of iridium according to the invention.
• Such a battery advantageously operates at a pH ranging from 5 to 9, preferably from 6 to 8.
• a battery according to the invention is a fuel cell (carbohydrate (s) and / or oligosaccharide (s)) / oxygen and in particular a glucose / oxygen fuel cell.
• a fuel cell carbohydrate (s) and / or oligosaccharide (s)
• oxygen and in particular a glucose / oxygen fuel cell.
• the reaction taking place at the cathode of the cell is the reduction of oxygen to H 2 O according to the following equation:
• the organometallic complex may for example represent from 1 to 30% by weight of the total weight of the anode, in particular from 10 to 30% by weight of the total weight of the anode.
• the organometallic complex is advantageously used in a form associated with a support material.
• a support material that is suitable for the invention may be chosen from mono- or multi-walled carbon nanotubes, carbon powder, graphene, graphite, carbon fibers, and fullerenes.
• the organometallic complex is implemented in a form associated with carbon nanotubes, in particular multi-walled carbon nanotubes.
• multi-walled carbon nanotubes which may be suitable for the present invention, mention may be made especially of those supplied by NANOCYL.
• Carbon nanotubes that may be suitable for the invention may have a diameter of about 9.5 nm, and a purity of at least 95% or more.
• Multi-walled carbon nanotubes suitable for the invention comprise at least two walls.
• the organometallic complex is associated with an electronically conductive support type carbon nanotubes via a polar solvent.
• the organometallic complex is associated with the carbon nanotubes using a solvent, preferably THF.
• a polar solvent that is suitable for the invention is a physiologically acceptable solvent.
• the composite carbon nanotubes / organometallic complex obtained after evaporation of the solvent can then be used to form an ink.
• the carbon nanotube / complex composite can be directly dispersed without evaporation of the solvent.
• the organometallic complex may be associated with different carbon supports (graphite powder, graphene, carbon foam, etc.)
• the composite resulting from the combination of the organometallic complex with the carbon support can be deposited on a porous or ion-conductive membrane (proton, hydroxyl ions).
• this membrane may be formed from one type material based fluoropolymer copolymer tétrafluoroéhtylène sulfonated, and may preferably be a membrane of NAFION ®.
• a porous conductive metal may be deposited on the anode of a battery according to the invention as an electronic collector.
• the battery comprises as an electronic collector a conductive metal grid deposited on the anode.
• a gold electrode deposited by a magnetron sputtering technique.
• this grid improves the collection of electrons, while allowing the fuel to pass to the catalytic sites.
• the skilled person is able to determine the deposition conditions of this grid.
• the deposit is made under vacuum.
• the cathode may comprise an organometallic compound based on cobalt and / or iron adsorbed onto a carbon support preferably selected from carbon nanotubes and carbon powder, or platinum nanoparticles on carbon support.
• a porous conductive metal can be deposited on the cathode of a battery according to the invention as an electronic collector.
• catalysts can be envisaged: for example C / Pt, CNT / Pt (CNT: Carbon Nanotubes Metal), graphene / Pt.
• a fuel cell is constituted.
• the glucose is oxidized, releasing electrons that flow to the cathode via an external circuit to participate in the reduction of oxygen at the cathode.
• This flow of electrons, from the negative to the positive electrode, induces at the same time the circulation of an electric current in the external circuit.
• the catalyst for the oxidation of glucose is an organometallic complex based on iridium (II) and / or (III).
• an ink is first prepared. It comprises Nafion ®, multiwall carbon nanotubes provided by NANOCYL and tris [2- (4,6-difluorophenyl) pyridinato-C 2, N] iridium (III). A dispersion of 1.46g of complex is dissolved in 200 mL of THF. The carbon nanotubes are added gradually and dispersed in water (3 g / l). lg of NAFION ® 5% is added.
• This ink is then dispersed by an aerosol technique (spray) on a membrane of a fluorinated sulfonic acid polymer (NAFION ® ) and then allowed to dry at room temperature for 10 hours.
• aerosol technique spray
• NAFION ® fluorinated sulfonic acid polymer
• the cathode consists of a platinum carbon catalyst (Pt / C) (Johnson Mathey 60% 0, 1 mg / cm 2 ).
• the cathode is deposited by aerojet technique on the other side of the membrane and then covered by a gold grid of 100 nm thick deposited by PVD (Physical Vapor Deposition).
• the anode and cathode side contacts are made via two PCBs (anode and cathode).
• a tank is glued on the anodic side.
• 0.5M glucose is circulated in this reservoir via a peristaltic pump.
• the performance of the cell is evaluated by cyclic voltammetry with a scan at 2 mV / s.
• the power density of this cell (in mW / cm 2 ) was then measured as a function of the applied voltage (in V).
• the maximum power density is 0.025 mW / cm 2 and was observed at a voltage of 0.22 V ( Figure 1).
• This cell was prepared according to the same procedure as that of Example 1, with the difference that dichlorotetrakis (2- (2-pyridinyl) phenyl) diiridium (III) replaces tris [2- (4,6- difluorophenyl) pyridinato-C 2 , N] iridium (III) in similar amounts.
• the power density of this cell (in mW / cm 2 ) was then measured as a function of the applied voltage (in V) according to the same protocol as that described in Example 1.
• the maximum power density is 0.024 mW. / cm 2 and was observed at a voltage of 0.26 V ( Figure 2).
• the power density of this cell (in mW / cm 2 ) was then measured as a function of the applied voltage (in V) according to the same protocol as in Example 1.
• the maximum power density is 0.042 mW / cm 2 and was observed at a voltage of 0.27 V ( Figure 3).
• a cyclic voltammetry curve was then carried out on this cell using a saturated calomel reference electrode (SCE).
• SCE saturated calomel reference electrode
• the curve was plotted for a voltage applied between the anode and the cathode ranging from 0 to 600 mV with a scanning speed of 50 mV / s ( Figure 4) in 0.5 M sulfuric acid.

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