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WO2006063992A2 - Catalyseurs bases sur des metaux de transition, leur preparation et leur utilisation et piles a combustible les contenant - Google Patents

Catalyseurs bases sur des metaux de transition, leur preparation et leur utilisation et piles a combustible les contenant Download PDF

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Publication number
WO2006063992A2
WO2006063992A2 PCT/EP2005/056728 EP2005056728W WO2006063992A2 WO 2006063992 A2 WO2006063992 A2 WO 2006063992A2 EP 2005056728 W EP2005056728 W EP 2005056728W WO 2006063992 A2 WO2006063992 A2 WO 2006063992A2
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polymer
compound
metal
catalysts
platinum
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PCT/EP2005/056728
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WO2006063992A3 (fr
WO2006063992A8 (fr
Inventor
Pierluigi Barbaro
Paolo Bert
Claudio Bianchini
Giuliano Giambastiani
Simonetta Moneti
Adriana Scaffidi
Alessandro Tampucci
Francesco Vizza
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Acta S.P.A.
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Publication of WO2006063992A2 publication Critical patent/WO2006063992A2/fr
Publication of WO2006063992A8 publication Critical patent/WO2006063992A8/fr
Publication of WO2006063992A3 publication Critical patent/WO2006063992A3/fr

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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • 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
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of furfural
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/37—Lanthanum
    • 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
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • 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
    • B01J2531/821—Ruthenium
    • 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
    • B01J2531/822—Rhodium
    • 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
    • B01J2531/828—Platinum
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • 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 concerns catalysts for both anode and cathodes electrodes for fuel cells. State of the art
  • a fuel cell is a device capable of transforming directly chemical energy contained in a molecule into electrical energy.
  • a modern fuel cells with polymeric electrolyte working with pure or combined hydrogen is made up of two electrodes of porous and conductive material, separated by a polymeric membrane permeable to ions, called electrolyte ( Figure 1 ).
  • Hydrogen-fed fuel cells containing a polymeric membrane as solid electrolyte are known with the acronym PEMFC (Polymer Electrolyte Membrane Fuel Cell)
  • DFC Fuel Cell fed with aqueous solutions of compounds that carry combined hydrogen, generally alcohols
  • DFC which stands for Direct Fuel Cell.
  • the most diffused DFC makes use of methanol (CH 3 OH), and is known as DMFC (Direct Methanol Fuel Cell).
  • a common DMFC of the state of the art resembles a PEMFC in its configuration and working.
  • the electrolyte In DMFCs indeed the electrolyte consists of a polymeric membrane which is either proton or anion exchange membrane, and the electrocatalysts contain platinum or platinum alloys with other metals. When the electrolyte is an anion exchange membrane, the hydroxide ion generated at the cathode passes through the membrane to the anode thus closing the circuit.
  • catalysts or electrocatalysts which consist either of metallic sheets, or of highly dispersed metallic nano-particles (usually 2-50 nanometers, 10 ⁇ 9 m, large), supported on a porous and conductive material (for instance carbon black). It is an accepted fact that the activity of a catalyst and especially a bimetallic or trimetallic catalyst depends upon both electronic and structural factors. Structural factors are influenced by both the method of synthesis and the nature of the metals employed with platinum.
  • Italian patent application No. FI20040000162 describes novel cathode electrocatalysts obtained by the complexation of cobalt salts alone or in combination with other metals, from templating polymers described in the international patent application N.° WO 2004/036674, followed by chemical reduction using state of the art methodology.
  • Catalysts containing nanometric or sub nanometric (10 ⁇ 9 m) metal particles are described in the Italian patent application No. FI20040000154 which refers to the preparation using templating polymers described in international patent application No. WO 2004/036674 of anodic electrocatalysts containing Pt and its alloys with other metals used in fuel cells fed with hydrogen or compounds containing hydrogen.
  • copolymeric resins obtained by the condensation, in basic or acidic conditions, of acetophenone (hydroxy or aminoacetophenone) with formaldehyde/furfural and hydroxyaromatic compounds or substituted aromatic acids (chloro, amino, nitro) like the synthesis of various copolymeric resins obtained by condensation of 4- ⁇ 1 -[(2,4-dinitrophenyl)-hydrazone]-ethyl ⁇ -benzene-1 .3-diol ⁇ with a series of hydroxyaromatic compounds or substituted aromatic acids (chloro, amino, nitro) and formaldehyde or furfural. All of the resins described are used exclusively as biologically active agents (antibacterial and antifungal) or as ion exchange resins.
  • FIG. 1 Simplified scheme of a fuel cell operating with a catalyst of the invention.
  • Fig. 2 Histogram showing the particle size distribution in a Fe 30 -Co 30 -Ni 40 catalyst containing 2.1 wt% overall metal loading with respect to the metal/support (Vulcan XC-72) catalytic system, realised as in method 4.
  • Fig. 3 Histogram showing the particle size distribution in a Pt catalyst (1 .2 wt% metal loading) with respect to the metal/support (Vulcan XC-72) catalytic system obtained using the method described in 5.
  • Fig. 4 Histogram showing the particle size distribution in a Ni catalyst (1 .5 wt% metal loading) with respect to the metal/support (Vulcan XC-72) catalytic system obtained using the method described in 6.
  • Fig. 5 Polarisation curve of a PEMFC ⁇ Nation 9 '-1 12, H 2 SO 4 1 N) comprised of an anode catalysed with 0.10 mg Pt 50 -Ru 50 ZCm 2 (2.0% metal/C) and a cathode catalysed with 0.10 mg Ni/cm 2 (1.0% metal/C) at 60 °C, with pure H 2 (1 bar) (curve a) or contaminated with 200 ppm of CO (curve b).
  • Fig. 6 - Polarisation curve of a DMFC (Nation ® - 1 12, H 2 SO 4 1 N) comprised of an anode catalysed with 0.20 mg Pt 50 -Ru 50 /cm 2 (2% metal/C) and a cathode catalysed with 0.10 mg Ni/cm 2 (1.0% metal/C) at. 65 °C, fed with an aqueous solution of MeOH at 15% (v:v).
  • Fig. 7 Polarisation curve of a DEFC I ⁇ elemion AMW, K 2 CO 3 1 N) comprised of an anode catalysed with 0.10 mg Fe 30 -Co 30 -Ni 40 /cm 2 (2% metal/C) and a cathode catalysed with 0.10 mg
  • Fig. 8 Variation of current density with time at constant potential (0.5 V) for a mono-planar cell comprised of an anode with catalyst Fe 30 -Co 30 -Ni 40 (0.20 mg/cm 2 ) and a cathode of Co (0.20 mg/cm 2 ) (30 °C; ethanol 10% w).
  • This invention refers to a polymeric resin of formula (A) obtained from the condensation of 4- ⁇ 1 -
  • this invention refers to metal complexes formed from the above resin and a transition metal salt alone or in combination with other salts or other metal compounds useful as catalysts to produce anodes and cathodes for fuel cells.
  • Transition metals are defined as preferably Fe, Ni, Ru, Co, Rh, Ir, Ni, Pt, Pd, Mo, Sn, La, V, Mn and
  • this invention refers in particular to the embodiment of anodic and cathodic electrodes with catalysts containing iron, cobalt and nickel (anode) and with cobalt or nickel (cathode) for DFC type fuel cells that don't use precious metals and allow the use of fuels containing hydrogen including aldehydes, acids, hydrazine, metallic borohydrides in aqueous solution or alcohols up to 50 wt%.
  • this invention refers to anodes and cathodes for DAFC type fuel cells that contain platinum only or in combination with other metals for example Fe, Ni, Ru, Co, Rh,
  • Ir, Ni, Pd, Mo, Sn, La, V, Mn and Cu that allows the use of alcoholic fuels such as methanol, ethanol, ethylene glycol, or sugars like glucose and sorbitol, in aqueous solutions with concentrations up to 50 wt% using a quantity of platinum non superior to 0.30 mg/cm 2 , preferably less than or equal to 0.20 mg/cm 2 and, more importantly allows the exploitation of all energy possible from a particular fuel converting it completely to CO 2 .
  • this invention refers to anodes and cathodes for DFC type fuel cells that contain platinum only or in combination with other metals for example Fe, Ni, Ru, Co, Rh, Ir, Ni, Pd, Mo, Sn, La, V, Mn and Cu, that allows the use of alcoholic fuels such as methanol, ethanol, ethylene glycol, or sugars like glucose and sorbitol, in aqueous solutions with concentrations up to 50 wt% using a quantity of platinum non superior to 0.30 mg/cm 2 , preferably less than or equal to 0.20 mg/cm 2
  • This invention refers in particular to the embodiment of cathodes for fuel cells of DAFC and AFC type that contain cobalt or nickel only or with Cu that allow the use of fuels such as alcohols e.g. methanol, ethanol, ethylene glycol, or sugars glucose and sorbitol in aqueous solutions with concentrations up to 50 wt%.
  • fuels such as alcohols e.g. methanol, ethanol, ethylene glycol, or sugars glucose and sorbitol in aqueous solutions with concentrations up to 50 wt%.
  • this invention refers to cathodes for DAFC and AFC type fuel cells that contain platinum only or in combination with other metals for example Fe, Ni, Ru, Co, Rh, Ir, Ni, Pd, Mo, Sn, La, V, Mn and Cu, that allows the use of alcoholic fuels such as methanol, ethanol, ethylene glycol, or sugars like glucose and sorbitol, in aqueous solutions with concentrations up to 50 wt% using a quantity of platinum non superior to 0.30 mg/cm 2 , preferably less than or equal to 0.20 mg/cm 2
  • this invention refers to the use of metal complexes formed from a salt or transition metal compound alone or in combination with other salts or metal compounds and copolymeric resins obtained from the condensation of hydroxy or aminoacetophenones with formaldehyde or furfural and hydroxyl-aromatic compounds or substituted aromatic acids fchloro, amino, nitro) and also with o/m-alkyl benzoic acids, o/m/p-chloroaniline, o/m/p-toluene, chloroacetophenone, naphthol, bis-phenols, phenophthelein and hydroxyquinoline in the presence of either acid or basic catalysts in water/alcohol mixtures and at temperatures between 20 and 150 °C and an eventual molecular weight distribution between 1000 and 50000 for the preparation of anodic and cathodic catalysts for fuel cells.
  • this invention refers to the use of metal complexes formed from a salt or transition metal compound alone or in combination with other salts or metal compounds and copolymeric resins obtained from the condensation of 4- ⁇ 1 -[(2,4-dinitro-phenyl)-hydrazone]-ethyl ⁇ -benzene-1 ,3- diol ⁇ with a series of substituted hydroxyl or acidic aromatic compounds (chloro, amino, nitro) and also with o/m-alkyl benzoic acids, o/m/p-chloroaniline, o/m/b-toluene, chloroacetophenone, naphthol, bis-phenols, phenophthelein and hydroxyquinoline and formaldehyde or furfural in the presence of either acid or basic catalysts in water/alcohol mixtures and at temperatures between 20 and 150 °C and an eventual molecular weight distribution between 1000 e 50000 for the preparation of anodic and cathodic catalysts for fuel cells.
  • the resins can be obtained from the condensation of hydroxy or aminoacetophenones with formaldehyde or furfural and hydroxy aromatic compounds or substituted aromatic acids fchloro, amino, nitro) and also with o/m alkyl benzoic acids, o/m/p-chloroaniline, o/m/p-toluene, chloroacetophenone, naphthol, bis-phenols, phenophthelein and hydroxyquinoline in the presence of either acid or basic catalysts in water/alcohol mixtures and at temperatures between 20 and 150 °C and a molecular weight distribution between 1000 and 50000.
  • the resins may be obtained from the condensation of 4- ⁇ 1 -[(2,4-dinitro-phenyl)- hydrazone]-ethyl ⁇ -benzene-1 ,3-diol ⁇ with a series of substituted hydroxyl or acidic aromatic compounds (chloro, amino, nitro) and also with o/m-alkyl benzoic acids, o/m/p-chloroaniline, o/m/p- toluene, chloroacetophenone, naphthol, bis-phenols, phenophthelein and hydroxyquinoline and formaldehyde or furfural in the presence of either acidic or basic catalysts in water/alcohol mixtures and at temperatures between 20 and 150 °C and an eventual molecular weight distribution between 1000 e 50000.
  • a series of substituted hydroxyl or acidic aromatic compounds chloro, amino, nitro
  • o/m-alkyl benzoic acids o/m/p-chloroaniline,
  • the hydroxyacetophenones above can have the formula (B) and the substituted aromatic compounds can have the formula (C).
  • R- I in the compound of formula (B) represents an O, N, N-NH 2 , NHCONH 2 and R 2 and R 3 represent independently H and OH and R 4 , R 5 , R 6 , R 7 , Rs and Rg in the compound of formula (C) independently represent a group comprised of H, OH, ether, ammine, acid, nitro, halogen, aryl and alkyl groups both linear or branched, having from 1 to 15 carbon atoms possibly functionalised with OH, ketone, or joined in some way so as to form condensed or non-condensed cycles with the aromatic ring of group (C). In all cases there must be at least two C-H groups in the aromatic ring of group (C).
  • the 4- ⁇ 1 -[(phenyl-2,4-disubstituted)-hydrazone]-alkyl ⁇ -benzene-1 ,3-diol is a compound of formula (D) and the substituted aromatic compound has the formula (C) as defined above.
  • R 10 can be one of the following group: H or a radical hydrocarbon having from 1 to 10 carbon atoms, possibly halogenated;
  • Rn e Ri 2 independently represent an electron attracting group chosen from the following; hydrogen, halogen, acyl, ester, carboxylic acid, formyl, nitrile, sulfonic acid, aryl groups or alkyl groups linear or branched having 1 to 15 carbon atoms possibly functionalised with halogens or arranged in a way so as to form one or more condensed cycles with the phenyl ring and nitro groups.
  • R, R 2 , R 3 , R 4 ,R 51 R 61 R 7 , R 8 , R 9 are defined above.
  • the said copolymeric resins are polymers that may be represented by the formula (G) e (H).
  • the metalized polymeric resins described above may be absorbed onto conductive supports typically amorphous carbon or highly porous graphite and once reduced with gaseous hydrogen or with other reducing agents, or pyrolised at temperatures above 500 °C, produces efficient catalytic materials for anodic and cathodic electrodes for fuel cells of the type PEMFC and DAFC (DMFC, DEFC).
  • the catalysts obtained by the applicant are characterised by a very high metal dispersion with particle dimensions from 0.3 to 10 nanometri (10 ⁇ 9 m), with the major frequency of particle size between 0.3 and 1 nm.
  • the same catalysts may be employed on non-conductive support materials such as porous organic oxides e.g. silica, alumina, magnesia, zirconia and ceria.
  • non-conductive support materials such as porous organic oxides e.g. silica, alumina, magnesia, zirconia and ceria.
  • a suspension in water (120 ml_) comprised of 4- ⁇ 1 -[(2,4-dinitrophenyl)-hydrazone]-ethyl ⁇ -benzene- 1 .3-diol ⁇ or resacetophenone (0.028. mol), a substituted phenol or a substituted benzoic acid (0.028 mol), p-formaldehyde or furfural (0.056 mol) and 40 ml_ of KOH (5%), is kept at reflux for 6- 12 h at 1 10°C. The solid that forms is filtered and washed thoroughly and then dried under vacuum at 60 °C to constant weight.
  • Method 2 Method 2
  • a suspension comprised of a 4- ⁇ 1 -[(2, 4-dinitrophenyl)-hydrazone]-ethyl ⁇ -benzene-1 .3-diol ⁇ , (0.028 mol) or resacetophenone, a substituted phenol or a substituted benzoic acid (0.028 mol), formaldahyde or furfural (2.84 mol) and 13.6 ml_ of KOH (40%) is kept at reflux for 6-12 h at 1 10 0 C for 8-10 h.
  • the solid that forms is filtered and washed thoroughly with cold water and then with hot water (50 0 C) to remove low molecular weight fractions and is then dried under vacuum at 60 °C to constant weight.
  • Method 3 A suspension comprised of 4- ⁇ 1 -[(2, 4-dinitrophenyl)-hydrazone]-ethyl ⁇ -benzene-1 .3-diol ⁇ , (0.028 mol) or resacetophenone a substituted phenol or a substituted benzoic acid (0.028 mol), formaldahyde or furan (2.84 mol) and 57 ml_ of HCI (2M), is kept at reflux at 11 O 0 C for 8-10 h. The solid that forms is filtered and washed thoroughly with cold water and then with hot water (50 °C) to remove low molecular weight fractions and is then dried under vacuum at 60 °C to constant weight.
  • Method 4 For the preparation of catalysts for use in anodes for fuel cells it is possible to use methods 4, 5 and 6 as follows below.
  • the solid product that forms is filtered, washed with water and air dried.
  • the dry solid is added to a suspension in acetone or another organic solvent of a porous conductive carbon based material (amorphous or graphite based), e.g.
  • Vulcan XC-72 or activated carbon RDBA to name a few.
  • the resulting product is treated with a reducing agent of the state of the art (for example: NaBH 4 or NH 2 NH 2 ), filtered, washed with water, dried and conserved under an inert atmosphere (N 2 or Ar).
  • a reducing agent of the state of the art for example: NaBH 4 or NH 2 NH 2
  • the METALISED POLYMER once added to the porous conductive carbon based material, is isolated by evaporation of the solvent and then treated with a current of hydrogen gas at a temperature between 300 and 800 °C.
  • the METALISED POLYMER is reacted with a suspension of an activated porous metal oxide , like silica, alumina and ceria in acetone or another organic solvent. After stirring for a few hours, the material is filtered, washed with water, and dried; the metals complexed by the polymer and then supported are reduced by the same methods describe above.
  • the solid product that forms is filtered, washed with water and air dried.
  • the dry solid (METALISED POLYMER ) is added to a suspension in acetone or another organic solvent of a porous conductive carbon based material (amorphous or graphite based), e.g. Vulcan XC-72 or activated carbon RDBA, to name a few.
  • the resulting product is treated with a reducing agent of the state of the art (for example: NaBH 4 or NH 2 NH 2 ), filtered, washed with water, dried.
  • the METALISED POLYMER once added to the porous conductive carbon based material is isolated by evaporation of the solvent and then treated with a current of hydrogen gas at a temperature between 300 and 800 °C.
  • the METALLISED POLYMER once added to the porous conductive carbon based material in acetone is isolated by evaporation of the solvent and then heated under a flow of nitrogen gas to 800 °C.
  • the METALISED POLYMER is reacted with a suspension of an activated porous metal oxide , come silica, alumina and ceria in acetone or another organic solvent. After stirring for a few hours, the material is filtered, washed with water, and dried; the metals complexed by the polymer and then supported are reduced by the same methods describe above.
  • a metal salt or metal compound for example nickel acetate tetrahydrate dissolved in water, alone or together with another transition metal, chosen preferably from Fe, Ru, Co, Rh, Ir, Pt, Pd, Mo, Sn, La, V, Mn, Cu, dissolved in water is added to an aqueous suspension of POLYMER. After a few hours the solid product that forms is filtered, washed with water and dried. This dried solid (METALISED POLYMER), is added to a acetone suspension of porous carbon like Vulcan XC-72 or activated carbon RDBA (to name a few). After stirring for a couple of hours a state of the art reducing agent e.g. NaBH 4 or NH 2 NH 2 is added in excess. The solid product obtained is filtered, washed and dried.
  • another transition metal chosen preferably from Fe, Ru, Co, Rh, Ir, Pt, Pd, Mo, Sn, La, V, Mn, Cu
  • Another transition metal chosen preferably from Fe,
  • the METALISED POLYMER once added to the porous conductive carbon based material is isolated by evaporation of the solvent and then treated with a current of hydrogen gas at a temperature between 300 and 800 °C.
  • the METALISED POLYMER once added to the porous conductive carbon based material in acetone is isolated by evaporation of the solvent and then heated under a flow of nitrogen gas to 800 °C.
  • the METALISED POLYMER is reacted with a suspension of an activated porous metal oxide, like silica, alumina and ceria in acetone or another organic solvent. After stirring for a few hours, the material is filtered, washed with water, and dried; the metals complexed by the polymer and then supported are reduced by the same methods describe above.
  • the catalysts supported on conductive carbon prepared by methods 1 - 6 are suspended in a mixture of water/ethanol. To this vigorously stirred suspension is added PTFE (polytetrafluoroethylene) and the flocculent solid obtained is separated and spread on a conductive support like carbon paper, steel or nickel netting. These electrodes are then heated to 350 °C under a flow of inert gas (Ar, N 2 ). Method (b) The products obtained from the reaction of the metal salts or compounds with the POLYMER (METALISED POLYMER) are dissolved in a polar organic solvent like acetone or dimethylformamide. A portion of this solution is deposited on a disc of highly porous conductive material such as silver, nickel, ceramic powder (like Wc or MOc).
  • PTFE polytetrafluoroethylene
  • a metal salt or metal compound for example cobalt acetate tetrahydrate (Co(OAc) 2 .4H 2 0) dissolved in water, is added to an aqueous suspension of the POLIMERO.
  • the solid product formed after stirring for an hour is filtered, washed with water and dried.
  • This solid is added to a suspension of porous carbon like Vulcan XC-72 or activated carbon RDBA (to name a few) in acetone or dimethylformamide or another organic solvent. After stirring for a couple of hours the solvent is removed under reduced pressure and the solid obtained is heated to a temperature between. 500 and 900°C under an inert atmosphere (N 2 or Ar).
  • a metal salt or metal compound for example hexachloroplatinic acid (H 2 PtCI 6 ) dissolved in water, and a metal salt, preferably nickel, cobalt, molybdenum, lanthanum, vanadium and manganese, dissolved in water are added to an aqueous suspension of the POLYMER.
  • a metal salt preferably nickel, cobalt, molybdenum, lanthanum, vanadium and manganese
  • the highest frequency of the size distribution of the particles is no higher than 1 nm, and is clustered between 0.3 and 0.7 nm.
  • the metal loading of the reduced metal-supported material can be varied from between 0.1 and 50% in weight with respect to the support.
  • the metal particles of catalyst described in this invention are characterised by a very small quantity of atoms, no more than a dozen, which gives life to a structure capable of extraordinary reactivity in anodes and cathodes in various types of fuel cells containing solid electrolytes made of polymeric membranes either proton exchange (for example National ® ) or anionic (for example Flemion ® of Asahi Glass or Morgane ® of Solvay).
  • DRIFT Diffuse Reflectance Infrared Spectroscopy
  • the anodes made with the catalysts of this invention are able to convert gaseous hydrogen (pure or reformed), metal borohydrides, hydrazine and hydroxylamine into electrons and protons. They are also able to convert a great variety of compounds containing oxygen and hydrogen atoms into electrons and CO 2 .
  • gases for example methanol, ethanol, ethylene glycol, acetaldehyde, formic acid, glucose and sorbitol to name but a few all at ambient temperature and pressure.
  • the catalysts of the invention and the electrodes that they are contained in can be used to catalyse any fuel containing hydrogen even saturated hydrocarbons like methane (natural gas), ethane, propane and butane as well as gasoline and kerosene.
  • the cathodes made with the catalysts of this invention convert pure oxygen or that contained in air into water (when the electrolyte is a proton exchange membrane) or in hydroxide ions (OH " ) (when the electrolyte is an anion exchange membrane).
  • An anode of this invention in combination with a cathode of this invention or with a cathode for fuel cells of the state of the art and a cathode of this invention in combination with an anode of this invention or with any anode for fuel cells of the state of the art can be used to assemble fuel cells like that shown in Figure 1 .
  • this invention refers to the formation of anodic and cathodic electrodes catalysed preferably with iron, cobalt, nickel (anode) and with cobalt or nickel (cathode) for fuel cells of PEMFC and DAFC type.
  • anodic and cathodic electrodes catalysed preferably with iron, cobalt, nickel (anode) and with cobalt or nickel (cathode) for fuel cells of PEMFC and DAFC type.
  • a mixture of 2.45 g (0.026 mol) of phenol, 2.16 mL (0.026 mol) of 2-furfural and 20 mL of KOH (5%) is added to a suspension of 7 g (0.02 mol) of 4- ⁇ 1 -[(2,4-dinitrophenyl)-hydrazone]-ethyl ⁇ - benzene-1 ,3-diol in 60 mL of H 2 O.
  • the resulting suspension is kept at reflux for 6 h (1 10°C).
  • the red solid that forms is collected by filtration and washed thoroughly with water (4 x100 mL) and water/acetone (1 :1 v:v) to remove the low molecular weight fraction.
  • FT-IR (?/cm-1 ) : 3600-3120 (? OH); 3240 (? NH); 3100 (? CH aromatic); 1640 (? CN); 1610 (?as.CO2); 1585 (? NH); 1510 (?s.NO2); 1510 (?as.NO2); 1400 (?as CO2); (1330 (d OH); 830 (? C-NO 2 Ar.).
  • UV-Vis: ?max 380 nm; shoulder a 463 nm (DMSO, 294 K).
  • the reduction can be achieved using a current of hydrogen gas.
  • 5 g of the following mixture POLYMER-PI-Fe, Co, Ni and Vulcan (1 :5 wt/wt), is introduced into a quartz furnace heated at 360 °C under a flow of hydrogen gas for 2 h.
  • the product is conserved under an inert atmosphere (N 2 or Ar).
  • Atomic ratio Co 33 Ni 33 Fe 34
  • the reduction can be performed with a current of hydrogen gas.
  • 5 g of the mixture of POLYMER PI -Pt and Vulcan (1 :10 wt/wt) is reduced in a quartz furnace under a flow of hydrogen at 360 °C for 2 hours.
  • the percentage of Pt in weight is 0.55 % (ICP-AES analysis).
  • POLYMERS P2 and P3 can be used as described in examples 2 and 3.
  • the percentage of Pt in weight is 6 %, Ru 7% (ICP-AES analysis).
  • the reduction can be performed with a current of 1 bar hydrogen gas.
  • 5 g of the mixture of POLYMER PI -Pt-Ru and Vulcan (1 :10 wt/wt) is reduced in a quartz furnace under a flow of hydrogen at 360 °C for 2 hours.
  • the percentage of Pt in weight is 0.55 % and Ru 0.66 % (ICP-AES analysis).
  • Atomic ratio Pt 45 Ru 55
  • POLYMERS P2 and P3 can be used as described in examples 2 and 3.
  • the electrode thus formed is sintered in a furnace at 350 °C under a flow of inert gas for a few minutes (N 2 or Ar).
  • the electrode thus formed is sintered in a furnace at 350 °C under a flow of inert gas for a few minutes (N 2 or Ar).
  • the reduction of the metal can be obtained by introducing the support that has absorbed the METALISED POLYMER in a quartz reactor and is heated in under a flow of hydrogen gas at 365 for 2 h.
  • Other conductive substrates can be powdered ceramic materials like Wc, MOc amongst others.
  • the electrode thus formed is sintered in a furnace at 350 °C under a flow of inert gas for a few minutes (N 2 or Ar).
  • the supports are heated at 500 °C under a flow of inert gas for a few minutes.
  • conductive substrates can be powdered ceramic materials like Wc, MOc amongst others.
  • N 2 or Ar inert gas

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Abstract

L'invention porte sur des procédés de préparation de catalyseurs de métaux de transition nanostructurés, sur leur utilisation et sur les piles à combustible les contenant.
PCT/EP2005/056728 2004-12-13 2005-12-13 Catalyseurs bases sur des metaux de transition, leur preparation et leur utilisation et piles a combustible les contenant WO2006063992A2 (fr)

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EP2180539A1 (fr) 2008-10-21 2010-04-28 Commissariat à l'Energie Atomique Nouveaux matériaux et leur utilisation dans l'évolution électrocatalytique ou la capture de H2
JP2010194517A (ja) * 2009-02-27 2010-09-09 Hitachi Zosen Corp アンモニア分解触媒
JP2010194519A (ja) * 2009-02-27 2010-09-09 Hitachi Zosen Corp アンモニア分解触媒
US7803264B2 (en) 2003-10-10 2010-09-28 Ohio University Electro-catalysts for the oxidation of ammonia in alkaline media
US20110039176A1 (en) * 2008-11-12 2011-02-17 Ramot At Tel-Aviv University Ltd. Direct liquid fuel cell having ammonia borane or derivatives thereof as fuel
US7951903B2 (en) 2007-08-31 2011-05-31 Toyota Jidosha Kabushiki Kaisha Hydrazone compound, hydrazone compound for forming complex, ligand for forming metal complex, and monomer for manufacturing polymer compound
US7960501B2 (en) 2007-08-31 2011-06-14 Toyota Jidosha Kabushiki Kaisha Catalyst using hydrazone compound, hydrazone polymer compound, and catalyst using hydrazone polymer compound
CN102333590A (zh) * 2009-02-27 2012-01-25 日立造船株式会社 氨分解催化剂
US8216956B2 (en) 2003-10-10 2012-07-10 Ohio University Layered electrocatalyst for oxidation of ammonia and ethanol
US8216437B2 (en) 2003-10-10 2012-07-10 Ohio University Electrochemical cell for oxidation of ammonia and ethanol
US8221610B2 (en) 2003-10-10 2012-07-17 Ohio University Electrochemical method for providing hydrogen using ammonia and ethanol

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US8216956B2 (en) 2003-10-10 2012-07-10 Ohio University Layered electrocatalyst for oxidation of ammonia and ethanol
US7803264B2 (en) 2003-10-10 2010-09-28 Ohio University Electro-catalysts for the oxidation of ammonia in alkaline media
US8216437B2 (en) 2003-10-10 2012-07-10 Ohio University Electrochemical cell for oxidation of ammonia and ethanol
US8221610B2 (en) 2003-10-10 2012-07-17 Ohio University Electrochemical method for providing hydrogen using ammonia and ethanol
US8613842B2 (en) 2003-10-10 2013-12-24 Ohio University Layered electrocatalyst for oxidation of ammonia and ethanol
US7951903B2 (en) 2007-08-31 2011-05-31 Toyota Jidosha Kabushiki Kaisha Hydrazone compound, hydrazone compound for forming complex, ligand for forming metal complex, and monomer for manufacturing polymer compound
US7960501B2 (en) 2007-08-31 2011-06-14 Toyota Jidosha Kabushiki Kaisha Catalyst using hydrazone compound, hydrazone polymer compound, and catalyst using hydrazone polymer compound
US8895207B2 (en) 2008-10-21 2014-11-25 Commissariat A L'energie Atomique Et Aux Energies Alternatives Materials and their use for the electrocatalytic evolution or uptake of H2
EP2180539A1 (fr) 2008-10-21 2010-04-28 Commissariat à l'Energie Atomique Nouveaux matériaux et leur utilisation dans l'évolution électrocatalytique ou la capture de H2
US9553315B2 (en) * 2008-11-12 2017-01-24 Ramot At Tel-Aviv University Ltd. Direct liquid fuel cell having ammonia borane or derivatives thereof as fuel
US20110039176A1 (en) * 2008-11-12 2011-02-17 Ramot At Tel-Aviv University Ltd. Direct liquid fuel cell having ammonia borane or derivatives thereof as fuel
US20110053022A1 (en) * 2008-11-12 2011-03-03 Ramot At Tel Aviv University Ltd. Direct liquid fuel cell having hydrazine or derivatives thereof as fuel
US8475968B2 (en) * 2008-11-12 2013-07-02 Ramot At Tel-Aviv University Ltd. Direct liquid fuel cell having hydrazine or derivatives thereof as fuel
CN102333590A (zh) * 2009-02-27 2012-01-25 日立造船株式会社 氨分解催化剂
EP2402081A4 (fr) * 2009-02-27 2012-11-14 Hitachi Shipbuilding Eng Co Catalyseur de décomposition de l'ammoniac
JP2010194519A (ja) * 2009-02-27 2010-09-09 Hitachi Zosen Corp アンモニア分解触媒
JP2010194517A (ja) * 2009-02-27 2010-09-09 Hitachi Zosen Corp アンモニア分解触媒

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