WO2006124959A2 - Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates - Google Patents
Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution ratesInfo
- Publication number
- WO2006124959A2 WO2006124959A2 PCT/US2006/019017 US2006019017W WO2006124959A2 WO 2006124959 A2 WO2006124959 A2 WO 2006124959A2 US 2006019017 W US2006019017 W US 2006019017W WO 2006124959 A2 WO2006124959 A2 WO 2006124959A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal oxide
- platinum
- oxide
- tungsten
- fuel cell
- Prior art date
Links
Classifications
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- 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
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- 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
- B01J37/16—Reducing
-
- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- 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
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
-
- 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
-
- 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
-
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/24997—Of metal-containing material
Definitions
- the present invention relates to particle composites useful as catalysts, and particularly, oxygen-reducing electrocatalysts in fuel cells.
- the invention particularly relates to platinum- metal oxide composite electrocatalysts having reduced oxidation and dissolution rates of platinum in the oxygen-reducing cathode of fuel cells.
- a "fuel cell” is a device which converts chemical energy into electrical energy.
- a gaseous fuel such as hydrogen is fed to an anode (the negative electrode), while an oxidant such as oxygen is fed to a cathode (the positive electrode).
- Oxidation of the fuel at the anode causes a release of electrons from the fuel into an electrically conducting external circuit which connects the anode and cathode.
- the oxidant is reduced at the cathode using the electrons provided by the oxidized fuel.
- the electrical circuit is completed by the flow of ions through an electrolyte that allows chemical interaction between the electrodes.
- the electrolyte is ' typically in the form of a proton- conducting polymer membrane.
- the proton-conducting membrane separates the anode and cathode compartments while allowing the flow of protons between them.
- a well-known example of such a proton-conducting membrane is NAFION®.
- a fuel cell although having components and characteristics similar to those of a typical battery, differs in several respects.
- a battery is an energy storage device whose available energy is determined by the amount of chemical reactant stored within the battery itself. The battery will cease to produce electrical energy when the stored chemical reactants are consumed.
- the fuel cell is an energy conversion device that theoretically has the capability of producing electrical energy for as long as the fuel and oxidant are supplied to the electrodes.
- hydrogen/oxygen fuel cell hydrogen is supplied to the anode and oxygen is supplied to the cathode. Hydrogen molecules are oxidized to form protons while releasing electrons into the external circuit. Oxygen molecules are reduced at the cathode to form reduced oxygen species. Protons travel across the proton-conducting membrane to the cathode compartment to react with reduced oxygen species, thereby forming water.
- the reactions in a typical hydrogen/oxygen fuel cell are as follows:
- a hydrogen fuel is produced by converting a hydrocarbon- based fuel such as methane, or an oxygenated hydrocarbon fuel such as methanol, to hydrogen in a process known as "reforming".
- the reforming process typically involves the reaction of such fuels with water along with the application of heat. By this reaction, hydrogen is produced.
- the byproducts of carbon dioxide and carbon monoxide typically accompany the production of hydrogen by reforming processes.
- Other fuel cells known as “direct” or “non-reformed” fuel cells, oxidize fuels high in hydrogen content directly, without the need for hydrogen to be produced by a reforming process.
- electrocatalysts are catalysts that promote the rates of electrochemical reactions, and thus, allow fuel cells to operate at lower potentials.
- the cathode potential will vary between approximately 0.5 and 1 V.
- the cathode potential variation is caused by the fluctuating power requirements of a machine driven by the fuel cell. For example, an automobile operated by a fuel cell requires stopping and starting.
- the invention relates to platinum-metal oxide composite particles.
- the platinum-metal oxide composite particles contain a metal oxide core at least partially encapsulated by an atomically thin layer of zerovalent or partially charged platinum atoms.
- the metal oxide core is bound to zerovalent or partially charged platinum clusters.
- the platinum-metal oxide composite particles When directed to fuel cells, the platinum-metal oxide composite particles preferably contain a metal oxide core having an oxide composition capable of withstanding degradation under the operating conditions of a fuel cell.
- the metal oxide core includes an oxide of one or more metals selected from the group consisting of titanium, niobium, yttrium, zirconium, molybdenum, chromium, nickel, manganese, vanadium, tantalum, tungsten, rhenium, ruthenium, rhodium, and indium.
- the metal oxide core includes an oxide of one or more metals selected from the group consisting of titanium, niobium, molybdenum, chromium, nickel, manganese, vanadium, tantalum, tungsten, rhenium, ruthenium, rhodium, and iridium.
- the metal oxide core includes an oxide of one or more metals selected from the group consisting of titanium, niobium, molybdenum, chromium, nickel, manganese, vanadium, tantalum, rhenium, ruthenium, rhodium, and iridium.
- the metal oxide core of the platinum-metal oxide composite particles includes an oxide of tungsten.
- the oxide of tungsten is a sodium tungsten oxide.
- the sodium tungsten oxide is a sodium-tungsten bronze.
- the metal oxide core of the platinum-metal oxide composite particles is in the size range of one nanometer to five hundred microns. More preferably, the metal oxide core of the platinum-metal oxide composite particles is in the size range of approximately ten to fifty nanometers.
- each of the platinum clusters preferably independently includes approximately three to sixty platinum atoms.
- the metal oxide core is at least partially encapsulated by an atomically thin layer of zerovalent or partially charged platinum atoms
- the atomically thin layer is preferably a submonolayer, monolayer, bilayer, or trilayer, of zerovalent or partially charged platinum atoms.
- the invention relates to an oxygen-reducing cathode.
- the oxygen-reducing cathode includes an electrically conductive support bound to the platinum- metal oxide composite particles described above.
- the electrically conductive support is preferably selected from the group consisting of carbon black, graphitized carbon, graphite, and activated carbon.
- the invention in another embodiment, relates to a fuel cell.
- the fuel cell includes (i) the oxygen-reducing cathode described above; (ii) an anode; (iii) an electrically conductive contact connecting the oxygen-reducing cathode with the anode; and (iv) an ion-conducting electrolyte in mutual contact with the oxygen-reducing cathode and anode.
- the ion-conducting electrolyte is more preferably a proton-conducting electrolyte, and even more preferably a proton- conducting membrane.
- the invention in another embodiment, relates to a method for improving fuel cell stability by preventing or reducing platinum dissolution in an oxygen-reducing cathode of a fuel cell.
- the method includes incorporating platinum-metal oxide composite particles, as described above, into the oxygen-reducing cathode of a fuel cell.
- the invention relates to a method for producing electrical . energy.
- the method includes (i) contacting the oxygen-reducing cathode of a fuel cell, as described above, with an oxidant, such as oxygen; and (ii) contacting the anode of the fuel cell with a fuel source, such as hydrogen.
- the fuel source can be, for example, hydrogen gas.
- the hydrogen gas can be supplied directly, or alternatively, generated from the reformation of a fuel, such as from reformed methanol, reformed methane, or reformed gasoline.
- Some other fuel sources include, for example, alcohols, methane, gasoline, formic acid, dimethyl ether, and ethylene glycol.
- suitable alcohols include methanol and ethanol.
- the invention relates to platinum-metal oxide composite particles.
- the platinum-metal oxide composite particles are composed, minimally, of a metal oxide core at least partially encapsulated by an atomically thin layer of zerovalent or partially charged platinum atoms.
- the "atomically thin surface layer” is a layer of zerovalent or partially charged platinum atoms, preferably of sub-monoatomic, monoatomic, diatomic, or triatomic thickness, or any combination thereof.
- the atomically thin layer of platinum typically takes the shape of the metal oxide surface. Since a metal oxide carrier particle typically contains pores or channels on its surface, the atomically thin layer of platinum is typically non-continuous. For example, the platinum layer can be speckled with holes corresponding to such pores or channels. In addition, since the metal oxide surface contains at least two elements (i.e., metal and oxygen atoms), the platinum layer can assume a pattern by bonding preferentially to at least one of the elements.
- a layer of monoatomic thickness of platinum atoms i.e., an atomic monolayer, is a single layer of close-packed platinum atoms on the surface of the metal oxide carrier particle. An atomic monolayer has a surface packing parameter of 1.
- a layer of sub-monoatomic coverage i.e., an atomic submonolayer
- an atomic submonolayer is a layer of platinum atoms which is less dense than an atomic monolayer (i.e., not close-packed). Accordingly, an atomic submonolayer has a surface packing parameter of less than 1. For example, a surface packing parameter of 0.5 indicates half the density of platinum atoms as compared to a platinum atomic monolayer.
- a layer of diatomic thickness refers to a bilayer (two-atom thick) of zerovalent or partially charged platinum atoms.
- a layer of triatomic thickness refers to a trilayer (three-atom thick) of zerovalent or partially charged platinum atoms.
- an atomic submono layer of platinum contains only platinum atoms in the absence of other co-deposited metal atoms.
- an atomically thin layer of platinum atoms includes one or more co-deposited other metals to form an atomically thin layer of platinum alloy.
- an atomic submonolayer of platinum atoms includes one or more co-deposited atomic submonolayers of another metal to form a platinum alloy monolayer.
- the co-deposited metal(s) can be, for example, a main group, transition, lanthanide, or actinide metal.
- the co-deposited metal(s) in a platinum alloy monolayer provide such advantages as, for example, further reduction in platinum loading as compared to a pure platinum monolayer, reduction in catalytic poisoning, and/or enhancement of catalytic activity.
- some metals, particularly some of the transition metals have the ability to adsorb hydroxyl groups
- the co-depositing metal is more preferably a metal known to adsorb OH, e.g., iridium (Ir), ruthenium (Ru), osmium (Os),' rhenium (Re), and combinations thereof.
- a metal known to adsorb OH e.g., iridium (Ir), ruthenium (Ru), osmium (Os),' rhenium (Re), and combinations thereof.
- the ratio of co-deposited metal to platinum in such a platinum alloy monolayer is not particularly limited.
- a platinum alloy monolayer can be a binary alloy according to the formula M x Pt j. x (1), wherein M is any of the metals described above.
- M is any of the metals described above.
- the value of x is not particularly limited.
- x can have a
- x can have a maximum value of about 0.99, 0.9, 0.8, 0.7, 0.6, or 0.5.
- platinum binary alloy monolayers of formula (1) are represented by the formulas Ir x Pt ⁇ x , Ru x Pti -x , Os x Pt 1-x , or Re x Pt 1-x .
- platinum binary alloy monolayers of formula (1) are represented by the formulas Ir x Pt ⁇ x , Ru x Pti -x , Os x Pt 1-x , or Re x Pt 1-x .
- alloy monolayers include Ir 0 ⁇ 1 PtC 99 , fro.iPto.9, Iro ⁇ Ptcs, Iro.3Pto.7, fro.sPto.s, Ir 0 . 7 Pt 0 .3, Iro.sPto.2,
- the platinum alloy monolayer can additionally be a ternary alloy.
- the platinum alloy monolayer can be a ternary alloy according to the formula M x N y Pt 1-x-y (2).
- x and y may independently have a value of about 0.01 to a
- the sum of x and y has a minimum value of about 0.1 and a maximum value of about 0.9.
- ternary platinum-metal alloy monolayers include
- Iro.oiOso.oiPto.98 IrC 1 OsCiPt 0-8 , ⁇ ro.2 ⁇ s 0 .iPto.7, Ir 0-1 Os 0-2 Pt 0-71 Ir 0-01 Re 0- OiPt 0 SS, Ir 0-1 Re 0 JPt 0-8 ,
- the platinum alloy monolayer can additionally be a quaternary alloy.
- the platinum alloy monolayer can be a quaternary alloy according to the formula M x NyT z Pt 1-x-y-z (3).
- M, N, and T are independently any of the suitable metals described above.
- the values of x, y, and z are not particularly limited. By the rules of chemistry, the sum of x, y, and z in formula (3) must be less than 1.
- x, y, and z may independently have a value of about 0.01 to a value of about 0.99 as long as the sum of x, y, and z is less than 1.0. More preferably, the sum of x, y, and z has a minimum value of about 0.1 and a maximum value of about 0.9.
- Some more specific platinum quaternary alloy monolayers of formula (3) are represented by the formulas Ir x Ru y Re z Pti -x .y -z or Ir x RU y Os 2 Pt 1 -x . y-z .
- Some specific examples of quaternary platinum alloy monolayers include Ir O-O iRu 0-O1 Re O-1 Pt 0-97 , Ir O-1 RUo -1 Re O-1 Pt O-7 , Ir 0-2 Ru 0-1 OSo -1 PtO -6 , and Ir O-1 Ru 0-2 Os 0- IPtO -6 .
- the atomically thin layer of platinum atoms covers the entire surface of the metal oxide particle. In another embodiment, the atomically thin layer of platinum atoms covers a portion of the metal oxide particle.
- the atomically thin layer of platinum surface atoms can be characterized as interconnected islands with some regions of monoatomic, diatomic, or triatomic depth.
- the platinum-metal oxide composite particles are composed, minimally, of a metal oxide core bound to zerovalent or partially charged platinum clusters.
- the platinum clusters can also be in combination with the atomically thin platinum layer described above.
- the platinum clusters can include other elements thereby resulting in platinum alloy clusters.
- the one or more alloying elements can be any of the alloying elements described above for an atomically thin layer of platinum alloy.
- each platinum cluster independently includes at least two platinum atoms.
- each platinum cluster can have a minimum of two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, twenty, thirty, or forty platinum atoms.
- the platinum clusters are preferably less than approximately one nanometer in any dimension. Accordingly, the platinum clusters preferably contain up to a maximum number of platinum and other atoms corresponding to a cluster size not greater than approximately one nanometer.
- the maximum number of platinum and other atoms in the platinum clusters is dependent on the morphology and packing arrangements of the cluster. Depending on morphology and packing arrangements, the platinum core can have a maximum number of platinum atoms of, for example, forty-five, fifty, fifty-five, or sixty.
- suitable platinum clusters include clusters containing nuclear cores of Pt 3 , Pt 4 , Pt 5 , Pt 6 , Pt 9 , Pt 12 , Pt 13 , Pt 18 , Pt 20 , Pt 24 , Pt 26 ,
- a pure platinum cluster having a spherical shape with a close-packed arrangement preferably contains no more than approximately sixty platinum atoms. More preferably, the platinum clusters preferably contain approximately three to sixty platinum atoms.
- the atomically thin layer of platinum, or the platinum clusters, as described above, are preferably bound to the metal oxide core. The term "bound" indicates a bond or interaction strong enough to keep the platinum attached to the metal oxide core during use. The bond or interaction between platinum and the metal oxide can be covalent or non-covalent.
- the metal oxide core is composed of an oxide of one or more metals.
- the composition of the metal oxide core is any metal oxide composition which is capable of withstanding degradation under the operating conditions of a fuel cell.
- the oxide composition can withstand an operating temperature of at least approximately 80°C, more preferably 100°C, and even more preferably 12O 0 C, which is the maximum operating temperature for most polymer electrolyte fuel cells (PEFCs).
- PFCs polymer electrolyte fuel cells
- Even more preferred are oxide compositions which can withstand operating temperatures of at least 200°C, and even more preferably at least 25O 0 C 3 which is the maximum operating temperature for most alkaline and phosphoric acid fuel cells.
- the oxide composition is also preferably capable of withstanding any one or more of the various electrolytes used in fuel cells.
- the oxide composition is preferably capable of withstanding any one or more of the neutral, mildly acidic, strongly acidic, mildly alkaline, or strongly alkaline electrolytes used in fuel cells.
- the oxide composition when used in a fuel cell having an aqueous-based electrolyte, is preferably not water soluble.
- the metal oxide core can be non-conductive, semiconductive, or conductive.
- Non- conductive metal oxide particles can be made at least semiconductive by, for example, doping with a suitable amount of a conductive species. Conductive metal oxide particles can have the advantage of being used in a fuel cell electrode directly, i.e., without requiring an electrically conductive support for imparting conductivity.
- the oxide core is composed of an oxide of one or more metals selected from titanium, niobium, yttrium, zirconium, molybdenum, chromium, nickel, manganese, vanadium, tantalum, tungsten, rhenium, ruthenium, rhodium, and iridium. More preferably, the oxide core is composed of an oxide of one or more metals selected from titanium, niobium, molybdenum, chromium, nickel, manganese, vanadium, tantalum, tungsten, rhenium, ruthenium, rhodium, and iridium.
- the oxide core is composed of an oxide of one or more metals selected from titanium, niobium, molybdenum, chromium, nickel, manganese, vanadium, tantalum, rhenium, ruthenium, rhodium, and iridium.
- the metal oxide compositions of titanium, niobium, yttrium, zirconium, molybdenum, chromium, nickel, vanadium, tantalum, tungsten, rhenium, ruthenium, rhodium, and iridium are particularly suitable for use in mildly acidic to strongly acidic environments.
- the manganese oxide compositions are generally more suitable for use in mildly alkaline to strongly alkaline environments.
- the metal oxide core can also include an oxide of one or more rare-earth metals.
- the metal oxide core can include an oxide of one or a combination of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, or terbium.
- any of the metal oxide compositions described above can further include one or more metals selected from the alkali, alkaline earth, main group, transition, lanthanide, and actinide classes of metals.
- the metal oxide compositions can further include the various silica and alumina compositions.
- suitable silica and alumina compositions include SiO 2 , Al 2 O 3 , SiO 2 -Al 2 O 3 , SiO 2 -B 2 O 3 , SiO 2 -P 2 O 5 , SiO 2 -SnO 2 , Al 2 O 3 -B 2 O 3 , Al 2 O 3 -P 2 O 5 ,
- the metal oxide compositions also include any of the hydrated forms.
- titanium oxide compositions suitable as the metal oxide core include titanium (IV) oxide (TiO 2 ), titanium (III) oxide (Ti 2 O 3 ), titanium (II) oxide (TiO), lithium titanium oxide (Li 2 TiO 3 ), barium titanium oxide (BaTiO 3 ), barium strontium titanium oxide (e.g.,
- Ba x Sn -x Ti0 3 aluminum titanium oxide (Al 2 TiO 5 ), calcium titanium oxide (e.g., CaTiO 3 and Ca 3 Ti 2 O 7 ), magnesium titanium oxide (MgTi 2 O 5 ), potassium titanium oxide (K 2 TiO 3 ), strontium titanium oxide (SrTiO 3 ), zirconium titanium oxide (ZrTiO 4 ), zinc titanium oxide (Zn 2 TiO 4 ), cobalt titanium oxide (CoTiO 3 ), manganese (II) titanium oxide (MnTiO 3 ), iron (III) titanium oxide (Fe 2 TiOs), lanthanum titanium oxide (e.g., La 2 O 3 -2TiO 2 ), lanthanum barium titanium oxide (e.g., Lai -x Ba x Ti0 3 ), gadolinium titanium oxide (e.g., Gd 2 Ti 2 O 7 ), and dysprosium (III) titanium oxide (e.g., Dy(TiO 3 ) 3
- niobium oxide compositions suitable as the metal oxide core include niobium (IV) oxide (NbO 2 ), niobium (V) oxide (Nb 2 O 5 ), niobium (II) oxide (NbO), barium niobium oxide (BaNb 2 O 6 ), cadmium niobium oxide (e.g., CdNb 2 O 6 and Cd 2 Nb 2 O 7 ), barium sodium niobium oxide (Ba 2 NaNb 5 O 15 ), barium strontium niobium oxide (e.g., Ba x Sr 1-x Nb 2 0 6 ), lithium niobium oxide (LiNbO 3 ), magnesium niobium oxide (MgNb 2 O 6 ), sodium niobium oxide (NaNbO 3 ), potassium niobium oxide (KNbO 3 ), strontium niobium oxide (e.g., S
- yttrium oxide compositions suitable as the metal oxide core include yttrium (III) oxide (Y 2 O 3 ), yttria-stabilized zirconium oxide (ZrO 2 + Y 2 O 3 ), iron yttrium oxide (Y 3 Fe 5 O 12 ), yttrium aluminum oxide (Y 3 Al 5 ⁇ 12 ), and the yttrium barium copper oxides (i.e., YBa 2 Cu 3 O x , YBa 2 Cu 4 O x , Y 2 BaCuO x , wherein x is typically 6.5-6.8).
- zirconium oxide compositions suitable as the metal oxide core include zirconium (IV) oxide (ZrO 2 ), calcia-stabilized zirconium oxide (ZrO 2 , 4% CaO), barium zirconium oxide (BaZrO 3 ), calcium zirconium oxide (CaZrO 3 ), cerium zirconium oxide (CeO 2 + ZrO 2 ), lead zirconium oxide (PbZrO 3 ), lithium zirconium oxide (Li 2 ZrOs), magnesium aluminum zirconium oxide (MgO-Al 2 O 3 -ZrO 2 ), manganese zirconium oxide, sodium zirconium oxide (Na 2 ZrO 3 ), strontium zirconium oxide (SrZrO 3 ), tungsten zirconium oxide (ZrW 2 O 8 ), zirconium dichloride oxide hydrates ⁇ e.g., ZrOCl 2 -SH 2 O), and zirconium dichloride oxide
- chromium oxide compositions suitable as the metal oxide core include chromium (III) oxide (Cr 2 O 3 ), chromium (IV) oxide (CrO 2 ), and chromium (VI) oxide (CrO 3 ).
- a suitable subclass of the chromium oxide compositions is the class of chromate compositions, in which chromium is hexavalent.
- X can be an alkali, alkaline earth, main group, transition or rare earth metal.
- Suitable chromates include barium chromate (BaCrO 4 ), lead chromate (PbCrO 4 ), calcium chromate (CaCrO 4 ), potassium chromate (K 2 CrO 4 ), strontium chromate (SrCrO 4 ), zinc chromate (ZnCrO 4 ), chromium chromate (Cr 2 (Cr0 4 ) 3 ), cobalt (II) chromate (CoCrO 4 ), and nickel (II) chromate (NiCrO 4 ).
- chromite compositions Another suitable subclass of the chromium oxide compositions is the class of chromite compositions, wherein chromium is trivalent.
- chromite compositions include sodium chromite (NaCrO 2 ), ferrochromite (FeCr 2 O 4 ), copper (II) chromite (CuCr 2 O 4 ), nickel (II) chromite (NiCr 2 O 4 ), cobalt (II) chromite (CoCr 2 O 4 ), zinc (II) chromite (ZnCr 2 O 4 ), lanthanum chromite (LaCrO 3 ), and calcium lanthanum chromite (Ca x Lai. x Cr0 3 ).
- Other suitable chromium oxides include the dichromates and CrO 2 Cl 2 .
- nickel oxide compositions suitable as the metal oxide core include nickel (II) oxide (NiO), nickel (II) hydroxide (Ni(OH) 2 ), nickel tin oxide (NiSnO 3 ), and nickel vanadium oxides (NiV x O, wherein O ⁇ x ⁇ 1).
- manganese oxide compositions suitable as the metal oxide core include manganese (II) oxide (MnO) 3 manganese (III) oxide (Mn 2 O 3 ), manganese (IV) oxide (MnO 2 ), lithium manganese (III, IV) oxide (LiMn 2 O 4 ), manganese (II) titanium oxide (MnTiO 3 ), and manganese zirconium oxide (MnO-ZrO 2 ).
- vanadium oxide compositions suitable as the metal oxide core include vanadium (II) oxide (VO or VO x , wherein x is typically between 0.9 and 1.3), vanadium (III) oxide (V 2 O 3 ), vanadium (IV) oxide (VO 2 ), vanadium (V) oxide (VzO 5 ), vanadium (IV 3 V) oxide (V 6 Oi 3 ), vanadium oxysulfate (VOSO 4 ), vanadium oxytrichloride (VOCl 3 ), magnesium vanadium oxide (MgV 2 O 6 ), and cadmium vanadium oxide (CdV 2 O 6 ).
- metavanadates and ortho vanadates.
- X can be an alkali, alkaline earth, main group, transition or rare earth metal.
- metavanadates include sodium metavanadate (NaVO 3 ), potassium metavanadate (KVO 3 ), ammonium metavanadate (NH 4 VO 3 ), magnesium metavanadate (Mg(VO 3 ) 2 ), calcium metavanadate (Ca(VO 3 ) 2 ), strontium metavanadate (Sr(V O 3 ) 2 ), barium metavanadate (Ba(V O 3 ) 2 ), copper (II) metavanadate (Cu(VO 3 ) 2 ), nickel (II) metavanadate (Ni(VO 3 ) 2 ), cobalt (II) metavanadate (Co(VO 3 ) 2 ), zinc metavanadate (Zn(VO 3 ) 2 ), lead metavanadate (Pb(VO 3 ) 2 ), cerium (III) metavanadate (Ce(VO 3 ) 3 ), and terbium (III) metavanadate (Tb(VO 3 ) 3 ) .
- X can be an alkali, alkaline earth, main group, transition or rare earth metal.
- suitable orthovanadates include sodium orthovanadate (Na 3 VO 4 ), potassium orthovanadate (K 3 VO 4 ), cesium orthovanadate (Cs 3 VO 4 ), magnesium orthovanadate (Mg 3 (VO 4 ) 2 ), calcium orthovanadate (Ca 3 (VO 4 ) 2 ), strontium orthovanadate (Sr 3 (VO 4 ) 2 ), barium orthovanadate (Ba 3 (VO 4 ) 2 ), copper (II) orthovanadate (Cu 3 (VO 4 ) 2 ), nickel (II) orthovanadate (Ni 3 (VO 4 ) 2 ), cobalt (II) orthovanadate (Co 3 (VO 4 ) 2 ), zinc orthovanadate (Zn 3 (VO 4 ) 2 ), lead orthovanadate (Pb 3 (VO 4 ) 2 ), cerium (III) orthovanadate (CeVO 4 ), terbium (III) orthovanadate (TbVO 4 ), and
- tantalum oxide compositions suitable as the metal oxide core include tantalum (V) oxide (Ta 2 Os), lithium tantalum oxide (LiTaO 3 ), sodium tantalum oxide (NaTaO 3 ), potassium tantalum oxide (KTaO 3 ), magnesium tantalum oxide (MgTa 2 O 6 ), calcium tantalum oxide (CaTa 2 O 7 ), barium tantalum oxide (BaTa 2 O 6 ), barium yttrium tantalum oxide (Ba(Y 0.5 Tao.
- lead tantalum oxide PbTa 2 O 6
- barium iron tantalum oxide Ba(Fei /3 Ta 2/3 )O 3
- barium magnesium tantalum oxide Ba(Mgi /3 Ta 2/3 )O 3
- cadmium tantalum oxide CdTa 2 O 7
- potassium tantalum niobium oxide KTa 0 . 65 Nbo. 35 ⁇ 3
- yttrium tantalum oxide YTaO 4
- rhenium oxide compositions suitable as the metal oxide core include rhenium (IV) oxide (ReO 2 ), rhenium (VI) oxide (ReO 3 ), rhenium (VII) oxide (Re 2 O 7 ), ammonium perrhenate (NH 4 ReO 4 ), and sodium perrhenate (NaReO 4 ).
- ruthenium oxide compositions suitable as the metal oxide core include ruthenium (IV) oxide (RuO 2 ), ruthenium (III) oxide (Ru 2 O 3 ), sodium ruthenate (Na 2 RuO 4 ), potassium ruthenate (K 2 RuO 4 ), bismuth ruthenate (Bi 2 Ru 2 O 7 ), sodium perruthenate (NaRuO 4 ), and potassium perruthenate (KRuO 4 ).
- the metal oxide core Particularly preferred for the metal oxide core are the molybdenum oxide and tungsten oxide compositions.
- Some examples of simple molybdenum oxides include molybdenum trioxide (MoO 3 ) and molybdenum dioxide (MoO 2 ).
- Some examples of simple tungsten oxides include tungsten trioxide (WO 3 ) and tungsten dioxide (WO 2 ).
- Also included in the molybdenum and tungsten oxide compositions are the non-stoichiometric molybdenum and tungsten oxides.
- a suitable subclass of the molybdenum and tungsten oxides includes the molybdates and tungstates.
- X can be an alkali, alkaline earth, main group, transition or rare earth metal.
- Suitable molybdates include aluminum molybdate (Al 2 (MoO 4 ) 3 ), barium molybdate (BaMoO 4 ), cadmium molybdate (CdMoO 4 ), cerium molybdate (Ce 2 (MoO 4 ) 3 ), cesium molybdate (CsMoO 4 ), cobalt molybdate (CoMoO 4 ), nickel molybdate (NiMoO 4 ), copper molybdate (CuMoO 4 ), silver molybdate (Ag 2 MoO 4 ), lithium molybdate (Li 2 MoO 4 ), sodium molybdate (Na 2 MoO 4 ), potassium molybdate (K 2 MoO 4 ), rubidium molybdate (Rb 2 MoO 4 ), magnesium molybdate (MgMoO 4 ), calcium molybdate (CaMoO 4 ), strontium molybdate (SrMoO 4 ), aluminum moly
- Suitable tungstates include aluminum tungstate (A1 2 (WO 4 ) 3 ), manganese tungstate (MnWO 4 ), barium tungstate (BaWO 4 ), cadmium tungstate (CdWO 4 ), cerium tungstate (Ce 2 (WO 4 ) 3 ), cesium tungstate (CsWO 4 ), cobalt tungstate (CoWO 4 ), nickel tungstate (NiWO 4 ), copper tungstate (CuWO 4 ), silver tungstate (Ag 2 WO 4 ), lithium tungstate (Li 2 WO 4 ), sodium tungstate (Na 2 WO 4 ), potassium tungstate (K 2 WO 4 ), rubidium tungstate (Rb 2 WO 4 ), magnesium tungstate (MgWO 4 ), calcium tungstate (CaWO 4 ), strontium tungstate (SrWO 4 ), and zinc tungstate (ZnWO 4 ).
- a particularly preferred subclass of the tungstate A particularly preferred subclass
- the tungsten bronzes can be represented by the general formula X n WO 3 wherein X is any positively charged species and O ⁇ n ⁇ 1.
- X can be an alkali, alkaline earth, main group, transition or rare earth metal.
- the tungsten bronzes tend to be inert and are generally at least partially conductive.
- the tungsten bronzes with n ⁇ 0.3 are generally semiconductive. Particularly preferred are the tungsten bronzes with n > 0.3, since these compositions are extremely inert and have good conductive properties.
- metal oxide core is the class of sodium tungsten oxides.
- the sodium tungsten oxides include, minimally, sodium, tungsten, and oxygen, in any stoichiometric ratio.
- a more preferred class of the sodium tungsten oxides is the class of sodium tungsten bronzes.
- the sodium tungsten bronzes can be represented by the formula Na n WO 3 wherein n typically is within the range of approximately 0.3 to 0.95.
- Some examples of sodium tungsten bronze compositions include Nao. 25 W0 3 , Na 0 . 3 WO 3 , Na 0-4 WO 3 , Nao.sW0 3 , Na 0-6 WO 3 , Na 0-7 WQ 3 ,
- molybdenum and tungsten oxide compositions include polyoxometalates, in particular those based on compositions of the formulas: MO 6 , MO 2 Cl 2 ,
- the metal oxide core has a high surface area.
- a high surface area allows for better dispersion of the platinum catalyst, and hence, greater efficiency of the oxygen reduction process. Since surface area increases with decreases in particle size, smaller metal oxide cores are preferred. Particularly preferred are metal oxide cores of nanoscale dimensions.
- the maximum size of the metal oxide core is preferably approximately five hundred microns, more preferably one hundred microns, more preferably fifty microns, more preferably ten microns, more preferably one micron, more preferably five hundred nanometers, more preferably one hundred nanometers, and even more preferably fifty nanometers.
- the metal oxide core can have a minimum size of approximately one nanometer, five nanometers, ten nanometers, twenty nanometers, thirty nanometers, or forty nanometers.
- the metal oxide core can also be a large molecular or supramolecular metal oxide cluster.
- Such oxide clusters include, for example, tetranuclear, pentanuclear, hexanuclear, heptanuclear, octanuclear, nonanuclear, decanuclear, undecanuclear, and dodecanuclear metal oxide species.
- the platinum-metal oxide composite particles described above can be in any suitable form.
- the platinum-metal oxide composite particles can be in a solid form, such as a powder.
- the platinum-metal oxide composite particles can be suspended or dispersed in a liquid phase.
- the liquid phase can be any suitable liquid phase.
- the liquid phase can be aqueous-based.
- the aqueous-based liquid phase can be completely water, or can include another suitable solvent.
- the aqueous-based liquid phase can be a water-alcohol mixture.
- the liquid phase can be, or include, an organic solvent.
- suitable organic solvents include acetonitrile, dimethylsulfoxide, dimethylformamide, toluene, methylene chloride, chloroform, hexanes, glyme, diethyl ether, and the like.
- the platinum-metal oxide composite particles can be approximately, or precisely, monodisperse in size. Alternatively, the particles can be anywhere from slightly to widely polydisperse in size.
- the platinum-metal oxide composite particles can also be of any shape.
- the particles can be approximately spherical, oblong, rectangular, square planar, pyramidal, trigonal bipyramidal, cuboidal, cylindrical, octahedral, cubooctahedral, icosahedral, rod-shaped, or amorphous.
- the particles can also be separate and distinct, or alternatively, agglomerated.
- the particles can assume, in certain circumstances, a low, moderate, or high degree of organization with respect to each other.
- the platinum-metal oxide composite particles can also have on their surface some trace chemicals.
- trace chemicals include halogens, carbon monoxide, charged species, and so on, as long as such trace chemicals do not obviate the intended use of the composite particles.
- the surfaces of the particles are free of any surface agents including ligands, polymers, surfactants, and so on.
- a surface active agent can be useful.
- Such surface active agents can be, for example, suitable metal-bonding ligands or surfactants bound to, or associated with, the surface of the composite particles.
- metal-bonding ligands include phosphines, amines, and thiols.
- phosphine ligands include trimethylphosphine, triethylphosphine, • triisopropylphosphine, triphenylphosphine, the diphosphines, and derivatives therefrom.
- amine ligands include pyridine, 2,2'-bipyridine, terpyridine (2,2';6'2"-terpyridine), piperidine, pyrrole, pyrazole, pyrrolidine, pyrimidine, imidazole, trimethylamine, triethylamine, triisopropylamine, ethylenediamine, and ethylenediaminetetraacetic acid (EDTA).
- thiol ligands include thiophenol, methanethiol, ethanethiol, 2-propanethiol, 2- methyl-2-propanethiol, octylthiol, decylthiol, dodecylthiol, methylsulfide, ethylsulfide, phenyldisulfide, thiophene, 2,2'-bithiophene, and tetrathiafulvalene.
- surfactants include the polyalkyleneoxides, polyvinylalcohols, polyvinylpyrrolidinones, siloxanes, albumin, sodium dodecyl sulfate, fatty acid salts, and the like.
- Some more specific examples of classes of polyalkyleneoxide surfactants include polymethyleneoxide, poly(methyleneoxide-ethyleneoxide), polyethyleneoxide, polypropylenenoxide, and poly(ethyleneoxide-propyleneoxide) surfactants.
- the invention relates to a catalyst.
- the catalyst includes the platinum-metal oxide composite particles as thus far described.
- the platinum-metal oxide composite particles in the catalyst are bound to a support.
- the support can be any suitable support.
- the support can be carbon, alumina, silica, silica-alumina, titania, zirconia, calcium carbonate, barium sulphate, a zeolite, interstitial clay, and the like.
- the platinum-coated particles in the catalyst are not bound to a support.
- One class of catalysis reactions for which the platinum-metal oxide composite particles are applicable includes hydrogenation and dehydrogenation reactions of hydrocarbons. Another class of applicable catalysis reactions includes carbon-carbon cross-coupling reactions. Yet another class of applicable catalysis reactions includes hydrosilylation reactions.
- the invention in another embodiment, relates to an electrocatalyst.
- the electrocatalyst includes the platinum-metal oxide composite particles described above bound to an electrically conductive support.
- the electrocatalyst is an oxygen-reducing electrocatalyst in an oxygen-reducing cathode.
- the electrically conductive support is carbon-based.
- Some examples of carbon-based electrically conductive supports include carbon black, graphitized carbon, graphite, and activated carbon.
- the electrically conductive support material is preferably finely divided.
- such macroscopic species as carbon fibers, rods, tubes, nanotubes, fullerenes, and the like, are not preferred.
- such macroscopic species are excluded.
- the invention in another embodiment, relates to a fuel cell.
- the fuel cell includes the oxygen-reducing cathode described above in electrical contact with a fuel-oxidizing anode.
- An ion-conducting electrolyte is in mutual contact with the oxygen-reducing cathode and anode.
- the structure of a typical electrode in a fuel cell includes 1) a fluid permeable side with hydrophobic characteristics and 2) a catalytic side provided with a particulate electrocatalyst.
- the catalytic side is in direct contact with a liquid or solid electrolyte (e.g., the proton-conducting medium).
- the hydrophobic characteristics on the electrode can be provided by one or more substances which are suitably hydrophobic, adhere to the electrode, and do not interfere with the electrochemical process.
- the hydrophobic substance can also be used as a binder for the supported or unsupported electrocatalyst.
- a preferred class of suitable hydrophobic substances is the class of fiuorinated polymers.
- Some examples of particularly preferred fiuorinated polymers include polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, and copolymers composed of tetrafluoroethylene and one or more other fiuorinated or non-fluorinated monomers.
- the hydrophobic substance is typically included in an amount of 20 to about 40 percent by weight of the amount of electrocatalyst and/or support.
- the electrodes can be any of various shapes, including tubular, rod-like, or planar.
- the electrodes are preferably in the form of thin sheets.
- the ion-conducting electrolyte conducts either protons or reduced oxygen species from one electrode to the other while separating the fuel at the anode from the oxidant at the cathode.
- the ion-conducting electrolyte is proton-conducting, i. e. , selectively conducts protons from the anode to the cathode.
- the ion-conducting or proton-conducting electrolyte is in the form of a membrane.
- the proton-conducting membrane can be in any of several suitable forms, for example, a liquid, solid, or semi-solid.
- a preferred class of proton-conducting polymer electrolytes are the commercially available copolymers of tetrafluoroethylene and perfluorinated vinyl ethers marketed by E. I. duPont de Nemours and Co under the trade name NAFION®. Such membrane-like materials are derivatized with acidic groups, such as sulfonic, carboxylic, phosphinic, or boric acid groups.
- the anode of the fuel cell can be any of the anodes known in the art.
- the anode can include supported or unsupported platinum or platinum-alloy compositions.
- the anode can also include a carbon monoxide-tolerant electrocatalyst.
- Such carbon monoxide tolerant anodes include numerous platinum alloys.
- a notable carbon monoxide-tolerant anode containing an atomically thin layer of platinum on ruthenium nanoparticles has been disclosed by Adzic et al. in U.S. Patent 6,670,301 B2.
- the foregoing patent to Adzic et al. is included herein by reference in its entirety.
- the fully assembled fuel cell can have stack designs to increase the electrical output.
- any of the known stack configurations designed for compactness and efficient supply of fuels to the anode and oxygen to the cathode can be used.
- the invention in another embodiment, relates to a method for producing electrical energy from the fuel cell described above.
- the fuel cell, as described becomes operational and produces electrical energy when the oxygen-reducing cathode is contacted with an oxidant, such as oxygen, and the fuel-oxidizing anode is contacted with a fuel source.
- an oxidant such as oxygen
- Oxygen gas can be supplied to the oxygen-reducing cathode in the form of pure oxygen gas. Pure oxygen gas is more preferable in the case of alkaline fuel cells. In the case of acid electrolyte fuel cells, the oxygen gas is more preferably supplied as air. Alternatively, oxygen gas can be supplied as a mixture of oxygen and one or more other inert gases. For example, oxygen can be supplied as oxygen-argon or oxygen-nitrogen mixtures.
- Some contemplated fuel sources include, for example, hydrogen gas, alcohols, methane, gasoline, formic acid, dimethyl ether, and ethylene glycol.
- suitable alcohols include methanol and ethanol.
- the hydrogen gas is preferably pure, and accordingly, free of contaminants such as carbon dioxide which degrade the strongly alkaline electrolyte.
- the fuels can be unreformed or reformed. Unreformed fuels are oxidized directly by the anode. Fuels can also be treated by a reformation process to produce hydrogen. By reforming, hydrogen is supplied to the anode indirectly. For example, hydrogen gas can be generated and supplied to the anode by reforming methanol, methane, or gasoline.
- the invention relates to a method for improving fuel cell stability by preventing or reducing platinum dissolution in an oxygen-reducing cathode of a fuel cell. The method requires incorporation of the electrocatalyst described above into the oxygen-reducing cathode of a fuel cell.
- the electrocatalyst can be incorporated by, for example, coating an electrode with the electrocatalyst in a suitable binder, as described above, and incorporating the coated electrode as an oxygen-reducing cathode in the fuel cell described above.
- the electrocatalyst is incorporated into the oxygen- reducing cathode by mixing the electrocatalyst with an appropriate amount of VulcanTM carbon and a fluorinated polymer, such as polytetrafluoroethylene. Any two of the foregoing ingredients can be pre-mixed before mixing with the third ingredient. The resulting mixture is preferably pressed onto a nickel net having a gold overlayer.
- the electrocatalyst of the invention increases stability primarily by preventing oxidation of the platinum catalyst.
- the platinum catalyst is believed to be prevented from oxidation through an electronic effect of the metal oxide core on the platinum. Specifically, the metal oxide is believed to exert a shift in the oxidation potential of the platinum catalyst, thereby making oxidation of platinum more difficult.
- the oxide material of the oxide core is also believed to be capable of regenerating the platinum catalyst by causing a post-reduction of oxidized platinum. Specifically, the oxide material is believed to adsorb oxidized platinum ions onto its surface oxide and hydroxyl groups. The adsorbed platinum ions, when exposed to decreasing potentials during operation of the fuel cell, are reduced to zerovalent or partially charged platinum, thereby regenerating the platinum catalyst.
- the platinum-metal oxide composite particles can be produced by any suitable method.
- the platinum-metal oxide composite particles can be produced by depositing an atomically thin layer of platinum or platinum clusters onto the surface of metal oxide substrate particles.
- Some methods for depositing platinum onto the surface of metal oxide substrate particles include reductive chemical methods in a liquid phase, electrodeposition, chemical vapor deposition (CVD), and physical vapor deposition (PVD).
- a preferred chemical method for depositing platinum onto the surface of oxide carrier particles includes adsorbing platinum ions onto the surface of the oxide particles followed by chemical reduction of the platinum ions. Chemical reduction of the platinum ions can be complete, thereby converting all of the platinum ions to zerovalent platinum. Alternatively, chemical reduction of the platinum ions can be partial, thereby converting a portion of the platinum ions to zerovalent platinum and having a portion of platinum remaining as charged platinum.
- platinum in the form of H 2 PtCl 4 can be contacted with oxide particles, thereby adsorbing platinum ions on the surface of the oxide particles in stoichiometric or excess amounts.
- non-adsorbed platinum ions are removed by, for example, rinsing, filtration or dialysis.
- the platinum-adsorbed oxide particles can then be treated with a reducing agent, such as, for example, NaBH 4 , citric acid, hypophosphorous acid, or hydrazine, to effect reduction of the adsorbed platinum.
- the platinum-adsorbed metal oxide particles can alternatively be electrolytically treated to effect reduction of the adsorbed platinum.
- the platinum-adsorbed oxide particles can be placed on an electrode and subjected to suitable reducing potentials.
- Chemical vapor deposition methods for depositing zerovalent or partially charged platinum onto metal oxide substrate particles involve the diffusion of volatile platinum precursor molecules onto the oxide surface and decomposition of the platinum precursor on the oxide surface to zerovalent or partially charged platinum.
- volatile platinum precursor molecules For example, cyclopentadienyltrimethylplatinum (CpPtMe 3 ) or (methylcyclopentadienyl)-trimethylplatinum
- MeCpPtMe 3 where Me is methyl and Cp is cyclopentadienyl, can be used as suitable volatile platinum precursor molecules in a CVD process.
- Physical vapor deposition methods for depositing zerovalent or partially charged platinum onto metal oxide particles involve the direct deposition of platinum atoms onto the oxide surface.
- a platinum source can be evaporated, sputtered, or laser ablated, thereby creating a vapor or plasma of platinum atoms.
- the platinum vapor or plasma condenses onto the oxide surface.
- the metal oxide substrate particles described above i.e., the metal oxide core
- Suitable solid-state methods for synthesizing metal oxide substrate particles typically include the application of heat.
- particles OfNiWO 4 and CoWO 4 can be produced by heating a combination of the corresponding metal nitrate and ammonium tungstate at approximately 600°C.
- Another example is the preparation of a metal tungsten bronze by heating the metal and tungsten trioxide at approximately 80O 0 C, or by heating a combination of a metal oxide, tungsten, and tungsten trioxide at approximately 1000°C.
- Suitable sol gel methods for synthesizing metal oxide substrate particles typically include the hydrolytic reaction between one or more metal alkoxides, metal amides, or metal carboxylates. Hydrolysis of the one or more oxide precursors is generally effected by water and can be further aided by catalytic amounts of an acid or base. Particle size can be adjusted by inclusion of surface active agents, complexants, or by the use of ordered mesoporous molecular sieves or zeolites. Partially hydrolyzed reaction products can also be thermally treated, pressurized, or sintered in the presence of oxygen to promote full conversion to the oxide particles.
- sol gel synthesis can be used to produce titanium oxide particles by hydrolysis of titanium isopropoxide, Ti[OCH(CH 3 ) 2 ] 4 ; or vanadium oxide particles by hydrolysis of vanadium (V) triisopropoxide oxide, VO[OCH(CH 3 ) 2 ] 3 .
- Another example is the synthesis of mixed tantalum-niobium oxide particles by hydrolysis of a mixture of tantalum ethoxide and niobium (V) ethoxide.
- An example of a suitable electrolytic method for synthesizing metal oxide substrate particles includes the electrolysis of a fused salt of a tungstate and tungsten trioxide.
- sodium tungsten bronzes can be prepared by electro lyzing a fused salt of sodium tungstate and tungsten trioxide.
- Another example of a suitable electrolytic method for synthesizing metal oxide substrate particles includes subjecting precursor zerovalent or partially charged metal particles to suitable oxidizing potentials.
- the oxidizing potential used is suitable when it can cause the conversion of such precursor reduced metal particles to the corresponding metal oxide composition.
- the precursor reduced metal particles are zerovalent metal particles, i.e., are composed of one or more zerovalent metals.
- the zerovalent metal particles can be held on an electrode for this purpose.
- ruthenium oxide particles can be produced by subjecting zerovalent ruthenium particles to an oxidizing voltage sufficient for converting ruthenium to ruthenium oxide.
- Such precursor metal particles can be obtained commercially or prepared by methods known in the art.
- a preferred preparative method includes chemical reduction of the corresponding metal salt(s) in a liquid phase.
- the liquid phase typically includes surface active agents and/or metal complexants to adjust particle sizes.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2006800174223A CN101180123B (en) | 2005-05-19 | 2006-05-16 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
JP2008512455A JP5518330B2 (en) | 2005-05-19 | 2006-05-16 | Electrocatalyst and dissolution rate for the reduction of oxygen by oxidation of reduced platinum. |
MX2007014374A MX2007014374A (en) | 2005-05-19 | 2006-05-16 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates. |
EP06759983A EP1883468A4 (en) | 2005-05-19 | 2006-05-16 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
KR1020077027117A KR101329783B1 (en) | 2005-05-19 | 2006-05-16 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
CA2607871A CA2607871C (en) | 2005-05-19 | 2006-05-16 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
HK08111689.5A HK1119619A1 (en) | 2005-05-19 | 2008-10-23 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/132,378 | 2005-05-19 | ||
US11/132,378 US8062552B2 (en) | 2005-05-19 | 2005-05-19 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2006124959A2 true WO2006124959A2 (en) | 2006-11-23 |
WO2006124959A3 WO2006124959A3 (en) | 2007-02-22 |
Family
ID=37432079
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2006/019017 WO2006124959A2 (en) | 2005-05-19 | 2006-05-16 | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
Country Status (10)
Country | Link |
---|---|
US (3) | US8062552B2 (en) |
EP (1) | EP1883468A4 (en) |
JP (1) | JP5518330B2 (en) |
KR (1) | KR101329783B1 (en) |
CN (1) | CN101180123B (en) |
CA (1) | CA2607871C (en) |
HK (1) | HK1119619A1 (en) |
MX (1) | MX2007014374A (en) |
RU (1) | RU2007146836A (en) |
WO (1) | WO2006124959A2 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1916728A1 (en) * | 2006-10-26 | 2008-04-30 | Samsung SDI Co., Ltd. | Electrode for fuel cell, and membrane-electrode assembly and fuel cell system including the same |
JP2008226824A (en) * | 2007-02-13 | 2008-09-25 | Hitachi Ltd | Fuel cell using metal cluster catalyst |
JP2009283213A (en) * | 2008-05-21 | 2009-12-03 | Hitachi Ltd | Catalyst for fuel cell, method for manufacturing catalyst for fuel cell, and electrode for fuel cell |
CN102593472A (en) * | 2011-01-13 | 2012-07-18 | 三星电子株式会社 | Catalyst including active particles, method of preparing the catalyst, fuel cell, electrode and lithium air battery |
US8252953B2 (en) | 2008-05-01 | 2012-08-28 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
RU2525543C1 (en) * | 2013-06-17 | 2014-08-20 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Method of obtaining of nanowhisker structures of oxide tungsten bronzes on coal material |
WO2015092371A1 (en) * | 2013-12-19 | 2015-06-25 | Johnson Matthey Fuel Cells Limited | Catalyst layer |
US10164265B2 (en) | 2015-10-23 | 2018-12-25 | GM Global Technology Operations LLC | Corrosion-resistant catalyst |
US10431831B2 (en) | 2010-10-08 | 2019-10-01 | Toyota Jidosha Kabushiki Kaisha | Catalyst particles, carbon-supported catalyst particles and fuel cell catalysts, and methods of manufacturing such catalyst particles and carbon-supported catalyst particles |
WO2021064007A1 (en) * | 2019-10-02 | 2021-04-08 | Robert Bosch Gmbh | Catlyst support materials for fuel cells |
Families Citing this family (111)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9005331B2 (en) | 2004-12-22 | 2015-04-14 | Brookhaven Science Associates, Llc | Platinum-coated non-noble metal-noble metal core-shell electrocatalysts |
US8062552B2 (en) * | 2005-05-19 | 2011-11-22 | Brookhaven Science Associates, Llc | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
US20070092784A1 (en) * | 2005-10-20 | 2007-04-26 | Dopp Robert B | Gas diffusion cathode using nanometer sized particles of transition metals for catalysis |
US20080280190A1 (en) * | 2005-10-20 | 2008-11-13 | Robert Brian Dopp | Electrochemical catalysts |
US7955755B2 (en) * | 2006-03-31 | 2011-06-07 | Quantumsphere, Inc. | Compositions of nanometal particles containing a metal or alloy and platinum particles |
US20070227300A1 (en) * | 2006-03-31 | 2007-10-04 | Quantumsphere, Inc. | Compositions of nanometal particles containing a metal or alloy and platinum particles for use in fuel cells |
KR101350865B1 (en) | 2006-07-24 | 2014-01-13 | 주식회사 동진쎄미켐 | Supported catalyst for fuel cell, method for preparing the same, electrode for fuel cell comprising the same, membrane electrode assembly comprising the electrode and fuel cell comprising the membrane electrode assembly |
KR100823021B1 (en) * | 2006-12-06 | 2008-04-17 | 광주과학기술원 | Liquid fuel mixture and fuel cell |
US20080220296A1 (en) * | 2007-01-08 | 2008-09-11 | University Of Maryland Office Of Technology Commercialization | PtRu core-shell nanoparticles for heterogeneous catalysis |
US7709413B2 (en) * | 2007-11-26 | 2010-05-04 | Kabuhsiki Kaisha Toshiba | Solid catalysts and fuel cell employing the solid catalysts |
EP2238640A2 (en) * | 2008-01-03 | 2010-10-13 | UTC Power Corporation | Protective and precipitation layers for pem fuel cell |
KR20090076408A (en) * | 2008-01-08 | 2009-07-13 | 삼성에스디아이 주식회사 | Biphase platinum catalyst and solar cell using the same |
KR100943952B1 (en) * | 2008-02-26 | 2010-02-26 | 삼성에스디아이 주식회사 | Catalyst for reformer of fuel cell, preparing method thereof, and reformer for fuel cell and fuel cell system including same |
US8389175B2 (en) * | 2008-05-16 | 2013-03-05 | Utc Power Corporation | Fuel cell having a stabilized cathode catalyst |
WO2009139747A1 (en) * | 2008-05-16 | 2009-11-19 | Utc Power Corporation | A stabilized platinum catalyst |
US9034165B2 (en) * | 2008-06-23 | 2015-05-19 | Brookhaven Science Associates, Llc | Underpotential deposition-mediated layer-by-layer growth of thin films |
KR100962082B1 (en) * | 2008-07-31 | 2010-06-09 | 희성촉매 주식회사 | Catalysts for NOx reduction employing H2 and a method of reducing NOx |
KR100893772B1 (en) * | 2008-08-21 | 2009-04-20 | 황부성 | A method for manufacturing hydrogen-oxygen generating electrode plate |
JP2012500896A (en) * | 2008-08-22 | 2012-01-12 | エージェンシー フォー サイエンス, テクノロジー アンド リサーチ | Methods and compositions comprising polyoxometalates |
CN102132447B (en) * | 2008-08-25 | 2013-12-18 | 3M创新有限公司 | Fuel cell nanocatalyst with voltage reversal tolerance |
US20100099012A1 (en) * | 2008-10-17 | 2010-04-22 | Brookhaven Science Associates, Llc | Electrocatalyst Synthesized by Depositing a Contiguous Metal Adlayer on Transition Metal Nanostructures |
US8699207B2 (en) * | 2008-10-21 | 2014-04-15 | Brookhaven Science Associates, Llc | Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer |
US8404613B2 (en) * | 2008-10-21 | 2013-03-26 | Brookhaven Science Associates, Llc | Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures |
US8357474B2 (en) * | 2008-12-17 | 2013-01-22 | Saint-Gobain Ceramics & Plastics, Inc. | Co-doped YSZ electrolytes for solid oxide fuel cell stacks |
KR100958169B1 (en) * | 2009-01-21 | 2010-05-14 | 황부성 | a hydrogen-oxygen generating electrode plate |
KR100930790B1 (en) * | 2009-02-18 | 2009-12-09 | 황부성 | A hydrogen-oxygen generating electrode plate and method for manufacturing the same |
US20100216632A1 (en) * | 2009-02-25 | 2010-08-26 | Brookhaven Science Associates, Llc | High Stability, Self-Protecting Electrocatalyst Particles |
JP5322733B2 (en) * | 2009-03-31 | 2013-10-23 | Jx日鉱日石エネルギー株式会社 | Method for producing catalyst for selective oxidation reaction of carbon monoxide |
US9850140B2 (en) | 2009-05-21 | 2017-12-26 | Cornell University | Conducting metal oxide and metal nitride nanoparticles |
US8309489B2 (en) * | 2009-06-18 | 2012-11-13 | University Of Central Florida Research Foundation, Inc. | Thermally stable nanoparticles on supports |
US8603400B2 (en) * | 2009-07-01 | 2013-12-10 | California Institute Of Technology | Nanostructured platinum alloys for use as catalyst materials |
WO2011004703A1 (en) * | 2009-07-07 | 2011-01-13 | 日本電気株式会社 | Oxygen reduction catalyst |
US8236915B2 (en) * | 2009-07-10 | 2012-08-07 | Momentive Performance Materials Inc. | Hydrosilylation catalysts |
US9312545B2 (en) | 2009-07-17 | 2016-04-12 | Danmarks Tekniske Universitet | Platinum and palladium alloys suitable as fuel cell electrodes |
CN102596398A (en) * | 2009-09-30 | 2012-07-18 | 戴姆勒股份公司 | Synthesis of stable and durable catalyst composition for fuel cell |
FR2953151B1 (en) * | 2009-12-01 | 2014-06-13 | Air Liquide | CATALYTIC REACTOR COMPRISING A CATALYTIC ALVEOLAR STRUCTURE AND ELEMENTS OPTIMIZING THE CONTACT OF THIS ALVEOLAR STRUCTURE WITH THE INTERNAL WALL OF THE REACTOR |
WO2011097461A1 (en) * | 2010-02-05 | 2011-08-11 | The Board Of Regents For Oklahoma State University | Colorimetric reagent for prevention of peroxide formation in solvents |
US9105934B2 (en) * | 2010-04-08 | 2015-08-11 | Georgetown University | Platinum adlayered ruthenium nanoparticles, method for preparing, and uses thereof |
US8450236B2 (en) * | 2010-04-13 | 2013-05-28 | Cristal Usa Inc. | Supported precious metal catalysts via hydrothermal deposition |
US20120058362A1 (en) * | 2010-09-08 | 2012-03-08 | Infineon Technologies Ag | Method for depositing metal on a substrate; metal structure and method for plating a metal on a substrate |
US8796170B2 (en) | 2011-02-04 | 2014-08-05 | Ford Global Technologies, Llc | Layered catalyst |
JP5153967B2 (en) * | 2011-02-21 | 2013-02-27 | 昭和電工株式会社 | Method for producing electrode catalyst for fuel cell |
CN107649110B (en) * | 2011-02-22 | 2021-02-02 | 奥迪股份公司 | Method for forming catalyst having atomic layer of platinum atom |
US9017530B2 (en) | 2011-03-23 | 2015-04-28 | Brookhaven Science Associates, Llc | Method and electrochemical cell for synthesis and treatment of metal monolayer electrocatalysts metal, carbon, and oxide nanoparticles ion batch, or in continuous fashion |
EP2736633B1 (en) | 2011-07-25 | 2018-10-24 | Ilika Technologies Ltd. | Cost-effective core-shell catalyst with high electrochemical stability |
US9782763B2 (en) | 2011-12-14 | 2017-10-10 | Momentive Performance Materials Inc. | Non-precious metal-based hyrdosilylation catalysts exhibiting improved selectivity |
KR101294592B1 (en) * | 2012-01-11 | 2013-08-09 | 한국과학기술연구원 | Catalyst for oxidative coupling reaction of methane, method for preparing the same, and method for oxidative coupling reaction of methane using the same |
CN104105681B (en) * | 2012-01-25 | 2016-11-09 | 大金工业株式会社 | For the method manufacturing Fluorine containing olefine |
US9550170B2 (en) | 2012-04-10 | 2017-01-24 | Brookhaven Sciecne Associates, LLC | Synthesis of nanoparticles using ethanol |
CN103515620B (en) * | 2012-06-20 | 2015-09-30 | 江苏氢阳能源有限公司 | A kind of electrode material, its application, direct fuel cell and electrochemical hydrogenation electrolysis tank |
US9343750B2 (en) * | 2012-06-26 | 2016-05-17 | Samsung Sdi Co., Ltd. | Supporter for fuel cell, and electrode for fuel cell, membrane-electrode assembly for a fuel cell, and fuel cell system including same |
US9153822B2 (en) | 2012-08-14 | 2015-10-06 | Ford Global Technologies, Llc | Nano-structured thin film catalyst |
US9447125B2 (en) | 2012-08-16 | 2016-09-20 | Momentive Performance Materials Inc. | Reusable homogeneous cobalt pyridine diimine catalysts for dehydrogenative silylation and tandem dehydrogenative-silylation-hydrogenation |
US9371340B2 (en) | 2012-08-16 | 2016-06-21 | Momentive Performance Materials Inc. | Dehydrogenative silylation, hydrosilylation and crosslinking using cobalt catalysts |
CN102794200B (en) * | 2012-08-31 | 2014-11-05 | 华南师范大学 | Preparation method of anode catalyst used for microbial fuel cells and application thereof |
US11579344B2 (en) | 2012-09-17 | 2023-02-14 | Government Of The United States Of America, As Represented By The Secretary Of Commerce | Metallic grating |
US9580828B2 (en) | 2012-09-17 | 2017-02-28 | The United States of America, as represented by the Secretary of Commerce (NIST) | Self-terminating growth of platinum by electrochemical deposition |
US20140178792A1 (en) * | 2012-12-20 | 2014-06-26 | Ford Global Technologies Llc | Electrochemical Device Including Amorphous Metal Oxide on Graphene |
GB2509916A (en) | 2013-01-16 | 2014-07-23 | Ilika Technologies Ltd | A mixed metal oxide material of tantalum and titanium |
GB201300810D0 (en) | 2013-01-16 | 2013-02-27 | Llika Technologies Ltd | Composite Materials |
GB2517394A (en) | 2013-01-16 | 2015-02-25 | Ilika Technologies Ltd | Composite materials |
WO2014182670A2 (en) | 2013-05-06 | 2014-11-13 | Momentive Performance Materials Inc. | Selective 1,2-hydrosilylation of terminally unsaturated 1,3-dienes using iron catalysts |
US9371339B2 (en) | 2013-05-06 | 2016-06-21 | Momentive Performance Materials Inc. | Saturated and unsaturated silahydrocarbons via iron and cobalt pyridine diimine catalyzed olefin silylation |
US10046313B2 (en) * | 2013-05-13 | 2018-08-14 | University Of Connecticut | Mesoporous materials and processes for preparation thereof |
US9716279B2 (en) | 2013-05-15 | 2017-07-25 | Brookhaven Science Associates, Llc | Core-shell fuel cell electrodes |
US9440999B2 (en) | 2013-05-15 | 2016-09-13 | Momentive Performance Materials Inc. | Activation of metal salts with silylhydrides and their use in hydrosilylation reactions |
US9343749B2 (en) | 2013-05-29 | 2016-05-17 | Ford Global Technologies, Llc | Ultrathin platinum films |
CN103560294A (en) * | 2013-11-05 | 2014-02-05 | 沈晓斌 | Application of zero power source-lithium ion battery battery pack as weeding machine power source |
CN105916870A (en) | 2013-11-19 | 2016-08-31 | 莫门蒂夫性能材料股份有限公司 | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation |
CN105916869B (en) | 2013-11-19 | 2019-11-22 | 莫门蒂夫性能材料股份有限公司 | Co catalysts and they be used for hydrosilylation and dehydrogenation silanization purposes |
CN105916871B (en) | 2013-11-19 | 2019-08-20 | 莫门蒂夫性能材料股份有限公司 | Co catalysts and its application for hydrosilylation and dehydrogenation silanization |
US9882222B2 (en) | 2013-11-27 | 2018-01-30 | Brookhaven Science Associates, Llc | Nitride stabilized core/shell nanoparticles |
WO2015138990A1 (en) * | 2014-03-13 | 2015-09-17 | The Regents Of The University Of California | Solar energy absorbing coatings and methods of fabrication |
JP6040954B2 (en) | 2014-04-16 | 2016-12-07 | トヨタ自動車株式会社 | Method for producing fuel cell catalyst |
JP5798670B2 (en) * | 2014-05-22 | 2015-10-21 | 国立大学法人 宮崎大学 | Method for producing fuel cell catalyst |
US9666876B2 (en) * | 2014-07-25 | 2017-05-30 | Ford Global Technologies, Llc | Oxygen reduction reaction catalyst having a non-conductive substrate |
US20170203973A1 (en) * | 2014-07-25 | 2017-07-20 | Suzhou Hans Energy Storage Technology Co., Ltd. | Applications of a tungsten-containing material |
US9809889B2 (en) | 2014-08-28 | 2017-11-07 | Toyota Motor Engineering & Manufacturing North America, Inc. | Water oxidation catalyst including cobalt molybdenum |
US9893365B2 (en) | 2014-08-28 | 2018-02-13 | N.E. Chemcat Corporation | Electrode catalyst, composition for forming gas diffusion electrode, gas diffusion elelctrode, membrane-electrode assembly, and fuel cell stack |
KR101670929B1 (en) * | 2014-10-21 | 2016-11-07 | 서울대학교산학협력단 | Catalytic materials and electrodes for oxygen evolution, and systems for electrochemical reaction |
US11332834B2 (en) | 2014-10-21 | 2022-05-17 | Seoul National University R&Db Foundation | Catalyst and manufacturing method thereof |
KR102235612B1 (en) | 2015-01-29 | 2021-04-02 | 삼성전자주식회사 | Semiconductor device having work-function metal and method of forming the same |
JP6433319B2 (en) * | 2015-02-04 | 2018-12-05 | 新日鐵住金株式会社 | METAL CATALYST PARTICLE FOR SOLID POLYMER FUEL CELL, PROCESS FOR PRODUCING THE SAME, CATALYST AND SOLID POLYMER FUEL CELL |
CN104681844B (en) * | 2015-02-15 | 2018-04-17 | 中国海洋大学 | The interior gravity flow microbiological fuel cell that is nested of in-situ remediation of underground water azotate pollution |
CN104818463B (en) * | 2015-04-09 | 2017-10-10 | 河南科技大学 | A kind of Platinum Nanoparticles coat the preparation method of gold grain film composite material |
CN105088157B (en) * | 2015-07-27 | 2017-12-15 | 河南科技大学 | A kind of method for preparing nanometer cobalt film coated copper Particles dispersed membrana granulosa |
US20190010609A1 (en) | 2015-12-23 | 2019-01-10 | Uniwersytet Warszawski | Means for carrying out electroless metal deposition with atomic sub-monolayer precision |
PL3184667T3 (en) | 2015-12-23 | 2020-05-18 | Uniwersytet Warszawski | Means for carrying out electroless metal deposition with atomic sub-monolayer precision |
US20190039051A1 (en) | 2016-02-29 | 2019-02-07 | N.E. Chemcat Corporation | Electrode catalyst, composition for forming gas diffusion electrode, gas diffusion electrode, membrane-electrode assembly, and fuel cell stack |
US10879539B2 (en) * | 2016-06-07 | 2020-12-29 | Cornell University | Mixed metal oxide compounds and electrocatalytic compositions, devices and processes using the same |
KR102474508B1 (en) * | 2016-12-16 | 2022-12-05 | 현대자동차주식회사 | Driving control method of fuel cell system |
FR3067023B1 (en) * | 2017-06-06 | 2019-06-28 | Universite Pierre Et Marie Curie (Paris 6) | POROUS MATERIAL IN THE FORM OF MICROSPHERES BASED ON IRIDIUM AND / OR IRIDIUM OXIDE, PROCESS FOR PREPARING THE SAME AND USES THEREOF |
CN107362793B (en) * | 2017-07-19 | 2019-12-03 | 江苏大学 | A kind of CeVO4-La2O3The preparation method and purposes of@HNTs composite photo-catalyst |
US11327040B1 (en) * | 2018-01-11 | 2022-05-10 | Alphasense Ltd. | Highly effective sensor for the vapors of volatile organic compounds |
KR102093263B1 (en) | 2018-04-30 | 2020-03-25 | 울산대학교 산학협력단 | Two-dimensional planar particulate catalyst and method for manufacturing the same |
US20200112031A1 (en) * | 2018-10-08 | 2020-04-09 | Toyota Motor Engineering & Manufacturing North America, Inc. | Cascade adsorption mechanism for overcoming activation energy barrier in oxygen reduction reaction |
CN111056598A (en) * | 2018-10-17 | 2020-04-24 | 湖北大学 | Electrochemical oxygen catalytic reduction cathode material for water treatment and preparation method thereof |
DE102019133872A1 (en) * | 2018-12-19 | 2020-06-25 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Fuel cell or electrolyzer |
TW202031354A (en) * | 2018-12-20 | 2020-09-01 | 日商出光興產股份有限公司 | Method for producing composite supporting metal and metal oxide |
US11639142B2 (en) | 2019-01-11 | 2023-05-02 | Ford Global Technologies, Llc | Electronic control module wake monitor |
US11322750B2 (en) * | 2019-04-24 | 2022-05-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | Surface modified platinum or platinum alloy catalyst for oxygen reduction reaction |
US11342566B2 (en) | 2019-11-06 | 2022-05-24 | Robert Bosch Gmbh | Conductive, anti-corrosive magnesium titanium oxide material |
US11316171B2 (en) | 2019-11-06 | 2022-04-26 | Robert Bosch Gmbh | Conductive, anti-corrosive magnesium titanium oxide material |
US11376565B2 (en) | 2019-11-06 | 2022-07-05 | Robert Bosch Gmbh | Conductive, anti-corrosive magnesium titanium oxide catalyst support material |
US11420879B2 (en) * | 2019-11-06 | 2022-08-23 | Robert Bosch Gmbh | Conductive, anticorrosive magnesium titanium oxide material |
CN111871409B (en) * | 2020-09-05 | 2022-11-18 | 兰州理工大学 | Having grain boundaries WO 3 Preparation method and application of tungstate composite photocatalytic material |
US11670778B2 (en) | 2020-09-28 | 2023-06-06 | Hyzon Motors Inc. | Electrodes with improved cell reversal tolerance through functionalized and stabilized metal oxides |
KR102517850B1 (en) * | 2020-11-30 | 2023-04-05 | 재단법인대구경북과학기술원 | Composite particle comprising a core of metal oxide particle and a shell of platinum group metal, and an electrode material for electrochemical reactions comprising the same |
CN113426444B (en) * | 2021-06-30 | 2022-07-19 | 青岛科技大学 | Ag loaded with platinum and silver nanoparticles0.333V2O5Nanorod composite material and preparation and application thereof |
CN114308057B (en) * | 2022-01-07 | 2023-03-28 | 成都理工大学 | Manganese-tungsten ore type oxide-supported cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
CN115094471B (en) * | 2022-06-16 | 2024-01-12 | 陕西科技大学 | Fullerene-loaded non-noble metal electrocatalyst, and preparation method and application thereof |
Family Cites Families (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB116477A (en) * | 1918-02-11 | 1918-06-13 | Alexander Franz Peeters | Improvements in or relating to Glass Furnaces. |
GB1164477A (en) * | 1965-12-28 | 1969-09-17 | Matsushita Electric Ind Co Ltd | Electrochemical Electrode |
US3645860A (en) * | 1969-03-04 | 1972-02-29 | Leesona Corp | Process for the preparation of an electrocatalyst |
US3953368A (en) * | 1971-11-01 | 1976-04-27 | Exxon Research And Engineering Co. | Polymetallic cluster compositions useful as hydrocarbon conversion catalysts |
US3776776A (en) * | 1972-01-21 | 1973-12-04 | Prototech Co | Gold-coated platinum-metal black catalytic structure and method of preparation |
US4090978A (en) | 1976-12-28 | 1978-05-23 | Uop Inc. | Electrocatalysts and a method for the preparation thereof |
US4232097A (en) * | 1979-03-07 | 1980-11-04 | The United States Of America As Represented By The United States Department Of Energy | Fuel cell oxygen electrode |
JP2909744B2 (en) * | 1988-06-09 | 1999-06-23 | 日新製鋼株式会社 | Method and apparatus for coating fine powder |
US5227030A (en) * | 1990-05-29 | 1993-07-13 | The Dow Chemical Company | Electrocatalytic cathodes and methods of preparation |
JPH05208135A (en) | 1991-02-23 | 1993-08-20 | Tanaka Kikinzoku Kogyo Kk | Electrode catalyst for negative electrode |
JPH0676216B2 (en) * | 1992-03-09 | 1994-09-28 | 工業技術院長 | Method for producing tungsten bronze and composite thereof |
US5298343A (en) * | 1992-06-19 | 1994-03-29 | Ecole Polytechnique De Montreal | Electrocatalysts for H2 /O2 fuel cells cathode |
US5853866A (en) * | 1993-12-10 | 1998-12-29 | Toto Ltd. | Multi-functional material with photocalytic functions and method of manufacturing same |
JP3833731B2 (en) * | 1995-01-20 | 2006-10-18 | 触媒化成工業株式会社 | Ammonia decomposition method |
US5733675A (en) * | 1995-08-23 | 1998-03-31 | Westinghouse Electric Corporation | Electrochemical fuel cell generator having an internal and leak tight hydrocarbon fuel reformer |
GB9622284D0 (en) * | 1996-10-25 | 1996-12-18 | Johnson Matthey Plc | Improved catalyst |
US6162530A (en) | 1996-11-18 | 2000-12-19 | University Of Connecticut | Nanostructured oxides and hydroxides and methods of synthesis therefor |
US6019946A (en) | 1997-11-14 | 2000-02-01 | Engelhard Corporation | Catalytic structure |
WO1999049108A1 (en) * | 1998-03-24 | 1999-09-30 | Drexel University | Process of making bipolar electrodeposited catalysts and catalysts so made |
US20030039857A1 (en) * | 1998-04-01 | 2003-02-27 | Zhang Wein-Xian | Nanoscale particles and the treatment of chlorinated contaminants |
US6165636A (en) * | 1998-04-14 | 2000-12-26 | De Nora S.P.A. | Composition of a selective oxidation catalyst for use in fuel cells |
US6559094B1 (en) | 1999-09-09 | 2003-05-06 | Engelhard Corporation | Method for preparation of catalytic material for selective oxidation and catalyst members thereof |
US6183894B1 (en) | 1999-11-08 | 2001-02-06 | Brookhaven Science Associates | Electrocatalyst for alcohol oxidation in fuel cells |
US6489052B1 (en) | 1999-11-18 | 2002-12-03 | Plug Power Inc. | Fuel cell air purification subsystem |
DE10013895A1 (en) | 2000-03-21 | 2001-10-04 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Water gas shift reaction, useful in mobile unit in vehicle for removing carbon monoxide from gas mixture containing hydrogen for fuel cell, uses catalyst based on noble metal coating on inert carrier |
JP2002050898A (en) * | 2000-08-04 | 2002-02-15 | Fuji Mach Mfg Co Ltd | Automatic re-tooling unit for wiring board supporting device, automatic re-tooling unit for wiring board holding device and method for setting wiring board support device |
WO2002027821A2 (en) | 2000-09-27 | 2002-04-04 | Proton Energy Systems, Inc. | Electrode catalyst composition, electrode and membrane electrode assembly for electrochemical cells |
US6541142B1 (en) | 2000-10-04 | 2003-04-01 | General Motors Corporation | Fuel cell system having a methanol decomposition reactor |
US7238472B2 (en) * | 2001-05-25 | 2007-07-03 | Nanosphere, Inc. | Non-alloying core shell nanoparticles |
JP4035654B2 (en) * | 2001-06-29 | 2008-01-23 | 株式会社デンソー | Catalyst particles and method for producing the same |
KR100438408B1 (en) * | 2001-08-16 | 2004-07-02 | 한국과학기술원 | Method for Synthesis of Core-Shell type and Solid Solution type Metallic Alloy Nanoparticles via Transmetalation Reactions and Their Applications |
JP2003089696A (en) * | 2001-09-19 | 2003-03-28 | Shingo Kaneko | Method for removing dioxin by catalyst ion-plasma reaction and device for removing the same |
US6680279B2 (en) | 2002-01-24 | 2004-01-20 | General Motors Corporation | Nanostructured catalyst particle/catalyst carrier particle system |
US6746597B2 (en) * | 2002-01-31 | 2004-06-08 | Hydrocarbon Technologies, Inc. | Supported noble metal nanometer catalyst particles containing controlled (111) crystal face exposure |
US7507447B2 (en) * | 2002-02-26 | 2009-03-24 | Fujifilm Corporation | Transparent conductive film, method for producing same and method for forming pattern |
US20040009388A1 (en) * | 2002-04-24 | 2004-01-15 | Peter Faguy | Electrocatalyst-containing layer |
JP2004079244A (en) | 2002-08-12 | 2004-03-11 | Toshiba Corp | Catalyst for fuel cell and fuel cell |
JP5082187B2 (en) * | 2003-10-06 | 2012-11-28 | 日産自動車株式会社 | Method for producing electrode catalyst particles for polymer electrolyte fuel cell |
JP4290524B2 (en) * | 2003-10-23 | 2009-07-08 | 株式会社キャタラー | Cathode catalyst for fuel cell |
JP2005125282A (en) * | 2003-10-27 | 2005-05-19 | Denso Corp | Catalyst particle and method for manufacturing the same |
US7541012B2 (en) * | 2004-07-07 | 2009-06-02 | The Hong Kong University Of Science And Technology | Catalytic material and method of production thereof |
US8062552B2 (en) * | 2005-05-19 | 2011-11-22 | Brookhaven Science Associates, Llc | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
US20090117020A1 (en) * | 2007-11-05 | 2009-05-07 | Board Of Regents, The University Of Texas System | Rapid microwave-solvothermal synthesis and surface modification of nanostructured phospho-olivine cathodes for lithium ion batteries |
-
2005
- 2005-05-19 US US11/132,378 patent/US8062552B2/en not_active Expired - Fee Related
-
2006
- 2006-05-16 CA CA2607871A patent/CA2607871C/en not_active Expired - Fee Related
- 2006-05-16 MX MX2007014374A patent/MX2007014374A/en active IP Right Grant
- 2006-05-16 JP JP2008512455A patent/JP5518330B2/en not_active Expired - Fee Related
- 2006-05-16 WO PCT/US2006/019017 patent/WO2006124959A2/en active Application Filing
- 2006-05-16 CN CN2006800174223A patent/CN101180123B/en not_active Expired - Fee Related
- 2006-05-16 RU RU2007146836/04A patent/RU2007146836A/en not_active Application Discontinuation
- 2006-05-16 KR KR1020077027117A patent/KR101329783B1/en not_active IP Right Cessation
- 2006-05-16 EP EP06759983A patent/EP1883468A4/en not_active Withdrawn
-
2007
- 2007-06-08 US US11/760,051 patent/US7704918B2/en not_active Expired - Fee Related
-
2008
- 2008-10-23 HK HK08111689.5A patent/HK1119619A1/en not_active IP Right Cessation
-
2011
- 2011-02-24 US US13/033,764 patent/US8308989B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
Title |
---|
None |
See also references of EP1883468A4 |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7910263B2 (en) | 2006-10-26 | 2011-03-22 | Samsung Sdi Co., Ltd. | Electrode including a heteropoly acid additive for fuel cell, membrane-electrode assembly for fuel cell including same, and fuel cell system including the same |
EP1916728A1 (en) * | 2006-10-26 | 2008-04-30 | Samsung SDI Co., Ltd. | Electrode for fuel cell, and membrane-electrode assembly and fuel cell system including the same |
JP2008226824A (en) * | 2007-02-13 | 2008-09-25 | Hitachi Ltd | Fuel cell using metal cluster catalyst |
US8252953B2 (en) | 2008-05-01 | 2012-08-28 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
US9163041B2 (en) | 2008-05-01 | 2015-10-20 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
US9944667B2 (en) | 2008-05-01 | 2018-04-17 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
JP2009283213A (en) * | 2008-05-21 | 2009-12-03 | Hitachi Ltd | Catalyst for fuel cell, method for manufacturing catalyst for fuel cell, and electrode for fuel cell |
US10431831B2 (en) | 2010-10-08 | 2019-10-01 | Toyota Jidosha Kabushiki Kaisha | Catalyst particles, carbon-supported catalyst particles and fuel cell catalysts, and methods of manufacturing such catalyst particles and carbon-supported catalyst particles |
CN102593472A (en) * | 2011-01-13 | 2012-07-18 | 三星电子株式会社 | Catalyst including active particles, method of preparing the catalyst, fuel cell, electrode and lithium air battery |
EP2477264A3 (en) * | 2011-01-13 | 2014-04-30 | Samsung Electronics Co., Ltd. | Catalyst including active particles, method of preparing the catalyst, fuel cell including the catalyst, electrode including the active particles for lithium air battery, and lithium air battery including the electrode |
US9123976B2 (en) | 2011-01-13 | 2015-09-01 | Samsung Electronics Co., Ltd. | Catalyst including active particles, method of preparing the catalyst, fuel cell including the catalyst, electrode including the active particles for lithium air battery, and lithium air battery including the electrode |
RU2525543C1 (en) * | 2013-06-17 | 2014-08-20 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Method of obtaining of nanowhisker structures of oxide tungsten bronzes on coal material |
WO2015092371A1 (en) * | 2013-12-19 | 2015-06-25 | Johnson Matthey Fuel Cells Limited | Catalyst layer |
US11158867B2 (en) | 2013-12-19 | 2021-10-26 | Johnson Matthey Fuel Cells Limited | Catalyst layer |
US11764367B2 (en) | 2013-12-19 | 2023-09-19 | Johnson Matthey Hydrogen Technologies Limited | Catalyst layer |
US10164265B2 (en) | 2015-10-23 | 2018-12-25 | GM Global Technology Operations LLC | Corrosion-resistant catalyst |
WO2021064007A1 (en) * | 2019-10-02 | 2021-04-08 | Robert Bosch Gmbh | Catlyst support materials for fuel cells |
US11757104B2 (en) | 2019-10-02 | 2023-09-12 | Robert Bosch Gmbh | Catalyst support materials for fuel cells |
Also Published As
Publication number | Publication date |
---|---|
US7704918B2 (en) | 2010-04-27 |
US8308989B2 (en) | 2012-11-13 |
KR101329783B1 (en) | 2013-11-22 |
CN101180123A (en) | 2008-05-14 |
EP1883468A2 (en) | 2008-02-06 |
US20070264189A1 (en) | 2007-11-15 |
US20060263675A1 (en) | 2006-11-23 |
EP1883468A4 (en) | 2012-01-25 |
HK1119619A1 (en) | 2009-03-13 |
RU2007146836A (en) | 2009-06-27 |
KR20080007622A (en) | 2008-01-22 |
JP5518330B2 (en) | 2014-06-11 |
CA2607871A1 (en) | 2006-11-23 |
MX2007014374A (en) | 2008-02-06 |
CA2607871C (en) | 2015-09-29 |
US20110151356A1 (en) | 2011-06-23 |
JP2008545604A (en) | 2008-12-18 |
WO2006124959A3 (en) | 2007-02-22 |
CN101180123B (en) | 2012-09-12 |
US8062552B2 (en) | 2011-11-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8308989B2 (en) | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates | |
Li et al. | Boosted performance of Ir species by employing TiN as the support toward oxygen evolution reaction | |
US7704919B2 (en) | Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof | |
US7855021B2 (en) | Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof | |
JP4971898B2 (en) | Supported catalyst for fuel cell and method for producing the same, electrode for fuel cell including the supported catalyst, membrane electrode assembly including the electrode, and fuel cell including the membrane electrode assembly | |
US7691780B2 (en) | Platinum- and platinum alloy-coated palladium and palladium alloy particles and uses thereof | |
JP5482095B2 (en) | Electrode containing platinum-containing catalyst, method for producing the same, and electrochemical device | |
JP5205013B2 (en) | Anode for fuel cell and fuel cell using the same | |
Cheng et al. | Investigation of Ti mesh-supported anodes for direct borohydride fuel cells | |
Meku et al. | Concentration gradient Pd-Ir-Ni/C electrocatalyst with enhanced activity and methanol tolerance for oxygen reduction reaction in acidic medium | |
Pushkarev et al. | Supported Ir-based oxygen evolution catalysts for polymer electrolyte membrane water electrolysis: a minireview | |
JP5679639B2 (en) | Gas diffusion electrode and manufacturing method thereof | |
JP2007042519A (en) | Catalyst for fuel cell, its manufacturing method, and electrode for fuel cell and fuel cell using it | |
JP5217236B2 (en) | Fuel cell catalyst containing RuTe2 and N element, fuel cell electrode material and fuel cell using the fuel cell catalyst | |
JP2008287929A (en) | CATALYST FOR FUEL CELL CONTAINING RuTe2 AND TUNGSTEN OXIDE, AND ELECTRODE MATERIAL FOR FUEL CELL USING THIS CATALYST FOR FUEL CELL, AND FUEL CELL | |
Seifitokaldani et al. | ARTICLE 1: ELECTROCHEMICAL AND PHYSICOCHEMICAL PROPERTIES OF TITANIUM OXY-NITRIDE ELECTROCATALYST (TIOXNY) PREPARED BY FOUR DIFFERENT SOL-GEL METHODS FOR THE OXYGEN REDUCTION REACTION (ORR) IN ACID MEDIUM | |
Martin | Synthesis and characterization of pt-sn/c cathode catalysts via polyol reduction method for use in direct methanol fuel cell |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200680017422.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2607871 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/a/2007/014374 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 2008512455 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077027117 Country of ref document: KR |
|
REEP | Request for entry into the european phase |
Ref document number: 2006759983 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006759983 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007146836 Country of ref document: RU |