US3511683A - Method of electrolessly depositing metals on particles - Google Patents

Method of electrolessly depositing metals on particles Download PDF

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US3511683A
US3511683A US647345A US3511683DA US3511683A US 3511683 A US3511683 A US 3511683A US 647345 A US647345 A US 647345A US 3511683D A US3511683D A US 3511683DA US 3511683 A US3511683 A US 3511683A
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metal
particles
substrate
platinum
deposition
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US647345A
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Wilton F Espenscheid
Israel J Heilwell
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Mobil Oil AS
ExxonMobil Oil Corp
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Mobil Oil AS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • 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
    • H01M4/92—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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the substrate particles may consist entirely of, or may be a nonmetal having a surface coating of, a metal which is, in the electromotive series, above the metal to be deposited on them.
  • the method involves dissolving a compound on the metal to be deposited on the substrate in a nonaqueous anhydrous solvent and adding the substrate to the resulting solution.
  • the field of the invention comprises metal deposition, including a method for the same and the resulting product.
  • Platinum and similar metals are deposited on colloidal particles composed entirely or partly of metal by immersion deposition in nonaqueous solutions.
  • the substrate particles have outer surfaces comprising a reactive metal which is above platinum in the EMF series, and on immersion of the same in a nonaqueous solution of a suitable platinum compound, they become coated by replacement of the reactive metal by platinum.
  • the invention is of particular value in providing for the deposition of platinum on high surface area colloidal particles for, as indicated, the published literature does not disclose a way which accomplishes this result.
  • the product is contemplated as having considerable importance in, among other applications, fuel cell and zinc-air battery technologies by permitting a decrease in platinum concentration presently required for air electrodes.
  • active metals such as the alkali and alkaline earth metals, and at the same time decrease the effects of any adverse surface chemistry of the substrate or of the deposit itself during deposition of metal thereon.
  • Platinum is one of a group of metals that either cannot be deposited on high surface area substrate particles, or can be deposited only with difiiculty.
  • Other metals of this group include palladium, ruthenium, rhodium, iridium, and osmium, which together with platinum are sometimes referred to as the platinum series of metals.
  • Group VIII metals generally. Although depositable with more ease, metals like silver, gold, and Group I-B metals are useful in the invention. For these, the invention offers a way of depositing them on the described substrates.
  • Other suitable metals are the alkali and alkaline earth metals which are too active to be deposited from aqueous solutions.
  • the less active metals like titanium, molybdenum, zirconium, tungsten, lead, tin, hafnium vanadium and germanium, which, although thermodynamically capable of depositing from aqueous solutions, do not do so because of solvation effects and the nonreactivity of their ions.
  • the depositable metals are those which form compounds soluble in the nonaqueous solvent and which, in the EMF series of metals, lie below the reactive metal of which the surfaces of the substrate are composed.
  • Preferred metals to be deposited are platinum, and the other members of the platinum series. It should be understood that more than one metal may be deposited; thus two or more metals may be deposited together or one after another to form layered deposits.
  • Compounds of the metal to be deposited include inorganic salts like platinum tetrachloride, palladium dichloride, silver perchlorate, ferric chloride, stannic chloride, stannous chloride, gold chloride, etc.
  • organometallic compounds conventionally used as petroleum additives comprising metal salts of alkyl, aryl, and alkyl-aryl dithiophoesphates, sulfonates, sulfates, carboxylates, phosphonates, phosphates, phenates, etc., the metal moiety of which is a metal of the groups described.
  • metal compounds are coordinated metal derivatives of olefins, acetylenes, and aromatics, as may be illustrated by such compounds as octadiene complexes of gold; silver acetylide; bis-acrylonitrile-metal derivatives; tris (pi-allyl)iridium; (arene)tungsten(CO) complexes where arene may be benzene, toluene, p-xylene, mesitylene, etc.
  • the metal compound may be used alone or in admixture with one or more other such compounds. It will be understood that the metal compound selected from the foregoing is soluble in the non-aqueous solvents contemplated herein.
  • the useful non-aqueous solvents for dissolving the metal compounds include both cyclic and aliphatic compounds.
  • the cyclics comprise aromatics like benzene, toluene, the xylenes, ethylbenzene, propylbenzene, the trimethylbenzenes, cymene, etc.; cycloalkanes like cyclohexane, methylcyclohexane, cyclopentane, etc.; heterocyclics like pyridine, furan, the picolines, etc.
  • Aliphatics preferably include such polar compounds as hydrazine; the alkyl formamides; alkyl sulfones and sulfoxides; alkyl halides; and various organic derivatives of carbonic acid like ethylene or propylene carbonates, etc.
  • solvents which are normally liquid, may be used singly or in combinations of two or more.
  • the presence of conventional auxiliary agents in the solution is frequently helpful, such as a mixture of acetic acid and acetic acid anhydride, or the latter alone, which helps to maintain anhydrous conditions and to insure uniform adhering films of deposited metal.
  • Other useful conventional auxiliary agents or modifiers for promoting deposition are phosphorodithioic acid; alkyl and aryl sulfonic acids and mixed alkyl-aryl sulfonic acids; and ethylenediamine and derivatives.
  • the high surface area substrate particles may, as noted, be entirely or partly of metal; in any event they have outer surfaces composed of a reactive metal which, in the EMF series, is above the metal of the metal compound dissolved in the nonaqueous solvent.
  • Particles entirely of metal may be chosen from any suitable metal that is obtainable in the colloid size range, including metals from Groups I-A, I-B, II-A, II-B, III-B, IV-B, V-B, VI-B, VII-B, VIII, III-A, IV-A, and V-A of the Periodic Table.
  • the colloid size range is considered to include particles having a diameter of 1 to 1000 millimicrons, or 10 to 10,000 angstrom units.
  • a preferred size range is 25 to 500, more preferably 50 to 200, angstrom units.
  • the substrate when coated with metal, comprises the product, the latter may determine the choice of such substrate characteristics as size, material, shape, etc.
  • Particles made partly of a nonmetal and partly of a metal may be obtained in accordance with the electroless deposition method described and claimed in said copending application Ser. No. 647,344, filed June 20, 1967, and as illustrated in Examples 2, 3 and 4 below.
  • colloid size particles of material like alumina are brought in contact with a sensitizing agent like stannous chloride to sensitize the particle surfaces; the particles are removed and freed of excess agent and then contacted with an activating agent such as palladium dichloride which forms palladium on the surfaces.
  • an activating agent such as palladium dichloride which forms palladium on the surfaces.
  • Such palladium functions as a catalyst for the next step, wherein the particles, after removal of excess activating agent, are mixed with a reducible salt of a metal of Groups I-B,
  • the resulting particles which comprise a core of alumina and an outer shell of nickel, may then be subjected to immersion deposition as described herein.
  • inorganic oxides particularly refractory oxides, may serve as the substrate or core, such as silica, silica-alumina, titania, thoria, zinc oxide, vanadia, chromia, zirconia, Inolybdena, etc.; also materials like carbon black, graphite, cellulose, glass, etc.; crystalline al-uminosilicate molecular sieves, natural and synthetic; polymers like the polyolefins, fluorinated hydrocarbon polymers, polyethers, polyamides, polysulfones, polystyrenes, vinyl polymers, acrylic polymers, and various natural and synthetic resins.
  • silica, silica-alumina, titania, thoria, zinc oxide, vanadia, chromia, zirconia, Inolybdena, etc. also materials like carbon black, graphite, cellulose, glass, etc.
  • crystalline al-uminosilicate molecular sieves natural and synthetic
  • a sensitizing agent like stannous chloride
  • suitable metal-coated particles may be produced according to a modification, also disclosed in said copending application, wherein the substrate particles, after treatment with the activating agent such as the palladium salt, are taken as the product; they thus comprise a core of nonmetallic material having a thin shell of palladium or other activating metal.
  • the method of immersion deposition comprises dissolving the metal compound in the solvent, adding one or more auxiliary agents of the type described, and dispersing the substrate particles in the solution.
  • Deposition of the metal of the metal compound on the substrate usually begins immediately, and at room temperatures, although higher temperatures, going up to refluxing, and even lower temperatures are suitable. Times of deposition are variable, depending on the desired thickness of deposit; thus they may extend for a minute or two to 1, 2, or 24 hours or more. Concentrations of metal compound in the solution are preferably saturation concentrations but it will be understood that lower concentrations are useful, going down to 1%, or less, by weight. Concentrations of the auxiliary agents are usually only 1 to 5% of that of the metal compound.
  • the substrate surfaces should, of course, be clean, and it may be observed that an advantage of using nonaqueous solutions is that a separate degreasing step is not generally required as the solvent can accomplish this operation during the deposition.
  • the action of depositing a metal on the substrate by immersion deposition involves a replacement of the metal of the metal compound by the metal of the substrate surfaces, provided of course that the metal of the compound is below that of the substrate surfaces in the EMF series.
  • the immersion deposition solution a potential difference exists between the two metals which increases as the metals are more and more removed from each other in the EMF series.
  • the metal higher up in the series is frequently described as more active, or less noble, or anodic, while the metal lower in the series in characterized as less active, or more noble, or cathodic.
  • It has a strongly adhering deposit of less active or more noble metal, the thickness of which may vary from a monolayer or two, or even a partial monolayer, up to several microns, depending on the time of contact of the substrate with the solution, the temperature, the concentration of metal compound, and the porosity of the substrate particle surfaces. Generally, thickness increases with time of contact, increases with increasing temperature and concentration, and increases with increasing porosity of the substrate. Adherence may be varied by use of different modifiers and substrates, and by varying the thickness, the adherence increasing as the thickness decreases.
  • the amount of deposit may range from less than 0.001 to 5 or 10%, or even to 50%, preferably 0.001 to 1 or 2%, by weight of the coated particle.
  • the product particles do not exhibit any substantial irreversible coagulation; especially is this the case when monodisperse substrate particles, like polystyrene, are used.
  • the color of the product particles varies, depending on the deposited metal. It may be added that the particles are conveniently handled in the form of suspensions.
  • the product is particularly useful as a catalyst, it being understood that the deposited metal is one known to be catalytic for a desired reaction.
  • This property is enhanced by the form of the product, i.e., by the fact that the metal may be in the form of very thin films, including monolayers, and partial monolayers, and because of the extremely large surface area which the product particles may exhibit.
  • the product particles have a core of nonmetallic material, particularly a refractory inorganic oxide
  • the surfaces of this core are not affected as they might be in the presence of aqueous solutions; thus with aqueous solutions such surfaces are modified by hydrolysis, hydration, and/or ion adsorption, with consequent adverse effects on a metal deposited thereover, particularly on its catalytic activity, adhesion, and the like.
  • the factors of thin films and high surface area are also of significance in other applications like fuel cell electrodes, filter material, deposition material for photographic films, paint pigments, inks, conducting plastics and magnetic microstructures for magnetic tapes or drums or discs.
  • Metal alloys may be deposited on a substrate by using two or more suitable metal compounds in the immersion deposition solution; for example, by using a mixture of platinum chloride and palladium chloride, an alloy of platinum and palladium may be deposited; a mixture of silver perchlorate and palladium chloride gives an alloy of silver and palladium; a mixture of stannic chloride and silver perchlorate gives an alloy of tin and silver; a mixture of stannic chloride and a zinc dithiophosphate gives an alloy of tin and zinc; a mixture of silver perchlorate, platinum chloride, and palladium chloride gives an alloy of silver, platinum, and palladium.
  • the outermost metal layer of the product may be coated over by immersion deposition, using a difierent metal compound in the deposition solution than the previous compound; or such product may be subjected to electroless deposition, followed or not by immersion deposition.
  • the product is reusable in the invention like other substrates.
  • EXAMPLE 1 Colloidal copper powder in an amount of 0.2 g. was dispersed in 15 ml. benzene that had been previously dried over a S-angstrom crystalline aluminosilicate molecular sieve. Then 0.2 g. silver perchlorate was added, with agitation. The copper powder turned black, indicating a deposition of silver, in about 3 minutes.
  • EXAMPLE 2 Platinum was deposited on colloidal carbon black using electroless deposition followed by immersion deposition.
  • 10 g. carbon black of 125 sq. m./ g. surface area was sensitized by treatment with 1 liter of an aqueous solution containing g. stannous chloride and 40 ml. concentrated HCl.
  • the resulting suspension was filtered through a 0.45 micron millipore membrane filter and then washed carefully, with filtration between washings, with 3 liters distilled water.
  • the wet particles were dispersed in 1 liter of an aqueous solution containing 0.5 m1. of a palladium dichloride solution and 1 ml. concentrated HCl, and after separation of the particles, they were washed in the manner described.
  • the wet particles were next dispersed in 1 liter of an aqueous solution containing 5 g. copper sulfate, 7 g. caustic soda, 10 g. of a 37% w./v. solution of formaldehyde, and 25 g. of sodium potassium tartrate (Rochelle salt).
  • the particles were separated and carefully washed with 4 liters distilled water followed by 500 ml. acetone and finally air dried.
  • 1 g. of the resulting copper-coated carbon black particles was placed in 10 ml. benzene containing 0.4 ml. acetic acid and 0.4 ml. acetic acid anhydride and 0.1 g. platinum tetrachloride and left overnight.
  • the particles were separated, washed with distilled water, then with acetone, and dried. Based on emission spectroscopic analysis, the particles had a metal content of 2% platinum and 0.8% copper.
  • EXAMPLE 3 Platinum was deposited on high surface area graphite particles by using the procedure of Example 2 except that graphite of surface area 235 sq. m./g., corresponding to a particle size of less than 130 angstroms, was employed instead of carbon black. Analysis showed the presence of 2.5% platinum and 0.7% copper by weight.
  • EXAMPLE 4 Platinum was deposited on high surface area alumina particles using the procedure of Example 2 except that colloidal alumina of 275 sq. m./g. surface area was used instead of carbon black, and high speed centrifugation instead of filtration. Analysis showed the presence of 1% platinum and 3% copper by weight on the particles.
  • EXAMPLE 5 Chemically pure mossy zinc was immersed in 10 ml. of benzene containing 0.2 ml. concentrated acetic acid, 0.2 ml. acetic acid anhydride, and enough platinum tetrachloride to saturate. A modifier, 0.1 g. of triethylenediamine, was also present. A black strongly adhering deposit of platinum was obtained.
  • EXAMPLE 7 A small piece of sodium was cut under dry benzene to expose a fresh surface and to remove any excess moisture. Then 0.2 g. of silver perchlorate was dissolved in dry benzene and added to the first-mentioned benzene. Deposition of silver on the sodium took place immediately.
  • the sequence of addition of the metal compound, solvent, and substrate is not material.
  • Method for depositing a metal on high surface area colloidal substrate particles comprising dissolving a compound of said metal in a nonaqueous anhydrous solvent in which said metal compound is soluble, adding to the resulting nonaqueous anhydrous solution said substrate particles, said substrate particles having at least the outer surfaces thereof comprised of a reactive metal which is above said first mentioned metal in the electromotive series, and thereby depositing said first mentioned metal on said substrate particles.
  • each substrate particle is comprised of a core of a nonmetal and an outer shell of said reactive metal.
  • said reactive metal is selected from the group comprising titanium, zirconium, molybdenum, tungsten, germanium, lead, tin, hafnium, and vanadium.
  • Method for depositiing platinum on high surface area colloidal substrate particles comprising electrolessly depositing on the particles a reactive metal which is above platinum in the electromotive series, then adding the particles to an anhydrous solution of a platinum compound dissolved in a non-aqueous solvent, and thereby depositing platinum on the particles.
  • electroless deposition comprises the steps of sensitizing the substrate, then activating the same, then treating the same with a reducible salt of a reactive metal, reducing said salt to form free reactive metal, and depositing said reactive metal on the substrate.
  • Method for depositing a metal on high surface area colloidal substrate particles comprising electrolessly depositing on the particles a reactive metal which is above said first mentioned metal in the electromotive series, then bringing the particles into contact with a solution of a compound of said first mentioned metal dissolved in a nonaqueous anhydrous solvent, and thereby depositing said first mentioned metal on the particles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
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  • Mechanical Engineering (AREA)
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US647345A 1967-06-20 1967-06-20 Method of electrolessly depositing metals on particles Expired - Lifetime US3511683A (en)

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JP (1) JPS5220937B1 (enExample)
DE (1) DE1771639B2 (enExample)
FR (1) FR1568675A (enExample)
GB (1) GB1181912A (enExample)
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Cited By (9)

* Cited by examiner, † Cited by third party
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US3647537A (en) * 1969-01-21 1972-03-07 Bell Telephone Labor Inc Method for making electro-optic dipoles
US3655423A (en) * 1970-03-03 1972-04-11 Hooker Chemical Corp Pretreatment of plastic surfaces before the application of an adherent organic coating
US3718594A (en) * 1970-11-30 1973-02-27 Eastman Kodak Co Method of preparing magnetically responsive carrier particles
US3830686A (en) * 1972-04-10 1974-08-20 W Lehrer Photomasks and method of fabrication thereof
US3853640A (en) * 1973-06-22 1974-12-10 Gen Electric Lubricants for pressing transition metal-rare earth powder to be sintered
US3856581A (en) * 1973-06-22 1974-12-24 Gen Electric Annealing air-stable magnetic materials having superior magnetic characteristics and method
US20040265214A1 (en) * 2003-06-06 2004-12-30 University Of Utah Composite combustion catalyst and associated methods
US20070031722A1 (en) * 2004-12-22 2007-02-08 Radoslav Adzic Electrocatalysts having platinum monolayers on palladium, palladium alloy, and gold alloy nanoparticle cores, and uses thereof
US20080213154A1 (en) * 2004-06-23 2008-09-04 Philippe Kalck Divided Solid Composition Composed of Grains Provided with Continuous Metal Deposition, Method for the Production and Use Thereof in the Form of a Catalyst

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JPS5554502A (en) * 1978-10-16 1980-04-21 Nippon Mining Co Ltd Production of noble metal plated composite powder
DE19757320C2 (de) * 1997-12-23 2001-08-02 Forschungszentrum Juelich Gmbh Elektrode mit guter Kohlenmonoxidverträglichkeit für Brennstoffzellen
DE102015101249B4 (de) * 2014-12-01 2021-02-11 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahren zur Herstellung eines Elektrokatalysators für eine Elektrode einer elektrochemischen Zelle, elektrochemischer Reaktor und Elektrokatalysator für eine elektrochemische Zelle

Citations (2)

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GB991231A (en) * 1962-12-12 1965-05-05 Bbc Brown Boveri & Cie Catalyst electrode insensitive to oxidation for electrochemical processes
GB1003575A (en) * 1962-04-19 1965-09-08 Sperry Gyroscope Co Ltd Chemical plating process

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
GB1003575A (en) * 1962-04-19 1965-09-08 Sperry Gyroscope Co Ltd Chemical plating process
GB991231A (en) * 1962-12-12 1965-05-05 Bbc Brown Boveri & Cie Catalyst electrode insensitive to oxidation for electrochemical processes

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647537A (en) * 1969-01-21 1972-03-07 Bell Telephone Labor Inc Method for making electro-optic dipoles
US3655423A (en) * 1970-03-03 1972-04-11 Hooker Chemical Corp Pretreatment of plastic surfaces before the application of an adherent organic coating
US3718594A (en) * 1970-11-30 1973-02-27 Eastman Kodak Co Method of preparing magnetically responsive carrier particles
US3830686A (en) * 1972-04-10 1974-08-20 W Lehrer Photomasks and method of fabrication thereof
US3853640A (en) * 1973-06-22 1974-12-10 Gen Electric Lubricants for pressing transition metal-rare earth powder to be sintered
US3856581A (en) * 1973-06-22 1974-12-24 Gen Electric Annealing air-stable magnetic materials having superior magnetic characteristics and method
US20040265214A1 (en) * 2003-06-06 2004-12-30 University Of Utah Composite combustion catalyst and associated methods
US7635461B2 (en) * 2003-06-06 2009-12-22 University Of Utah Research Foundation Composite combustion catalyst and associated methods
US20080213154A1 (en) * 2004-06-23 2008-09-04 Philippe Kalck Divided Solid Composition Composed of Grains Provided with Continuous Metal Deposition, Method for the Production and Use Thereof in the Form of a Catalyst
US7902104B2 (en) * 2004-06-23 2011-03-08 Arkema France Divided solid composition composed of grains provided with continuous metal deposition, method for the production and use thereof in the form of a catalyst
US20070031722A1 (en) * 2004-12-22 2007-02-08 Radoslav Adzic Electrocatalysts having platinum monolayers on palladium, palladium alloy, and gold alloy nanoparticle cores, and uses thereof
US7855021B2 (en) * 2004-12-22 2010-12-21 Brookhaven Science Associates, Llc Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof

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DE1771639A1 (de) 1971-12-30
GB1181912A (en) 1970-02-18
FR1568675A (enExample) 1969-05-23
NL6808510A (enExample) 1968-12-23
DE1771639B2 (de) 1977-02-24
JPS5220937B1 (enExample) 1977-06-07

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