EP1487572A1 - Procede d'immobilisation in situ de colloides d'oxyde metallique nanodisperses hydrosolubles - Google Patents

Procede d'immobilisation in situ de colloides d'oxyde metallique nanodisperses hydrosolubles

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Publication number
EP1487572A1
EP1487572A1 EP03709717A EP03709717A EP1487572A1 EP 1487572 A1 EP1487572 A1 EP 1487572A1 EP 03709717 A EP03709717 A EP 03709717A EP 03709717 A EP03709717 A EP 03709717A EP 1487572 A1 EP1487572 A1 EP 1487572A1
Authority
EP
European Patent Office
Prior art keywords
metal
catalysts
metal oxide
metals
oxide particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03709717A
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German (de)
English (en)
Inventor
Manfred Theodor Reetz
Marco Lopez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP1487572A1 publication Critical patent/EP1487572A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—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
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • B01J35/23—
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • H01M4/8605—Porous electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to particularly simple to produce heterogeneous catalysts which are generated by in situ immobilization of preformed mono- or multimetallic metal oxide particles on an oxidic or non-oxidic support.
  • Nanoscale transition metal colloids are of great interest in catalysis. Applications can be found, for example, in organic synthesis and as electrocatalysts for fuel cells. Furthermore, they serve as building blocks in materials science [G. Schmid, Clusters and Colloids, NCH, Weinheim, 1994]. Numerous methods are available for the representation of metal colloids. In addition to the physical methods such as metal evaporation or .
  • metal colloids are mainly obtained by reducing common metal salts dissolved in water or organic solvents, such as PdCl 2 , Pd (OAc) 2 , H 2 IrCl 6 , H 2 PtCl 6 , PtCl 4 , RuCl 3 , CoCl 2 , NiCl 2 , FeCl 2 or AuCl 3 , with a wide range of chemical reducing agents such as complex hydrides or lower alcohols.
  • reductive methods can also be used to obtain bimetallic colloids, although the metals used must have a similar redox potential, because otherwise no bimetallic colloids will be formed.
  • Catalyst systems consisting of more than one active component are often superior in performance to the corresponding monometallic systems.
  • a targeted representation of bimetallic and multimetallic systems is therefore becoming increasingly important in colloid chemistry.
  • platinum-rhodium mixed colloids [K. Siepen, H. Bönnemann, W. Brijoux, J. Rothe, J. Hormes, J Appl. Organom. Chem., 2000, 14, 549-556].
  • heterogenized colloid catalysts show a higher activity than corresponding commercial heterogeneous catalysts [a) H. Bönnemann, G. Braun, W. Brijoux, R. Brinkmann, A. Schulze-Tilling, K. Seevogel, K. Siepen, J. Organomet. Chem. 1996, 520, 143-162; b) H. Bönnemann, W. Brijoux, R. Brinkmann, R. Fretzen, T. Joußen, R. Köppler, B. Korall, P. Neiteler, J. Richter, J. Mol. Catal. 1994, 86, 129-177].
  • Platinum-ruthenium colloids stabilized by surfactants were also produced for use as polymer electrolyte membrane fuel cell (PEM-BZ) catalysts [U. A. Paulus, U. Endruschat, G. J. Feldmeyer, T. J. Schmidt, H. Bönnemann, R. j. Behm, J. of Catalysis, 2000, 195, 383].
  • PEM-BZ polymer electrolyte membrane fuel cell
  • the stabilizer only provides. a necessary auxiliary reagent. From an ecological and economic point of view, it would therefore be desirable in the preparation of heterogeneous catalysts prepared from preformed metal colloids to be able to dispense entirely with the stabilizer.
  • a process developed by Watanabe is mainly used for the production of the commercial platinum-ruthenium / Vulcan XC72 catalysts for low-temperature fuel cells. Platinum sulfite complexes are decomposed oxidatively and at the same time a ruthenium salt is absorbed. The disadvantage is that strict attention must be paid to certain pH values during the synthesis. Only in the last stage are the 3 - 4 nm platinum-ruthenium particles generated by reduction with hydrogen [M. Watanabe, M. Uchida, S. Motoo, J Electroanal. Chem, 1987, 229, 395].
  • Another example are fuel cell catalysts consisting of up to four metals from the group Pt, Rh, Ru, Pd, Ir.
  • the multimetallic catalysts are also produced using a complex two-stage absorption and reduction process [p. Hitomi JP 2001118582 A2, and DE 10047935 AI].
  • H 6 Pt (SO 3 ) a platinum salt which is previously obtained from H PtCl 6 by ligand exchange and subsequent treatment with an ion exchanger as a white solid, is used as the source of platinum colloids.
  • Disadvantages of this process are the use of the H 6 Pt (SO 3 ) 4 salt, which is initially difficult to produce, the high costs to be expected due to the use of numerous chemicals [ion exchange resin, sodium carbonate, sodium sulfite) and the multistage process which ultimately leads to a finished catalyst leads.
  • only a catalyst consisting of platinum as an active component is accessible by means of this method.
  • citrate as a reducing agent for the production of platinum colloids as a precursor for a fuel cell catalyst is also described [Y. Suguru, S. Terazono, E. Yanagsawa, JP 2001093531 A2].
  • the platinum colloids stabilized after the reduction by dodecylbenzyl sulfonate are deposited on Vulcan XC72R conductive carbon black activated beforehand by treatment with 60% nitric acid.
  • a disadvantage of this method is the need to use a stabilizer and a reducing agent.
  • only in a second step is the active component deposited on the carrier which is still to be activated.
  • the invention was therefore based on the object of avoiding these disadvantages.
  • the in situ immobilization of metal oxide colloids formed by basic hydrolysis on an oxidic or non-oxide carrier according to the invention represents an unexpected simple way of avoiding these disadvantages.
  • a heterogeneous catalyst is obtained which contains metal oxide particles as active component, which consist of one, two or more different, homogeneously mixed metal oxides.
  • the particles have an average diameter of 0.5 - 5 nm, predominantly 1 - 3 nm, and are uniformly distributed over the carrier.
  • the catalysts accessible with the inventive method also include the combinations with at least three subgroup metals which are interesting for fuel cell applications and in which the oxides of Pt and Ir are present, and any combinations of at least three oxides of metals selected from the group Pt, Ir, Ru, Os, W, Mo, Pd and Sn, so e.g. B. the combinations Pt / Ru / Mo, Pt / Ru Os, Pt / Ru / Sn, Pt / Ru / Os / Ir.
  • the metals of the sub-groups Illb, IVb, Vb, VIb, Vllb, VIII, Ib or Ilb of the PSE are suitable as subgroup metals.
  • a transfer of the metal oxides into the corresponding reduced form of the metals on the support can either during the later catalytic process or beforehand by treatment with z.
  • hypophosphite, formate or alcohols z. B. methanol, ethanol, etc.
  • electrically conductive carbon blacks as carriers, it is also possible to reduce the metal oxide particles in an electrochemical manner.
  • Another advantage of the method is that the catalyst is insensitive to atmospheric oxygen if carbon is used as a carrier. In contrast to, for example, platinum (0) on Vulcan XC72 no self-ignition of the carrier was observed here, since the metal is immobilized as a metal oxide.
  • this new process also called “instant process” by us
  • metal salts dissolved first by impregnation, precipitation or ion exchange are applied to a support and in one or more subsequent steps the active component is first applied to the support in its final shape and size, so the new process is particularly simple.
  • the new method of in situ immobilization of colloidal metal oxides has the following advantages, among others:
  • the metal or multimetal oxide particles obtained by hydrolysis and condensation have a high structural stability with high Temperatures on. For example, no significant particle growth was observed for platinum-ruthenium-osmium-iridium-oxide particles with an average size of 2 nm after treatment at 500 ° C. in the XRD / DFA experiment.
  • the aqueous solution or optionally suspension of a transition metal salt, or a mixture of two or more metal salts M m X n is added to the aqueous solution of a base and a suitable carrier.
  • the basic suspension of the metal salts and the carrier is stirred intimately at elevated temperature until the metal oxide colloids are completely immobilized. This initially leads to the hydrolysis of the metal salts and to condensation or co-condensation with the formation of colloids Monometal oxides or colloidal mixed metal oxides, which are briefly electrostatically stabilized by existing hydroxide ions.
  • the colloidal particles are successively immobilized on the support from the solution during the reaction without any undesired agglomeration or size increase of the particles occurring.
  • common salts of the metals of the sub-groups Illb, IVb, Vb, VIb, Vllb, NIE, Ib and Ilb of the periodic table are suitable as precursors; the same is possible using one or more of these salts in combination with the salt of a metal from the main groups of the periodic table, in particular salts of tin.
  • the bases used are carbonates, hydrogen carbonates, hydroxides, phosphates or hydrogen phosphates of the alkali and alkaline earth metals such as LiOH, ⁇ aOH, KOH, LiHCO 3 , ⁇ aHCO 3 , KHCO 3 , CsHCO 3 , Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 , Mg (OH) 2 , MgCO 3 , CaCO 3 , Li 3 PO 4 , Na 2 HPO 4 , Na 3 PO 4 or K 3 PO 4 .
  • Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , CsCO 3 or MgCO 3 are preferably used.
  • the reaction temperature used for the reaction is between 20 to 100 ° C, preferably between 50 ° C and 90 ° C.
  • the particle size of the nanostructured metal oxide colloids is between 0.5 nm and 5 nm, preferably between 1 and 3 nm.
  • the stoichiometric composition of the desired bimetal oxide and multimetal oxide colloids can easily be controlled via the correspondingly predetermined amount of the metal salts used.
  • the colloidal metal oxides obtained and the corresponding catalysts can be characterized using numerous physical methods, including TEM, HRTEM / EDX, SEM / EDX, XRD / DFA, XPS, UV spectroscopy and cyclic voltammetry in the case of particles immobilized on electrically conductive carbon blacks.
  • oxidic and non-oxidic solids can be used as carriers for the water-soluble metal oxide colloids for the production of heterogeneous catalysts, e.g. B. Al 2 O 3 , TiO 2 , SiO 2 , CaCO 3 , MgO, La 2 O 3 , carbon black or activated carbon.
  • heterogeneous catalysts e.g. B. Al 2 O 3 , TiO 2 , SiO 2 , CaCO 3 , MgO, La 2 O 3 , carbon black or activated carbon.
  • the metal, bimetallic or multimetal oxide colloids described here are used as catalysts or precursors of catalysts for organic chemical reactions such as hydrogenations, oxidations or C-C and other linkage reactions.
  • the use as electrocatalysts in fuel cells also lends itself and is of particular importance in view of the low manufacturing costs.
  • FIG. 1 TEM on the left.
  • 78 mg of the Vulcan XC72 conductive carbon black were then added and the mixture was stirred at 60 ° C. for a further 12 hours.
  • the suspension was sedimented in the centrifuge for 10 minutes at 5000 rpm.
  • the glass flasks used were cleaned of any metal traces before use with aqua regia. To remove any Leftover grease was then rinsed under hot water with an abrasive and for the same purpose with methyl tert-butyl ether.
  • the samples were first centrifuged at 14,000 rpm. At the beginning, the supernatant was diluted 1/100 and the 0.1 mM solution was measured. As soon as no absorption or a constant absorption in the UV spectrum was observed, the reaction was complete. The suspension was centrifuged and the solid washed three times with water / methanol (1/1) and centrifuged again. Finally, the loaded carbon black was freeze-dried.
  • Example 4 Double direct support of platinum on Vulcan XC72 carbon black
  • Example 6 Bi-, tri-, and tetrametallic systems according to the instant method

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

L'invention concerne des catalyseurs hétérogènes productibles de manière particulièrement simple. Ces catalyseurs sont générés par immobilisation in situ de particules d'oxyde métallique monométalliques ou multimétalliques préformées sur un support oxydant ou non oxydant. A cet effet, des colloïdes d'oxyde métallique stabilisés par des ions hydroxyde sont produits à partir de sels métalliques hydrosolubles d'usage courant par hydrolyse et condensation et immobilisés sur les supports présents dans la solution. Le procédé selon l'invention permet entre autres de générer des catalyseurs pour cellules électrochimiques.
EP03709717A 2002-03-16 2003-02-25 Procede d'immobilisation in situ de colloides d'oxyde metallique nanodisperses hydrosolubles Withdrawn EP1487572A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10211701A DE10211701A1 (de) 2002-03-16 2002-03-16 Verfahren zur in situ Immobilisierung von wasserlöslichen nanodispergierten Metalloxid-Kolloiden
DE10211701 2002-03-16
PCT/EP2003/001826 WO2003078056A1 (fr) 2002-03-16 2003-02-25 Procede d'immobilisation in situ de colloides d'oxyde metallique nanodisperses hydrosolubles

Publications (1)

Publication Number Publication Date
EP1487572A1 true EP1487572A1 (fr) 2004-12-22

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EP03709717A Withdrawn EP1487572A1 (fr) 2002-03-16 2003-02-25 Procede d'immobilisation in situ de colloides d'oxyde metallique nanodisperses hydrosolubles

Country Status (7)

Country Link
US (2) US7244688B2 (fr)
EP (1) EP1487572A1 (fr)
JP (1) JP2005526596A (fr)
AU (1) AU2003214069A1 (fr)
CA (1) CA2479261A1 (fr)
DE (1) DE10211701A1 (fr)
WO (1) WO2003078056A1 (fr)

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JP2005097642A (ja) * 2003-09-22 2005-04-14 Tanaka Kikinzoku Kogyo Kk 貴金属−金属酸化物複合クラスター
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JP4498843B2 (ja) * 2003-12-26 2010-07-07 日立マクセル株式会社 燃料電池用触媒及びその製造方法
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JP4875410B2 (ja) * 2006-06-13 2012-02-15 トヨタ自動車株式会社 微粒子担持カーボン粒子およびその製造方法ならびに燃料電池用電極
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WO2009021988A1 (fr) * 2007-08-14 2009-02-19 Universite Libre De Bruxelles Procédé de dépôt de nanoparticules sur un support
CA2737629A1 (fr) * 2008-09-18 2010-03-25 Northeastern University Electrocatalyseur en alliage de platine ayant une resistance amelioree a l'empoisonnement par un anion pour piles a combustible a basse ou moyenne temperature
EP2608298B1 (fr) * 2011-12-22 2018-07-04 Umicore AG & Co. KG Catalyseur électrique pour cellules de combustible ainsi que son procédé de fabrication
KR101446116B1 (ko) * 2012-09-18 2014-10-06 한화케미칼 주식회사 탄소나노튜브 제조용 금속촉매의 제조방법 및 이를 이용한 탄소나노튜브의 제조방법
US9889429B2 (en) 2012-10-16 2018-02-13 Bill W. Helton Hydrogen production catalysts and associated systems and methods
JP2017087151A (ja) * 2015-11-11 2017-05-25 国立大学法人東京工業大学 金属ナノクラスター触媒
CN106622229B (zh) * 2017-01-10 2019-06-28 湘潭大学 加氢催化剂的制备方法及苯酚选择性加氢制环己酮的方法
CN110380027B (zh) * 2019-06-28 2022-07-15 惠州学院 一种含碳双金属氧化物的制备方法

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AU2003214069A1 (en) 2003-09-29
DE10211701A1 (de) 2003-09-25
US20080044692A1 (en) 2008-02-21
US20050148464A1 (en) 2005-07-07
WO2003078056A1 (fr) 2003-09-25
CA2479261A1 (fr) 2003-09-25
JP2005526596A (ja) 2005-09-08
US7244688B2 (en) 2007-07-17

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