DE3341560A1 - Process for the preparation of organometallic catalysts - Google Patents

Process for the preparation of organometallic catalysts

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Publication number
DE3341560A1
DE3341560A1 DE19833341560 DE3341560A DE3341560A1 DE 3341560 A1 DE3341560 A1 DE 3341560A1 DE 19833341560 DE19833341560 DE 19833341560 DE 3341560 A DE3341560 A DE 3341560A DE 3341560 A1 DE3341560 A1 DE 3341560A1
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Prior art keywords
metal
plasma treatment
clusters
metal clusters
polymer
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DE19833341560
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German (de)
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Horst Dr Binder
Matthias Dr Selders
Claus Dr Tiby
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Battelle Institut eV
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Battelle Institut eV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Abstract

Organometallic catalysts containing catalytically active metal cluster centres are prepared by producing the metal clusters in the gas phase and incorporating them in a polymer structure by means of plasma discharge.

Description

Verfahren zur Herstellung vonProcess for the production of

organometallischen Katalysatoren Die Erfindung betrifft ein Verfahren zur Herstellung von organometallischen Katalysatoren durch Einbau katalytisch aktiver Metallclustern in Polymerstrukturen.organometallic catalysts The invention relates to a method for the production of organometallic catalysts by incorporating catalytically active ones Metal clusters in polymer structures.

Großtechnische Verfahren, wie Fetthärtung, Isomerisation von Alkanen, Oligomerisation von Alkenen und selektive Oxydation von Kohlenwasserstoffen werden unter Verwendung von Katalysatoren durchgeführt, bei denen die Oberfläche wirksam ist (heterogene Katalysatoren). Zum Einsatz kommen meist Übergangsmetalle,wie Chrom, Molybdän, Wolfram und Eisen,oder Edelmetalle,wie Silber, Platin und Palladium.Large-scale processes such as fat hardening, isomerization of alkanes, Oligomerization of alkenes and selective oxidation of hydrocarbons carried out using catalysts in which the surface is effective is (heterogeneous catalysts). Transition metals such as chromium are mostly used Molybdenum, tungsten and iron, or precious metals such as silver, platinum and palladium.

Die Untersuchung der Natur dieser katalytischen Reaktionen und der chemischen Mechanismen führte zu der Erkenntnis, daß die katalytisch aktivste Form eines Metalls kleine Metallteilchen (Cluster) darstellen, in denen maximal 15 - 20 Metallatome durch Metall-Metall-Bindungen miteinander verknüpft sind. Neben dieser Clusterart gibt es auch Metall-Cluster, die neben Metall-Metall-Bindungen auch Metall-CO-Bindungen enthalten, z.B. Metall-Carbonyl-Cluster. Die katalytische Reaktion findet an der Oberfläche der einzelnen Cluster statt. Ihre katalytische Aktivität ist jedoch nicht stabil, da Cluster von einigen Metallatomen zunächst Agglomerate zu bilden versuchen, um dann in metallische Form ("bulk"-Material) überzugehen. In der US-Patentschrift 4292253 wird ein Verfahren beschrieben, nach dem die Cluster an ein flüssiges Polymer angebunden werden können. Ein wesentlicher Nachteil besteht darin; daß die Metallcluster leicht von flüssigen Polymeren ganz umgeben werden, so daß keine katalytische Aktivität mehr vorhanden ist. Außerdem ist die Wahl von Metallciustern und Polymeren durch die beschränkte Mischbarkeit zwischen gasförmigen Metallclustern und flüssigem Polymer bestimmt.Studying the nature of these catalytic reactions and the chemical mechanisms led to the realization that the most catalytically active form of a metal represent small metal particles (clusters) in which a maximum of 15 - 20 metal atoms are linked by metal-metal bonds. Besides this There are also metal clusters which, in addition to metal-metal bonds, also metal-CO bonds contain, e.g. metal carbonyl clusters. The catalytic reaction takes place at the surface of the individual clusters. Your catalytic activity however, it is not stable because clusters of some metal atoms are initially agglomerates try to form in order to then pass into metallic form ("bulk" material). In US Pat. No. 4,292,253, a method is described by which the clusters can be bound to a liquid polymer. There is a major disadvantage in this; that the metal clusters are easily completely surrounded by liquid polymers, so that there is no longer any catalytic activity. Also, the choice of Metallic clusters and polymers due to the limited miscibility between gaseous Metal clusters and liquid polymer determined.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein neues Verfahren zur Herstellung von Metallcluster enthaltenden Katalysatoren zu entwickeln, die stabil und dauerhaft katalytisch aktiv sind.The present invention is based on the object of a new method for the production of catalysts containing metal clusters to develop the are stable and permanently catalytically active.

Diese Aufgabe ist erfindungsgemäß dadurch gelöst, daß die Metallcluster in der Gasphase erzeugt und mittels Plasmaentladung in die Polymerstruktur eingebaut werden. Die vorteilhafte Ausbildungen des erfindungsgemäßen Verfahrens sind in den Unteransprüchen 2 bis 7 erläutert.According to the invention, this object is achieved in that the metal clusters generated in the gas phase and built into the polymer structure by means of plasma discharge will. The advantageous embodiments of the method according to the invention are shown in Dependent claims 2 to 7 explained.

Durch geeignete Wahl der Verfahrensparameter können die Metallcluster so in das organische Polymer eingebaut werden, daß die Bindung Cluster - Polymer stark genug ist, um die Cluster zu stabilisieren. Andererseits darf die Bindung nicht zu stark sein, weil dann die katalytische Aktivität der Cluster durch die "dichte" Polymermatrix verloren geht.By suitable choice of the process parameters, the metal clusters are incorporated into the organic polymer in such a way that the cluster - polymer bond is strong enough to stabilize the clusters. On the other hand, the bond is allowed not be too strong because then the catalytic activity of the clusters by the "dense" polymer matrix is lost.

Erfindungsgemäß werden unter dem Ausdruck "Metallcluster" Gruppen von 3 bis 20 Atomen der Übergangsmetalle oder Edelmetalle desselben oder unterschiedlichen Atomtyps verstanden, in denen nur Metall-Metall-Bindungen vorkommen. Diese können aus Metallpulver oder aus anderen Formen des metallischen Zustandes in verschiedener und an sich bekannter Weise hergestellt werden. Die Auswahl der Methode hängt von den jeweiligen Eigenschaften des Metalls ab. Hierzu bieten sich das Verdampfen im Vakuum (z.B. thermisch oder durch Elektronenstrahl) oder die Zersetzung metallorganischer Verbindungen wie Carbonyle oder Metall-Carbonyl-Cluster an. Vorzugsweise werden die Cluster an dem Ort erzeugt, an dem auch die anschließende Umsetzung mit dem Monomeren oder Polymeren stattfindet.According to the invention, the expression “metal clusters” refers to groups from 3 to 20 atoms of the transition metals or noble metals of the same or different Understood atomic type in which only metal-metal bonds occur. these can the end Metal powder or from other forms of the metallic state in different and are produced in a manner known per se. The choice of method depends on the respective properties of the metal. Evaporation in the Vacuum (e.g. thermal or electron beam) or the decomposition of organometallic Compounds such as carbonyls or metal carbonyl clusters. Preferably be the cluster is generated in the same place as the subsequent implementation with the Monomers or polymers takes place.

Nach einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden die Metallcluster in Gasphase mit einem Monomeren zusammengebracht, wobei die Polymerisation des Monomeren unter gleichzeitiger Bildung von organometallischen Clusterzentren im Plasma erfolgt. Das Monomer wird im gasförmigen Zustand zugegeben. Durch die Variation der Plasmaentladungsbedingungen kann der Polymerisationsgrad in weiten Grenzen gezielt verändert werden, so daß hierbei auf Träger abgeschiedene Polymerkatalysatoren mit eingebauten Clusterzentren oder auch pulverförmige Substanzen erhalten werden können.According to a preferred embodiment of the method according to the invention the metal clusters are brought together in the gas phase with a monomer, wherein the polymerization of the monomer with the simultaneous formation of organometallic Cluster centers in the plasma takes place. The monomer is added in the gaseous state. By varying the plasma discharge conditions, the degree of polymerization can be specifically changed within wide limits, so that this deposited on the carrier Polymer catalysts with built-in cluster centers or powdery substances can be obtained.

Die Herstellung pulverförmiger Katalysatoren wird durch eine starke plasmainduzierte Polymerisation bewirkt. Das erhaltene Polymerisat wird dabei stark vernetzt und bindet die Metallcluster an seine funktionellen Gruppen. Die so eingebauten Metallcluster fallen pulverförmig aus der Gasphase aus.The production of powdered catalysts is through a strong causes plasma-induced polymerization. The polymer obtained thereby becomes strong links and binds the metal clusters to its functional groups. The built-in Metal clusters precipitate out of the gas phase in powder form.

Nach einer weiteren Ausführungsform wird zu den im Gasraum vorhandenen Metallclustern in Gegenwart eines herkömmlichen festen Trägers, z.B. poröse Sintertonerde, Zeolithe und dergleichen, ein gasförmiges Monomer zugegeben. Durch eine relativ schwache plasmainduzierte Polymerisation binden die funktionellen Gruppen die Metallcluster an und es erfolgt die Abscheidung eines Films auf dem Trägermaterial.According to a further embodiment, the existing ones in the gas space are used Metal clusters in the presence of a conventional solid support, e.g. porous sintered clay, Zeolites and the like, a gaseous monomer are added. By a relative weak plasma-induced polymerization bind the functional groups to the metal clusters on and it a film is deposited on the carrier material.

Die im Gasraum vorhandenen Metallcluster können auch auf der Oberfläche eines als Träger dienenden festen Polymerfilms fixiert werden. Die zur Fixierung der Metallcluster notwendigen funktionellen Gruppen werden durch eine geeignete Plasmabehandlung der festen Polymerfilme erzeugt.The metal clusters present in the gas space can also be on the surface a solid polymer film serving as a support. The one for fixation The functional groups necessary for the metal clusters are provided by a suitable Plasma treatment of the solid polymer films is generated.

Die erhaltenen Katalysatoren können durch eine anschließende abtragende Plasmaentladung unter Sauerstoffatmosphäre an der Oberfläche Von einem Polymerüberzug befreit und damit aktiviert werden. Sollte bei der Herstellung eine Oxydation der Metallzentren stattfinden, so ist eine zusätzliche Plasmaentladung unter reduzierender Atmosphäre (z.B. Wasserstoff) vorteilhaft.The catalysts obtained can be removed by a subsequent removal Plasma discharge under an oxygen atmosphere on the surface of a polymer coating freed and thus activated. Should an oxidation of the Metal centers take place, so an additional plasma discharge is under reducing Atmosphere (e.g. hydrogen) advantageous.

Zur Herstellung der erfindungsgemäßen Polymerkatalysatoren sind z.B. geeignet: Styrol, Acrylnitril, Ferrocen, Acrylsäure, Vinylferrocen, Ethylen, Propylen, Acetylen, Butadien, Vinylacetat, Propylenoxid, Methylethylen, Cyclohexen, Benzol, 1,3,5-Trichlorbenzol, Toluol, Anilin, Divinylbenzol, Xylol, Trifluorethylen, Tetrafluorethylen, Hexafluorpropan, Hydroperfluorpropan, Hexafluorpropylen, Chlordifluormethan, Chlortrifluorethylen, Perfluorbuten-2, Hexamethyldisiloxan, Hexamethyldisilazan, Triethylsilan, Diethylvinylsilan, Tetramethylsilan, Pyridin, N-Vinylpyrrolidon.For the preparation of the polymer catalysts according to the invention, e.g. suitable: styrene, acrylonitrile, ferrocene, acrylic acid, vinyl ferrocene, ethylene, propylene, Acetylene, butadiene, vinyl acetate, propylene oxide, methylethylene, cyclohexene, benzene, 1,3,5-trichlorobenzene, toluene, aniline, divinylbenzene, xylene, trifluoroethylene, tetrafluoroethylene, Hexafluoropropane, hydroperfluoropropane, hexafluoropropylene, chlorodifluoromethane, chlorotrifluoroethylene, Perfluorobutene-2, hexamethyldisiloxane, hexamethyldisilazane, triethylsilane, diethylvinylsilane, Tetramethylsilane, pyridine, N-vinylpyrrolidone.

Das erfindungsgemäße Verfahren:bietet den Vorteil, daß die Katalysatoren eine sehr große katalytische Aktivität bei hoher Selektivität besitzen. Die Selektivität wird durch die Verwendung verschiedener Monomerer, verschiedener Metalle und Metallegierungen sowie verschiedener Mischungsverhältnisse zwischen Metall und Monomer bestimmt.The inventive method: offers the advantage that the catalysts have a very high catalytic activity with high selectivity. The selectivity is made through the use of different monomers, different metals and metal alloys as well as various mixing ratios between metal and monomer are determined.

Die Erfindung wird anhand eines Ausführungsbeispieles näher erläutert.The invention is explained in more detail using an exemplary embodiment.

Beispiel In einer üblichen Plasmaentladungsanlage werden Nickel-Cluster erzeugt. Hierzu wird Nickelcarbonyl mit einer Plasmaentladung zugesetzt. Diese Methode hat den Vorteil, daß keine hohen Temperaturen notwendig sind. Der Gesamtdruck in der Entladungskammer beträgt 0,1 - 10 mbar.Example In a conventional plasma discharge system, nickel clusters generated. For this purpose, nickel carbonyl is added with a plasma discharge. This method has the advantage that no high temperatures are necessary. The total pressure in the discharge chamber is 0.1-10 mbar.

Als Monomer wird Ethylen, als Trägergas Argon zugegeben.Ethylene is added as a monomer and argon as a carrier gas.

Der Partialdruck des Ethylens beträgt 0,01 - 1 mbar.The partial pressure of the ethylene is 0.01-1 mbar.

Plasmabehandlung wird durch Wechselspannung von einigen hundert Volt mit einer Frequenz - 30 khz - 30MHz durchgeführt, wobei der Ethylen-Fluß bei einem Druck 1 Torr ca. 70 Ncm3/Min. beträgt. Auf einen in der Kammer vorhandenen Träger bildet sich ein Polyethylen-Film mit eingebauten Nickelclustern. Die Wachstumsgeschwindigkeit der abgeschiedenen Schicht beträgt 0,05 - 0,5 um/min.Plasma treatment is carried out using alternating voltage of a few hundred volts performed at a frequency - 30 khz - 30MHz, with the flow of ethylene at a Pressure 1 Torr approx. 70 Ncm3 / min. amounts to. On a carrier in the chamber a polyethylene film with built-in nickel clusters is formed. The speed of growth the deposited layer is 0.05-0.5 µm / min.

Claims (7)

Patentansprüche 1. Verfahren zur Herstellung von organometallischen Katalysatoren durch Einbau katalytisch aktiver Metallcluster in Polymerstrukturen, dadurch gekennzeichnet, daß die Metallcluster in der Gasphase erzeugt und mittels Plasmabehandlung in die Polymerstruktur eingebaut werden. Claims 1. Process for the production of organometallic Catalysts by incorporating catalytically active metal clusters in polymer structures, characterized in that the metal clusters are generated in the gas phase and by means of Plasma treatment can be built into the polymer structure. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß zu den in der Gasphase befindlichen Metallclustern ein gasförmiges Monomer zugegeben und die Polymerisation des Monomeren mit der Plasmabehandlung gegebenenfalls in Anwesenheit eines Trägergases herbeigeführt wird.2. The method according to claim 1, characterized in that the in a gaseous monomer is added to the metal clusters located in the gas phase and the Polymerization of the monomer with the plasma treatment, optionally in the presence a carrier gas is brought about. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß zur Erzielung pulverförmiger Ausscheidungen die Plasmabehandlung unter niedrigem Druck und kleinem Monomerfluß durchgeführt wird.3. The method according to claim 1 or 2, characterized in that for Achieving powdery precipitates the plasma treatment under low pressure and small monomer flow is carried out. 4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß zur Erzielung einer Filmabscheidung die Plasmabehandlung unter höherem Druck und großem Monomerfluß in Gegenwart eines Trägers durchgeführt wird.4. The method according to claim 1 or 2, characterized in that for Achieving a film deposition plasma treatment under higher pressure and large Monomer flow is carried out in the presence of a carrier. 5. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Metallcluster in Anwesenheit eines Polymerträgers erzeugt werden, dessen Oberfläche durch die Plasmabehandlung aktiviert wird.5. The method according to claim 1 or 2, characterized in that the Metal clusters are generated in the presence of a polymer carrier, the surface of which activated by the plasma treatment. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß durch eine anschließende abtragende Plasmaentladung'unter Sauerstoffatmosphäre die Katalysatoroberfläche aktiviert wird.6. The method according to any one of claims 1 to 5, characterized in that that by a subsequent erosive plasma discharge under an oxygen atmosphere the catalyst surface is activated. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß anschließend eine Plasmaentladung unter Wasserstoffatmosphäre durchgeführt wird.7. The method according to claim 6, characterized in that then a plasma discharge is carried out under a hydrogen atmosphere.
DE19833341560 1983-11-17 1983-11-17 Process for the preparation of organometallic catalysts Withdrawn DE3341560A1 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367417A1 (en) * 1988-10-24 1990-05-09 Fuel Conservation Corporation Improved energy releasing catalyst and use thereof
DE4200193A1 (en) * 1992-01-07 1993-07-08 Fraunhofer Ges Forschung Prodn. of quantum point systems - by vaporising cluster-forming atoms and polymerising monomers between electrodes in high vacuum, and coalescing clusters in electron beam
DE4439841A1 (en) * 1994-11-08 1996-05-09 Bosch Ten Peter Thin film with fine, even microstructure for ultrafiltration or catalytic membranes
DE19705469C1 (en) * 1997-02-13 1998-10-22 Forschungszentrum Juelich Gmbh Fuel cell electrolyte layer production
WO2013076701A1 (en) 2011-11-25 2013-05-30 University Of Cape Town Stabilized and activated metal cluster complex based catalysts and their preparation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367417A1 (en) * 1988-10-24 1990-05-09 Fuel Conservation Corporation Improved energy releasing catalyst and use thereof
DE4200193A1 (en) * 1992-01-07 1993-07-08 Fraunhofer Ges Forschung Prodn. of quantum point systems - by vaporising cluster-forming atoms and polymerising monomers between electrodes in high vacuum, and coalescing clusters in electron beam
DE4439841A1 (en) * 1994-11-08 1996-05-09 Bosch Ten Peter Thin film with fine, even microstructure for ultrafiltration or catalytic membranes
DE4439841C2 (en) * 1994-11-08 1998-04-23 Bosch Ten Peter Process for producing a thin film with a two-dimensional microstructure having pores and thin film produced by this process
DE19705469C1 (en) * 1997-02-13 1998-10-22 Forschungszentrum Juelich Gmbh Fuel cell electrolyte layer production
WO2013076701A1 (en) 2011-11-25 2013-05-30 University Of Cape Town Stabilized and activated metal cluster complex based catalysts and their preparation

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