WO2003094195A1 - Method for the production of catalysts - Google Patents

Method for the production of catalysts Download PDF

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Publication number
WO2003094195A1
WO2003094195A1 PCT/EP2003/004553 EP0304553W WO03094195A1 WO 2003094195 A1 WO2003094195 A1 WO 2003094195A1 EP 0304553 W EP0304553 W EP 0304553W WO 03094195 A1 WO03094195 A1 WO 03094195A1
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Prior art keywords
characterized
method according
catalysts
substrate
catalytically active
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PCT/EP2003/004553
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German (de)
French (fr)
Inventor
Mario Birkholz
Thomas Jung
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Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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Priority to DE10219643.5 priority Critical
Priority to DE2002119643 priority patent/DE10219643B4/en
Application filed by Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Publication of WO2003094195A1 publication Critical patent/WO2003094195A1/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/228Gas flow assisted PVD deposition
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/04Foraminous structures, sieves, grids, honeycombs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/06Fabrics or filaments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/347Ionic or cathodic spraying; Electric discharge
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349Irradiation 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/3407Cathode assembly for sputtering apparatus, e.g. Target

Abstract

The invention relates to a method for the production of catalysts, wherein a porous carrier structure and/or at least one catalytically active substance is deposited onto a substrate. The invention also relates to catalysts produced according to said method. The catalysts are used, inter alia, in the reduction of exhaust gas emissions of internal combustion engines, fuel cells and in organic synthesis.

Description

A process for the preparation of catalysts

The invention relates to a process for the preparation of catalysts in which on a substrate a porous support structure and / or at least one catalytically active substance is deposited. The invention also relates to catalysts thus prepared. are used, these catalysts, among others internal combustion engines in the field of reduction of exhaust emission of comparison, the fuel cell as well as in organic synthesis.

Under catalysis, the support of a chemical process by the addition of a material is meant in which the reactants are rapidly reacted with an increased product concentration or selectivity, energy or raw materials gentler than without the addition, and wherein the catalyst material is only participating in the reaction without being consumed or is consumed only a very limited extent. The term for- mixer process involves both electrochemical, photochemical or photoelectrochemical processes.

JE Otterstedt and DA Branreth enter Chapter 7, "Catalyst Supports and Small Particles Catalysts" her monograph "Small Particles Technology" (Plenum Press, 1998) an overview of modern catalysts and the importance of small particles, ie those with dimensions in the nanometer range for catalysis.

Examples of the use of catalysts in the art are: reduction of the N0 2 - and CO emissions, or elimination of soot particles in the exhaust gas of internal combustion engines, cathode-side oxygen reduction in the polymer fuel cell (PEMFC), Methanolrefor- optimization. for hydrogen production, organic syntheses, such as tetrahydrofuran (THF) of n-butane, petrochemical refinery operations and many On the other acid, used in the energy and drive systems as well as the chemical and pharmaceutical industry processes.

Characteristic of a catalyst is a large inner surface and a structure in the form of a com- sits, that is a heterogeneous structured material system. The catalytically active substances are often highly dispersed, that is, extremely finely divided metal particles, which are brought down to a ceramic support structure, automotive exhaust catalysts are characterized by a porous ceramic structure, usually made of alumina or cordierite consisting, on which noble metal or general transition metal particles are applied. But with the catalytically activated ven species may be metal compounds also, such as vanadium phosphorus oxides in the case of THF synthesis or Übergangsmetallchalkoge- halides, such as MoS 2, NiS or CoS in reducing the sulfur content in petroleum and its derivatives.

Typical process steps in the manufacture of catalysts have the impregnation to which a drying and calcining step follows. In the impregnation, the catalytically active metals are applied in the form of their compounds, such as carbonates, nitrates, or other wet-chemically to the ceramic support structure, and subsequently transferred to the metals. While the water introduced only is evaporated at 100-200 ° C in the drying step, process temperatures are used by several hundred to over one thousand degrees Celsius to decompose the carbonate or nitrate to the metal upon calcination. As the support structures existing particle dispersions are often made of metal oxide or hydroxide used (washcoat), which were applied by wet-chemical preparation steps to a base support structure. The latter is usually only the shape and structural stability of the catalyst, but has too small an internal surface area - in order to act as carriers of the catalytically active centers. Often, the drying and calcination is also connected a so-called. Reduction step, in which the present in oxidized form metal is reduced by the influence of hydrogen or other "reducing agent.

Catalysts are used in different forms: as powder, compacts, etc. in the so-called fixed bed when introduced into clay minerals and pumice dispersions in gases flowing through fibrous structures, etc., etc. .. A widely used method for.

Producing a close spatial contact between reactants and catalyst is the use of so-called. Monolith. In these, the catalytically active substances are applied to surfaces that are flowed through by a liquid or gaseous phase. By a parallel arrangement of these units, such as in a honeycomb structure to be conveyed many of the chemical reaction take place in parallel. The supporting structures of the monolith may be composed of metal, ceramic or other, forming materials, in some cases it is useful to imagine the catalyst of three different materials or structures constructed, namely the base support, such as a metallic monolith, the carrier , for example a washcoat, and the active spe- zies, for example, can be formed by noble metal particles.

The disadvantages of the known methods for the preparation of catalysts are:

• The impregnation water is used in the material system introduced which are driven by a further process step e nergieverbrauchenden mu.

• The introduced with the impregnating metals are in the preliminary stage of nitrates or carbonates th before, and are only transferred by energy-consuming calcination into the actual catalytically active metal particles tive.

• The processes are often very time-consuming and engrossing.

• - The wet chemical process control, and the subsequent temperature treatments allow only MAN gelhafte control of the particle size distribution function of the catalytically active metal particles, whereby the selectivity of the process may be unnecessarily limited.

The hollow cathode discharge occurs in the method for plasma-assisted surface treatment application. It is based on the hollow cathode effect, that is a process taking place in a dilute gas Glimmentla- fertil with high densities of electric charge carriers, ie ionized gas atoms and free electrons. The cathode is designed as a hollow body, in whose interior there is for superimposing the negative Glimmlichter. Geometrically, a hollow cathode is characterized in that the ratio of cathode area to open area is greater than 1. For the occurrence of the hollow cathode effect, the condition of 0, that the product of one of the cathode dimensions times the working pressure p must be within the range of 0.1 mbar cm to 10 mbar cm D, KDP <10 mbar cm (G. Schaefer & KH Schoenbach: "Basic mechanis s contributing to the hollow cathode effect", in:. NATO Asi series - Advanced science institute series H. 219 (1990), 55 ff).

In the hollow cathode principle based coating processes are characterized by a plasma discharge, ixe of the to be deposited material is removed either by sputtering from a source or by decomposition of chemical substances in the

Gas plasma phase is formed. In many cases, hollow-cathode based processes operate at relatively high pressures of 1 mbar, so that only a small vacuum-technical expenditure for the evacuation of the process chamber is to operate. Secondly, high deposition rates occur in this pressure regime, so that rapid coating processes can be carried out as they are needed in the industry. In an important variant of the method, the hollow cathode Gasflußsputtern, a hollow cathode of an sides is te with a working gas such as argon purged. detached by sputtering atoms are carried out subsequently on the other side, with which a coating process can be carried out. With a hollow cathode-based processes, coatings can be prepared from virtually any rigid material, that is GE einele enti- substances such as pure metals, alloys, metal compounds such as oxides, hydroxides, nitrides, sulfides, etc. are generated. Amorphous or crystalline structure and porous or compact morphology of the off zuscheidenden substances can be set by process control.

Starting herefrom, it was the object of the present invention to eliminate the known from the prior art drawbacks and to provide an easy-to-use and thus can be carried out in a short time process for the preparation of catalysts from the viewpoint of cost reduction.

This object is achieved by means of the generic method with the characterizing features of claim 1 as well as the here over catalysts prepared according to Claim 20th The further dependent claims reveal advantageous developments. Applicable methods fertil of the catalysts produced in this way is represented in the claims 23 to 26th

According to the invention a process for the preparation of catalysts is provided in which on a substrate a porous support structure and / or at least one catalytically active substance is deposited. The coating is carried out by means of a plasma treatment fektes utilizing the Hohlkathodenef-.

By comparison with the prior art entfallenen process steps of drying, calcination and reduction plasma enhanced hollow cathode processes allow faster production of catalysts possible. In addition, the sintering of the catalytically active metal particles is avoided because after production no temperature treatments are carried out. By the in situ growth of the particles in the gas phase, agglomeration of catalytic sodium is nopartikel avoided so that subsequent, complicated measures can be omitted for deagglomeration.

As a result, these points cause the grain size distribution function of the catalytically active centers can be set defined than in the known from the prior art. This will save the replacement of the catalytically active metals, which are often for expensive precious metals, and enables improved catalytic specific activity.

Surprisingly, it was shown that the hollow cathode coating process leads to 1 mbar to-1 formation of nanometer-sized particles in the gas phase in the pressure range. By depositing such nanogranularer particles on support structures or on substrates active centers can thus be prepared for catalysts particularly easy.

As catalytically active substances transition metals and / or their compounds are preferably used, wherein the nanogranulären particles preferably have a diameter between 1 and 100 nm. For example only, are here platinum and rhodium, but also called vanadium phosphorus oxides, Molybdensulfide, nickel sulphides or cobalt sulfides.

Preferably, for the preparation of the porous support structure metal compounds, such as metal oxides or metal hydroxides can be used.

As the substrate, a monolith is used preferably, the support structure may be deposited on its inner and outer surfaces. Alternatively, however, porous shaped donor such as grids, wire mesh, steel wool, metal gauze, glass cloth, PUL- can ver, activated carbon, carbon nano rolls or spheres are used with diameters between 100 nm and 1 cm.

The substrate is preferably made of a metal or a ceramic metal, such as aluminum oxide or cordierite. The porous support structure is preferably constructed of metal compounds, especially metal oxides or metal hydroxides.

In a further variant, the porous support structure may be coated in a first step and the at least one catalytically active substance to be deposited in a subsequent step.

the catalytically active substance is preferred in

Form volatile precursor introduced into the cavities of the .porösen support structure. Due to the hollow cathode-based coating process results in the formation of a plasma discharge in the hollow spaces, which leads to the decomposition of the precursor into the to be deposited atoms. This pre-located in the gas phase atoms can be subsequently deposited on the inner surfaces of the cavities. In such an approach, the nanogranu- stellar particles preferably have a diameter between 1 and 100 nm.

In an analogous method, the substrate is preferably provided by Plasmabehaήdlung with the metal compounds composed of the support structure. Again, the hollow cathode effect is to be utilized.

To this end, various options are available. Thus, the substrate may be provided by oblique or waste separation without applying an electrical bias with the porous support structure. On planar substrates then a columnar growth morphology of the layer whose pore size distribution function such as total pressure, geometry of the source-substrate configuration, and rate parameters can be specifically adjusted by Prozeßpa- results in general.

Alternatively, it is also possible to generate the porous structure by depositing a dispersion of two phases on the substrate, wherein one of the two phases is removed with formation of the cavities in the connector. This method is based on that two different chemical phases o- either by getrenn- th growth of the particles in the gas plasma phase of the dispersed by precipitation due to the thermodynamic properties of the two-phase system. One of the two phases is to be selected so that they can be removed by a subsequent process step more easily from the layer as the other phase. Preferably, this process will zeßschritte as chemical etching or plasma etching used. Depending on the relative volume fraction of both phases and respective nanogranularer structure, the coating can be made so that subsequently a einko ponentiger film with adjustable porosity results.

The technical implementation of the plasma treatment can be performed by three basic alternatives. The first is based on a plasma treatment by sputtering the coating material as physical vapor deposition, also called PVD. In the second variant, the coating material is reacted by sputtering and the chemical reaction tion with a reactive gas component, and then separated. Here we also speak of reactive PVD process. In the third variant, the coating material from a chemical reaction of the gases supplied is formed, and subsequently deposited. This procedure is known as chemical vapor deposition (CVD).

Preferably, the plasma treatment is carried out at a working pressure of between 0.01 mbar and 1 bar, preferably between 0.1 mbar and 1 mbar.

Respect to the design of the hollow cathode discharge, various of apparatus variants. Thus, the hollow cathode can be formed as, pipe as well as an assembly of two or more parallel or mutually inclined plates. It is also possible, that the hollow cathode is a metal mesh, wherein the gas introduced to switch the network one or more times by flows. The hollow cathode discharge can be controlled so that the material deposition takes place inside the hollow cathode (so-called. Inside Hollow Cathode, IHC). A re weite- process variant provides that the hollow cathode discharge takes place at a rolling metal strip, wherein the hollow cathode discharge between the two portions of the sheet is operated in a loop. The excitation voltages for the hollow cathode discharge between 1 V and 2000 V. The plasma can then be entertained by direct or alternating current. As a frequency range of low, medium and high frequency range are suitable. Similarly, a powered microwave plasma can be used.

Similarly, a catalyst prepared by the novel method is provided. The porous support structure and the at least one catalytically active substance are deposited as a heterogeneous distributed dispersion nanogranularer particles on the substrate. The deposited nanogranu- stellar particles have a diameter between 1 and 100 nm. Such catalysts are characterized by their high activity, at the same time the proportion of the catalytically active metals used is very low.

Use finds method of the invention in the preparation of catalysts for the reduction of NO x - and CO emission or reduction of soot particles in Abga-- .. of internal combustion engines. Likewise, catalysts thus prepared can (PEM) will used for the ka-side Thode oxygen reduction in fuel cells, particularly polymer fuel cells. Another field of application concerns the methanol reforming in hydrogen synthesis. Ultimately, the catalysts are also used in organic synthesis. For example only, the synthesis of tetrahydrofuran from n-butane and the petrochemical refining is to be mentioned here. While also all synthesis processes in the energy and drive technology as well as the chemical and pharmaceutical industries are suitable as application fields.

Use the following figures and the following example of according to the application object is to be explained in more detail, without limiting executive forms to these special education.

Fig. 1 shows schematically two variants of the coating process of the invention.

Fig. 2 shows a further variant of the process according to the invention using two hollow cathodes.

Fig. 3 shows schematically a further variant in which the coating on a rolling

Band is done.

In Fig. La), the method for coating a monolith sheet 4 is represented. 1 via the gas supply gas is passed through the hollow cathode 2, wherein it comes to the plasma discharge. 3 The atomic coating material thus formed was then separated on ' "• - deposited the monolith Plates 4 £.. -

In Fig. Lb) is a hollow cathode 2 from two opposite parallel plates is illustrated. Via the gas feeder 1, the gas is passed between the plates, whereby a hollow cathode discharge in the region. 3 As the substrate, a mono- lith is shown here, which consists of a plurality of honeycomb-shaped segments. In this way a loading layering of the inner and outer surfaces of these segments can now take place.

Fig. 2 shows a variant in which two hollow cathode 2, 6 may be used. The hollow cathode 2 serves the deposition of the support structure, while the hollow cathode 6, the deposition of the catalytically active substance is used. In this process variant, it is possible to produce heterogeneous distributed particle dispersions of the catalytically active substance and the carrier structure on the substrate. 4

In Fig. 3 shows a variant for the continuous implementation of the coating process is illustrated. Through feed rollers 7, a tape 2, for example made of metal material, transported. The gas supply 1 is arranged such that the hollow cathode discharge occurs in the gap 3 between the opposing tape sections. 2

example

Activation of monolithic sheets

Starting material are coated with a washcoat of aluminum metal sheets which are designed in such a way that they can be inserted into one another, thus forming parallel channels through. The object of the method is to activate the washcoat layer by applying a nanogranular noble metal layer (platinum / rhodium), For this purpose, the output plates are flußsputterquelle with a gas-coated, the cathode of which consists of precious metal to be deposited. For the production of the metal particles have a gas-flow tube type will pienten used in a Vakuumrezi-. Here, the existing of platinum and rhodium pipe is set to a negative electrical ULTRASONIC potential and flushed from one side with argon, dimensions of the tube source, argon flow and total chamber pressure are turned to each other so that in the source to the ignition of a self-sustaining plasma discharge comes. In a typical arrangement, the tube source is purged with an argon flow rate of a standard liter per minute, and it turns out - depending on the suction capacity of the pump stand and the size of the recipient - a total pressure of 0.5 mbar. The hollow cathode was applied to an inner diameter of 30 mm and with an e- lektrischen power of 2 kW, which serves to maintain the plasma discharge, by sputtering individual atoms from the tube hollow cathode are knocked out and worn out Ström with the gas, This leads in the gas plasma phase due to impacts of the metal atoms the formation of nanometer-sized particles, the

Size distribution function can be specifically adjusted by the Ar flow rate, the voltage applied to the tube source power, the distance between source and sheet metal, and other process parameters. At a distance of a few centimeters of the particulate-containing argon stream strikes the monolith sheets where the Edelϊϊe- be eliminated tallpartikel off on the alumina washcoat. The density of the particles is set over the time period which is allowed to act on the process, the monolith sheet.

The execution of the method may also be such that the gas stream behind the gas-flow is directed directly onto the apertures of the monolith or of a segment of the monolith and the activation of the washcoat layer by an inner coating with precious metal or precious metal particles occurs.

Claims

claims
1. A process for the preparation of catalysts in which on a substrate a porous Trägerstruk- structure and / or at least one catalytically active
Substance is deposited,
characterized ,
that the deposition takes place by means of a plasma treatment by making use of the hollow cathode effect.
The method of claim 1,
characterized in that the porous support structure and / or the at least one catalytically active substance in the form of nanogranular particles is deposited.
A method according to claim 2,
characterized in that the nanogranular particles have a diameter between 1 and 100 nm.
, A method according to any one of claims 1 to 3,
characterized in that are used as catalytically active substances, the transition metals and / or compounds thereof. A method according to any one of claims 1 to 4,
characterized in that are used for producing the porous support structure metal compounds, such as metal oxides or metal hydroxides.
6. A method according to any one of claims 1 to 5,
characterized in that a monolith is used as a substrate.
7. A method according to any one of claims 1 to 5
characterized in that tissue as a substrate networks, wire mesh, steel wool, metal gauze, fiber glass, powder, activated carbon, carbon
Nanotubes or balls are used with diameters between 100 nm and 1 cm.
8. A method according to any one of claims 1 to 7,
characterized in that a metallic or a ceramic substrate such as alumina or cordierite, is used.
9. A method according to any one of claims 1 to 8,
characterized in that first the porous support structure and the at least one catalytically active substance is deposited in the terminal.
10. The method according to at least one of claims 9 or 10
characterized in that the substrate is provided by oblique deposition or without electrical bias having a porous structure Trägerstruk-.
11. The method of claim 9,
characterized in that the at least one catalytically active substance introduced in the form of volatile precursor in voids of the porous support structure in which there powered plasma is decomposed and deposited on the inner surface of the cavities.
12. A method according to any one of claims 1 to 8,
characterized in that the deposition of the porous support structure and the at least one catalytically active substance is performed simultaneously with the formation of a particle dispersion.
13. A method according to any one of claims 1 to 12,
characterized in that the porous structure is made by depositing a dispersion of two phases on the substrate, wherein one of the two phases is removed with formation of the cavities in the connector.
14. The method according to claim 13,
characterized in that the one phase is removed by chemical etching or plasma etching.
15. A method according to any one of claims 13 or 14,
characterized in that the porosity on the volume ratio of the two phases is adjustable.
16. The method according to at least one of claims 1 to 15,
characterized in that the plasma treatment by cathodic sputtering of the coating material as a physical vapor deposition (PVD) is carried out.
17. The method according to claim 16,
characterized in that the plasma treatment is performed by cathode sputtering of the coating materials and chemical reaction with a reactive gas component as the reactive PVD.
18. The method according to at least one of claims 1 to 15,
characterized in that the plasma treatment takes place by chemical reaction of the supplied gas as a chemical vapor deposition (CVD).
19. The method according to at least one of claims 1 to 18,
characterized in that the plasma treatment mbar bar at a working pressure of between 0.01 mbar and 1, preferably takes place between 0.1 mbar and 1 mbar.
20 catalyst produced by the process according to any one of claims 1 to nineteenth
21. Catalyst according to claim 18,
characterized in that the porous support structure and the at least one catalytically ak ¬ tive substance is excreted as off heterogeneous distributed dispersion nanogranularer particles on the substrate.
22. A catalyst according to any one of claims 20 or 21,
characterized in that the nanogranular particles have a diameter between 1 and 100 nm.
23. Use of the method according to any one of claims 1 to 19 for the manufacture of catalysts for the reduction of NO x - and CO emission or reduction of soot particles in the exhaust gas of internal combustion engines.
24. Use of the method according to any one of claims 1 to 19 for the manufacture of catalysts for the cathode-side oxygen reduction in fuel cells.
25. Use of the method according to any one of claims 1 to 19 for the manufacture of catalysts for the methanol reforming for hydrogen synthesis.
26. Use of the method according to at least one of claims 1 to 19 for the preparation of catalysts for organic synthesis.
PCT/EP2003/004553 2002-05-02 2003-04-30 Method for the production of catalysts WO2003094195A1 (en)

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