MXPA06007496A - Preparation of metal/metal oxide supported catalysts by precursor chemical nanometallurgy in defined reaction chambers of porous supports using organometallic and/or inorganic precursors and reductants containing metal. - Google Patents

Abstract

The invention relates to a catalyst containing a porous support, which has cavities that open onto at least one face. Said openings have a diameter of approximately 0.7 to 20 nm, at least in one extension direction. The support has a specific surface area of at least 500 m2/g and is also charged with a content of at least one catalytically active metal component amounting to at least 2.5 m2 per gram of catalyst. The invention also relates to a method for producing a catalyst of this type and to the use of the latter in methanol synthesis or as a reformer in fuel-cell technology.

Description

The catalyst is characterized in that the proportion of the pores with a diameter in the area of 20 to 75 Á is at least 20% and the proportion of the pores with a diameter greater than 75 Á is 80% maximum. The ratio of Cu / Zn atoms is found. between 2.8 and 3.8, preferably between 2.8 and 3.2, and the proportion of AI2O3 is from 8 to 12% by weight. A similar catalyst for the synthesis of methanol is known from DE-A-44 16 425. It has a Cu / Zn atom ratio of 2: 1 and generally consists of 50 to 75% by weight of CuO, in 15 to 35% by weight of ZnO and still contains 5 to 20% by weight of AI2O3. Finally, document ?? -? - 0 152 809 discloses a catalyst for the synthesis of alcohol mixtures containing methanol and higher alcohols which contains, in the form of a precursor of oxide (a) copper oxide and zinc oxide, (b) aluminum oxide as thermal stabilization substance and (c) at least one alkali carbonate or alkali oxide, with the oxide precursor having a pore ratio with a diameter between 15 and 7.5 nm of 20 to 70% of the volume total, the alkali content is 13 to 130 x 10 ~ 6 for each gram of the oxide precursor and the aluminum oxide component has been obtained from aluminum hydroxide (sol or aluminum hydroxide gel) distributed in colloidal form.

With the methods used hitherto for the production of catalysts for the synthesis of methanol, after the loading of the carrier with the precursor compounds of the corresponding catalytically active metals, it is passed, generally at relatively high temperatures, by several oxidative preparation stages and / or reductive, most of the time with air respectively oxygen as an oxidizing agent and hydrogen as a reductive agent. In addition, these methods generally comprise several stages of calcination, typically between 250-400 ° C. In these steps of the method there is a growth of particles of the catalytically active reaction centers which causes a decrease in the catalytic activity. The Cu / ZnO system is the basis of the industrialized synthesis of methanol and an important component of fuel cell technology (reformer). It is considered as a prototype for the investigation of reciprocal synergetic activities between metal and support in heterogeneous catalysis [P.L. Hansen, J.B. Wagner, S. Helveg, J.R. Rostrup-Nielsen, B.S. Clausen, H. Tops0e, M. Science 2002, 295, 2053-2055]. Thus, studies using high-resolution in situ transmission electron microscopy (TEM) showed dynamic changes of Cu nanocrystallites on ZnO supports (2-3 nm) as a function of the redox potential of the gas phase. Under the reductive conditions (H2 / CO) of the methanol synthesis, a flattening of the Cu particles occurs with considerably increased humidification ... of the ZnO support. Important is also the formation of Cu / Zn alloys, as proves the promotion of surfaces · Cu (III) due to deposition of Zn. Structures of zeolites and similar to zeolites such as, for example, mordenite, VPI-5 or cloverite, as well as mesoporous periodic silicate minerals (PMS) such as MC-41, MCM-8 or SBA-15, have been shown to be excellent supports for many catalytically active species, thanks to its very high specific surface area and the pore structure adjustable precisely in the nm area, and in particular Cu / PMS materials respectively CiOx / PMS are analyzed. These materials, however, are not active - or clearly less - in relation to methanol synthesis [K. Hadjiivanov, T. Tsoncheva, M. Dimitrov, C. Minchev, H. Knózinger, "Characterization of Cu / MCM-41 and Cu / MCM-48 mesoporous catalysts by FTIR spectroscopy of adsorbed CO", Applied Catalysis A-Genreral 2003, 241 , 331] and do not contain the ZnO component. The loading of PMS with metals and metal oxides by chemical organometallic deposition in the vapor phase is known for some metals, for example, for Au [M.

Okumura, S. Tsubota, M. Iwamoto, M. Haruta, "Chemical vapor deposition of gold nanoparticles on MCM-41 and their catalytic activities for the low-temperature oxidation of CO and of H2", Chemistry Letters 1998, 315.] or Pd [C. P. Mehnert, D. W. Weaver, J. Y. Ying, "Heterogeneous Heck catalysis with palladium-grafted molecular sieves", Journal of the American Chemical Society 1998, 120, 12289.] and for A1203 [A. . Uusitalo, TT Pakkanen, M. Koger-Laukkanen, L. Niinisto, K. Hakala, S. Paavola, B. Lofgren, "Heterogenization of racemic ethylenebis (1-indenyl) zirconium dichloride on trimethylaluminum vapor modified silica surface", Journal of Molecular Catalysis A-Checimal 2000, 160, 343.]. The invention is based on the objective of offering a method for the production of catalysts, in particular for the synthesis of methanol, which makes it possible to obtain catalysts with a very high activity. This objective is achieved by a method with the features of claim 1. Advantageous improvements of the inventive method are subject of the dependent claims. The invention provides a method for the production of a catalyst comprising a porous support, at least one active metal and at least one promoter. The catalyst is particularly suitable for the synthesis of methanol. In the production a porous support having a specific surface area of at least 500 m2 / g is prepared. In the porous support is applied at least one active metal precursor comprising at least one active metal in a reducible form, as well as at least one group which is linked to the active metal atom through a ligand atom which is preferably selected between oxygen, sulfur, nitrogen, phosphorus and carbon. The active metal precursor is reduced with a reductant comprising at least one promoter metal and at least one hydride group and / or an organic group that is linked to the promoter atom through a carbon atom. The reductant, respectively the promoter metal contained therein, is still finally transferred to the promoter. The promoter is formed, in this, generally with an oxide of the promoter metal. The active metal precursor preferably comprises at least two groups that are linked through a linking atom with the active metal atom, which is selected from oxygen, sulfur, nitrogen, phosphorus and carbon. The reductant also preferably comprises at least two hydride groups and / or organic groups which are linked through a carbon atom with the promoter atom, preferably from a group which is formed by alkyl groups, alkenyl groups, aryl groups, a cyclopentadienyl radical and its derivatives. By a "porous support" is meant preferably a support comprising cavities that are open at least to one side. The opening of these cavities comprises at least along one. direction of extension a diameter of about 0.7 to 20 nm, preferably 0.7 to 10 nm, particularly preferably about 0.7 to 5 nm. The term "cavity" should be understood, in this, in a broad sense .. Such a cavity can be, for example, an approximately spherical cavity, or a channel with a defined geometry, such as is realized, for example, in zeolite materials . But the cavity can also be made between two layers, for example in sheet silicates. The cavity has, however, a comparatively small opening, so that the active metal precursor diffuses in a controlled manner into the interior of the cavity and precipitates therein. In the case of layered silicates, the diameter described above of about 0.7 to 20 nm corresponds, therefore, essentially to the distance between layers. In the case of spherical cavities, the porous support has pores with an approximately circular circumference. The extension of the opening of the cavity can be determined by measurement of nitrogen adsorption according to the BJH method (DIN 66134). The porous supports preferably have a pore volume greater than 0.09 cm 3 / g, in particular higher than 0.15 cm3 / g. If zeolites are used as support, then the pore volume is preferably less than 1.5 cm3 / g. Suitable as supports are also MOF systems (metal-organic framework, for its acronym in English). These systems comprise metal atoms that are bonded through organic ligands in three-dimensional form to establish a structure and which are suitable, for example, for the storage of hydrogen. These compounds are characterized by very high pore volumes up to 10 cm3 / g, as well as by very high specific surfaces of more than 1000 m2 / g, particularly preferably above 2000 m2 / g. The porous support is characterized by a high specific surface area of at least 500 m2 / g, preferably al. less 600 m2 / g, with particular preference more than 1000 m2 / g. The specific surface is determined in this by measurement of nitrogen adsorption according to the BET method (DIN 66131). In the porous support is applied at least one active metal precursor comprising at least one active metal in a reducible form, as well as at least one group which is linked to the active metal through a linking atom. That is, in the active metal precursor the active metal atom is present at an oxidation level higher than 0. By an active metal is meant in this a metal having in the finished catalyst a catalytic activity in the reaction that must be catalyzed. In a catalyst for the synthesis of methanol this is, for example, copper which is present as a metal in the activated form of the catalyst. By an active metal precursor is meant, correspondingly, a compound that allows the release of the active metal. In the inventive method, compounds which contain at least one active metal atom as well as at least one group which is linked through a linking atom to the active metal atom are used as active metal precursors. The ligand atom is selected here as oxygen, sulfur, nitrogen, phosphorus and carbon. The active metal preferably carries organic groups, that is to say groups which have, in addition to the O, S, N and P ligand atoms, at least one carbon atom. Preferably, the organic groups have 1 to 24 carbon atoms, in particular 1 to 6 carbon atoms. Other heteroatoms, respectively groups of heteroatoms which are coordinated in the active metal as Lewis bases and which can stabilize the active metal precursor in this way, can still be linked to the carbon structure. Suitable organic groups are, for example, alkoxides or alkoxides with amino functions. The precursor of active metal is reduced with a reducer to precipitate the active metal in the walls of the pores. By a reductant is meant a metal-organic compound that can "reduce the active metal precursor to precipitate the active metal in the porous support." The promoter metal is released from the reductant which, as a promoter, generally in the form of an oxide, is precipitated in the support preferably in nano-dispersed form The reducer therefore comprises at least one promoter metal and at least one hydride group and / or an organic radical which is linked through a carbon atom to the promoter metal. The binding can be carried out here either by a bond s or by a p-bond. Preferably, the groups in the active metal precursor are linked to the active metal by another linking atom than carbon, preferably by means of an oxygen or nitrogen atom. But if the groups in the active metal and the metal promoter are both bound by a carbon atom to the metal atom, then the molecular weight of the redoubt groups r is preferably smaller than the groups of the active metal precursor. The groups bound in the reductant are preferably between 1 and 24, particularly preferably between 1 and 6 carbon atoms and may optionally contain groups linked by a heteroatom which can stabilize the reductant as Lewis bases. The groups in the reductant are preferably selected from alkyl groups, alkenyl, aryl, a cyclopentadienyl radical and its derivatives, as well as a hydride group. By metal promoter is meant the metal that forms the promoter in the finished catalyst. The promoter is generally present as oxide. In the case of a catalyst for the synthesis of methanol, the promoter metals are zinc and possibly aluminum. That is to say, as active metal precursors, respectively as reducing agents, certain metal-organic compounds can advantageously be considered for the inventive method. Metal-r-organic compounds should be understood as follows: 1. Metallic complexes in which the presence of direct metal-carbon bonds is present.; 2. Metal complexes in which, despite the absence of metal-carbon bonds, there is a content of ligands (linked in a coordinative way) that are organic in nature, that is, they belong to the family of hydrocarbon compounds, respectively derivatives of these, "metal-organic", therefore, differ from purely inorganic metal complexes that do not contain metal-carbon bonds or organic ligands. The sequence in which the at least one active metal precursor is applied and the at least one reducer on the porous support is not limited in this way in any way. It is possible to first impregnate the support with the active metal precursor and subsequently apply the reductant to precipitate the active metal in the support. But it is also possible to first apply the reductant to the support and then the active metal precursor. It is also possible to apply the active metal precursor and the reductant in the support repeatedly in alternating form. The active metal precursor, or the reducing agent, is absorbed there first physically or chemically at the surfaces of the porous support, in particular at the surfaces of the cavities. The active metal of the active metal precursor is then freed and precipitated by addition of the respective complementary component. In the inventive method, special support materials are used in which the active metal and the promoter are precipitated. The support materials are characterized by a high porosity that can be adjusted in the nanometer area and with this by an extremely high specific surface area. The inventors start from the ideal model that the cavities respectively the pores act as dimensionally delimited reactive chambers for the reduction of the active metal precursor, so that an undesirable particle growth during the preparation of the catalyst is avoided. The cavity has a comparatively small opening, so that the active metal precursor can diffuse into the cavity in a controlled manner and precipitate there. In each cavity, therefore, only a limited amount of the active metal is precipitated. On the walls of these reaction chambers, the metal. active is found after the release, therefore, in a nano-dispersed form. The maximum diameter of the particles does not exceed - in at least one direction - the diameter of the pores that are located, when using for example an MCM-41 - around 2 nm. In other steps of the method, in which the catalyst is heated, for example, at higher temperatures, an exchange between the different cavities is no longer present, so that a growth of the catalytically active particles is suppressed and the nanoparticular distribution is retained. dispersed from catalytically active centers. In addition, the long-term stability of the catalysts under process conditions is favorably influenced. The active metal precursors and reducing agents are preferably adsorbed on the inner surface of these support materials and thus make immediate chemical contact in a very controlled manner. This has a favorable effect on the efficiency of the reductive process, the dispersion of the active metal particles and the promoter components. In this way, a contact on the surface, respectively, on the sufficiently tight limiting surfaces of support, active metal particles and promoter components is guaranteed in a novel manner. If the catalytically active metal component comprises several metals or metal compounds, for example metal oxides, then these have intensive contact since the individual components are present in each case in nano-dispersed form. The particular feature of the inventive method is that - contrary to other known impregnation methods, by a chemical reaction between the active metal precursors and the reducing agents (reduction, respectively link metathesis or similar) the active metal is separated and chemically fixed in a reactive chamber delimited to nanometer-scale dimensions, ie in close contact in a catalytically relevant manner. In the storage form of the air-stable catalyst, the active metals are generally present in the form of an oxide. Exceptions form very precious active metals, such as Pt and Pd, etc. The oxides are formed as a result of atmospheric oxidation after the preparation of the catalyst. However, it is possible with methods established according to the state of the art to oxidize the metallic form only in parts, by means of special stabilization measures. The active metal is then passivated by a thin layer of oxide. After loading the reactor, the catalyst can be transferred back to its active form by a new soft and simple reduction. For this purpose, for example, these oxide layers are reduced with hydrogen. In particular in consideration of catalyst regenerations, the quality of the catalytic activity of the system is not modified, as well as its chemical composition and structural characteristics by repeated oxidation and reduction cycles.; that is, a corresponding catalyst regeneration is advantageously made possible to re-establish the original catalytic activity. The active metal is preferably selected from the group consisting of Al, Zn, Sn, Bi, Cr, Ti, Zr, Hf, V, Mo, W, Te, Cu, Ag, Au, Ni, Pd, Pt, Co, Th, Go, Faith, Ru, as well as You. It is possible for the active metal to comprise only one metal from the group mentioned above, for example copper or zinc. However, it is also possible that the active metal comprises several metals of the group referred to, for example, two or three metals. The metals can be present, in this form, in reduced form as pure metal or also as metal compound, in particular metal oxide. As already mentioned, the active metal is generally present, in the transportable presentation of the catalyst, in at least partially oxidized form, so that the catalyst is sufficiently stable also being exposed to air. According to a preferred embodiment, the promoter metal is selected from the group consisting of Al, Zn, Sn, rare alkali metals, as well as alkali metals and ferrous alkalines. Suitable as ferrous alkali or alkali metals are, for example, Li, Na, K, Cs, Mg and Ba. For the catalyst, the active metal and the promoter metal are selected so that they are different. That is to say, in the inventive method, special reduction means containing metals are used which are referred to herein as reducing agents. These reducers release the active metals, essential for the catalytic characteristics, of the respective previous chemical stages (precursors of active metal), in which these metals are present bound in a defined manner, by means of a particularly efficient chemical reaction but simultaneously very careful. As reducing agents they find use metal-organic compounds such that they contain a metal that acts as a promoter of the active metal that is catalytically active. When producing a catalyst for the synthesis of methanol according to the inventive method, or a reformer for fuel cell technology, the catalyst preferably comprises the Cu / Zn / Al system. The proportions of atomic numbers of Cu / Zn / A are in the typical area between 1: 2: 0.1 to 2: 1: 1. Copper can be introduced into this by an appropriate active metal precursor, zinc by a reducer and aluminum through the porous support. The active metal precursor is preferably a compound with the formula MeXpLc, where I designates an active metal, X is selected from the group of alcoholates (OR *), amides (NR2 *), β-diketonates (R * ( = 0) CHC (= 0) R *) and its nitrogen analogues, in particular ß-ketoiminates (R * (= 0) CHC (= NR *) R *) and ß-diiminates (R * (= NR *) CHC (= NR *) R *), | carboxylates (R * C00), oxalates (C2O4), nitrates (NO3) and carbonates (CO3), where R * denotes an alkyl radical with 1 to 6 carbon atoms, an alkenyl radical with 2 to 6 carbon atoms, an aryl radical with 6 to 18 carbon atoms and in addition the radicals R * may be the same or different, p is an integer corresponding to the valence of the promoter metal, or is an integer between 0 and the amount of free coordination sites of the metal promoter atom and L is an organic ligand of Lewis base comprising oxygen or nitrogen as a ligand atom. L and X may comprise, in this, only one type of the referred radical ligands respectively. It is possible, however, also to provide for combinations of the referred groups. According to one embodiment of the inventive method, the reductant is a compound of the formula MRnLm, where M represents a promoter metal, R is an alkyl radical with 1 to 6 carbon atoms, an alkylene radical with 2 to 6 carbon atoms, an aryl radical with 6 to 1.8 carbon atoms, a cyclopentadienyl radical or its derivatives or a hydride group, where the radicals R can be the same or different, n is an integer corresponding to the valence of the metalL is an organic ligand of Lewis base comprising oxygen or nitrogen as a ligand atom and an integer number between 0 and the amount of free coordination sites of the active metal atom. Also in the case of the reductant it is valid that as the radical R and the ligands L only one type of the referred groups can be used. But it is also possible to combine different groups. According to one embodiment of the inventive method, the reductant is a compound of the formula MRnLm, where M denotes a promoter metal, R is an alkyl radical with 1 to 6 carbon atoms, an alkylene radical with 2 to 6 carbon atoms, an aryl radical with 6 to 18 carbon atoms, a cyclopentadienyl radical or its derivatives, or a hydride group, where the radicals can be the same or different, n is an integer corresponding to the valence of the metal, L an organic ligand of Lewis base comprising oxygen or nitrogen as a ligand atom, and m an integer between 0 and the number of free coordination sites of the active metal atom. Also in the case of the reducer it applies that for the radical R and the ligand L only one type of the referred groups can be used. But it is also possible to combine different groups. As ligands, for example, compounds of the formula OR 'R "or NR'R" R "' may be used, where the radicals R ', R" and R "' denote an alkyl group having 1 to 6 carbon atoms, two of these radicals can also form a ring together with the heteroatom, Particularly preferred are reductants of the formula MRnLm selected from ZnR2Lm and AlR3Lm, with m = 0, 1 or 2, where R and L have the meaning indicated above In general, the active metal precursors with which the porous support is loaded are selected in such a way that they react with each other respectively with the aforementioned reducers due to a complete or partial X / R exchange in the bounded reactive chambers to form types of the composition MeRx (x = m), which in turn are then transformed by reductive elimination of R2 or fragments of R2 due to ß-? elimination and separation of hydrogen / alkene or radical decomposition to the elemental metal or a reduced form compared to the active metal precursor MeXpL0. The aforementioned active metal precursors and reducers can be applied in solution in the porous support. The solvent, as well as the active metal precursors or the reductants are adjusted to each other in such a way that decomposition does not occur in the solvent. After loading the support with the active metal precursor, the solvent is removed together with the excess active metal precursor. In order to remove solvent residues, the charged porous support can first be dried first. The reducer, which is again a metal-organic compound, is then applied to the porous support. The reductant reduces the active metal precursor applied first, so that the catalytically active active metal is precipitated and fixed in the porous support. This procedure can be carried out without. However, also in reverse order, that is, the porous support is loaded first with the reducer and then with the active metal precursor. It is particularly preferred that the components of the individual metal oxides or metals are, however, applied by chemical vapor deposition (CVD) in the porous support. In this case, the active metal precursors or precursors are preferably at 298 K at a vapor pressure of at least 0.1 mbar. In a particularly preferred embodiment of the inventive method, metal-organic complexes are therefore used both as active metal precursors and also as reducing agents. Also combinations of these methods are possible. It is possible, for example, to apply the active metal precursor in solution and then the reductant by chemical deposition in the vapor phase. The active metal precursor can also be applied firstly by chemical vapor deposition and then the reductant in solution. The porous support may consist of a discretionary matter. The support should include, however, the cavities described above comprising a relatively small opening with the dimensions mentioned above. Suitable, for example, are the aforementioned MOF systems as porous support materials. Because the catalysts are used mainly at higher temperatures, it is preferred that the support be constituted of an inorganic material. Examples of suitable inorganic materials are zeolites, PMS, layered silicates such as bentonite, clay or pillars, hydrotalcites, as well as heteropoly acids, for example molybdenum and tungsten. In particular, however, mesoporous silicate materials (PMS) are preferred since they have a very high specific surface and the pore structure can be precisely adjusted. Examples of the above are MCM-41, MCM-48 or SBA-15. In the case of zeolites, on the other hand, those having a large pore radius are preferred. Zeolites with a pore radius of = 0.7 nm are, for example, mordenite, VPI-5 or cloverite. The production of the catalyst is carried out under extremely mild conditions. For example, a temperature of 200 ° C is preferably not exceeded in the production of the catalyst. The active metal is deposited, thanks to this, in highly dispersed form, the diameter of the produced particles of the active metal being generally located in the area of approximately 0.5 to 10 nm, preferably 0.5 to 5 nm. The promoter is also precipitated in highly dispersed form, so that a very large contact area between the active metal and the promoter can be achieved. This produces catalysts with very high activity. Object of the invention is, therefore, also a catalyst, in particular for the synthesis of methanol, comprising a porous support, as well as at least one active metal deposited in the porous support and at least one promoter deposited in the porous support, wherein the porous support has a specific BET surface of at least 500 m2 / g, the active metal a specific metal surface of at least 25 active m2metai / active gmetai and the promoter a specific surface area of at least 100 m2 / gpr0motor preferably at least 500 m / gpromotor. The specific surface area of the active metal can be determined by the gas adsorption / desorption method or by the reactive gas adsorption / desorption method. Such a method is, for example, reactive N20 front chromatography to determine the specific surface area of copper. Analogous methods can be used for other active metals. They are generally based on the coating of the metal surface with a molecule with a known space requirement, being that "the amount of adsorbed molecules is determined." The specific surface of the promoter can be estimated by determining the degree of aggregation by analysis of X-ray absorption and by determination of BET surface in the charged support The content of the promoter component can be determined by elemental analysis (for example, atom absorption spectroscopy or energy dispersion X-ray absorption spectroscopy). distinguishing characteristic of the catalysts produced according to the inventive method in comparison with catalysts produced according to alternative methods, in particular by Co / calcination precipitation, is the extremely low degree, until almost nil, of the promoter component (detectable by absorption analysis of X-rays) , having simultaneously a high BET surface of the active catalyst of preferably much greater than 500 m2 / g. It is usually not possible to determine a measurable degree of coordination. When measuring the catalysts with X-ray fraction methods it is not possible, in this case, to observe fraction reflections for the promoter. When measuring the catalyst with X-ray absorption spectroscopy, only very low aggregation states are obtained. This means that the atoms next to the adjacent ones, respectively, next to these of a promoter atom are generally not promoter atoms. In general, maximally the atom next to the contiguous atom or the one following it is again a promoter atom. In other words, the promoter is preferably present in the form of a promoter of two or three layers at most. In addition, a very low degree of aggregation of the active metal component is typical, which is noted in particular because the metal particles, for example copper, are distributed on the (internal) surface of the support in such a homogeneous manner and with such low dimensionality , which can not be detected and characterized as well formed particles by transmission electron microscopy methods, while a low but detectable degree of aggregation of most particles can be characterized by X-ray absorption measurements, such as It has been described. The active metal preferably has an average coordinated number of 10 in the inventive catalyst. Preferably, the coordinate number is less than 10, with particular preference between 4 and 7. Often a coordinate number of about 6 is observed. As the active metal particles are preferably very small, the coordinate number does not change if the metal active is transferred to the oxidized form, for example for transportation from the production site to the synthesis reactor. The maximum crystallite size of the active metal respectively of the promoter is delimited in each case by the maximum pore diameter in one dimension. The inventive catalyst comprises a porous support preferably having cavities open to one side. The opening of these cavities has at least along a dimensional direction a diameter of about 0.7 to about 20 nm, preferably 0.7 to 10 nm, particularly preferably about .7 to 5 nm. The porous support is further characterized by a high specific BET surface area of at least 500 m2 / g. preferably at least about 600 m2 / g, particularly preferably at least about 800 m2 / g. These high specific surfaces are also measured in the finished catalyst. The specific surface is certainly reduced a little by the coating with the active metal and the promoter. But the finished catalyst still has a very high BET surface compared to conventional catalysts of at least 500 m2 / g, preferably at least about 600 m2 / g, particularly preferably at least about 800 m2 / g. The porous support has a charge with at least one catalytically active metal component that is present in highly dispersed form. In this case, the load amounts to at least about 2.5 m2 active catalyst / preferably about 3 m active metal 9"catalyst", particularly preferably about 5 m2 active catalyst "It is possible, however, to achieve a charge still higher. This is in the area greater than 10 Kl2metal activeg '' 'catalyst up to 20 m2 active metal 1catalyst · In other words, the loading with the active metal reaches at least about 25 m2metai active g_1metai active, preferably at least about 35 m2metai active g ~ Snetai active / with Particular preference is given to at least about 50 m2 active m active g_1metai- In particularly preferred cases, the load reaches more than 100 active m m2 active g_1metai, in particularly preferred cases more than 200 m active metal and active metal- The loading of the catalyst with the metal active is preferably selected in the area of. about 0.05 to 0.50 active g-1 catalyst / preferably about 0.1 to 0.45 active gmetai g-1 catalyst, particularly preferably about 0.1 to 0.30 active gmetai g-1 catalyst / Y the charge with the promoter is preferably selected in the area of about 0.01 to 0.3 gPromotor _1cataiizador / preferably from approximately 0.05 to '0.2 gPromotor g ^ cataiizador with particular preference approximately 0.05 to 0.15 gpromotor g_1cataixzador · The indicated values respectively areas of values refer in every case to the metal respectively to the metal promoter. The proportion of active metal / metal promoter is normally selected in the. area from about 10: 1 to 1: 5, preferably from 5: 1 to 1: 2, in particular from about 5: 1 to 1: 1. During the production of the catalyst, both active metal and as little promoter as possible are preferably introduced. possible. Preferred supports, metals and promoters have already been explained in the context of the inventive method. The catalyst that can be obtained by the inventive method entails a series of advantages, as explained below by means of the example of an embodiment of the inventive catalyst as a catalyst for the synthesis of methanol. The inventive catalyst differs from the known Cu / Zn / Al catalysts for the synthesis of methanol by the following criteria: (1) The dispersion of the Cu component (respectively of the active metal) is greater, at least 25%. , with the same mass proportion of catalytically active Cu component, the inventive catalyst is more active, respectively, for the same activity a lower proportion of copper (active metal) is sufficient in the inventive catalyst compared to the known catalyst. The analytical characterization of the catalyst by EXAFS (extended X-ray absorption fine structure spectroscopy) and CDR (X-ray diffraction) prove that most Cu particles have one dimension near or below 1 nm, which typically means aggregations about 10-20 Cu atoms, the minority of Cu particles have channel width dimensions respectively pore of the PMS support matter, at most. (2) Unlike known Cu / ZnO / Al203 catalysts, the components of ZnO and aluminum oxide (promoter) are not added in an orderly manner. They form, according to the EXAFS data, rather a thin coating of the inner walls respectively of the surfaces of the support material. In this way, the specific surface area of the ZnO component achieves the magnitude of the specific surface area of the support material (> 500 m2 / g) and exceeds by much surface-rich ZnO support materials, known hitherto, with its surfaces Specific BETs of up to approximately 150 m2 g-1. [M. Kurtz, N. Bauer, C. Büscher, H. Wilmer, O. Hinrichsen, R. Becker, S. Rabe, K. Merz, M. Driess, RA Fischer, M. Muhler, "New synthetic routes to more active Cu / ZnO catalysts used for methanol synthesis ", Catalysis Letters 2004, 92, 49; C. R. Lee, H. W. Lee, J.S. Song, W.W. Kim, S. Park, "Syn-thesis and Ag recovery of nanosized ZnO powder by Solution combustion process for photocatalytic applicatlons", Journal of Materials Synthesis and Processing 2001, 9, 281; T. Tani, L. Madler, S. E. Pratsinis, "Homogeneous ZnO nanoparticles by fíame spray pyrolysis", Journal of Nanoparticle Research 2002, 4, 337.]. The inventive catalyst does not have - unlike the catalysts Cu / ZnO / Al2C > 3. known - nanocrystalline components of ZnO respectively Al203 detectable with TEM or XRD methods. These criteria are not valid only for a catalyst for the synthesis of methanol with the Cu / ZnO / Al203 system but are also transferable to all the catalysts that can be obtained by the inventive method. The inventive catalysts are characterized by a very high activity referred to the mass ratio of the catalytically active metal components. They are particularly suitable, therefore for use as a catalyst for the synthesis of methanol or as a reformer in the cell technology of gas. In summary it can be said that the advantages of the invention, considering preferred embodiments, "consist 1. of mild process conditions (in particular lower preparation temperatures, in particular temperatures below 200 ° C) which suppresses particle growth processes. which are unavoidable according to the state of the art 2. In the combination of active metal precursors with reducing agents containing metals (reducing agents) which allow an unusually high dispersion of active metal components (active metals) and promoter components simultaneously with high surface contact respectively of metal-metal oxide-promoter boundary area 3. In the possibility conditioned to the new method of controlling the composition of the catalyst system without undermining the high dispersion by permutation and / or cyclic repetition of the stages load individual respectively reaction; 4. in the omission of charges salt or stabilizer problems, as required in impregnation technologies based on colloidal chemistry methods, according to previous technology; 5. in the use of porous support materials such as reaction chambers dimensionally limited for the metathetic surface reaction, critical for success, between different precursors. The dimensionally constrained reaction chambers (defined geometrically by the pore characteristic of the porous support system) suppress undesirable particle growth thanks to their own geometry. This is supported in a particularly favorable manner by the higher optimated ratio compared to less porous supports from surface to volume in porous supports. The mentioned support characteristics therefore counteract the segregation of the components. This guarantees a high dispersion of the catalytically active components and a high specific loading of the support. The invention is explained below by means of examples as well as with reference to the appended figures. In these show: Figs. la: le: strongly schematized representation of the mechanism that regulates the deposition of the active metal and the promoter metal according to the inventive method; Fig. 2: X-ray powder diffractograms of the samples: a) the previous stage obtained at room temperature Cu / [Zn (OCH eCH2NMe2) 2] / MCM-41, b) the catalytically active sample Cu / ZnO / MCM- 41 as well as c) the comparative sample ZnO / MCM-41 and 'd) the comparative sample Cu / MCM-41. As an orientation, the polycrystalline copper reflection positions are marked on the abscissa (111), (200) and (220).

Fig. 3: small angle powder diffractograms of a) calcined vacuum MCM-41 and b) Cu / ZnO / MCM-41. The characteristic intensity reduction of b) with respect to a) gives an indication of the pore load. In the TEM shot shown additionally, the intact pore structure is clearly visible; Copper or zinc oxide particles, however, can not be identified due to their tiny size. The presence of copper and zinc is checked by the associated EDX spectrum (X-ray fluorescence analysis of scattered elements, for its acronym in English). Figs. 4a-4c: 4a) CuK-XANES spectra and 4b) CuK-EXAFS (amount of Fourier transforms) with Cu / ZnO / MCM-41 and reference substances, 4c) Cu / ZnO / MCM-41 spectrum analysis; model parameter: contiguous: Cu; distance (R) = 2.512 ± 0.002 Á, number of coordinates (N) = 5.8 ± 0.3, Deby-Waller factor (s2) = 9.6 ± 0.4) * 10"3 Á2 Contiguous O: R = 1.86 ± 0.04 Á, N = 0.3 ± 0.1, s2 = (7 + 0.11) * 10 ~ 3 Á2 Fig. 5: Reaction of [Cu (OCHMeCH2NMe2) 2 with diethyl zinc in the nanotubules of support material MCM-41 'Figs. they show a schematic representation of the mechanism that controls the depoeition of the active metal and the promoter according to the inventive method It is understood that this represents only a model concept and should not have any limiting effect on the scope of the invention. Fig. 1 shows a section through a porous support 1 in which a pore 2 which is open towards the external face of the support 1 extends. The support 1 can be, for example, a zeolite. A precursor 3 of active metal and a reducing agent 4 are diffused. The charge can be carried out in this way in such a way that the porous support 1 is charged with the precursor 3 of active metal and then with the reducer 4. But it is also possible to load the porous support 1. first with the reducer 4 and then with the precursor 3 of active metal. If the mixture of precursor 3 of active metal and reducing agent 4 is sufficiently stable at charging temperature, it is also possible to carry out the charging simultaneously. The active metal precursor 3 comprises an active AM metal in which groups L are bound. In FIG. 1, the active AM metal carries two L groups for reasons of greater clarity. But it is also possible that the active metal precursor 3 comprises more than two L groups. In addition to the L groups, the active AM metal can still carry other ligands that stabilize the active metal precursor, for example, by coordinative binding. The L groups are linked to the active AM metal by a ligand atom (not shown). The ligand atom is selected from oxygen, sulfur, nitrogen and carbon. The reductant 4 comprises a PM metal promoter in which organic R groups are linked through a carbon atom. In Fig. 1, the reducer comprises, for reasons of clarity, only two R groups. But it is also possible that there are more than two R groups linked to the PM metal promoter or that, in addition to the R groups, others are still linked. Groups with the metal PM promoter. The letters x and y correspond to the molar ratio used of promoter 3 of active metal and reducer 4. As a key step of the deposition, an exchange of ligands is now carried out between the active AM metal and the metal PM promoter. This is shown in Fig. Ib. A reactive intermediate compound 5 comprising the active AM metal as well as the R groups is generated. In addition, the promoter compound 6 comprising the PM metal promoter as well as the L groups is obtained. The reactive intermediate compound 5 is then decomposed. This decomposition process is supported or initiated, for example, by heating. The active metal contained in the reactive intermediate compound 5 is reduced in this to the active AM metal and is deposited in nanodisperse form as crystallites 7 in the walls of the pores 2 (Fig. 11). Simultaneously generated from the R groups, for example, in a metathetic reaction, the compound R-R. This can be aspirated as an exit gas. The promoter compound 6 is still oxidized, so that the promoter metal is deposited as a PR promoter, for example in the form of an oxide, also in the nanodisperse form as crystallites 8 in immediate vicinity with the crystallites 7 of active metal in the walls of the pores 2. The L groups are released in this and can also be sucked together with the exit gas. Example 1: Cu / ZnQ / MCM-41 MCM-41 freshly synthesized, calcined and dried (350 mg) is placed together with a portion of approximately .0 g of [Cu (OCHMeCH2NMe2) 2] in separate glass vessels in a tube bond and heat in the static vacuum (0.1 Pa) for 2 h at 340 K. A sample of 200 mg of the blue product material and approximately 0.5 g of diethyl zinc are placed next to each other in the same manner as described in the foregoing and left for 2 h in the static vacuum (0.1 Pa) at room temperature. The variation of evaporation time, temperature, amount of substance and PMS material produces different loads (table 1). To produce the ZnO, the sample Cu / [Zn (OCHMeCH2NMe2) 2] / MCM-41 was removed under protection gas and then tempered in the dynamic vacuum (0.1 Pa) at 623 K (2 h). Proceed in a corresponding manner with the other PMS materials, such as MCM-48. Example 2: Cu / MCM-41 and ZnO / MCM-41 Temperate [Cu (OCHMeCH2NMe2) 2] / MCM-41 (see above) in the dynamic vacuum (0.1 Pa) at 523 K (20 min) produces Cu / MCM- 41 Analogously, ZnO / MCM-41 is obtained using [Zn (OCHMeCH2NMe2) 2] as a precursor of ZnO after the intermediate stage [Zn (OCHMeCH2NMe2) 2] / MCM-1 is cooled to 623 K (0.1 Pa, 2h). [Zn (OCHMeCH2NMe2) 2] / MCM-41 was obtained by impregnation of MCM-41 with a solution of [Zn (OCHMeCH2NMe2) 2] (1.0 g) in pentane (40 ml) and repeated washing of the separated solid substance. Alternatively ZnO / PMS can be obtained by treating the supports with diethyl zinc steam followed by calcination. Characterization of the samples X-ray powder diffractograms (PXRD) were plotted using a DQ-Advance Bruker AXS diffractometer with Cu? A radiation (? = 1.5418 Á) in T-20 geometry and a position sensitive detector (capillary technique, protection gas). All diffractograms were adjusted using Profile Plus 2.0.1 software using a pseudo-Voigt function. TEM analyzes were performed with a Hitachi H-8100 device at 200 kV with a tungsten filter (preparation under exclusion of air, Gold-Grids Plano, vacuum transfer support). X-ray absorption spectra (XAS) were taken at the Hasylab (DESY, Hamburg) in station XI in a double crystal monochromator Si (311) in transmission (Software VIPER). Measurements of nitrogen adsorption were made with a Quantachrome Autosorb-1 MP device. The pore diameter was calculated according to the Barrett-Joyner-Halenda method (BJH). The specific surface area (SBET) of the empty calcined MCM-41 and the CuOx / MCM-41 was determined with the help of the data of the linear part of the BET graph (p / p0 = 0.05-0.35). Table 1 properties relevant to the catalysis of Cu / ZnO / PMS samples. production rate 1 in [μta? 1? ß ??, 8"'?»? · 1 ?!] m Cu Cu ZnOlh] 71 86 80 13.8 10-90 10-75 167 184 172 27 30-50. 20-40 Cu ZnO / MCM-41 19 4.1 · · 6.85 10.44 Cu / ZnO / MCM-41 36 5.8 9.30 15.57 CWZnO / AfeOj MC - 62 10.2 8.70 14.5 41 (@% by weight Al: 6.3) Cu / ZnOMC S 130 22.4 10.62 21.95 Cu- surface Cu / MC -41 5-7 mW nn w · | 10-12 Kat ZnO / MCM-41 - - nn M - 20.75 [a] The copper surface was determined by N20-RFC. After pretreatment with a dilute atmosphere of H2 (2% by volume), N20 (1% by volume N20 in He, 300 K) was passed through a catalyst and the copper surface was calculated based on the amount of nitrogen released (density of Cu surface atoms: 1.47 | 1019 rcf2). The methanol synthesis activity was analyzed under normal pressure and at a temperature of 493 K. A mixture of 72% H2, 10% CO, 14% C02 and 14% He was used as synthesis gas. The indicated data were obtained after a reaction time of 2 h. Based on the low transformation of the substance at normal pressure, no other products apart from methanol could be detected. [b] specific catalysis data of catalysts produced by co-precipitation, whose MeOH synthesis capacity was determined under conditions analogous to the Cu / ZnO / PMS samples. They were interpolated (Cu / ZnO) respectively extrapolated (Cu / ZnO (A1203) from the regression analysis (production rate as a function of the Cu surface of the catalysts of different metal concentration) the production rates in relation to the surfaces of Cu found in Cu / ZnO / PMS The data for the comparative samples come from: T, Genger, Dissertation, Ruhr-Universitát Bochum, 2000. [c] unverifiable Additional characterization of the samples: if a portion is exposed ( 350 mg) of pure, freshly calcined MCM-41 (0 BJH = 2.7 nm, SBET = 712 m2 g_1) in the static vacuum (0.1 Pa) to the steam of a portion (1.0 g) placed next to the blue Cu precursor violet [Cu (OCH eCH2NMe2) 2] (1) at 340 K in a tight-sealed connection tube, then the originally colorless silica material is colored light blue.The Cu precursor [Cu (OCHMeCH2N e2) 2] remains in this intact, as the comparison of the IR data of the MCM-4a loaded with [Cu (OCH MeCH2NMe2) 2] pure. The adsorption is strong, since [Cu (OCHMeCH2NMe2) 2] can not desorbérse neither at higher temperatures (373 K) in the dynamic vacuum (0.1 Pa, 24 h). The absence of IR absorption observed in other circumstances at 3745 cm "1 for free silanol groups indicates a reciprocal activity of the pore walls with [Cu (OCHMeCH2NMe2) 2], probably through hydrogen bonds. then in a second stage the support loaded with [Cu (OCHMeCH2NMe2) 2] with diethyl zinc vapor, placing both samples in a connecting tube next to each other and evacuated under seal (0.5 g, ZnEt2, 300 K, 0.1 Pa), then there is a successive color change from light blue to red brown In the X-ray powder diffractogram of a sample of the matter prepared in a capillary under inert gas it is presented at 2 T = 44-70 ° a weak, very broad structure that can be associated with the reflection of the network plane [111] of small particles of Cu. {Flg. 2 and 3) The NMR spectroscopy of solid bodies proves the presence of [Zn (OCHMeCH2NMe2) 2] (2) as a secondary product.This reaction occurs in the The nano-tubules of the PMS correspond to the reconstructable quantitative transformation at the scale of .grams of preparation, according to Flg. 5, in which Cu metal (XRD) is precipitated, the zinc alkoxide [Zn (OCHMeCH2NMe2) 2] remains in solution (NMR identification) and butane escapes as gas (GC-MS). It should be noted that in a reduction of the reactivity of the zinc alkyl used, for example by the use of very large alkyl radicals such as C (SiMe3), the alkyl / alkoxide metathesis is removed and zinc complexes were isolated and characterized structurally. alkyl / copper alkoxide in the form, whose solid substance pyrolysis hitherto only produced catalytically inactive microcrystalline Cu / ZnO materials. Careful tempering of the samples thus obtained from Cu / [Zn (OCHMeCH2NMe2) 2] / PMS at 623 K in the dynamic vacuum (0.1 Pa, 2 h) produces materials largely free of CHX that still show a Cu (111) - very wide. But there are no genographic indications of ZnO nanocristalites [Flg-. 2) . The specific Cu surfaces of the Cu / ZnO / PMS samples were determined before and after the catalysis tests with respectively 5-6 m2Cu-g_1 (Table 1). The methanol production capacities between 19 and 130 μ? T ??? . g_1Kat | h-1 are in the area of the binary Cu / ZnO catalysts, prepared by co-precipitation / calcination, respectively, they surpass them in the case of the sample of MCM-48 with surprising clarity. The three-dimensional pore structure of the MCM-48 support allows more efficient diffusion compared to NCM-41. The reduction (H2) of samples stored in the air, completely oxidized (disappearance of the Cu (111) reflex) regenerated the original activity respectively the Cu surface. The comparative samples of Cu / MCM-41 (10-12% by weight; 5-7 m2Cu.g-1Kat and ZnO / MCM-41 that were obtained by tempering with [M (OCHMeCH2NMe2) 2] / MCM-41 (M = Zn, Cu), respectively treatment of MCM-41 with zinc diethyl vapor and calcination, turned out to be inactive. For freshly prepared samples of Cu / ZnO / PMS, unusually high values for Cu surfaces of up to 50-60 m2C- _1Kat / were measured in the first oxidation / reduction cycles (N2O / H2) but decreased in the subsequent course of the characteristic level of 5-6 m2Cu · g_1Kat · This discrepancy is apparently not due to the sintering of the Cu particles, but is conditioned by groups of O-Zn-C2H5 bound to the pore wall of the PMS and surplus, with reference to the scheme 1, which are also oxidized by N20. . The EXAFS spectra (Figs 4a - 4c) confirm the presence of very small Cu aggregates. The determined number of coordinates of 5.8 and the Debye-Waller factor quite high already from the first metal layer indicate a high degree of lack of order. If the presence of spherical, mono-dispersed particles is assumed, a diameter of 0.7 nm can be calculated, which corresponds to an aggregate of 13 Cu atoms. Even assuming an excessively low estimate of particle size due to the correlation of number of coordinates and Debye-aller factor, 'the total absence of higher coordination layers indicates that the characteristic dimension of the particles is surely below 2- 3. nm. Cu aggregates are present in a particle size distribution, from which the X-ray deflection only records the coarse dispersion proportions (about 2 nm). The Cu-Cu contact, calculated from the position of reflections of 2 T = 44.35 °, of 2.50 Á corresponds to the value obtained from the EXAFS data of 2.51 Á is shorter compared to the Cu Cu distance of the phase of Bulk with 2.56 Á (effect of small particles). The origin of Cu-0 coordination can not be interpreted with confidence. In view of the low average particle size it is apparent that the oxygen atoms of the pore wall are already detectable in the EXAFS spectrum, as described in the literature. It can not be excluded, therefore, that a small proportion of copper is present in the form of Cu +. The comparison of the ZnK spectra with test substances (not shown) does not produce a match either for ZnO or for Zn. Thus, for the first sphere of 0 an intensity is too low and the second sphere (Zn) is almost completely absent. With Si and Zn, as neighbors closest to the next, the adequacy is good, which indicates - in coincidence with the NMR data of solid bodies and IR (absence of free groups of silanol) a coating of the pore wall with ZnO The degree of aggregation of the ZnO components, therefore, is almost nil. Similar is true for the ZnO / PMS materials that were obtained by aqueous impregnation and calcination techniques. It was not possible to extract clear indications about CuZnOx species, respectively Cu-O-Zn coordination. Methanol catalysts based on Cu can be grouped into three classes: in binary systems Cu / Al203 (I), Cu / ZnO (II) and the ternary system Cu / ZnO / Al203 (III). For materials prepared in classical form, the activity is correlated at different levels in each case, increasing from I to III, in linear form depending on the specific Cu surface. The activity that we have found for the sample Cu / ZnO / MCM-48 of 130 μp ??? . g_1Kat.h_1 is now located far above the value that can be expected for binary Cu / ZnO catalysts with the same specific surface and is already in area III. Reciprocal activity of the Cu particles with the silica matrix is hardly the cause of this, since comparative Cu / PMS samples were inactive and the pore walls of the active Cu / ZnO / PMS samples are apparently coated with ZnO, such as explained in the foregoing. It seems rather that the high simultaneous dispersion of the Cu and ZnO components is a new effect, positive. A crystalline, aggregated ZnO (nano-) phase, as necessarily present after the co-precipitation / calcination formulas, are not necessary, quite clearly, for the synergistic effect. This coincides with the formation of Cu / Zn alloys referred to initially, as well as with our additional observations, in the sense that a Cu / Al203 catalyst produced with classical methods experienced a jump in activity following a brief treatment with zinc vapor. dietary beyond the region of ternary systems. In addition, the use of a special nanodisperse ZnO support material, in particular rich in surface or defects (153 m2.g_1) which was obtained by solid substance pyrolysis of [(Me3SiO) nMe] 4, produced a Cu / ZnO catalyst unusually active binary. The perspectives of the inventive method for the loading of PMS support materials, in particular for the preparation of Cu / ZnO catalysts, are: Not only the variation of dimension and structure of the pores (for example, CM-41 vs. MCM-48) or other suitable support materials), but also the utilization of the chemistry of the precursor substances allows a molecular control through the contact of active metal / promoter, for example, - Cu / ZnO. The results are interpreted to mean that the inventive method [surprisingly] allows simultaneous maximization of the specific active metal surfaces (for example, of the copper surfaces and the Cu / ZnO boundary area contact respectively of the dispersion of ZnO) and the boundary area contact between active metal / metal oxide respectively promoter and with this in principle nothing seems to inhibit a growth of catalytic activity much further than is possible until now.

Claims (6)

1. Method for the production of a catalyst comprising a porous support, at least one active metal and at least one promoter that is particularly suitable for the synthesis of methanol, characterized in that a porous support having a specific surface area of at least 500 m2 / g, at least one active metal precursor comprising at least one active metal in a reducible form is applied in the porous support, as well as at least one group that is linked by a ligand atom to the active metal atom, which preferably is selected from oxygen, sulfur, nitrogen phosphorus and carbon, the active metal precursor is reduced by a reductant comprising at least one promoter metal and at least one hydride group and / or an organic group that is linked by a carbon atom with the promoter atom, and the reducer is transformed into the promoter.

2. Method according to claim 1, characterized in that the at least one organic group in the reductant is selected from alkyl groups, alkenyl groups, aryl groups, a cyclopentadienyl radical and its derivatives, as well as a hydride group. Method according to claim 1 or 2, characterized in that the active metal is selected from the group consisting of Al, Zn, Sn, Bi, Cr, Ti, Zr, Hf, V, Mo, W, Re, Cu, Ag , Au, Ni, Pd, Pt, Co, Rh, Go, Faith, Ru, as well as Os. Method according to one of the preceding claims, characterized in that the promoter metal is selected from the group consisting of Al, Zn, Sn, rare alkali metals, as well as ferrous alkali and alkali metals. Method according to one of the preceding claims, characterized in that the active metal precursor is a compound of the formula MeXpLQ in which I denotes an active metal precursor, X is selected from the group of alcoholates (OR *), amides ( NR2 *), ß-diketonates (R * (= 0) CHC (= 0) R *) and their nitrogen analogues, in particular β-ketoiminates (R * (= 0) CHC (= NR *) R *) and ß-diiminates (R * (= NR *) CHC (= NR *) R *), carboxylates (R * C00), oxalates (C204), nitrates (N03) and carbonates (CO3), where R * denotes a radical of alkyl having 1 to 6 carbon atoms, an alkenyl radical with 2 to 6 carbon atoms, an aryl radical with 6 to 18 carbon atoms and in addition the radicals R * may be the same or different, p is a whole number which corresponds to the valence of the metal promoter, or is an integer between 0 and the amount of free coordination sites of the promoter metal atom and L is an organic ligand of Le is that comprises oxygen or nitrogen as a ligand atom. Method according to one of the preceding claims, characterized in that the reductant is a compound of the formula MRnLm, where M represents a promoter metal, R is an alkyl radical with 1 to 6 carbon atoms, an alkylene radical with 2 to 6 carbon atoms, an aryl radical with 6 to 18 carbon atoms, a cyclopentadienyl radical or its derivatives or a hydride group, where the radicals R can be the same or different, n is an integer corresponding to the valence of the metal, L an organic ligand of Lewis base comprising oxygen or nitrogen as a ligand atom and m an integer between 0 and the amount of free coordination sites of the active metal atom. 7. Method according to one of the preceding claims, characterized in that the active metal is copper and the zinc and aluminum promoter metal. Method according to one of the preceding claims, characterized in that the active metal promoter and / or the reductant are applied to the porous support by vapor deposition. Method according to one of the preceding claims, characterized in that the porous support is selected from the group consisting of porous silica minerals, zeolites, sheet silicates, clays, column clays, hydrotalcites, as well as heteropoly acids of molybdenum and tungsten. 10. Method according to one of the preceding claims, characterized in that the support is selected from the group of supports that is formed by mordenite, MCM-41, MCM-48, SBA-15, VPI-5 and cloverite. Method according to one of the preceding claims, characterized in that a maximum temperature of 200 ° C is not exceeded during the production of the catalyst. 12. Catalyst, in particular for the synthesis of methanol, comprising a porous support, as well as at least one active metal precipitated in the support and at least one promoter precipitated in the support, characterized in that the porous support has a specific surface area of at least 500 m2 / g, the active metal has a specific surface area of at least 25 active m2metai / active gmetai and the promoter has a specific surface area of at least 100 / 9promotor 1

3. Catalyst according to claim 12, characterized in that the catalyst has an average coordination number of maximum 10. 1

4. Use of a catalyst according to claim 12 for the synthesis of methanol or as a reformer for fuel cell technology .