Metal oxides produced from metal-organic framework materials

Translation of description of equivalent WO 2007118843 A1

p0001Metal oxides from metal organic frameworks

p0002description

p0003The present invention relates to methods for producing metal oxides from the porous metal organic framework materials, metal oxides, which are obtainable from these methods and their use.

p0004Metal oxides are an interesting group of substances or phrases to be used for numerous arrival.

p0005Not least for this reason, there are numerous methods in the art to obtain such metal oxides. In addition to attracting example from ores, the large-scale display, particularly high-purity metal oxides a possibility represents.

p0006Starting materials such representation methods can be of various kinds. For example, α-alumina is produced from bauxite. γ-Al₂θ3, which is known for its porosity, can be represented for example, gibbsite or boehmite are the, which at a temperature above 1000 ° C, the γ-Al₂θ3 in OC-AI₂O3 passes. Y-AI₂O₃ for example, serves as an adsorbent, catalyst or catalyst support.

p0007For the production of metal oxides, organometallic compounds. The presentation of the metal oxides may eg be generated using a chemical vapor deposition. This layer may be formed on respective substrates in particular. Moreover, sol-gel method, freeze drying or the production by flame are known.

p0008An interesting approach to representation of zinc oxide is from CY. Su et al., J. Am. Chem. Soc. 126 (2004), described 3576-3586. Here, first metal-organic framework materials are prepared, on the one hand from a metal ion (zinc) and an organic ligand (3-amino-1, 2,4-triazole or 3-amino-1, 2,4-triazole-5-carboxylic acid) is a form porous three-dimensional metal-organic framework. The heating of the framework material in an oxygen atmosphere leads at temperatures above 600 ° C the formation of zinc oxide.

p0009Porous metal-organic framework materials based on zinc are known in the literature and are characterized by a relatively high specific surface area, so that these materials are often proposed, for example, Adsorption of gases perform. Here, zinc terephthalate (MOF-5) is the best known.

p0010However, it is not known in the prior art, if the zinc oxide formed from a metal-organic framework material has properties which can represent the use of such an oxide as promising.

p0011An object of the present invention is thus to provide methods for the production of metal oxides and such metal oxides in order to supply them to a suitable application.

p0012The object is achieved by a method for producing a metal oxide which comprises the step

p0013- Heating a porous metal-organic framework material, wherein the scaffold material comprises at least one at least one metal ion coordinated to at least bidentate organic compound and the metal ion is selected from the metals consisting of Groups 2 to 4 and 13 of the Periodic Table of the Elements, on the complete decomposition temperature of the framework.

p0014The object is further achieved by a metal oxide obtainable by the method according to the invention.

p0015It has been found that the oxides of the above metals of the 2nd to 4th and 13th group which are prepared by the inventive process, have a comparatively high specific surface area and can be used as particularly in fields of use of the adsorption of substances. This compared to the prior art relatively high specific surface areas could therefore be explained by that the framework structure of the organometallic framework material is at least partially retained in the structure of the corresponding metal.

p0016Surprisingly, it has been found, however, that the known in the prior art zinc look of a metal organic framework having very low specific surface and thus is not particularly suitable to be fed to appropriate uses. It is therefore all the more surprising that this is possible with the metals according to the invention.

p0017The inventive method for producing a metal oxide is thus based on a step, wherein the porous metal organic framework material is heated. Here, the material may be present in a dispersion or as a dry solid. Furthermore, the metal-organic framework material can be present as a powder or as a shaped body or both. Heating takes place preferably with a porous metal organic framework in powder form.

p0018The heating may be effected by known methods to the skilled artisan. Typically, the heating is carried out in a suitable oven to, such as a muffle furnace or rotary kiln. When using an oven, it is also appropriate that opportunities are available to carry out the heating in the presence of a suitable atmosphere. For this purpose can be attached according a feed for a corresponding gas or gas mixture such in or on the oven so that the furnace chamber containing the porous metal organic framework can be flooded with the appropriate gas or gas mixture.

p0019The porous metal-organic framework material is heated to the extent as is necessary to convert the organometallic framework material in the corresponding metal oxide. Here, therefore, heated over the complete decomposition temperature of the metal organic framework.

p0020In the present invention, "complete decomposition temperature" is the temperature to be understood, wherein the porous metal organic framework begins to convert into the corresponding metal. However, it is also possible that the metal-organic framework material is converted to the metal oxide via intermediate stages. For example, could have been formed prior carbonate formation of the metal oxide, a carbonyl. In such a case, under the "complete decomposition temperature" is the temperature to be understood, which is required to convert the respective last intermediate for metal.

p0021The determination of the complete decomposition temperature can be carried out using the methods known by the skilled person. For example, can be determined by thermogravimetry this temperature, with accompanying analysis by also, the formation of the corresponding metal can be performed.

p0022The complete decomposition temperature which is necessary to produce a porous metal-organic framework material the corresponding metal oxide, is typically in the range of 250 ° C to 1000 ° C. Further preferably, the complete decomposition temperature is in a range of 350 ° C to 800 ° C. Particularly preferred are the complete decomposition temperature is in the range of 450 ° C to 650 ° C. If the metal oxide in various modifications before, which may be obtained by heat treatment, the thermally higher level (s) modification (s) are obtained from the metal organic framework by applying the appropriate temperature level or it will create the / the tieferstuf strength (s) Modifikati - receive on (s) and in a further step can then take place in the conversion of the desired modification.

p0023As mentioned above, the heating of the porous metal organic framework can take place in a suitable atmosphere. If the porous metal-organic framework comprises at least one at least bidentate organic compound which has enough oxygen itself, it is not necessarily required to be provided from outside an oxygen-supplying substance available to convert the porous metal organic framework into a metal oxide. Examples of such at least bidentate organic compounds that are oxygen-containing, are carboxylic acids, alcohols, ketones, aldehydes, ethers, esters and phenols. In this respect, the heating of the porous metal organic framework in a vacuum could be done. Conveniently, however, the heating is carried out under atmospheric conditions. In such a case, therefore, could take place in the presence of an inert atmosphere and heating the porous metal organic framework. Such atmospheres may be formed by gases such as nitrogen, noble gases such as helium or argon, and mixtures thereof. This, however, represents an exception.

p0024However therefore preferably takes place the heating of the porous metal-organic framework in the presence of an oxidizing atmosphere with an oxygen-donating constituent instead. This can be ensured that sufficient oxygen for the conversion of the porous metal organic framework into the corresponding metal available. This particular can also help to ensure that the above-mentioned intermediates are "skipped". Such oxidizing atmospheres can be obtained by corresponding oxygen-supplying gases or gas mixtures. The simplest and preferred gas mixture in this case is to call air, which normally contains a sufficiently high proportion of molecular oxygen. Optionally, the air can be used enriched with additional oxygen. Finally, it is of course also possible that pure oxygen is used as the oxidizing atmosphere. Moreover, other gases or gas mixtures can be used, which are enriched for example with molecular oxygen. In this case, inert gases would be particularly preferred. Thus, suitable gas mixtures for producing an oxidizing atmosphere at heating the porous metal organic framework helium, argon, Nitrogen or mixtures thereof are used each enriched with oxygen.

p0025The porous metal organic framework may be exposed to an oxidizing atmosphere art way which avoids the atmosphere does not change during heating. The gas or gas mixture surrounding the porous metal organic framework material is thus not exchanged, so that the oxygen-supplying component of the atmosphere decreases during heating.

p0026Moreover, it is possible, the atmosphere during heating, in relation to their oxygen-donating constituent by tracking at least to keep this component approximately constant.

p0027However, it is preferred that the oxygen-supplying component is increased during the heating. This can be used for temperature control of the exothermic reaction. A possible embodiment is that the atmosphere is replaced by a gas or gas mixture with a higher proportion of oxygen-supplying component. This can in particular be such that the atmosphere after the start of heating oxygen is supplied, until finally there is a certain oxygen atmosphere. The increase may be gradual or continuous.

p0028The porous metal-organic framework material for the inventive process for producing a metal oxide must have that the metal of the metal metal ion. The porous metal-organic framework can also comprise a plurality of metal ions. In this case then formed according to a metal oxide, which is also composed of several metals.

p0029In the event that a plurality of metal ions are present in the metal-organic framework material, at least one of these metal ions must be capable of at least one at least bidentate organic compound coordinately bind to obtain the corresponding porous metal organic framework material. In addition, where one or more metals in ionic form exists, can this or can also by coordination of at least one at least bidentate organic compounds or further at least bidentate organic compounds in the structure of the metal organic framework may be present. In addition, however, it is also possible that this is not the case. Finally, if a plurality of metal ions may be added in a stoichiometric ratio, the ratio of the ions. In addition, may also be a non-stoichiometric ratio. In this connection, also be assumed that a so-called dope porous metal organic framework. Such do- oriented frameworks are described for example in the German patent application with the application number 10 2005 053 430.0 of the applicant. Such doped porous metal-organic framework materials are characterized by the fact that the distribution of the dopant metal is random.

p0030In addition, may be impregnated well by another metal, for example in the form of a salt, the porous metal organic framework. A method of impregnating is described for example in EP-A 1,070,538.

p0031In the present invention, two metal ions are one and the same metal of different oxidation state as two different metal ions. Thus, in this case, an appropriate metal oxide can be obtained in which the metal is in different oxidation states. Preferably, however, such a metal is present exclusively in the highest stable oxidation state as the metal oxide, in particular in the presence of an oxidizing atmosphere.

p0032In the present invention, it is preferred that the porous metal-organic framework material exclusively a metal ion of a metal, in particular an oxidation stage comprises.

p0033The one or more metal ions are selected from the metals consisting of Groups 2 to 4 and 13 of the Periodic Table of Elements.

p0034Particularly suitable metals of group 2 of the Periodic Table of the Elements are beryllium, magnesium, calcium, strontium and barium.

p0035Particularly suitable metals of group 3 of the periodic table of elements are scandium, yttrium, lanthanum and the lanthanides.

p0036Particularly suitable metals of group 4 of the Periodic Table of the Elements are titanium, zirconium and hafnium.

p0037Particularly suitable metals of group 13 of the periodic table of the elements are aluminum, boron, gallium and indium.

p0038Further preferred are the metals magnesium, calcium, strontium, barium, zirconium, and aluminum.

p0039Very particularly preferred is the metal ion or the metal ions from the group of metals consisting of aluminum, magnesium and zirconium. In the event that more than one metal in the porous metal-organic framework materials exists, can especially aluminates of the formula M¹AIO₂ or M¹¹AI₂O₄ are obtained, M¹ represents a monovalent metal ion and M 'is a divalent metal ion. In particular, spinels may be obtained.

p0040In the event that the metal-organic framework material contains in addition to titanium, other metals, it is possible, titanates, in particular ilmenite (FeTiOs), but also MgTiO₃, MnTiO₃, FeTiO₃, CoTiO₃, NiTiO₃, CaTiO₃, SrTiO₃, BaTiO₃, Mg₂TiO₄, Zn₂TiO₄ and Mn₂TiO₄ To obtain.

p0041When using zirconium in the metal organic framework and beyond at least one other metal ion corresponding zirconates can be obtained.

p0042Suitable porous metal-organic framework materials are known from the prior art or can be prepared analogously using the procedures described in the prior art. Metal organic frameworks are described for example in US 5,648,508, EP-AO 790 253, MO Keeffe et al., J. sol. State Chem., 152 (2000), page 3-20, H. Li et al., Nature 402, (1999), page 276, M. Eddaoudi et al., Topics in Catalysis 9, (1999), page 105 to 11 1, B. Chen et al., Science 291, (2001), page 1021-1023, DE-A-101 1 1 230, WO-A 2005/049892 and AC Sudik et al., J. Am. Chem. Soc. 127 (2005), 7110-7118.

p0043Porous metal-organic framework materials based on aluminum and magnesium are also described in particular in DE A 10 2005 039 623 and the literature cited therein.

p0044Porous metal-organic framework materials based on zirconium and titanium derin described by Attorney Docket B06 / 0128EP especially in the copending European patent application of the notification.

p0045The term "at least bidentate organic compound" refers to an organic compound containing at least one functional group which is able at a given metal ion is at least two, preferably two, coordinate bonds, and / or two or more, preferably two, metal atoms each form a coordinate bond.

p0046As functional groups via which the abovementioned coordinate bonds can be formed, in particular, for example, the following functional groups are: -CO₂H, -CS₂H, -NO₂, -B (OH)₂, -SO₃H, -Si (OH)₃, Ge (OH)₃, Sn (OH)₃, Si (SH)₄. Ge (SH)₄, Sn (SH)₃, -PO₃H, -AsO₃H, -AsO₄H, -P (SH)₃, -As (SH)₃, -CH (RSH)₂, -C (RSH)₃ CH (RNH₂)₂ -C (RNH₂)₃, -CH (ROH)₂, -C (ROH)₃, -CH (RCN)₂, -C (RCN)₃ where R for example, preferably an alkylene group having 1, 2, 3, 4 or 5 carbon atoms such as a methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene or n-pentylene group, or an aryl group containing 1 or 2 aromatic rings, for example 2 C₆Rings that can optionally be condensed and independently of one another each having at least one substituent may be suitably substituted, and / or which may contain at least one heteroatom such as N, O and / or S independently of each other. According to preferred embodiments also may be mentioned functional groups, in which the above-mentioned radical R is not present. In this regard are, inter alia, -CH (SH)₂, -C (SH)₃, -CH (NH₂)₂, -C (NH₂J₃, -CH (OH)₂, -C (OH)₃, -CH (CN)₂ or -C (CN)₃ to call.

p0047The at least two functional groups can in principle be bound to any suitable organic compound, it is ensured that these functional groups containing organic compound is capable of forming the coordinate bond and of producing the framework.

p0048Preferably, the organic compounds containing at least two functional groups of a saturated or unsaturated aliphatic compound or an aromatic compound or a both aliphatic and aromatic compound derived.

p0049The aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound can be linear and / or branched and / or cyclic, with a plurality of cycles per compound also being possible. More preferably, the aliphatic compound or the aliphatic part of both aliphatic and aromatic compound is 1 to 15, further preferably 1 to 14, more preferably 1 to 13, more preferably 1 to 12, more preferably 1 to 1 1, and particularly preferably from 1 to 10 carbon atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Particularly preferred in this context are, inter alia, methane, adamantane, acetylene, ethylene or butadiene.

p0050The aromatic compound or the aromatic part of the both aromatic and aliphatic compound can have one or more rings, for example two, three, four or five cores, the cores can least two nuclei in condensed form separated and / or. Particularly preferably, the aromatic compound or the aromatic part of the both aliphatic and aromatic compound has one, two or three rings, whereby at one or two cores are particularly preferred. Independently addition, each nucleus of said compound at least one heteroatom such as N, O, S, B, P, Si, Al, preferably N, O and / or S. More preferably, the aromatic compound or the aromatic part of the both aromatic and aliphatic compound comprises one or two C₆Cores, with the two being present separately from one another or in condensed form. In particular, as the aromatic compounds are benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl mentioned.

p0051More preferably, the at least bidentate organic compound of a di-, tri-, or tetracarboxylic acid or a sulfur analogue thereof derives. Sulfur analogues are the functional groups -C (= O) SH and its tautomer and C (= S) SH, which can be used in place of one or more carboxylic acid groups.

p0052The term "derived" means in the context of the present invention, the at least bidentate organic compound in the framework can be present in partially deprotonated or completely deprotonated form. Furthermore, the at least bidentate organic compound can comprise further substituents such as for example two OH, NH₂, -OCH₃, -CH₃, NH (CH₃) -N (CH₃J₂, -CN And halides.

p0053For example, in the context of the present invention, dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid, 1, 4-butanedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic acid, 1, 6-hexanedioic acid, dodecanedioic acid, 1, 8-Heptadecandicar- bonsäure, 1, 9-heptadecanedicarboxylic, heptadecanedicarboxylic acid, acetylenedicarboxylic bonsäure, 1, 2-benzenedicarboxylic acid, 2,3-pyridine dicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1, 3-butadiene-1, 4-dicarboxylic acid, 1, 4-benzenedicarboxylic acid, p-Benzoldicarbon- acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2, 3-dicarboxylic acid, 4,4'-Diaminphenylmethan-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-lsopropylimidazol- 4,5-dicarboxylic acid, tetrahydropyrane-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, Perylendicarbonsäure, Pluriol e 200 dicarboxylic acid, 3,6-Dioxaoctandicarbonsäure, 3,5- cyclohexadiene-1, 2-dicarboxylic acid, Octadicarbonsäure, pentane-3,3-carboxylic acid, 4,4'-diamino-1, 1 'diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1, 4-bis- (phenylamino) -benzene-2,5-dicarboxylic acid, 1, V-di- naphthyl-5,5'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, anthraquinone-1 -Anilino- 2,4'-dicarboxylic acid, polytetrahydrofurane-250-dicarboxylic acid, 1, 4-bis- (carboxymethyl ) -piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1 - (4-carboxy) -phenyl-3- (4-chloro) -phenylpyrazolin-4,5-dicarboxylic acid, 1, 4,5,6,7,7, -Hexa- chloro-5-norbornene-2,3 -dicarboxylic acid, phenylindanedicarboxylic acid, 1, 3-dibenzyl-2-oxo-imidazolidin-4,5-dicarboxylic acid, 1-cyclohexanedicarboxylic acid, naphthalene-1, 8-dicarboxylic acid, 2-benzoylbenzene-1, 3-dicarboxylic acid, 1, 3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic, O-Hydroxybenzophenondicarbonsäure, Pluriol® e 300- dicarboxylic acid, Pluriol® e 400-dicarboxylic acid, Pluriol® e 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic, 5,6-dimethyl-2,3-pyrazinedicarboxylic, 4,4 Diaminodiphenyletherdiimiddicarbonsäure , 4,4'-Diaminodiphenylmethandiimiddicarbon- acid, 4,4'-Diaminodiphenylsulfondiimiddicarbonsäure, 2,6-naphthalenedicarboxylic acid, 1, 3-adamantanedicarboxylic acid, 1, 8-naphthalenedicarboxylic, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3 -naphthalindicarbonsäure, 8-nitro-2,3-naphthoic acid, 8-sulpho-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2 ', 3'-diphenyl-p-terphenyl-4,4 "-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1 H) -Oxothiochromen-2,8-dicarboxylic acid, 5-tert-butyl-1, 3-benzoldicarbon- acid, 7.8 -Chinolindicarbonsäure, 4.5-lmidazoldicarbonsäure, 4-cyclohexene-1, 2-dicarboxylic acid, Hexatriacontandicarbonsäure, tetradecanedicarboxylic acid, 1, 7-dicarboxylic acid hepta-, 5-hydroxy-1, 3-benzenedicarboxylic, pyrazine-2,3-dicarboxylic acid, Fu - ran-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, Eicosendicarbonsäure, 4,4'-di- hydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo -9,10-dihy- droanthracen-2,3-dicarboxylic acid, 2,5-pyridine dicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2, 9-Dichlorfluorubin-4, 1 1 -dicarboxylic acid, 7-chloro-3- mtehylchinolin-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2 ', 5'-dicarboxylic acid, 1, 3-benzenedicarboxylic acid, 2,6-pyridine dindicarbonsäure, 1-methylpyrrole-3,4-dicarboxylic acid, 1- benzyl-1 H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1, 5-dicarboxylic acid, 3,5-pyrazoledicarboxylic, 2-nitrobenzene-1, 4- dicarboxylic acid, heptane-1, 7-dicarboxylic, cyclobutane-1 , 1 -dicarboxylic acid 1, 14-tetra- decanedioic acid, 5,6-Dehydronorbornan-2,3-dicarboxylic acid or 5-ethyl-2,3-pyridine dindicarbonsäure,

p0054Tricarboxylic such as

p00552-hydroxy-1, 2,3-propanetricarboxylic, 7-chloro-2,3,8-chinolintricarbonsäure, 1, 2,4- benzenetricarboxylic acid, 1, 2,4-butanetricarboxylic acid, 2-phosphono-1, 2,4- butantricarbon- acid, 1, 3,5-benzenetricarboxylic acid, 1-hydroxy-1, 2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1 H-pyrrolo [2,3-f] quinoline -2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-me- thylbenzol-1, 2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1, 2,4-tricarboxylic - acid, 1, 2,3-propane or aurintricarboxylic acid,

p0056or tetracarboxylic acids such as 1, 1-Dioxidperylo [1, 12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, Perylentetracarbon- acids such as perylene-3,4,9,10-tetracarboxylic acid, or perylene-1, 12-sulfone-3, 4,9,10- tetracarboxylic acid, butane tetra carboxylic acids such as 1, 2,3,4-butanetetracarboxylic acid or meso-1, 2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1, 4.7, 10,13,16- hexaoxacyclooctadecane-2,3,11, 12-tetracarboxylic acid, 1, 2,4,5-benzene tetracarboxylic acid, 1, 2, 11, 12-Dodecantetracarbonsäure, 1, 2,5,6-Hexantetracarbonsäure, 1, 2,7,8-octane tetracarboxylic acid, 1, 4,5,8-naphthalenetetracarboxylic acid, 1, 2,9,10-Decantetracarbon- acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, tetra- or hydrofurantetracarbonsäure cyclopentane tetracarboxylic acids such as cyclopentane 1, 2,3,4-tetracarboxylic acid

p0057to call.

p0058Very particularly preferably substituted mono-, di-, tri-, tetra- or polynuclear aromatic di-, tri- or tetracarboxylic acids may be optionally at least easily inserted, each of the cores may contain at least one heteroatom, wherein two or more cores are identical or different heteroatoms may contain. For example, preferably mono-ring dicarboxylic acids, one-ring tricarboxylic acids, mononuclear tetracarboxylic acids, two-ring dicarboxylic acids, ring tricarboxylic acids, two-ring tetracarboxylic acids trinucleic dicarboxylic acids, ring tricarboxylic acids, trinucleic tetracarboxylic acids, tetranucleic dicarboxylic acids, tetra tricarboxylic acids and / or tetranucleic tetracarboxylic acids. Suitable heteroatoms include N, O, S, B, P, Si, Al, and preferred heteroatoms are N, S and / or O, Suitable substituents here are, inter alia, -OH, a Nit rogruppe, an amino group or an alkyl to name or alkoxy -.

p0059Particularly preferred as at least acetylenedicarboxylic acid (ADC), benzene, naphthalene, biphenyl dicarboxylic acids such as 4,4'-biphenyl (BPDC) Bipy- ridindicarbonsäuren such as 2,2'-bipyridinedicarboxylic such as 2,2'-bipyridine 5,5-dicarboxylic acid, benzenetricarboxylic such as 1, 2,3-benzenetricarboxylic or 1, 3,5-benzenetricarboxylic (BTC), Adamantantetracarbon- acid (ATC), Adamantandibenzoat (ADB) benzenetribenzoate (BTB), Methantetrabenzoat (MTB), adamantanetetrabenzoate or dihydroxyterephthalic such as 2,5-dihydroxyterephthalic (DHBDC) used.

p0060Very particular preference among other isophthalic acid, terephthalic acid,

p00612.5 dihydroxyterephthalic, 1, 2,3-benzenetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid,

p00621, 3,5-benzenetricarboxylic acid, fumaric acid, succinic acid, maleic acid, glutaric acid, 2,6-naphthalenedicarboxylic acid, 1, 2,4,5-benzene tetracarboxylic acid, citric acid, tartaric acid or oxalic acid used. Particularly preferred are oxalic acid, isophthalic acid or terephthalic acid.

p0063It is preferred if the at least one at least bidentate organic compound only of the elements carbon, hydrogen and oxygen constructed. It is preferred that the molar ratio C: O <3, more preferably <2.

p0064In addition to these at least bidentate organic compounds, the MOF can also comprise one or more monodentate ligands.

p0065Suitable solvents for the preparation of MOF include ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethyl formamide, dimethyl sulfoxide, water, hydrogen peroxide, methyl amine, sodium hydroxide, N-methylpolidone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and mixtures thereof. Further metal ions, at least bidentate organic compounds and solvents for the preparation of MOF are described inter alia in US-A 5,648,508 or DE-A 101 1 1 230th

p0066The metal-organic framework materials for the process according to the invention comprise pores, in particular micropores and / or mesopores. Micropores are defined as those having a diameter of 2 nm or less and mesopores are defined by a diameter in the range of 2 to 50 nm, respectively according to the definition given in Pure Applied Chem. 57 (1985), pages 603-619 specified particular page 606th The presence of micropores and / or mesopores can be checked by means of sorption measurements, these measurements, the absorptive capacity of the metal-organic framework materials for nitrogen at 77 kelvin in accordance with DIN 66131 and / or DIN 66134..

p0067the specific surface area is preferably - calculated according to the Langmuir model (DIN 66131, 66134) for an MOF in powder form is more than 5 m²/ G, more preferably about 10 m²/ G, more preferably more than 50 m²/ G, more preferably more than 500 m²/ G, more preferably more than 1000 m²/ G and more preferably more than 1500 m²/G.

p0068Moldings of metal organic frameworks can have a lower specific see own surface; However, preferably more than 10 m²/ G, more preferably more than 50 m²/ G, more preferably more than 500 m²/ G, particularly more than 1000 m²/G.

p0069The pore size of the porous metal organic framework, through the choice of the suitable ligand and / or the at least bidentate organic compound being controlled. In general, the larger the organic compound, the pore size is the greater. the pore size of 0.2 nm to 30 nm is preferable, particularly preferably the pore size in the range of 0.3 nm to 3 nm on the crystalline material.

p0070In a molding of the metal organic framework, however, also occur, larger pores whose size distribution can vary. Preferably, however, more than 50% of the total pore volume, in particular more than 75%, formed of pores having a pore diameter of up to 1000 nm. Preferably, however, a majority of the pore volume of pores from two diameter ranges is formed. It is therefore further preferred for more than 25% of the total pore volume, in particular more than 50% of the total pore volume is formed by pores which are in a diameter range from 100 nm to 800 nm and more than 15% of the total pore volume, in particular more than 25% of the total is Porenvo- lumens formed by pores which are in a diameter range of up to 10 nm. The pore distribution can be determined by mercury porosimetry.

p0071The production of moldings from metal organic frameworks is described for example in WO-A 03/102000.

p0072Another object of the present invention is a metal oxide obtainable from the process for producing this metal oxide according to the invention.

p0073Due to the fact that porous metal organic framework materials are used as precursors for the corresponding metal oxides and thereby at least partially the framework structure of the metal-organic framework is reflected in the oxide and also partially against the corresponding metal oxides in the prior art results in higher specific surface areas, are the invention by the to consider methods available metal oxides as novel substances.

p0074Since the framework structure is at least partially retained, it is preferable if - and so far as this is the case - the specific surface area (N₂ Langmuir) of organometallic framework material to oxide preferably <50: 1: 1, particularly preferably <20: 1, more preferably still <15: 1 and in the case of metal-organic framework materials from main group metals in particular <5: 1 and even more preferably <4 ,

p0075In the event that the metal oxide AI₂O₃ is, it is preferable if the specific surface area of ​​at least 400 m²/ G (N₂ is determined by the Langmuir). In the event that the metal oxide is MgO, it is preferred if its specific surface area of ​​at least 100 m²/ G (N₂ is determined by the Langmuir).

p0076In the event that the metal oxide is ZrO₂ is, it is preferred if its specific surface area at least 50 m²/ G (N₂ is determined by the Langmuir).

p0077The metal oxides may be incurred in the form in which the metal organic framework was used in each case. Preferably, the organometallic framework material is used as powder.

p0078The metal oxides of the invention differ in particular in their specific morphology of conventionally produced metal oxides. Accordingly, the metal oxides of the invention have improved properties for specific applications have. This is also the metal oxides by known manu- facturing process different pore size distribution, which usually corresponds to the framework material, noted that may cause a change in behavior in adsorption and separation processes. In addition can be carried out the simple production of doped metal oxides. Finally, the production of highly concentrated dispersions can be.

p0079The metal oxides of the invention which are obtainable by the novel process can in principle be used for all applications which are known for conventionally obtained metal oxides.

p0080In particular, such applications of interest, in which a very high specific surface is advantageous.

p0081Exemplary uses a metal oxide according to the invention are those wherein the metal capacitor as a ceramic material, as a catalyst, in particular photocatalyst, pigment, for example, sunscreen pigment carrier, for example, as a catalyst support, adsorbent, for example, for storage or separation of substances, in particular liquids or gases, is used as insulation material, abrasive materials or filler.

p0082Examples

p0083Example 1: Manufacture of aluminum oxide

p008423.9 kg of terephthalic acid (BDC) and 28 kg AI₂(SO₄)₃^*18H₂O are suspended in 150 kg of DMF and the mixture 24 hours at 130 ° C was stirred. Subsequently, the Solids filtered, washed with 4 × 10 kg of methanol and N₂ 96 hours trockengestrippt.

p0085This results in a surface area (determined by N₂ Langmuir) of 1381 m²/G.

p0086The resulting scaffolding material in the form of a powder is calcined for about 24 h in an air atmosphere in a muffle furnace at about 475 to 500 ° C. Here, the carbon is almost quantitatively removed (residual content 0.35 wt.%). The product is an amorphous aluminum oxide with a N₂Surface area of ​​452 m²/ G (Langmuir).

p0087Figure 1 shows the electron microscopy (SEM) of the metal-organic framework (A) and the oxide (B), wherein in the upper half of a scale of 1000: 1 and in the lower half of a scale of 20,000: 1 is present. As Figure 1 shows the morphology of the original particle remains largely intact.

p0088Comparative Example 2

p0089Compared to Example 1, the specific surface area of ​​conventionally produced and commercially available alumina is determined. This resulted for samples Versal 200 (UOP LLC, Des Piaines, US), Spheralite (Procatalyse Usine de Salindre, FR), AI₂O₃ Fa. Alcoa Inc. (Pittsburgh, US), Versal 250 (Euro Support, KH Amersfoort, NL), a value for the specific surface area ranging from about 320 to 350 meters²/G.

p0090Example 3 Preparation of magnesium oxide 10.984 g magnesium nitrate^*6 (H₂O) are dissolved in 68.5 g DEF. In a Autoklavenbecher (Teflon liner) 6.657 g of 2,6-naphthalenedicarboxylic acid in 68.5 g DEF are suspended. Subsequently, the magnesium salt-containing solution is added and stirred for 10 min.. The synthesis is then carried out in a closed autoclave at 105 ° C for 24 hours. The yellow crystals are filtered off. The filter cake is slurried with 250 ml of DMF and stirred for 20 min.. The product is filtered off, then first then washed with DMF and treated with chloroform. The mixture is then dried in air.

p0091The N₂Surface area (Langmuir) of thus prepared Mg-naphthalenedicarboxylic acid-MOF is typically in the range of 80 to 120 m²/G.

p0092The magnesium-2,6-naphthalene-MOF is calcined at 650 ° C for 5 hours. The product is a magnesium oxide having a N₂Surface area of ​​133 m²/ G (Langmuir). Figures 2 and 3 show the X-ray diffraction (XRD) of framework material (Fig. 2) and oxide (Fig. 3), where I is the intensity (Lin (courts)) specifies and 2 Θ 2- theta scale.

p0093The morphology of the original particles also remains largely intact.

p0094Example 4: Preparation of zirconia

p00955 g ZrOCb and 9.33 g of terephthalic acid are stirred in 300 ml of DMF in a glass flask for 17 h at 130 ° C under reflux. The precipitate is filtered, washed with 3 x 50 ml DMF and 4 x 50 ml of methanol and pre-dried 4 days in a vacuum oven at 150 ° C. Finally, it is calcined for 2 days in a muffle furnace at 275 ° C (100 l / h of air). There are obtained 5.17 g of a brown material.

p0096This results in an N₂Surface area of ​​836 m²/ G (Langmuir).

p0097It is calcined for 48 hours at 500 ° C.

p0098The product is a zirconia with an N₂Surface area of ​​61 m²/ G (Langmuir). The distribution of the pore diameter is substantially retained.

p0099Example 5: Preparation of a mixed Al / Zr-oxide

p0100From 5 g AICI₃^*6H₂O, 2.25 g ZrOCl₂ and 8.14 g of terephthalic acid is obtained by precipitation in 300 ml of DMF (130⁰C, h) produced 17 a Zr-doped Al-terephthalic acid MOF. After filtering and washing with DMF and methanol that is kuumtrockenschrank firstly predried at 150 ° C in vacuum and then calcined at 330 ° C for 48 h in a muffle furnace under air supply. The MOF has an N₂Surface area of ​​1448 m²/ G (Langmuir) and contains 8.5 wt .-% Al and 9.8 wt .-% Zr.

p0101The MOF-precursor is calcined for 48 hours at 500 ° C, and thus converted into a mixed Al / Zr-oxide. The product has a Langmuir surface area of ​​358 m²/G.

p0102Comparative Example 6: Preparation of zinc oxide

p010396.7 g Zn (NO₃)₂^*4H₂O and 20.8 g of terephthalic acid are suspended in 2825 g DEF. The reaction mixture is kept at 130 ° C for 3.5 hours. After cooling, the solid is filtered and washed with 4 x 500 ml of anhydrous acetone. The solid is first pre-dried at room temperature in nitrogen stream for 2 to 4 days and then in a vacuum oven 16 hours evacuated (<1 mbar).

p0104The zinc-terephthalic acid MOF (MOF-5) has an N₂Surface area of ​​2811 m²/ G (Langmuir) on. The obtained powder is calcined at 500 ° C for 16 h. The product is a zinc oxide having a N₂Surface area of ​​only 20 m²/ G (Langmuir). Figure 4 shows the electron micrograph (SEM) of MOF-5 (left) and oxide (right) at a resolution of 500: 1. It can be seen that the MOF structure has largely decomposed.

p0105Example 7 Preparation of an aluminum oxide

p010627.8 g AI (NO₃)₃^*9H₂O and 4.3 g of fumaric acid are suspended in 520.5 g of DMF and stirred for 3 days at 130 ° C in a glass flask. The product is filtered off and washed with 2 x 100 ml DMF and 4 x 100 ml of MeOH. There are 4.5 g of an Al-fumaric MOFs with an N₂Surface area of ​​776 m²obtain / g (Langmuir). After annealing in air at 500 ° C is an alumina having a surface area of ​​510 m²/ G.