MXPA06005336A - Method for the controlled storage and release of gases using an electrochemically produced crystalline, porous, organometallic skeleton material - Google Patents

Abstract

The invention relates to a method for the absorption and/or storage of gases. According to said method, the gas to be stored is brought into contact with an electrochemically produced, organometallic skeleton material in conditions that are favourable for gas absorption. The gas is absorbed by the organometallic skeleton material and the conditions are subsequently modified in such a way that the gas is released.

Description

METHOD FOR THE CONTROLLED GASES RELEASED ALiiACEPJAKIEMTO ¥ USING A MATERIAL OF GRASAFFOifiEtÁ ARGUMENT Ígß. POROUS. CRFSTALICIO PRODUCED £ tE € ¥ ROQyía§lCA & iEMTE The present invention relates to a method of storage and / or storage of gases in a controlled manner using a metal-organic, porous, crystalline structure, prepared electfo t iEnicantei te. The metallic structure included in the structure is at least partially provided by means of anoxic oxidation. The structure prepared electrochemically is very suitable as a storage medium for gases. The crystalline porous metal-organic structures. { MOFs) that have particular porous poles or eti fi cients and large specific surface areas have recently become the most recent object of the work) ®? & amp; complete investigation. Therefore, as a matter of fact, US Pat. No. 5,848,508 discloses micro and porous organic structures which are prepared from a metal ion and a ligand in the presence of a template compound under mild reaction conditions. WO 02/088148 describes the preparation of a series of compounds having the same structure topology.

These structures are IMOFs (metal-organic structures isoreticuiares) with iRonocristaiÉeías and ntesoporosas structures that have a very high gas storage capacity. Eddaoudi et ai. Science 295 (2002), 489-472, describes, for example, the preparation of a MOF-5, in which "na sai de zinc, viz. Zinc nitrate is used as the starting material and this salt and 1,4-benzenediearboxyl acid. { BBC) are dissolved in N, N'-diethylformamide (BEF) to synthesize the phthalic acid. Chen et a !, Science 2S1 | 2001 > r 1021-1023, describes, for example, the preparation of an MGF-14 in which a copper salt, viz. Copper nitrate is used as starting material and this salt and 4,4 \ 4"-benzene-1, 3,5-triylphenomenate (H3BTC) are dissolved in N. N'-dimeti? Form.anKda fB-ÜF) and water to synthesize feftOF. Consequently, the processes described in the prior art for the preparation of these porous metal-organic strains are those in which the metal ion for which the ligands are coordinated is provided by means of a metal salt solution and in any case a solution comprising the dissolved metal salt is contacted with a ligand in the presence of a suitable template compound. This procedure has safety problems since, for example, in the preparation of metal-organic structures comprising copper, not only the copper ions but also in many cases also the nitrate anions which are introduced into the reaction system to Through the sa of copper are present in the solution. The synthesis then results in metal complexes of high surface area in concentrated nitrogen comprising phases in which the organic solvents are also included. These phases can decompose spontaneously to overheating. If, on the other hand, a solution based on hairs, as it is written in the same way in many cases in the prior art, is used instead of a metallic sai solution containing nitrate, this leads to corrosion in industrial use. Facto of the components of the apparatus, which is why expensive materials resistant to corrosion are required. To avoid the disadvantages described, the Applicant has developed a process for the electrochemical preparation of MOFs, which is the subject matter of the German patent application 103 55 f Sf. S of November 24, 2003 which has the title "Verfahren". zur eleMrocheí? iiscíien Herstellung eines kristallinen porosen metaiíorganischen Gerustraateríals ". The process described in it takes a completely different approach to which the metallic? which ligand of Sa structure is coordinated though not by means of a metal salt but through electrochemical means .. Said at least one metal ion in the metal-organic structure is introduced at least into the reaction system so less partially through anodic oxidation. The above-cited patent application relates to a process for the electrochemical preparation of a porous crystalline metal-organic structure comprising at least one coordinated bidentate organic compound for at least one metal ion in a reaction medium comprising said less a bidentate organic compound * wherein at least one metal ion is provided in the reaction medium through the oxidation of said at least one anode comprising the corresponding metal. The storage of gases using organometallic structures (MGFs) is the subject matter of patent application WO 03/064030. This application describes the storage of several gases including H2, CH »noble and similar gases using metal-organic structures. Metal-organic structures are well suited for absorbing gases as a result of their high internal surface areas, and the release of gases is also possible. However, the method of the aforementioned patent application using conventional metal-organic structures has the disadvantage that anions originating from storage materials, for example NOS or Cl, are still present in the filOF and the Storage properties are adversely affected as a result, due for example to interactions. In particular, the storage capacity of the materials is reduced as a result, since the free storage sites are occupied. It is therefore an object of the present invention to provide a method in which the aforementioned disadvantages are avoided. Preferably it will be possible to improve the method of WO 03/064030 in such a way that interactions between stored gases and anions do not occur. In particular, the storage capacity of the MOFs will be optimized, that is, a storage method will be made available that will have a maximum storage capacity. The applicant has found year that the meta-organic structures according to the German patent application 103 55 087.5, which are in themselves novel and differ from the corresponding metal-organic structures prepared by wet chemical means, are highly suitable for the storage and / or release of gases. This object is achieved through a method of absorption and / or storage of gases, in which, the gas to be stored is put in contact with a metal-organic structure prepared electrochemically under conditions suitable for gas absorption, with the absorption of the gas within the metal-organic structure that occurs, and if appropriate, the conditions are changed in a subsequent manner so that the release of the stored gas occurs. The method of the invention makes possible the effective storage of large quantities of gas. The term "OF used in the context of the present patent application is equivalent to the term" metal-organic structure. "Those terms in each case therefore refer to the polymer obtained after the preparation and after the removal of impurities, the which are formed of metal ions and binding ligands and can even comprise impurities that can not be eliminated through purification, for example anions originating from the synthesis MOF does not comprise additional or auxiliary substances, for example binders, lubricants and extrusion aids that have been used in the processing of the OFs in order to produce, for example, tablets or extracted The method of the invention is suitable for storage is suitable for storing substances that are preferably gas at temperature However, it is also possible to store materials that have a boiling point tion above room temperature. In this case, the storage process is generally carried out by means of the material to be stored within the gas phase if necessary and put in contact in the gaseous state with an MOF under suitable conditions. The stored gas can, subsequently, also be maintained at temperatures at which it is once again present as a liquid. To release the stored medium, it may be necessary to heat again until a temperature is present in gaseous form. The method of the invention is suitable in principle for the storage and / or release of all the chemical compounds that are in gaseous form at about room temperature, but also above room temperature. It is possible to store an individual compound, or a mixture of two or more compounds. Examples include saturated and unsaturated hydrocarbons, saturated and unsaturated alcohols, oxygen, nitrogen, noble gases (Ue, Arr r, Xe, Rui.), CO, CO ?, synthesis gas (in general CO / H2) V also gases natural gases of all possible compositions Eff absorbed gas may also comprise compounds that generate the gases that are subsequently released by the teF.Gas that are preferred for the purposes of the present invention comprise Kz gas mixtures comprising H2, compounds that produce or release H2, methane, ethane, propane, butanes, ethylene, pf & amp;pitepo "acetylene ,, Me, Ar, Kr" Xe, CO and CO2. Particular preference is given to H2, CH4, Kr, Xe, CO2, CO. When the term "storage *" of one or more gases is used in the context of the present patent application, it refers to a process in which the gas comes in contact with the MOF, penetrates into the present voids and is absorbed. In this way, the gas is stored.After this storage, the MOF loaded with the gas can, if appropriate, be maintained for a period before the "release" of the gas or gas mixture occurs. As mentioned above, storage is generally carried out at a temperature at which the compound or mixture of compounds to be stored in gaseous form is present. The storage is preferably carried out at a temperature from 0 to 10 ° C, in particular from 10 to 30 ° C. Furthermore, storage of the gas or gaseous mixture is generally carried out at atmospheric pressure, preferably from 1 to 300 bar (absolute), in particular from 1 to 150 bar (absolute), more preferably from 1 to 80 bar (absolute), even more preferably in the range from 45 to 80 bar and in particular in the range from 50 to 80 bar (absolute). In the storage and / or release according to the invention, the MOF is generally present in a gas-tight container. At the end of the storage process, the container that accommodates the MOF has the internal pressure that corresponds to the previously applied external pressure. The MOF that receives the gas or the gas mixture is therefore under external pressure as well. To release the gas or gas mixture, the pressure acting on the MOF is generally reduced, usually by opening the container accommodating the II0F. To effect gas / gaseous mixture release, it is also possible to heat MOF. This can occur in addition to the pressure reduction, but also as a single measure, in particular in cases in which the pressure acting on the MOF is not as high as the atmospheric pressure. Therefore, the present invention also comprises a gas-tight container accommodating a MOF material, an opening through which the gas to be stored can enter and a closing mechanism by means of which the interior of the container it can stay under pressure. Such containers may, for example, be used in the context of a fuel cell which is used to store and release energy in apparatuses in which the external energy supply is not possible or undesirable and therefore not used. This is the case, for example, in the operation of stationary, mobile and / or portable systems or applications. Examples are power stations, motor vehicles such as passenger cars, vehicles and buses for products and wireless applications in electronic components, for example, telephones or laptops. This container can in principle have any suitable geometry. Due to the low pressures that are possible according to the invention, the containers that deviate from the standard cylindrical geometry and the respective requirements, for example to be susceptible to being adapted to the specific space available in the construction of automobiles, are also possible in a preferable way. As a result, containers that can be variably configured can be adapted to hollow spaces of a car that may not otherwise be used and valuable storage and usable space can be gained.

The electrochemically prepared MOFs which are used according to the invention for storage are described in greater detail below. The MOFs are formed by metal ions that are joined together through bidentate organic compounds so that a three-dimensional structure is formed that has internal voids (pores). The pores are defined by the metal atoms and the organic compounds that connect them. An MOF may have only the same metal ions or may have two or more different metal ions. The term "electrochemical preparation" refers here to a method of preparation in which the formation of at least one reaction product is associated with the migration of electronic charges or the occurrence of electric potentials. The term "at least one metallic in" refers herein to embodiments in which at least one ion of a metal or at least one ion of a first metal and at least one ion of at least one second is provided metal that is different from the first metal through anodic oxidation. Accordingly, the electrochemically prepared MOF materials also comprise embodiments in which at least one ion of at least one metal is provided through anodic oxidation and at least one ion of at least metal is provided by means of a metal salt , with said at least one metal in the metal salt and said at least one metal which is provided as a metal ion by means of anodic oxidation which is capable of being identical or different. That is, for example, an embodiment in which the reaction medium comprises one or more different salts of a metal and the metal comprised in that salt or in those salts is further provided through anodic oxidation of at least one anode which includes this metal. This is a similar embodiment in which the reaction medium comprises one or more different salts of at least one metal and at least one metal that is different from those metals is provided as a metal ion by means of anodic oxidation in the medium of reaction. In a preferred embodiment, said at least one metal ion is provided through anodic oxidation of at least one anode comprising said at least one metal and without further metal being provided through a metal salt. Therefore, an embodiment is comprised in which said at least one anode comprises a single metal or two or more metals and when the anode comprises an individual metal, this metal is provided by means of anodic oxidation and when the anodes comprise two or more metals, at least one of those metals is provided by means of anodic oxidation. In addition, a mode in which said at least two anodes are used may be identical or different. Each of said at least two anodes may comprise an individual metal or two or more metals. It is possible, for example, for two different anodes that comprise the same metals although in different proportions. It is also possible, for example, in the case of different anodes that a first anode comprises a first metal and a second anode comprises a second metal, with the first anode not comprising e! second metal and / or the second anode that does not comprise the first metal. The term "metal *" comprises all elements of the Periodic Table that can be provided in a reaction medium through an electrochemical pathway that involves anodic oxidation and are capable of reacting with at least one organic bidentate compound to form at least one porous metaf-organic structure For the purposes of the present invention * particular preference is given to the elements of the groups la, lia, illa, l Va to Vi l la and Ib and Vlb of the Periodic Table of the Elements. elements, preference is given to Mg, Ca, Sr, Ba, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, MR, Re, Faith, Ru, Os, Cor Rhr!? \ Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, in, You, Si, Ge, Sn, Pb, As, Sb and Bi. Of greater preference to Zn, CEI, Mi * Pd ,, Pt, Rie, Rii, Fe, Mn, Ag and Co. For the purposes of the present invention, Cu, Fe, Co, Zn, Mn and Ag, are more preferable It gives very particular preference to Cu, Fe and Zn. As metal ions which can be provided in the reaction medium by means of anodic oxidation, mention can be made, in particular, of Mg2 *, Ca2 *, Sr2 *, Ba2J \ Se3 *, Y3 *, Ti + Zr4 *, H , V4 +. V3 *, V2 *, M3 *, Ta3 *, Cr3 *, Mo3 *, W3 \ M ', Mn2 *, Re3 * Re2 *, Fe3 *, Fe2 *, Ru * \ Ru2 + r Os3 *, Os2 *, Co3 *, Co2 *, Rh2 *, Rh *. Ir2 * Ir *, Ni2 *, IST, Pd2 *, Pd *, Pt2 *, Pff, Cu2 *, Cu *, Ag *, Au *, Zn2 *, Cd2 * Hg2 *, Ai3 *, Ga3 *, to3 *, Ti3 *, Si Si2 *, Ge4 *, Ge2 *, Sn4 *, Sn2 *, Pb4 * Pb2 *, As5 *, As3 *, As *, Sb5 *, Sb3 *, Sb \ BE5 *, Bi3 * and Bi *. Particular preference is given to Cu2 *, Cu *, Fe2 *, Fe3 *, Zn2 *, Co3 *, Co2 *, Ag *, Mg2 * and Mn2 *. Particular preference is given to Co2 *, Cu *, Fe2 *, Fe3 * and Zn2 *. It is possible to use an anode comprising copper and / or an anode comprising iron and / or an anode comprising zinc and / or an anode comprising silver and / or an anode comprising manganese as a metal ion source. It is also possible to use an anode comprising copper and / or an anode comprising iron and / or an anode comprising zinc and / or an anode comprising manganese as a metal ion source. Preference is given to the use of an anode comprising copper and / or an anode comprising iron and / or an anode comprising zinc as a metal source. The conformation of the anode used in principle can be freely selected, insofar as it is ensured that said at least one metal ion can be available by catalytic oxidation in the reaction medium for the formation of the porous metal-organic structure. Preference is given, among others, to the anodes in the form of a bar and / or a ring and / or a disk, for example, an annular disk, and / or a plate and / or a tube and / or a bed and / or a cylinder and / or a cone and / or a frusto of a cone. In a preferred embodiment, the MOF is prepared electrochemically using at least one sacrificial anode. The term "sacrificial anode" refers to an anode that dissolves at least partially during the course of the process. The modalities in which at least part of the anodic material is replaced during the course of the process are also included here. This, for example, can be originated by at least one new anode which is introduced into the reaction system or, in a preferred embodiment, an anode which is introduced into the reaction system either continuously or discontinuously during the course of the process according to the invention. Preference is given to the use of anodes which consist of at least one metal serving as a metal ion source or comprises said at least one metal applied to at least one suitable support material. The geometry of said at least one support material is essentially not subject to restrictions. For example, it is possible to use support materials in the form of a woven fabric and / or a thin sheet and / or a felt and / or a mesh and / or a bar and / or a candle and / or a cone, and / or a frusto a cone and / or a ring and / or a disk and / or a plate and / or a tube and / or a bed and / or a cylinder. Possible support materials that can be used are, for example, metals such as at least one of the aforementioned metals, alloys such as steels or bronzes or brasses, graphite, felt or foams.

Particular preference is given to anodes consisting of at least one metal serving as a metal ion source. The conformation of the cathode used can, in principle, be selected freely, insofar as it is ensured that at least one metal ion can be available by means of anodic oxidation in the reaction medium for formation of the porous metal-organic structure. In a preferred embodiment, the electrically conductive electrode material of at least one cathode is selected so that no interferent secondary reaction occurs in the reaction medium. Preferred cathode materials are, inter alia, graphite, copper, zinc, tin, manganese, silver, gold, platinum, or alloys such as steels, bronzes or brass. As preferred combinations of the anode material serving as a metal source and the electrically conductive cathode material, there may be mentioned, for example, the following: The geometry of at least one cathode is essentially not subject to restrictions. It is possible, for example, to use cathodes in the form of a bar and / or a ring and / or a disk and / or a plate and / or a tube. Basically it is possible to use any of the types of cells customary in electrochemistry. In the process according to the invention, very particular preference is given to an electrolysis cell which is suitable for the use of sacrificial electrodes. In principle it is possible, inter alia, to use divided cells having, for example, a parallel arrangement of flat electrodes or electrodes in the shape of a candela. As a means of separation between the cell compartments, it is possible to use, for example, ion exchange membranes, microporous membranes, diaphragms, filter fabrics comprising non-electron conducting materials, glass frits and / or porous ceramics. Preference is given to the use of ion exchange membranes. In particular, ion exchange membranes, among which preference is given to membranes comprising a tetrafluoroethylene copolymer and a perfluorinated monomer comprising groups of suifonic acid. In a preferred embodiment, one or more undivided cells are used. Accordingly, the present invention also provides a method as described above, wherein the process is carried out in an undivided electrolysis cell.

Particular preference is given to combinations of anode and cathode geometries in which the sides of the anode and the cathode facing each other together form a space of homogeneous thickness. In said at least one undivided cell, the electrodes, for example, are preferably arranged in parallel with each other with the electrode space having a homogeneous thickness in the range from, for example, 0.5 mm to 30 n, preference in the range from 0.75 mm to 20 mm and particularly preferably in the range from 1 to 10 n. In a preferred embodiment, it is possible, for example, for a cathode and an anode to be placed parallel to each other so that an electrode space having a homogeneous thickness in the range from 0.5 to 30 mm preferably in the range from 1 up to 20 m, more preferably in the range from 5 to 15 mm and particularly preferably in the range from S to 12 mm, for example in the region from about 10 mm, is formed in the resulting cell. For the purposes of this invention, this type of cell will be referred to as a "space cell". In a preferred embodiment, the cell described above is used as a bipolar cell. Apart from the cell described above, the electrodes are used individually, or as an attachment of a plurality thereof in an equally preferred embodiment of the method of the invention. In the latter case, the electrodes are stacked electrodes which are preferably connected in series in a bipolar manner in which they are accordingly referred to as a plate stacking cell. Particularly when the process of the invention is carried out on an industrial scale, preference is given to the use of at least one crucible cell and particularly preferably plate stacking cells connected in series whose construction is in principle described in DE 195 33 773 A1, the relevant contents of which are incorporated by reference in the present patent application. In the preferred embodiment of plate stacking cell, example preference is given to sheets of suitable material, for example copper sheets, which are placed parallel to each other so that a space having a homogeneous thickness in the range from 0.5 to 30 mm, preferably in the range from 0.6 to 20 mm, more preferably in the range from 0.7 to 10 mm, more preferably in the range from 0.8 to 5 mm and in particular in the range from 0.9 to 2 m, for example in the region of approximately 1 m, is formed between each of the individual sheets. The distances between the individual sheets can be identical or different, and in a particularly preferred embodiment the distances between the sheets are essentially identical. In a further embodiment, the material of a sheet of the plate stacking cell may differ from a material from one sheet to another in the plate stacking cell. For example, one sheet of graphite can be made and another sheet can be made of copper, with the copper sheet which is preferably connected with the anode and the graphite sheet which is preferably connected as a cathode. Preference is also given to the use of "sharpening" cells as described, for example, in J. Ghaussard et al., J. Appl. Elctrochem. 19 (1989) 345-348, whose relevant contents are fully incorporated with reference to the present patent application. Particular preference is given to the use of sharpening electrodes having sharp bar electrodes that can be used additionally in the process according to the invention. Accordingly, the present invention also provides, in particular, a method as described above, wherein the process is carried out in a cell space or cell stacking plate. Cells in which the electrode gap is less than or equal to 1 mm are referred to as capillary space cells. In an equally preferred embodiment, electrolysis cells having, for example, porous electrodes formed by metal beds or having, for example, porous electrodes made of metal meshes or have, for example, both electrodes formed of metal beds and have, for example, electrodes made of metal mesh. In a further preferred embodiment, the process according to the invention is carried out using electrolysis cells having at least one sacrificial anode having a rounded disc-shaped cross-section and at least one cathode having a cross section. annular transverse, with the diameter of the preferably cylindrical anode which is particularly preferably smaller than the internal diameter of the cathode and the anode which is installed in the cathode in such a way that a space having a homogeneous thickness is formed between the external cylindrical surface of the anode. anode and the internal surface of the cathode that at least partially surrounds the anode. It is also possible to reverse the polarity to convert the original anode into the cathode and the original cathode at the anode. In this process variant, it is possible, for example, to select electrodes that comprise different metals so that a metal is oxidized to ndcatting first to make it available as a metal cation for the formation of the metal-organic structure and, in a second stage after the reversal of the polarity, an additional metal is made available for the formation of the metal-organic structure. It is also possible to cause polarity inversion through the application of alternating current. In principle it is possible to carry out the process batch or continuously or in a mixed mode. Preferably the process is carried out continuously in at least one flow cell. The voltages employed can be coupled to said at least one metal of at least one anode which serves as a source of metal ion for the metal-organic structure and / or for the properties of said at least one bidentate organic compound and / or, if appropriate, for the properties of said at least one solvent described below and / or, if appropriate, for the properties of said at least one electrolyte salt described below and / or for the properties of said at least one cathodic depolarization compound described below. In general, the voltages per electrode pair are in the range from 0.5 to 100 V, preferably in the range from 2 to 40 V and particularly preferably in the range from 4 to 20 V. Examples of preferred ranges are from about 4 to 10 V and from 10 to 20 V and from 20 to 25 V and from 1 0 to V and from about 4 to 20 V and from 4 to 24 V. The voltage may be constant during the course of the process of the invention or It can change continuously or discontinuously during the course of the process. For example when the copper is anodically oxidized in the range from 3 to 20 ¥, preferably from 3.5 to 15V and particularly preferred in the range from 4 to 15 V. Current densities that occur in the preparation of organic structures porous materials are generally in the range from 0.01 to 1000 rnMcm2, preferably in the range from 0. 1 to 1000 mA / em2, more preferably in the range from 0.2 to 200 mA / cm2, most preferably in the range from 0.3 to 100 mA / cm2 and particularly preferred in the range from 0.5 to 50 mA / cm2. The loading quantities. { A.M} used in the preference process are in the range from 30 to 200% of the amount of the charge that is necessary to bind the amount of the acid equivalents preferably used of at least one bidendate compound. The process is generally carried out at a temperature in the range from 0 ° to the boiling point of the respective reaction medium or at least one solvent used, preferably in the range from 20 ° C to the boiling point , preferably under atmospheric pressure. It is also possible to execute the process under superatmospheric pressure, with the pressure and temperature being preferably selected so that the reaction mixture is preferably, at least in part, liquid.

In general, the process is carried out at a pressure in the range from 0.5 to 50 bar, preferably in the range from 1 to 6 bar and particularly preferably at atmospheric pressure. Depending on the type and state of the material of the reaction medium components, the electrochemical preparation of the porous metal-organic structure can in principle also be carried out without additional solvent. In particular, this is the case when, for example, at least one of the bidentate compounds functions as a solvent or as a solvent mixture in the reaction medium. In principle, it is also possible to carry out the process without the use of a solvent, for example in the melting, in which case at least one component of the reaction medium is present in the molten state. In a preferred embodiment, the reaction medium comprises at least one suitable solvent in addition to at least one bidentate organic compound and, if appropriate, said at least one electrolyte salt and, if appropriate, at least one compound of cathodic depolarization. Here, the chemical nature and the amount of said at least one solvent must be matched for said at least one bidentate compound and / or for said at least one electrolyte salt and / or said at least one cathodic depolarization compound and / o for said at least one metal ion. Accordingly, the present invention also provides a method as described above, wherein the reaction medium further comprises at least one solvent in addition to said at least one bidentate organic compound. In principle, the solvents considered are all solvents or all solvent mixtures in which the starting materials used in the process can be dissolved or suspended at least partially under the reaction conditions, for example pressure and temperature, selected.

Examples of preferred solvents are, among others, water; - alcohols having 1, 2, 3 or 4 carbon atoms, for example, methanol, ethanoi, n-propanoi, isopropanol, n-buanol, isobutanol, ter-foutaooi; - carboxylic acids having 1, 2, 3 or 4 atoms, for example formic acid, acetic acid, propionic acid or butanoic acid; - nitriles such as acetonitrinyl or cyanobenzene; ketones such acetone; - at least halogen-substituted lower alkanes individually, such as methylene chloride or 1,2-dichloroethane; acidic amides such as lower carboxylic acid amides, for example, carboxylic acids having 1, 2, 3 or 4 carbon atoms, for example formic acid, acetic acid, propionic acid or butanoic acid, for example formamide, ethylformamide (DMF), diethylformamide (OEF), t-butylformamide, acetamide, dimethylacetamide, diethylacetamide or t-butylacetamide; - cyclic ethers such as tetrahydrofuran or dioxane; N-formylamides or H-acetylamines or symmetric or non-symmetrical urea derivatives of primary, secondary or cyclic amines such as ethylamine, di-lactate, piperdine or morpholine; - amines such as ethanolamine, triethylamine or eiylenediamine; - dimethyl sulfoxide; - pyridine; - trialkyl phosphites and phosphates; or mixtures of two or more of the aforementioned compounds. The term "solvent" as used above includes both pure solvents and solvents comprising small amounts of at least one compound such as, preferably, water. In this case, the water contents of the aforementioned solvents are in the range from 1% by weight, preferably in the range from 0.5% by weight, particularly preferably in the range from 0.0 to 0.5% and in particular in the range from 0.1% to 5% by weight. The term "methanol" or "ethanol" or "acetonitrile" or "DilF" or "DEF" includes, for example, a solvent which may in each case comprise, particularly preferably, water in the range from 0.1 to 0.5% by weight The preferred solvents for use are methane, ethanol, acetonitrile, DMF and DEF and mixtures of two or more of these compounds. Particular preference is given to methanol, ethanol, DMF, DEF and mixtures of two or more of these compounds as a solvent. In a preferred embodiment, at least one protic solvent is used as the solvent. This is, in other words, used in particular when the cathodic hydrogen formation is to be achieved in order to avoid redeposition as described further ahead of at least one metal ion provided by the anodic oxidation at the cathode. When methanol is used as a solvent, the temperature under atmospheric pressure <; it is usually in the range from 0 to 90 ° C; preferably in the range from 0 to 65 ° C and particularly preferably in the range from 25 to 65 ° C.

When ethanol is used as a solvent, for example, the temperature under atmospheric pressure is generally in the range from 0 to 100 ° C; preferably in the range from 0 to 78 ° C and particularly preferably in the range from 25 up to 78 ° C. The pH of the reaction medium is set so that it is advantageous for synthesis or stability or preferably for the synthesis and stability of the structure. For example, the pH can be adjusted by means of said at least one sai of electrolyte. If the reaction is carried out as a batch reaction, the reaction time is generally in the range up to 30 hours, preferably in the range up to 20 hours, more preferably in the range from 1 to 10. hours and particularly preferably in the range from 1 to 5 hours. The term "at least one bidentate organic compound" refers to an organic compound comprising at least one functional group that is capable of forming at least two, preferably two, coordinated bonds for a given metal ion and / or to form a coordinated link for each two or more, preferably two, metal atoms Examples of functional groups through which the aforesaid coordinate bonds can be formed are, in particular, the following functional groups: -CO2H, -CS2H, -N O2, B (OH) 2, -SO3H, S? COK) j, -Sn (GH) 3, -Ge (SB.) .4, -Sn (SH) 3, -PO3H, - AsO3H, -AsO4H, - P (SH) 3 r As. {SH) 3r -CH (RSH) 3>, -CH (RNH 2) 2>, - C (R NH 2) 3, -CH (ROH) 2, -C. ROH) 3, -CH (RCM) 2, -C (RCN) 3>, where R is, for example, preferably an alkylene group having 1, 2, 3, 4 or 5 carbon atoms, for example a methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene or n-pentylene group or an aryl group having 1 or 2 aromatic rings, for example 2 Cs rings, which can be optionally fused and can, independently of one another, be suitably substituted by at least one substituent each and / or independently of each other , each comprises at least one heteroatom such as N, O and / or S. In likewise preferred embodiments, mention may be made of functional groups in which the aforementioned radical R is not present. In this regard, there may be mentioned, among others, -CH (SH) 2, -C (SH) 3, -CHCMH2) 2f -CH | I «IH2) 3, -CH (OH) a, -C (OH) 3, -CH (CN) 2 or -C (CN) 3. Said at least two functional groups can in principle be linked to any suitable organic compound, so long as it is ensured that the organic compound that holds those functional groups is capable of forming the coordinated bond and producing the structure. The organic compounds comprising said at least two functional groups are preferably derived from a saturated or unsaturated aliphatic compound or an aromatic compound or both a fatty and aromatic compound.

The aliphatic compound or the aliphatic part of the aliphatic and aromatic compound can be linear, and / or branched and / or cyclic, with a plurality of rings per compound which is also possible. More preferably, the aliphatic compound or the aliphatic portion of the aromatic and aliphatic compound comprises from 1 to 15, more preferably from 1 to 14, more preferably from 1 to 13, more preferably from 1 to 12, more preferably preferred from 1 to 11 and particularly preferably from 1 to 10 carbon atoms, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Particular preference is given here, inter alia, to methane, adamantane, acetylene, ethylene or butadiene. The aromatic compound or the aromatic part of the aromatic and aromatic compound may have one or more rings, for example, two, three, four or five rings, in which case the rings may be present separately from each other and / or At least two rings may be present in a fused form. The aromatic compound or the aromatic part of the aromatic and aliphatic compound preferably has one, two or three rings, with one or two rings that are particularly preferred. In addition, each ring of the aforementioned compound can independently comprise 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 aromatic and aliphatic compound comprises one or two Cs rings, both of which are present separately from one another or in a fused form. In particular, mention may be made of benzene, naphthalene and / or ββ-fenii © and / or bipyridyl and / or pyridine as aromatic compounds. Examples that may be mentioned are, inter alia, trans-muconic acid and fumaric acid and phenlienbic acid. For the purposes of the present invention, mention can be made, for example, of the dicarboxylic acids such as 1,4-butanedicarboxylic acid, tartaric acid, glandic acid, oxaic acid 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decandicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetyldenecarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid , 1,3-butadiene-1,4-diearboxylic acid, 1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylq-inolin-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxalin-2,3-dicarboxylic acid, 4,4 * -diovanophenylmethane-3,3'-dicarboxylic acid, quinolin-3,4 acid -dicarboxylic acid, 7-color-4-hydroxyquinoline-2,8-dicarboxylic acid , dydimidic acid carboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazoi-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydroacetic acid? ran-4,4-dicarboxylic acid, peri len-3, 9-dicarboxylic acid, periendiearboxiiieo acid, Pluriol E 200-dicarboxylic acid, 3,6-dloxaoctanedicarboxylic acid, 3,5-cyclohexadien-1,2-dicarboxylic acid, Octandicarboxylic acid, pentan-3,3-carboxylic acid, 4,4'-diamin-1, 1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,35-dicarboxylic acid, benzidin- 3,3'-dicarboxylic acid 1,4-bis- (phenylamine) -benzene-2,5-dicarboxylic acid, l-β-binaphthyl-S'-dicarboxylic acid, 7-chloro-8-methylquinquin-2,3 acid -dícafboxííco, acid 1-aníiínaníraquinon-2,4'-dicarboxíüco, acid polytetrahydrofuran-250-dicarboxílico, acid 1, 4-bis- (carboxy ethyl) piperazin-2,3-dicarboxylic, acid 7-cf croquiñol in-3, 8-dicarboxylic acid 1-. { 4-carboxy) phenyi-3. { 4-chloro) phenylpyrazoline-4,5-dicarboxylic acid, 1, 4, 5, 6, 7, 7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindandicarboxylic acid, 1,3-dibenzyl-2-oxo acid -imidazolidin-4,5-dicarboxylic acid, 1,4-hexahexandicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, and 1,3-dibenzyl-2-oxoimidazolidin-4 acid, 5-cis-dicarboxylic acid, 2,2'-biquinoin-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxtyl acid, acid 3,6, S-trioxaundecandicarboxilic acid, O-hydroxybenzophenonecarboxylic acid, Pluriol E 300-dicarboxylic acid , Pluriol E 400-carboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazindicarboxylic acid, 5,6-dimethyl-2,3-pyridzindicarboxylic acid, 4,4-diamino (diphenyl ether) -diimidicarboxylic acid, 4,4'-diaminodiphenyl ethanediimidocarboxylic acid, 4,4"-diamino (diphenyl sulfota) diimidocarboxylic acid, 2,6-naphthalenecarboxylic acid, 1,3-ad acid amantandicarboxylic acid, 8-naphthalenedicarboxylic acid, 2,3-naphniandicarboxylic acid, 8-? netox-2,3-naphthalenedicarboxylic acid, 8-n? tro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3 acid - naphthalenedicarboxylic acid, anifaeen-2,3-dicarboxylic acid, 2 ', 3'-diphenyl-p-terpheni-4,4"-dicarboxyphosphonic acid, (dipheniyl ether) -4,4'-dicarboxylic acid, γidazide 4,5-diearboxiiie ©, 4 (1 H) -oxothiochromen-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolindicarboxylic acid, 4,5-imidazole dicarboxylic acid, 4-cyclohexen-1, 2-dicarboxylic acid, hexatriacontanedicarboxylic acid, 1-tetradecanedicarboxylic acid, 1, 7-heptanedicarboxylic acid, 5-hydroxy-1, 3- acid benzenecarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-diearboxylic acid, 1 -nonen-6,9-d? carboxylic acid, eicosendicarboxylic acid, 4,4'-dihydroxydiphenimethane-S-carboxylic acid, 1-amino-4-methyl-9, 10-dioxo-9, 10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexe-t-2,3-dicarboxylic acid, acid 2, 9- dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinolin-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2,5-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridine acid? carboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-beneyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazodicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, reptan-1, 7-dicarboxylic acid, cyclobutane-1, 1-dicarboxylic acid, 1,4-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid or 5-ethyl-2,3-pyridinedicarboxylic acid, tricarboxylic acids such as 2-hydroxy-1, 2,3-pr-pantricarboxylic, acid 7-phosphorus, 2,3, 8-quinolinetricarboxylic acid, , 2,4-benzenecarboxylic acid, 1,2-butanetricarboxylic acid, 2-phospho-5? -1,2,4-butanetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1-hydroxy-1,2 acid, 3-propanedicarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrroli2,3-FJquinrin-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methybenzene-1,2 acid 4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1, 2,4-tricarboxylic acid, 1,2-propanedicarboxylic acid or aurintricarboxylic acid, or tetracarboxylic acids such as 1,1-dioxidoperiole 1,12 -BCDJ-thiophene-3,4,9,10-tricarboxylic acid, perylentetracarboxylic acids s such as perylene-3,4,9, 10-tetracarboxylic acid or perylene-1r 12 -syifon-3,4,9,10-tetracarboxylic acid, butentracarboxylic acids such as 1, 2,3,4-butane tetracarboxylic acid or acid meso-1,2,3,4-butantetracarboxííico, acid decan-2,4,6,8-tetracarboxíliCo, acid 1,4,7, 10, 13, 16-hexaoxaciciooetadecan-2,3,11,12- tetracarboxílico, 1, 2,4,5-benzenestracarboxylic acid, 1, 2,11, 12-dodecanecarboxylic acid, 1, 2,5,6-hexantetracarboxylic acid, 1, 2,7,8-octane tetracarboxylic acid, 1,4 acid, 5,8-naphthalenetetracarboxylic acid, 1, 2,9, 10-decarboxycarboxylic acid, benzophenotetracarboxylic acid, 3,3% 4,4'-benzophenonetetracarboxylic acid, tetrahydrofuranecarboxylic acid or cyclopentanetracarboxylic acids such as c-clopentan-1,2 acid, 3,4-tetracarboxylic. Particular preference is given to the optional use of at least mono-substituted aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids having one, two, three, four or more rings, with each of the rings being able to comprise at least one heeroerous © and two or more rings that are capable of understanding identical or different heteroatoms. Examples of preferred carboxylic acids of this type are dicarboxylic acids of one ring, tricarboxylic acids of one ring, tetracarboxylic acids of one ring, dicarboxylic acids of two rings, tricarboxylic acids of two rings, tetracaboxylic acids of two rings, dicarboxylic acids of three rings, three-ring tricarboxylic acids, three-ring tetracarboxylic acids, four-ring dicarboxylic acids, four-ring tricarboxylic acids and / or four-ring tetracarboxylic acids. Suitable heteroatoroes are, for example, N, O, S, B, P, Si, AI. and the heteroatoms herein are N, S and / or O. Suitable substituents are, inter alia, -OH, a nitro group, an amino group or an alkyl or akoxy group. As bidentate organic compounds, particular preference is given to the use of acetyl-dicarboxylic acid (ADC), benzenedicarboxylic acids, naphthalenedicarboxylic acids, biphenyldicarboxylic acids such as hydroxyacetylcarboxylic acid., 4'-biphenyldicarboxylic acid (BPDC), bipyridinediamphoboxylic acids such as 2,2'-biritiriticarboxylic acids, for example 2,2'-bipyridin-5,5'-dicarboxylic acid, beneentricarboxylic acids such as 1, 2, 3-benzenecarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC), adama ntan-tetracarboxylic acid (ATC), adamantanedibenzoate (ADB), benzenetribenzoate (STB), methanetetrabenzoate (MTB), adamantantetrabenzoate or dihydfoxitrelate acids such as 2,5-dihydroxyterephthalic acid ( OHBDC). Particular preference is given to the use, inter alia, of terephthalic acid, 2,5-dihydroxy terephthalic acid, 1,3-benzenetricarboxylic acid, 1,3,5-benzenecarboxylic acid or 2,2'-bipyridin-5 acid, 5'-dicarboxylic. In a preferred embodiment, 1, 3, 5-benzenetricarboxylic acid is used as said bidentate organic compound. If at least one solvent is used, preference is given to the use, for example, of methane! or ethanoi or methanol and ethanol co or solvent. Of particular preference jump to ethanol. In a further preferred embodiment, 1, 2,3-benzenetricarboxylic acid is used as said bidentate organic compound. If at least one solvent is used, preference is given to the use, for example, of methanol or ethanoi or methanol and ethane! as solvent. Particular preference is given to methane !. In a further preferred exemplary embodiment, terephthalic acid is used as said bidentate organic compound. If at least one solvent is used, preference is given to the use, for example, of diethylformamide or dimethylformamide and diethylformamide as the solvent. Particular preference is given to diethylformamide. In a further preferred exemplary embodiment, the dihydroxyterephthalic acid is used as the bidentate organic compound. If at least one solvent is used, preference is given to the use, for example, of dimethylforma.-ida.-dimethylformamide or dimethylformamide and dimethylformamide as a solvent. Particular preference is given to dlethylphoramide. In a further preferred exemplary embodiment, naphthalene-2-6-dicarboxylic acid is used as said bidentate organic compound. If at least one solvent is used, preference is given to the use of, for example, methanol or ethanol or methanol and ethanol as the solvent. Particular preference is given to methanol. Said at least one bidentate organic compound is used in a concentration which is generally in the range from 0.1 to 30% by weight, preferably in the range from 0.5 to 20% by weight and particularly preferably in the range from 2 to 20% by weight. up to 10% by weight, in each case based on the total weight of the reaction system minus the weight of the anode and the cathode.

Accordingly, the term "concentration" in this case comprises the amount of the bidentate compound dissolved in the reaction system and, for example, the amount of said at least one bidentate compound which can, if appropriate, be suspended in the system of reaction. In a preferred embodiment, said at least one bidentate compound is added continuously and / or discontinuously as a function of the progress of electrolysis and in particular as a function of the decomposition of the anode or the release of at least one metal ion and / or as a function of the formation of the metal-organic structure. The following metal combinations from which said at least one metal cation is provided are provided by means of anodic oxidation, by at least the bidentate compound and the solvent, are preferred, for example: Zn / BCD / DEF; Zn / DKBDC / DEF; ZttJHzBDC / DttF; Zn / BDC / DMF, MeOH; Zn / H2BDC / DMF; Zni 4,4'-BP-2,2'-DClDEF Zn / 2,6-NDC / DEF; Zn / H3BTB / H2Q, DMF EtOH; Zn / H2BBC / DdASO; Zn / 1, 4-NDC / DMF; Zn / H3BTB / DMF, EtOH; Zn / H2BDC / D IF, AN; Zn / H2BDC / DMSO; Zn / H2BDC / D SO, MeOH; Zn / HjBDC / DMSO, n-propanol; Zn / H2BDC / NMP; Zn / M-BDC / D ^ F, AM; Znl1.4-MDC / DMF, EtO «; Zn / H2N-BDC / DEF, EtOH; Zn / 1, 4-N DC / DEF; Zn / 2,6-MDC / DEF; Zn / PDC / DEF; Cu / BDC / DEF; Cu 1, 3.5, -BTC / EtOH; Cu / 1, 2, 3-BTC / MeO H; Cu / H3BTB / H2O, Df F, EtOH; Cu / H2BDC (OK) 2 # DMF; Cu / thiophenedicarboxylic acid / DEF; Cu / thiophenedicarboxylic acid / DMF; Cu / thiophenedicarboxylic acid / MeO H; Cu / malonic acid / DMF; Glutamione / FMO; Cu / Tartaric acid / DMF; Fe / H2BDC / DlftF; Fe / K3BDC / DSAF; Faith BTC / DMF; Faith / BDC / DMF, EtOH; Fe / BPOC / OMF, n-propanof; Fe / m-BDC / pyridine; Fe / m-BDC / DMF, píridtna; Co / BDC / MeOH; Co / H2BDC / NMP; Co / H2BDC / DM F; Pb / H2BDC / BMF, EtOH.

Here, the following abbreviations apply: BDC benzenedicarboxylic acid m-BDC acid-benzenecarboxylic acid H2BDC dihydroterephthalic acid H2N-BDC aminoterephthalic acid 4,4'-BP-2,2'-DC 4,4'-biphenyl-2,2'-dicarboxylic acid 4,4'-BPDC 4t4'-biphenyldicarboxylic acid H3BTB bencentribenzoate 1, 3,5-BTC 1,3, 5-benzenecarboxylic acid 1, 2,3-BTC 1,2,, 3-benzenetricarboxylic acid DHBDC 2,5-dihydroxyterephthalic acid 2,6-N DC 2,6-naphthalenedicarboxylic acid 1, 4-NDC 1, 4-áe? D © naphtalendicarboxílico PDC pyrendicarboxylic acid In a particularly preferred embodiment, the reaction medium comprises at least one sai of suitable electrolyte. Depending on at least one compound used and / or the solvent that is used if appropriate, it is also possible, in the process according to the invention, to carry out the preparation of said bidentate without an additional electrolysis salt. The electrolyte salts which can be used in the process according to the invention for the metal-organic structure are essentially not subject to restrictions. Preference is given to the use, for example, of salts of mineral acids, sulfonic acids, phosphonic acids, boronic acids, alkoxysuiphobic acids or earboxy acids or other acidic compounds such as sulfamides or imides. The possible anionic components of said at least one electrolyte salt are consequently and among others, sulfate, nitrate, nitrite, sulfite, disuipitate, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonates or hydrogencarbonate. Possible cation components of the electrolyte salts which can be used according to the invention are, inter alia, alkali metal ions such as Li *, Na *, K * or Rb *, iron alkali metal ions such as Mg2 *, Ca2 *, Sr2 * or Ba2 *, ammonium ions or phosphonium ions. Among the ammonium ions, quaternary ammonium ions and protonated monoanes, diamines and triamids can be mentioned. Examples of quaternary ammonium ions which are preferably used are, inter alia, symmetrical ammonium ions such as co or tetraacylammonium which preferably have, for example, methylethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, for example tetraethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, or asymmetric ammonium ions such as asymmetric tetraalkylammonium having preferably Ct-C4 -alkyl, for example methyl, ethyl, n-propyium, isopropyl, n-butyl, isobutyl, tert-butyl, for example methylbutyl onium, or ammonium ions having at least one aryl, for example phenyl or naphtyl, or at least one alkaryl, for example benzyl, or at least one arachidyl and at least one alkyl, preferably Cf-Ct-alkyl, for example methyl, ethyl, n-propyium, isopropyl, n-butsl,? butyl, tert-butyl, for example aryltrialkyl, for example benzytrimethylammonium or benzytriethylammonium. In a particularly preferred embodiment, at least one electrolyte sai comprises a methyltributylammonium ion as at least one cationic component. In a particularly preferred embodiment, methyltributylammonium methylsulfate is used as the electrolyte salt. Ionic liquids such as methylethylimidazole chloride or methylbutyramidium chloride can also be used as electrolyte salts in the process according to the invention. In an equally preferred embodiment, the methanesulfonate is used as the electrolyte salt. As the cation component of at least one electrolyte salt, mention may also be made in accordance with the invention of protonated or quaternary heterocyclics such as imidazolium ion. In a preferred embodiment, the compounds which are used for the formation of the metal-organic structure can be introduced into the reaction medium through the cationic and / or anionic component of at least one electrolyte salt. These compounds are compounds that influence the formation of the structure of the metal-organic framework although they are not included in the resulting structure and also compounds that are included in the resulting structure. In particular, at least one compound that is comprised in the resulting metal-organic structure can be introduced by means of said at least one electrolyte sai in the process of the invention. Preference is given, for example, in this regard, inter alia, to tetraalkylammonium carboxylate such as monotetraalkyl ammonium salt or 3,5-benzenetricarboxylic acid salt. In this embodiment, preference is given, inter alia, to the use of 1, 3,5-benzene-tricarboxylic acid together with tetraalkylammonium hydroxide in methanol as the solvent. This method of carrying out the process offers, inter alia, the advantage that tetraalkylammonium hydroxide is generally used as an aqueous solution and therefore water immediately becomes an essential component of the reaction medium. In one embodiment, it is therefore possible for the metal ion to be introduced into the reaction medium through the cationic component of at least one electrolyte sai in addition to said at least one anode as a source of metal ion. It is also possible that said at least one metal ion which is different from said at least one metal ion introduced by means of anodic oxidation into the reaction medium through the cationic component of said at least one electrolyte sai. In this case, the difference may be in the valence of the cation and / or the type of metal. It is also possible to use salts whose anion component or anion components are / are a compound / compounds used for the formation of the metal-organic structure as electrolyte salts in the process of the invention. In particular, it is therefore possible to make use of the electrolyte salts whose anion component is, for example, the onocarboxylate or dicarboxylate or tr? Carboxylate or tetracarboxyiate? Monosulfonate or disulfonate or trisulfonate or tetrasulfonate, preferably a dicarboxylate or tricarboxylane or tefracarboxylate and more preferably dicarboxylate or tricarboxylate or tetracarboxylate, of the aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids which are preferably used. The present invention further provides the method as described above wherein said at least one electrolyte salt comprises a quaternary ammonium ion as a cation component and a carboxylate of at least one bidentate organic compound as an anion component. In the process according to the invention, the concentration of said at least one electrolyte salt is generally in the range from 0.01 to 10% by weight, preferably in the range from 0.05 to 5% by weight and so particularly preferably in the range from 0.1 to 3% by weight, in each case based on the sum of the weights of all the electrolyte salts present in the reaction system and also based on the total weight of the reaction system without taking account for anodes and cathodes. An important advantage of the described process is that none of the critical anions described above such as halides or nitrate, which in conventional processes are introduced into the reaction medium through said at least one metal salt, are used in stoichiometric quantities although instead, said at least one electrolyte salt is introduced in substoichiometric amounts, that is to say in essentially catalytic amounts, if any. If the process is carried out in the batch mode, the reaction medium comprising the starting materials generates it! they are provided first, the current is applied subsequently and the reaction mixture is then re-directed by means of pumping. If the process is carried out continuously, an undercurrent is usually discharged from the reaction medium, the crystalline porous metal-organic structure comprised therein is isolated and the mother liquor is returned. A further advantage of the aforementioned method over the methods known from the prior art which start from metal salts in the preparation of the porous metal-organic structures is the fact that according to the invention it is possible to achieve a higher content of solids in the reaction medium per synthesis batch, since the solids content is not limited by the amount of starting salt used. This is because the cation metal can be introduced into any additional quantities through the anode. The term "solids content" as used for the purposes of the present invention refers to the amount of solids separated after the reaction, based on the total amount of the reaction mixture. In contrast to the preparation methods of the prior art, in which not only the ligand but also the metal salt is to be dissolved, said at least one solvent is available in its entirety for dissolving and / or suspending, preferably for dissolve the ligand, in the context of the aforementioned method. This applies in a particular way in a continuous variant of the aforementioned process in which the anode is further fed to the extent to which it is consumed by the anodic oxidation. That is, as described above, executed for example, in a grinding cell. In a manner analogous to the additional introduction of the anode, additional amounts of said at least one bidentate compound are introduced. The resulting suspension comprising the metal-organic structure can then be discharged continuously.

The economy of the process for preparing the porous metal-organic structures is considerably improved through this additional introduction of the metal cation by means of the additional introduction of the anode which can be carried out experimentally in a simple manner. In general, the solids content is at least 0.5% by weight, particularly preferably in the range from 0.5 to 50% by weight. In a particularly preferred embodiment, the aforementioned process is carried out in such a way that the redeposition of the metal ion that has been released by the anodic oxidation in the cathode is prevented. This redeposition is preferably avoided by, for example, using a cathode having an appropriate hydrogen over-release in a suitable reaction medium. Said cathodes are, for example, the aforementioned cathodes of graphite, copper, zinc, tin, manganese, silver, gold, platinum or cathodes comprising alloys such as steels, bronzes or brass. Preferably, the redepository is also avoided by, for example, an electrolyte which favors the cathodic formation of hydrogen I which is used in the reaction medium. In this case, preference is given, among others, to an electrolyte comprising at least one protic solvent. The preferred examples of said solvents have been provided in advance. Particular preference is given to alcohols, in particular methanol and ethanol.

The redeposition is also preferably avoided by, for example, a compound that leads to the cathodic depolarization that is comprised in the reaction medium. For the purposes of the present invention, a compound that leads to cathodic depolarization is any compound that is reduced to the cathode under the given reaction conditions. Preferred cathodic depolarizers are, among others, compounds that are hydrodimerized at the cathode. Examples of compounds that are particularly preferred in this context are acrylonitrile, acrylic esters and a-aesic esters such as, most preferably, dimethyl malonate. As cathode depolarizers, preference is also given, inter alia, to compounds comprising at least one carbonyl group that is reduced at the cathode. Examples of such compounds comprising carbonium groups are esters such as dialkyl phthalates and ketones such as acetone. As cathode depolarizers, it is preferable, inter alia, to compounds having at least one nitrogen-oxygen bond, a nitrogen-nitrogen bond and / or a nitrogen-carbon bond which is / are reduced / reduced at the cathode. Examples of such compounds are compounds having a nitro group, compounds having an azo group, compounds having an azoxy group, oximes, pyridines, i nases, nitriles and / or cyanates. In the described process, it is also possible to combine at least two of the aforementioned measures to avoid cathodic redeposition. For example, it is possible to use an electrolyte which promotes the cathodic formation of hydrogen and also to use an electrode having an appropriate hydrogen overflow. It is also possible to use an electrolyte that promotes the cathodic formation of hydrogen and add at least one compound that leads to cathodic depolarization. It is also possible to add at least one compound that leads to the cathodic depolarization and to use a cathode having an appropriate hydrogen overvoltage. It is also possible to use an electrolyte which favors the cathodic formation of hydrogen and employ an electrode which has an appropriate hydrogen overvoltage and also add at least one compound which leads to cathodic depolarization. Accordingly, the present invention also provides a process as described above in which the cathodic redeposition of said at least one metal ion is avoided at least partially by means of at least one of the following measures: (i) use of an electrolyte that favors the cathodic formation of the hydrogen; (ii) addition of at least one compound that leads to cathodic depolarization; (ii i) use of a cathode © that has an appropriate hydrogen overvoltage. Therefore, the present invention also provides a method as described above, in which the electrolyte according to (i) comprises less than one protic solvent, in particular an alcohol, more preferably methane! and / or ethane. The present invention provides for both Io likewise a method as mentioned above, in which the cathodic depolarization Ei is a hidrodiroerización, in particular a maleic diester of a hydrodimerization, most preferably dimethyl maleate. The present invention particularly preferably comprises a method as described above, in which at least one protic solvent, preferably one alcohol, more preferably methane! or etanoi or a mixture of methanol and ethanol, and ío least one compound capable of cathodic hydrodimerization, preferably a maleic tíiéster and most preferably dimethyl maleate, is used to avoid redeposition. In a particularly preferred embodiment, the process of the invention is operated in the circulation mode. For the purposes of the present invention, this "electrolysis circuit" refers to any process configuration in which at least part of the reaction system present in the electrolysis is discharged from the electrolysis cell, if appropriate subject to at least one intermediate treatment step such as at least one heat treatment or addition and / or removal of at least one component from the discharged stream and returned to the electrolysis cell. For the purposes of the present invention, such as an electrolysis circuit is particularly preferably operated in combination with a plate-holding cell, a tube cell or a grinding cell. After the preparation is complete, the generally crystalline structure is present in the form of primary crystals in the mother liquor. After the preparation of the organic structure is completed, the solid of the structure is separated from its mother liquor. This separation process can in principle be carried out by any suitable method. The solid structure is separated preferably by solid-liquid separation, centrifugation, extraction, filtration, membrane filtration, crossflow filtration, DIAF? Ltration, uitrafiitración, flocculation using flocculants such as nonionic auxiliaries, cationic and / or anionic, pH displacement by the addition of additives such as salts, acids, bases, flotation, spray drying, spray granulation or evaporation of the mother liquor at elevated temperatures and under reduced pressure and solid concentration. The separation can be followed by at least one additional washing step, at least one additional drying step and / or at least one additional calcination stage. If at least one washing step is carried out, the washing is carried out using at least one solvent used in the synthesis. If at least one drying step is used, if appropriate after at least one washing step, then the solid of the structure is generally dried at temperatures in the range from 20 to 120 ° C, preferably at the range from 40 to 100 ° C and particularly preferably in the range from 56 to 60 ° C. Preference is also given to drying under reduced pressure, with temperatures that are generally susceptible to be selected so that at least one washing liquid is at least partially, preferably completely, removed from the metal-organic structure. crystalline porous and frame structure at the same time rto is destroyed. The drying time is usually in the range from 0.1 to 1 5 hours, preferably in the range from 0.2 to 5 hours and of particular preference in the range from 0.5 to 1 hour. If said at least one washing step is appropriate and if appropriate said at least one drying step may be followed by at least one calcination step at which the temperatures are preferably selected so that the structure of the Frame is not destroyed. Washing and / or drying and / or calcination, in particular, make it possible, for example, to achieve the preferable and essentially quantitative, at least partial removal of a template compound which may have been used, if appropriate, for the preparation electrochemistry of the structure according to the invention. As with the electrochemical preparation method, the present invention also relates to the porous metal-organic structure itself that is prepared through the process described above.

The crystalline porous metal-organic structure is generally obtained as a fine powder, with the crystals having a size in the range from 0.1 to 100 f? I? T, determined by means of SEM (scanning electron microscope). The pore sizes of the porous metal-organic structures prepared electrochemically can be set within wide ranges through the type and number of per bidentate organic compound and / or type and, if appropriate, oxidation state of said by at least a metallic ton. Consequently, it is possible that the structure comprises micropores or esoporos or macropores or micropores and mesopores or micropores and acroporos or mesopores and macropores or micropores and mesopores and macropores. The structures prepared according to the invention particularly preferably comprise micropores or mesopores or micropores and mesopores. AND! The term "micropores" as used for the purposes of the present invention refers to pores having a diameter of up to 2 nm. The term "mesopores" as used for the purposes of the present invention refers to pores having a diameter from> 2 nm to 50 nm.These definitions correspond to the definitions given in Pure Appl. Chem. 45 (1976). , P. 71 ft., in particular P. 79. The presence of micropores and / or mesopores can be determined through measurements of nitrogen adsorption at 77K according to DIN 66131 and DIN 66 135 and DIN 66 134. The area The specific surface area of the crystalline porous metal-organic structures prepared according to the invention, determined in accordance with DIN 66 135, is generally at least 5 m2 / g, in particular greater than 5 m2 / g, of greater preference of at least 10 m2 / g, in particular greater than 10 m2 / g, more preferably of at least 50 m2 / g, in particular greater than 50 m2 / g, more preferably by I © minus 100 m2 / g in particular greater than 100 m2 §r of greater preference of at least 25 m2 (g, in particular r greater than 250 2 / g, more preferably at least 500 m2 / g, in particular greater than 500 m2 / g with the specific surface area which is likely to be more than 1000 m2 / g, for example higher of 2000 i? i2 / g, as an additional example greater than 3000 m2 / g and as a particular example greater than 4000 m2 / g. AND! The term "specific surface area" refers in the present context to the surface area determined according to the Langmuir model at 77K in accordance with DIN 66135. In a further embodiment, the porous metal-organic structure that has been separated from it has mother liquor is formed to produce one or more bodies formed. The possible geometries of these formed bodies are not subject in an essential way to restrictions. Examples, among others, are pellets such as disc-shaped pellets, pills, spheres, granules, extracted such as bar extrudates, honeycombs, grids and hollow bodies. In principle all appropriate processes are possible to produce those formed bodies. Among others, the following methods are preferred: Kneading the structure either alone or together with at least one binder and / or at least one pulping agent and / or at least one template compound to provide a mixture; forming the resulting mixture by means of at least one suitable method, for example extrusion; optionally washing and / or drying and / or calcining the extracted; optionally, finished. - Application of the structure to at least one porous support material, if appropriate. The material obtained can be further processed through the method described above to produce a formed body. - Application of the structure to at least one porous substrate is appropriate. Kneading and training can be carried out by any suitable method, as described, for example, in Ullmanns Enzyklopadíe der Techntschen Chemie, 4a. edition, Volume 2, p. 313 ft. (1972), whose relevant contents are fully incorporated by reference within the present patent application. For example, the kneading and / or forming can preferably be carried out by means of a piston press, roller press in the presence or absence of at least one binder material, compounding, pelletizing, tabletting. extrusion, coextrusion, foaming, rotation, coating, granulation, preferably spray granulation, spraying, spray drying or a combination of two or more of those methods. The pellets and / or tablets are produced particularly preferably in the process of the invention. The kneading and / or forming can be carried out at elevated temperatures, for example in the range from room temperature to 300 ° C, and / or at elevated pressure, for example in the range from atmospheric pressure to a few hundred bars, and / or in a protective gas atmosphere, for example in the presence of at least one noble gas, nitrogen or a mixture of two or more thereof. The kneading and / or forming are, according to a further embodiment, executed with the addition of at least one binder, with the binder used which is susceptible in principle to be any chemical compound that ensures the desired viscosity for kneading and / or formation - of the composition that is to be kneaded and / or formed. Accordingly, the binders may, for the purposes of the present invention, be viscosity increase or viscosity reduction compounds.

Preferred binders include, for example, aluminum oxide or binders comprising aluminum oxide as described, for example, in WO 94/29408, silicon dioxide as described, for example, in EP 0 592 050 A1, mixtures of silicon dioxide and aluminum oxide as described, for example, in WO 94/13584, clay minerals as described, for example, in JP 03-037156 A, for example montmoriionite, kaolin, bentonite, halosite, dike, naer The anaxitates, alkoxysilanes are described, for example, in EP 0 102 544 B1, for example tetraalkoxysilanes such as tetra-ethoxysilane, tera-ethoxysilane, tetrapropoxysilane, tetrabutoxysilane and, for example, triazeoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxisi lano, alkoxytitanates, for example tetraalkoxytitanates, such as tetramethoxytitanate, tetratetex? titanate, tetrapropoxytitanate, tetrabutoxytitanate and, for example, triacytitanatos such as trimethoxy Tiyana, triethoxytitanate, tripropoxytiitanate, tributoxytitanate, alkoxydecyanates, for example tetraacycoxitanises such as tetramethoxyzirconate, tetraethoxyizirconate, tetrapropoxyizircinate, tetrabutoxyzirconate, and, for example, trialkoxyzirconates such as trimethoxyzirconate, frietoxysirconate, tripropoxyzirconate, tributoxizirconate, silica solutions, amphiphilic substances and / or graphite. Particular preference is given to graphite. As a compound of viscosity increase, it is also possible, for example, to use, if appropriate in addition to the aforementioned compounds, an organic compound and / or a hydrophobic polymer such as cellulose or a cellulose derivative tai such as methylcellulose and / or polyacrylate. Ate and / or polymethyl alcohol and / or polyvinyl alcohol and / or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran. As a paste-forming agent, preference is given to the use, inter alia, of water or at least one alcohol, for example a monoalcohol having from 1 to 4 carbon atoms, for example methane, ethanol, n-propanoi, isopropane, 1-butanol, 2-butanol, 2-methy1-1-propanol © 2-metii-2-propanol, or a mixture of water and at least one of the mentioned alcohols or an alcohol, monohydric such as a rubber , preferably a water-miscible polyhydric alcohol, either alone or as a mixture with water and / or at least one of the monohydric alcohols mentioned. Additional additives which may be used for kneading and / or forming are, inter alia, amines or amine derivatives such as tetraalkylammonium compounds or amino alcohols and carbonate-comprising compounds such as calcium carbonate. Said additional additives are described, for example, in EP 0 389 041 A1. EP O 200 260 A1 or WO 95/1 S222. In principle, the order of the additives such as template compound, binder, paste-forming agent, viscosity-increasing substance in the formation and kneading is not critical. In a further preferred embodiment, the formed body obtained by means of kneading and / or forming is subjected to at least one drying operation which is generally carried out at a temperature in the range from 25 to 300 ° C, preferably in the range from 50 to 300 ° C and particularly preferably in the range from 10 to 300 ° C. It is also possible to carry out the drying under reduced pressure bajo under an atmosphere of protective gas or by means of spray drying. In a particularly preferred embodiment, the structure is applied to at least one porous material if appropriate. Preferably a porous substrate is used here. This application is particularly preferably carried out by means of impregnation with a liquid, saturation in a liquid, spraying, deposition from a liquid phase, deposition from the gas phase (vapor deposition), precipitation, coprecipitation, coating. As a porous substrate, if appropriate, preference is given to the use of aluminum oxide, silica gel, diatomaceous earths, kaolin, magnesium oxide, activated carbon, titanium dioxide, phosphates and / or zeolites. If, for example, non-porous substrates are used, it is possible, in a further embodiment, to produce coating structures as are known from coated catalysts by means of the application of the porous metal-organic structure for a non-porous formed body. . Of course, it is also possible to add at least one suitable pore former in the production of the formed bodies. The pore formers that can be used in the process according to the invention are all compounds that result in a particular pore size, a particular pore size distribution and / or particular pore volumes in the finished formed body. The pore formers used in the process according to the invention are preferably, among others, polymeric vinyl compounds such as polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides and polyesters. Particularly preferred pore formers are, for example, compounds that can be removed at least partially, preferably essentially completely, at the calcination temperatures of the process of the invention. An example is malonic acid. For the purposes of the present invention, porous metal-organic structures prepared electrochemically are used to absorb and / or store and release liquids and / or gases. The metal-organic structures can for this purpose be comprised in a formed body. Accordingly the present invention also provides the use of an electrochemically porous metal-organic structure preparable to purify at least one liquid and / or at least one gas or as a storage medium for at least one liquid and / or minus one gas The following examples illustrate the present invention.

Examples It was used in all the Cu? OF examples that have been prepared electrochemically as described in example DE 103 55 087.

Example 1: Methane adsorption The methane was adsorbed in 3 m extruded EMOF to ° C. The measurement was carried out in a common equilibrium. The sample was dried at 120 ° C and at a pressure of < 1 mbar for approximately 20 hours. The E OF has a surface area of 616 m2 / g. The following values were determined: Eqd = equilibrium distribution The results are shown graphically in figure 1 Example 2: CO2 adsorption CO2 was adsorbed on 3 mm extrusions of the EMOF at 25 ° C. The measurement was carried out in a common equilibrium. The sample was dried at 120 ° C and a pressure of < 1 mbar for approximately 20 hours. The EMOF has a surface area of 616 m2 / g. The following values were determined: Eqd /% Pressure / bar 0 0.00 3.625 0.43 19.805 10.84 21.617 13.87 24.006 18.83 20.798 12.23 18.136 7.75 14.505 3.85 11.130 2.16 The results are shown graphically in figure 2.

Example 3: Sorption of propene The propene portion was made at 70 ° C. The sample was dried at an equilibrium at 70 ° C for about 2.5 hours. The EMOF was in powder form and has a surface area of 1649 m2 / g. The results are shown in figure 3.

Example 4 (comparison): C02 sorption in molecular sieve 13x The sorption was carried out at 25 ° C. The 13x molecular sieve was dried at 25 ° C and < 0.1 mbar for approximately 5 hours. The molecular sieve had a surface area of 730 m2 / g. The following values were determined: The results are shown graphically in figure 4.

Example 5: Methane sorption in conventional MOF-5 (non-electrochemically prepared) The methane was adsorbed on extrudes of 3 m of EMO F at 25 ° C. The measurement was carried out in a common equilibrium. The sample was dried at 120 ° C and at a pressure of < 1 mbar for approximately 40 hours. The EMOF had a surface area of 2380 m2 / g. The following values were determined: The results are reported in figure 5.

Claims (17)

1. REIVI NDICATIONS 1 . A method of absorption and / or storage of gases, in which the gas to be stored is put in contact with a metal-organic structure prepared electrochemically under conditions suitable for the absorption of the gas, with absorption of the gas that occurs within the metal-organic structure and, if appropriate, the conditions are subsequently changed so that the release of the stored gas occurs.
2. 2. The method according to claim 1, characterized in that the gases that are stored or released are: saturated and unsaturated hydrocarbons, saturated and unsaturated alcohols, oxygen, nitrogen, noble gases, CO, CO2, synthesis gas, natural gases of all possible compositions or compounds that generate the gases that are subsequently released by the MOF.
3. 3. The method according to claim 1 or 2, characterized in that the gas that is stored or released is selected from H2; gas mixture comprising H2; compounds that produce © release H2; methane, ethane, propane, butanes, ethylene, propylene, acetylene, Ne, Ar, Kr, Xe, CO2 and CO2.
4. 4. The method according to any of claims 1 to 3, characterized in that the storage is carried out at a temperature from 0 to 100 ° C.
5. 5. The method according to any of claims 1 to 4, characterized in that the storage is carried out at a pressure from 1 to 300 bar (abs).
6. 6. The method according to any of claims 1 to 5; characterized in that the stored gas is released again to reduce the pressure or increase the temperature.
7. 7. The method according to any of claims 1 to 6, characterized in that the phthaoF is present in a gas-tight container.
8. The method according to claim 7, characterized in that the container is connected to or is part of a fuel cell.
9. 9. The method according to claim 8, characterized in that the fuel cell is used in a power station, motor vehicle or wireless application in electronic components 10.
10. The method according to any of claims 1 to 9, characterized in that the metal-organic structure prepared electrochemically comprises a metal of the groups la, lila, lila, IVa up to Villa and ib and Vlb of the Periodic Table of the Elements. 1.
11. The method according to claim 10, characterized in that the metal is selected from! group comprising Zn, Co, Ni, Pd, Pt, Ru, Rh, Fe, Mnt Ag and Co.
12. 12. A method for producing an electrochemically prepared metal-organic structure comprising a gas, wherein the gas is brought into contact with the structure and is absorbed in it.
13. 13. A metal-organic structure obtainable through a method according to claim 12.
14. 14. A fuel cell or container comprising an MOF material according to claim 13.
15. 15. A system comprising a material of according to claim 13 or a fuel cell according to claim 14, in particular for power stations, motor vehicles, preferably passenger cars, vehicles for products and buses.
16. 16. An application of a material according to claim 13 or a fuel cell according to claim 14, in particular for wireless applications in electronic components, preferably for mobile phones and laptops.
17. 17. The use of a metal-organic structure prepared electrochemically to store or release gases. IMMEDIATE SUMMARY The invention relates to a method for the absorption and / or storage of gases. According to said method, the gas to be stored is contacted with an organometallic framework material, produced electrochemically under conditions which are favorable for the absorption of gas. The gas is absorbed by the organometallic framework material and the conditions are subsequently modified in such a way that the gas is released. V5 Figure 1 or o Pressure / bar Ptesiortíbar Load equ? L? Bpo X%