WO2012077030A1

WO2012077030A1 - Process for coating support surface with porous metal-organic framework

Info

Publication number: WO2012077030A1
Application number: PCT/IB2011/055446
Authority: WO
Inventors: Manuela Gaab; Andrea Weber; Milan Kostur; Ulrich Mueller
Original assignee: Basf Se; Basf (China) Company Limited
Priority date: 2010-12-07
Filing date: 2011-12-05
Publication date: 2012-06-14
Also published as: AU2011340166A1; MX2013006021A; BR112013012870A2; CN103249738A; CA2818825A1; KR20130135882A; EP2649081A4; EP2649081A1; RU2013130865A; JP2014500143A

Abstract

Provided is a process for coating at least part of a surface of a support with a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion. The process comprises the following steps: (a) spraying the at least one part of the support surface with a first solution comprising the at least one metal ion; (b) spraying the at least one part of the support surface with a second solution comprising the at least one at least bidentate organic compound; wherein step (b) is carried out before, after or simultaneously with step (a), to form a layer of the porous metal-organic framework.

Description

PROCESS FOR COATING SUPPORT SURFACE WITH POROUS METAL-ORGANIC FRAMEWORK

Description The present invention relates to a process for coating at least part of a surface of a support with a porous metal-organic framework ("MOF").

Processes for coating with metal-organic frameworks have been described in the prior art.

WO2009/056184 A1 describes, for example, spraying a suspension comprising a metal-organic framework onto materials such as nonwovens.

DE 10 2006 031 31 1 A1 proposes applying adsorptive materials such as metal-organic frameworks to support materials by adhesive bonding or another method of fixing.

The formation of a layer of MOF by means of bonding to gold surfaces by means of self-assembly monolayers is described by S. Hermes et al., J. Am. Chem. Soc. 127 (2005), 13744-13745 (see also S. Hermes et al. Chem. Mater. 19 (2007), 2168-2173; D. Zacher et al., J. Mater. Chem. 17 (2007), 2785-2792; O. Shekhah et al., J. Am. Chem. Soc. 129 (2007), 151 18-151 19; A. Schroedel et al., Angew. Chem. Int. Ed. 49 (2010), 7225-7228).

MOF layers on silicone supports are described by G. Lu, J. Am. Chem. Soc. 132 (2010), 7832-7833.

MOF layers on polyacrylonitrile supports are described by A. Centrone et al., J. Am. Chem. Soc. 132 (2010), 15687-15691 . Copper-benzenetricarboxylate MOF on copper membranes is described by H. Guo et al., J. Am. Chem. Soc. 131 (2009), 1646-1647.

The production of an MOF layer on an aluminum support by dipping and crystal growing is described by Y.-S. Li et al., Angew. Chem. Int. Ed. 49 (2010), 548-551 . Similar subject matter is described by J. Gascon et al., Microporous and Mesoporous Materials 1 13 (2008), 132-138 and A. Demessence et al., Chem. Commun. 2009, 7149-7151 and P. Kusgen et al., Advanced Engineering Materials 1 1 (2009), 93-95. The electrodeposition of an MOF film is described by A. Domenech et al., Electrochemistry Communications 8 (2006), 1830-1834.

MOF layers have likewise been used for coating capillaries (N. Chang et al., J. Am. Chem. Soc. 132 (2010), 13645-13647).

Despite the processes for coating a support surface with a porous metal-organic framework which are known from the prior art, there is a need for improved processes. It is an object of the present invention to provide an improved process.

The object is achieved by a process for coating at least part of a surface of a support with a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion, which comprises the steps

(a) spraying of the at least one part of the support surface with a first solution comprising the at least one metal ion;

(b) spraying of the at least one part of the support surface with a second solution comprising the at least one at least bidentate organic compound, where step (b) is carried out before, after or simultaneously with step (a), to form a layer of the porous metal-organic framework.

It has been found that spraying-on of the first and second solution results in spontaneous formation of the metal-organic framework in the form of a layer on the support surface. Here, it is particularly advantageous that homogenous layers can be obtained. Spraying enables a faster production process than dipping processes to be carried out. The adhesion can be increased, so that bonding agents may be able to be dispensed with.

Step (a) can be carried out before step (b). Step (a) can also be carried out after step (b). It is likewise possible for step (a) and step (b) to be carried out simultaneously.

The resulting layer of the porous metal-organic framework can preferably be dried. If step (a) and (b) are not carried out simultaneously, a drying step can additionally be carried out between the two steps.

The drying of the resulting layer of the porous metal-organic framework can, in particular, be effected by heating and/or by means of reduced pressure. Heating is carried out, for example, at a temperature in the range from 120°C to 300°C. The layer is preferably dried at at least 150°C.

Spraying can be carried out by means of known spraying techniques. Spraying with the first, second or both with the first and the second solution is preferably carried out in a spraying drum.

The solutions can be at different temperatures or the same temperature. This can be above or below room temperature. The same applies to the support surface. The first solution or the second solution or both the first and the second solution is/are preferably at room temperature (22°C).

The first and second solutions can comprise identical or different solvents. Preference is given to using the same solvent. Possible solvents are solvents known in the prior art. The first solution or the second solution or both the first and second solutions is/are preferably an aqueous solution.

The support surface can be a metallic or nonmetallic, optionally modified surface. Preference is given to a fibrous or foam surface.

Particular preference is given to a sheet-like textile structure comprising or consisting of natural fibers and/or synthetic fibers (chemical fibers), in particular with the natural fibers being selected from the group consisting of wool fibers, cotton fibers (CO) and in particular cellulose and/or, in particular, with the synthetic fibers being selected from the group consisting of polyesters (PES); polyolefins, in particular polyethylene (PE) and/or polypropylene (PP); polyvinyl chlorides (CLF); polyvinylidene chlorides (CLF); acetates (CA); triacetates (CTA); polyacrylic (PAN); polyamides (PA), in particular aromatic, preferably flame-resistant polyamides; polyvinyl alcohols (PVAL); polyurethanes; polyvinyl esters; (meth)acrylates; polylactic acids (PLA); activated carbon; and mixtures thereof.

Particular preference is given to foams for sealing and insulation, acoustic foams, rigid foams for packaging and flame-resistant foams composed of polyurethane, polystyrene, polyethylene, polypropylene, PVC, viscose, cellular rubber and mixtures thereof. Very particular preference is given to foam composed of melamine resin (Basotect).

A particularly suitable support material is filter material (including dressing material, cotton cloths, cigarette filters, filter papers as can, for example, be procured commercially for laboratory use). The first solution comprises the at least one metal ion. This can be used as metal salt. The second solution comprises the at least one at least bidentate organic compound. This can preferably be in the form of a solution of its salt.

The at least one metal ion and the at least one at least bidentate organic compound form the porous metal-organic framework by contacting of the two solutions directly on the support surface to form a layer. Metal-organic frameworks which can be produced in this way are known in the prior art.

Such metal-organic frameworks (MOF) are, for example, described in US 5,648,508, EP-A-0 790 253, M. O'Keeffe et al., J . Sol. State Chem., 152 (2000), pages 3 to 20, H. Li et al., Nature 402, (1999), page 276, M. Eddaoudi et al., Topics in Catalysis 9, (1999), pages 105 to 1 1 1 , B. Chen et al., Science 29J., (2001 ), pages 1021 to 1023, DE-A-101 1 1 230, DE-A 10 2005 053430, WO-A 2007/054581 , WO-A 2005/049892 and WO-A 2007/023134.

As a specific group of these metal-organic frameworks, "limited" frameworks in which, as a result of specific selection of the organic compound, the framework does not extend infinitely but forms polyhedra are described in the recent literature. A.C. Sudik, et al., J. Am. Chem. Soc. 127 (2005), 71 10-71 18, describe such specific frameworks. Here, they will be described as metal-organic polyhedra (MOP) to distinguish them.

A further specific group of porous metal-organic frameworks comprises those in which the organic compound as ligand is a monocyclic, bicyclic or polycyclic ring system which is derived at least from one of the heterocycles selected from the group consisting of pyrrole, alpha-pyridone and gamma-pyridone and has at least two ring nitrogens. The electrochemical preparation of such frameworks is described in WO-A 2007/131955.

The general suitability of metal-organic frameworks for absorbing gases and liquids is described, for example, in WO-A 2005/003622 and EP-A 1 702 925

These specific groups are particularly suitable for the purposes of the present invention.

The metal-organic frameworks according to the present invention comprise pores, in particular micropores and/or mesopores. Micropores are defined as pores having a diameter of 2 nm or less and mesopores are defined by a diameter in the range from 2 to 50 nm, in each case corresponding to the definition given in Pure & Applied Chem. 57 (1983), 603 - 619, in particular on page 606. The presence of micropores and/or mesopores can be checked by means of sorption measurements which determine the absorption capacity of the MOF for nitrogen at 77 kelvin in accordance with DI N 66131 and/or DI N 66134.

The specific surface area, calculated according to the Langmuir model (DIN 66131 , 66134), of an MOF is preferably greater than 10 m²/g, more preferably greater than 20 m²/g, more preferably greater than 50 m²/g. Depending on the MOF, it is also possible to achieve greater than 100 m²/g, more preferably greater than 150 m²/g and particularly preferably greater than 200 m²/g.

The metal component in the framework according to the present invention is preferably selected from groups la, lla, Il ia, IVa to Vil la and lb to VIb. Particular preference is given to Mg, Ca, Sr, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb and Bi, where Ln represents lanthanides.

Lanthanides are La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, Yb. As regards the ions of these elements, particular mention may be made of Mg²⁺, Ca²⁺, Sr , Ba²⁺, Sc³⁺, Y³⁺, Ln³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh⁺, Ir²", lr⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺, Ga³⁺, ln³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sb⁺, Bi⁵⁺, Bi³⁺ and Bi⁺.

Very particular preference is given to Mg, Ca, Al, Y, Sc, Zr, Ti, V, Cr, Mo, Fe, Co, Cu, Ni, Zn, Ln. Greater preference is given to Mg, Ca, Al, Mo, Y, Sc, Mg, Fe, Cu and Zn. In particular, Mg, Ca, Sc, Al, Cu and Zn are preferred. Very particular mention may here be made of Mg, Ca, Al and Zn, in particular Al.

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

As functional groups via which the abovementioned coordinate bonds are formed, particular mention may be made by way of example of the following functional groups: -C0₂H, -CS₂H, -N0₂, -B(OH)₂, -S0₃H, -Si(OH)₃, -Ge(OH)₃, -Sn(OH)₃, -Si(SH)₄, -Ge(SH)₄, -Sn(SH)₃, -P0₃H, -As0₃H , -As0₄H, -P(SH)₃, -As(SH)₃, -CH(RSH)₂, -C(RSH)₃ -CH(RNH₂)₂ -C(RN H₂)₃, -CH(ROH)₂, -C(ROH)₃, -CH(RCN)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 comprising 1 or 2 aromatic rings, for example 2 C₆ rings, which may optionally be fused and may, independently of one another, be appropriately substituted by at least one substituent in each case and/or may, independently of one another, in each case comprise 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 abovementioned radical R is not present. In this respect, mention may be made of, inter alia, -CH(SH)₂, -C(SH)₃, -CH(NH₂)₂, -C(NH₂)₃, -CH(OH)₂, -C(OH)₃, -CH(CN)₂ or -C(CN)₃.

However, the functional groups can also be heteroatoms of a heterocycle. Particular mention may here be made of nitrogen atoms.

The at least two functional groups can in principle be bound to any suitable organic compound as long as it is ensured that the organic compound bearing these functional groups is capable of forming the coordinate bond and of producing the framework. The organic compounds comprising the at least two functional groups are preferably derived from a saturated or unsaturated aliphatic compound or an aromatic compound or a both aliphatic and aromatic compound.

The 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 rings per compound also being possible. The aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound more preferably 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 from 1 to 1 1 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 to, inter alia, methane, adamantane, acetylene, ethylene or butadiene.

The 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 rings, with the rings being able to be present separately from one another and/or at least two rings being able to be present in fused form. The aromatic compound or the aromatic part of the both aliphatic and aromatic compound particularly preferably has one, two or three rings, with one or two rings being particularly preferred. Furthermore, each ring of said compound can independently comprise at least one heteroatom, for example N, O, S, B, P, Si, Al , preferably N, O and/or S. The aromatic compound or the aromatic part of the both aromatic and aliphatic compound more preferably comprises one or two C₆ rings, with the two being present either separately from one another or in fused form. In particular, mention may be made of benzene, naphthalene and/or biphenyl and/or bipyridyl and/or pyridyl as aromatic compounds.

The at least bidentate organic compound is more preferably an aliphatic or aromatic, acyclic or cyclic hydrocarbon which has from 1 to 18, preferably from 1 to 10 and in particular 6, carbon atoms and additionally has exclusively 2, 3 or 4 carboxyl groups as functional groups.

The at least one at least bidentate organic compound is preferably derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid.

For example, the at least bidentate organic compound is derived from a dicarboxylic acid such as oxalic acid, succinic acid, tartaric acid, 1 ,4-butanedicarboxylic acid, 1 ,4- butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1 ,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1 ,8-heptadecanedicarboxylic acid, 1 ,9- heptadecanedicarboxlic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1 ,2-benzenedicarboxylic acid, 1 ,3-benzenedicarboxylic acid, 2,3- pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1 ,3-butadiene-1 ,4-dicarboxylic acid, 1 ,4-benzenedicarboxylic acid, p-benzenedicarboxylic 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'- diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro- 4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6- dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1 ,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-dicarboxylic acid, 4,4'-diamino-1 , 1 '-biphenyl-3,3'- dicarboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'- dicarboxylic acid, 1 ,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1 , 1 '-binaphthyl- dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1 -anilino- anthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran 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)phenylpyrazoline-4,5-dicarboxylic acid, 1 ,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1 ,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1 ,4-cyclohexane- dicarboxylic acid, naphthalene-1 ,8-dicarboxylic acid, 2-benzoylbenzene-1 ,3- dicarboxylic acid, 1 ,3-dibenzyl-2-oxoimidazolidene-4,5-cis-dicarboxylic acid, 2,2'- biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9- trioxaundecanedicarboxylic acid, hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3- pyrazinedicarboxylic acid, 4,4'-diamino(diphenyl ether)diimidedicarboxylic acid, 4,4'- diaminodiphenylmethanediimidedicarboxylic acid, 4,4'-diamino(diphenyl sulfone) diimidedicarboxylic acid, 1 ,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1 ,3-adamantanedicarboxylic acid, 1 ,8-naphthalenedicarboxylic acid, 2,3- naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3- naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene- 2,3-dicarboxylic acid, 2',3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, (diphenyl ether)- 4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1 H)-oxothiochromene-2,8- dicarboxylic acid, 5-tert-butyl-1 ,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1 ,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1 ,7-heptane- dicarboxylic acid, 5-hydroxy-1 ,3-benzenedicarboxylic acid, 2,5-dihydroxy-1 ,4- dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1 -nonene- 6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'- dicarboxylic acid, 1 -amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3- dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9- dichlorofluorubin-4,1 1 -dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorbenzophenone-2',5'-dicarboxylic acid, 1 ,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1 -benzyl-1 H- pyrrole-3,4-dicarboxylic acid, anthraquinone-1 ,5-dicarboxylic acid, 3,5- pyrazoledicarboxylic acid, 2-nitrobenzene-1 ,4-dicarboxylic acid, heptane-1 ,7- dicarboxylic acid, cyclobutane-1 ,1 -dicarboxylic acid 1 ,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid or camphordicarboxylic acid,

Furthermore, the at least bidentate organic compound is more preferably one of the dicarboxylic acids mentioned by way of example above as such.

The at least bidentate organic compound can, for example, be derived from a tricarboxylic acid such as

2-hydroxy-1 ,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid,

1.2.3- , 1 ,2,4-benzenetricarboxylic acid, 1 ,2,4-butanetricarboxylic acid, 2-phosphono-

1.2.4- butanetricarboxylic 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-methylbenzene-1 ,2,4-tricarboxylic acid, 3-amino- 5-benzoyl-6-methylbenzene-1 ,2,4-tricarboxylic acid, 1 ,2,3-propanetricarboxylic acid or aurintricarboxylic acid.

Furthermore, the at least bidentate organic compound is more preferably one of the tricarboxylic acids mentioned by way of example above as such.

Examples of an at least bidentate organic compound derived from a tetracarboxylic acid are 1 , 1 -dioxidoperylo[1 , 12-BCD]thiophene-3,4,9, 10-tetracarboxylic acid, perylenetetra- carboxylic acids such as perylene-3,4,9, 10-tetracarboxylic acid or (perylene-1 ,12- sulfone)-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic 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, 1 1 , 12-tetracarboxylic acid, 1 ,2,4,5-benzenetetracarboxylic acid, 1 ,2,1 1 , 12-dodecanetetracarboxylic acid, 1 ,2,5,6-hexanetetracarboxylic acid, 1 ,2,7,8-octanetetracarboxylic acid, 1 ,4,5,8- naphthalenetetracarboxylic acid, 1 ,2,9, 10-decanetetracarboxylic acid, benzo- phenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic acids such as cyclopentane-1 ,2,3,4-tetracarboxylic acid.

Furthermore, the at least bidentate organic compound is more preferably one of the tetracarboxylic acids mentioned by way of example above as such. Preferred heterocycles as at least bidentate organic compound in which a coordinate bond is formed via the ring heteroatoms are the following substituted or unsubstituted ring systems:

Very particular preference is given to using optionally at least monosubstituted aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids which can have one, two, three, four or more rings, with each of the rings being able to comprises at least one heteroatom and two or more rings being able to comprise identical or different heteroatoms. For example preference is given to one-ring dicarboxylic acids, one-ring tricarboxylic acids, one-ring tetracarboxylic acids, two-ring dicarboxylic acids, two-ring tricarboxylic acids, two-ring tetracarboxylic acids, three-ring dicarboxylic acids, three- ring tricarboxylic acids, three-ring tetracarboxylic acids, four-ring dicarboxylic acids, four-ring tricarboxylic acids and/or four-ring tetracarboxylic acids. Suitable heteroatoms are, for example, N, O, S, B, P, and preferred heteroatoms are N, S and/or O. Suitable substituents here are, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.

Particularly preferred at least bidentate organic compounds are imidazolates such as 2-methylimidazolate, acetylenedicarboxylic acid (ADC), camphordicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid (BDC), aminoterephthalic acid, triethylenediamine (TEDA), methylglycinediacetic acid (MGDA), naphthalenedicarboxylic acids (NDC), biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), pyrazinedicarboxylic acids such as 2,5-pyrazinedicarboxylic acid, bipyridinedicarboxylic acids such as 2,2'-bipyridinedicarboxylic acids such as 2,2'-bipyridine-5,5'-dicarboxylic acid, benzenetricarboxylic acids such as 1 ,2,3-, 1 ,2,4-benzenetricarboxylic acid or 1 ,3,5-benzenetricarboxylic acid (BTC), benzenetetracarboxylic acid, adamantanetetracarboxylic acid (ATC), adamantanedibenzoate (ADB), benzenetribenzoate (BTB), methanetetrabenzoate (MTB), adamantanetetrabenzoate or dihydroxyterephthalic acids such as 2,5-dihydroxyterephthalic acid (DHBDC), tetrahydropyrene-2,7-dicarboxylic acid (HPDC), biphenyltetracarboxylic acid (BPTC), 1 ,3-bis(4-pyridyl)propane (BPP).

Very particular preference is given to using, inter alia, 2-methylimidazole, 2-ethylimidazole, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid , 1 ,4-naphthalenedicarboxylic acid, 1 ,5-naphthalene- dicarboxylic acid, 1 ,2,3-benzenetricarboxylic acid, 1 ,2,4-benzenetricarboxylic acid, 1 ,3,5-benzenetricarboxylic acid, 1 ,2,4,5-benzenetetracarboxylic acid, aminoBDC, TEDA, fumaric acid, biphenyldicarboxylate, 1 ,5- and 2,6-naphthalenedicarboxylic acid, tert-butylisophthalic acid, dihydroxybenzoic acid, BTB, HPDC, BPTC, BPP.

Apart from these at least bidentate organic compounds, the metal-organic framework can also comprise one or more monodentate ligands and/or one or more at least bidentate ligands which are not derived from a dicarboxylic, tricarboxlic or tetracarboxylic acid.

Apart from these at least bidentate organic compounds, the metal-organic framework can also comprise one or more monodentate iigands.

Preferred at least bidentate organic compounds are formic acid, acetic acid or an aliphatic dicarboxylic or polycarboxylic acid, for example malonic acid, fumaric acid or the like, in particular fumaric acid, or are derived from these.

For the purposes of the present invention, the term "derived" means that the at least one at least bidentate organic compound is present in partially or fully deprotonated form. Furthermore, the term "derived" means that the at least one at least bidentate organic compound can have further substituents. Thus, a dicarboxylic or polycarboxylic acid can have not only the carboxylic acid function but also one or more independent substituents such as amino, hydroxyl, methoxy, halogen or methyl groups. Preference is given to no further substituent being present. For the purposes of the present invention, the term "derived" also means that the carboxylic acid function can be present as a sulfur analogue. Sulfur analogues are -C(=0)SH and its tautomer and -C(S)SH.

Suitable solvents for preparing the metal-organic framework are, inter alia, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpyrrolidone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and mixtures thereof. Further metal ions, at least bidentate organic compounds and solvents for the preparation of MOFs are described, inter alia, in US-A 5,648,508 or DE-A 101 1 1 230.

The pore size of the metal-organic framework can be controlled by selection of the appropriate ligand and/or the at least bidentate organic compound. In general, the larger the organic compound, the larger the pore size. The pore size is preferably from 0.2 nm to 30 nm, particularly preferably in the range from 0.3 nm to 3 nm, based on the crystalline material.

Examples of metal-organic frameworks are given below. In addition to the designation of the framework, the metal and the at least bidentate ligand, the solvent and the cell parameters (angles α, β and γ and the dimensions A, B and C in A) are also indicated. The latter were determined by X-ray diffraction.

MOF-n Constituents Solvent a β Y a b c Space molar ratio s group M+L

MOF-0 Zn(N0₃)₂-6H₂0 ethanol 90 90 120 16.71 1 16.71 1 14.189 P6(3)/

H₃(BTC) Mem

MOF-2 Zn(N0₃)₂-6H₂0 DMF 90 102.8 90 6.718 15.49 12.43 P2(1 )/n

(0.246 mmol) toluene

H₂(BDC)

0.241 mmol)

MOF-3 Zn(N0₃)₂-6H₂0 DMF 99.72 1 1 1.1 1 108.4 9.726 9.91 1 10.45 P-1

(1.89 mmol) MeOH

H₂(BDC)

(1.93 mmol)

MOF-4 Zn(N0₃)₂-6H₂0 ethanol 90 90 90 14.728 14.728 14.728 P2(1 )3

(1.00 mmol)

H₃(BTC)

(0.5 mmol)

MOF-5 Zn(N0₃)₂-6H₂0 DMF 90 90 90 25.669 25.669 25.669 Fm-3m

(2.22 mmol) chloro¬

H₂(BDC) benzene

(2.17 mmol) MOF-38 Zn(N0₃)₂-6H₂0 DMF 90 90 90 20.657 20.657 17.84 I4cm (0.27 mmol) chloro-

H₃(BTC) benzene

(0.15 mmol)

MOF-31 Zn(N0₃)₂-6H₂0 ethanol 90 90 90 10.821 10.821 10.821 Pn(-3)m Zn(ADC)₂ 0.4 mmol

H₂(ADC)

0.8 mmol

MOF-12 Zn(N0₃)₂-6H₂0 ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn₂(ATC) 0.3 mmol

H₄(ATC)

0.15 mmol

MOF-20 Zn(N0₃)₂-6H₂0 DMF 90 92.13 90 8.13 16.444 12.807 P2(1 )/c

ZnNDC 0.37 mmol chloro-

H₂NDC benzene

0.36 mmol

MOF-37 Zn(N0₃)₂-6H₂0 DEF 72.38 83.16 84.33 9.952 11.576 15.556 P-1

0.2 mmol chloro- H₂NDC benzene

0.2 mmol

MOF-8 Tb(N0₃)₃-5H₂0 DMSO 90 1 15.7 90 19.83 9.822 19.183 C2/c

Tb₂ (ADC) 0.10 mmol MeOH

H₂ADC

0.20 mmol

MOF-9 Tb(N0₃)₃-5H₂0 DMSO 90 102.09 90 27.056 16.795 28.139 C2/c Tb₂ (ADC) 0.08 mmol

H₂ADB

0.12 mmol

MOF-6 Tb(N0₃)₃-5H₂0 DMF 90 91.28 90 17.599 19.996 10.545 P21/C

0.30 mmol MeOH

H₂ (BDC)

0.30 mmol

MOF-7 Tb(N0₃)₃-5H₂0 H₂0 102.3 91.12 101.5 6.142 10.069 10.096 P-1

0.15 mmol

H₂(BDC)

0.15 mmol

MOF-69A Zn(N0₃)₂-6H₂0 DEF 90 1 11.6 90 23.12 20.92 12 C2/c

0.083 mmol H₂0₂

4,4'BPDC MeNH₂

0.041 mmol

MOF-69B Zn(N0₃)₂-6H₂0 DEF 90 95.3 90 20.17 18.55 12.16 C2/c

0.083 mmol H₂0₂

2,6-NCD MeNH₂

0.041 mmol

MOF-11 Cu(N0₃)₂-2.5H₂0 H₂0 90 93.86 90 12.987 11.22 11.336 C2/c Cu₂(ATC) 0.47 mmol

H₂ATC

0.22 mmol

MOF-11 90 90 90 8.4671 8.4671 14.44 P42/ Cu₂(ATC) mmc dehydr.

MOF-14 Cu(N0₃)₂-2.5H₂0 H₂0 90 90 90 26.946 26.946 26.946 lm-3

Cu₃ (BTB) 0.28 mmol DMF

H₃BTB EtOH

0.052 mmol

MOF-32 Cd(N0₃)₂-4H₂0 H₂0 90 90 90 13.468 13.468 13.468 P(-4)3m

Cd(ATC) 0.24 mmol NaOH

H₄ATC

0.10 mmol

MOF-33 ZnCI₂ H₂0 90 90 90 19.561 15.255 23.404 Imma

Zn₂ (ATB) 0.15 mmol DMF

H₄ATB EtOH

0.02 mmol

MOF-34 Ni(N0₃)₂-6H₂0 H₂0 90 90 90 10.066 11.163 19.201 P2i2i2i

Ni(ATC) 0.24 mmol NaOH

H₄ATC

0.10 mmol

MOF-36 Zn(N0₃)₂-4H₂0 H₂0 90 90 90 15.745 16.907 18.167 Pbca

Zn₂ (MTB) 0.20 mmol DMF

H₄MTB

0.04 mmol

MOF-39 Zn(N0₃)₂4H₂0 H₂0 90 90 90 17.158 21.591 25.308 Prima

Zn₃0(HBTB) 0.27 mmol DMF

H₃BTB EtOH

0.07 mmol

NO305 FeCI₂-4H₂0 DMF 90 90 120 8.2692 8.2692 63.566 R-3c

5.03 mmol

formic acid

86.90 mmol

N029 Mn(Ac)₂-4H₂0 DMF 120 90 90 14.16 33.521 33.521 P-1 MOF-0 0.46 mmol

similar H₃BTC

0.69 mmol

BPR48 Zn(N0₃)₂ 6H₂0 DMSO 90 90 90 14.5 17.04 18.02 Pbca A2 0.012 mmol toluene

H₂BDC

0.012 mmol

BPR69 Cd(N0₃)₂4H₂0 DMSO 90 98.76 90 14.16 15.72 17.66 Cc B1 0.0212 mmol

H₂BDC

0.0428 mmol

BPR92 Co(N0₃)₂-6H₂0 NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1 A2 0.018 mmol H₂BDC

0.018 mmol

BPR95 Cd(N0₃)₂4H₂0 NMP 90 1 12.8 90 14.460 11.085 15.829 P2(1 )/n C5 0.012 mmol

H₂BDC

0.36 mmol

Cu C₆H₄0₆ Cu(N0₃)₂-2.5H₂0 DMF 90 105.29 90 15.259 14.816 14.13 P2(1 )/c

0.370 mmol chloro- H₂BDC(OH)₂ benzene

0.37 mmol

M(BTC) Co(S0₄) H₂0 DMF like MOF-0

MOF-0 0.055 mmol

similar H₃BTC

0.037 mmol

Tb(C₆H₄0₆) Tb(N0₃)₃-5H₂0 DMF 104.6 107.9 97.147 10.491 10.981 12.541 P-1

0.370 mmol chloro- H₂(C₆H₄0₆) benzene

0.56 mmol

Zn (C₂0₄) ZnCI₂ DMF 90 120 90 9.4168 9.4168 8.464 P(-3)1 m

0.370 mmol chloro- oxalic acid benzene

0.37 mmol

Co(CHO) Co(N0₃)₂-5H₂0 DMF 90 91.32 90 11.328 10.049 14.854 P2(1 )/n

0.043 mmol

formic acid

1.60 mmol

Cd(CHO) Cd(N0₃)₂-4H₂0 DMF 90 120 90 8.5168 8.5168 22.674 R-3c

0.185 mmol

formic acid

0.185 mmol

Cu(C₃H₂0₄) Cu(N0₃)₂-2.5H₂0 DMF 90 90 90 8.366 8.366 11.919 P43

0.043 mmol

malonic acid

0.192 mmol

Zn₆ (NDC)₅ Zn(N0₃)₂-6H₂0 DMF 90 95.902 90 19.504 16.482 14.64 C2/m MOF-48 0.097 mmol chloro-

14 NDC benzene

0.069 mmol H₂0₂

MOF-47 Zn(N0₃)₂ 6H₂0 DMF 90 92.55 90 11.303 16.029 17.535 P2(1 )/c

0.185 mmol chloro-

H₂(BDC[CH₃]₄) benzene

0.185 mmol H₂0₂

M025 Cu(N0₃)₂-2.5H₂0 DMF 90 1 12.0 90 23.880 16.834 18.389 P2(1 )/c

0.084 mmol

BPhDC

0.085 mmol

Cu-Thio Cu(N0₃)₂-2.5H₂0 DEF 90 1 13.6 90 15.474 14.514 14.032 P2(1 )/c

0.084 mmol 7

1.23 mmol

AS54-3 FeBr₂ DMF 90 109.98 90 12.019 15.286 14.399 C2

0.927 anhydr.

BPDC n-propanol

0.927 mmol

AS61 -4 FeBr₂ anhydrous 90 90 120 13.017 13.017 14.896 P6(2)c

0.927 mmol pyridine

m-BDC

0.927 mmol

AS68-7 FeBr₂ DMF 90 90 90 18.340 10.036 18.039 Pca2i

0.927 mmol anhydr. 7

m-BDC pyridine 1.204 mmol

Zn(ADC) Zn(N0₃)₂-6H₂0 DMF 90 99.85 90 16.764 9.349 9.635 C2/c

0.37 mmol chloro- H₂(ADC) benzene

0.36 mmol

MOF-12 Zn(N0₃)₂-6H₂0 ethanol 90 90 90 15.745 16.907 18.167 Pbca

Zn₂ (ATC) 0.30 mmol

H₄(ATC)

0.15 mmol

MOF-20 Zn(N0₃)₂-6H₂0 DMF 90 92.13 90 8.13 16.444 12.807 P2(1 )/c

ZnNDC 0.37 mmol chloro-

H₂NDC benzene

0.36 mmol

MOF-37 Zn(N0₃)₂-6H₂0 DEF 72.38 83.16 84.33 9.952 11.576 15.556 P-1

0.20 mmol chloro-

H₂NDC benzene

0.20 mmol

Zn(NDC) Zn(N0₃)₂-6H₂0 DMSO 68.08 75.33 88.31 8.631 10.207 13.114 P-1

(DMSO) H₂NDC

Zn(NDC) Zn(N0₃)₂-6H₂0 90 99.2 90 19.289 17.628 15.052 C2/c

H₂NDC

Zn(HPDC) Zn(N0₃)₂-4H₂0 DMF 107.9 105.06 94.4 8.326 12.085 13.767 P-1

0.23 mmol H₂0

H₂(HPDC)

0.05 mmol

Co(HPDC) Co(N0₃)₂-6H₂0 DMF 90 97.69 90 29.677 9.63 7.981 C2/c

0.21 mmol H₂0/

H₂ (HPDC) ethanol

0.06 mmol

Zn₃(PDC)2.5 Zn(N0₃)₂-4H₂0 DMF/ CIBz 79.34 80.8 85.83 8.564 14.046 26.428 P-1

0.17 mmol H₂0/ TEA

H₂(HPDC)

0.05 mmol

Cd₂ (TPDC)2 Cd(N0₃)₂-4H₂0 methanol/ 70.59 72.75 87.14 10.102 14.412 14.964 P-1

0.06 mmol CHP H₂0

H₂(HPDC)

0.06 mmol

Tb(PDC)1.5 Tb(N0₃)₃-5H₂0 DMF 109.8 103.61 100.14 9.829 12.11 14.628 P-1

0.21 mmol H₂0/

H₂(PDC) ethanol

0.034 mmol

ZnDBP Zn(N0₃)₂-6H₂0 MeOH 90 93.67 90 9.254 10.762 27.93 P2/n

0.05 mmol

dibenzyl phosphate

0.10 mmol

Zn₃(BPDC) ZnBr₂ DMF 90 102.76 90 11.49 14.79 19.18 P21/n

0.021 mmol

4,4'BPDC 0.005 mmol

CdBDC Cd(N0₃)₂-4H₂0 DMF 90 95.85 90 11.2 11.11 16.71 P21/n

0.100 mmol Na₂Si0₃

H₂(BDC) (aq)

0.401 mmol

Cd-mBDC Cd(N0₃)₂-4H₂0 DMF 90 101.1 90 13.69 18.25 14.91 C2/c

0.009 mmol MeNH₂

H₂(mBDC)

0.018 mmol

Zn₄OBND Zn(N0₃)₂-6H₂0 DEF 90 90 90 22.35 26.05 59.56 Fmmm C 0.041 mmol MeNH₂

BNDC H₂0₂

Eu(TCA) Eu(N0₃)₃-6H₂0 DMF 90 90 90 23.325 23.325 23.325 Pm-3n

0.14 mmol chloro-

TCA benzene

0.026 mmol

Tb(TCA) Tb(N0₃)₃-6H₂0 DMF 90 90 90 23.272 23.272 23.372 Pm-3n

0.069 mmol chloro-

TCA benzene

0.026 mmol

Formate Ce(N0₃)₃-6H₂0 H₂0 90 90 120 10.668 10.667 4.107 R-3m

0.138 mmol ethanol

formic acid

0.43 mmol

FeCI₂-4H₂0 DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol

formic acid

86.90 mmol

FeCI₂-4H₂0 DEF 90 90 90 9.9364 18.374 18.374 Pbcn 5.03 mmol

formic acid

86.90 mmol

FeCI₂-4H₂0 DEF 90 90 90 8.335 8.335 13.34 P-31 c 5.03 mmol

formic acid

86.90 mmol

NO330 FeCI₂-4H₂0 form- 90 90 90 8.7749 11.655 8.3297 Pnna

0.50 mmol amide

formic acid

8.69 mmol

N0332 FeCI₂-4H₂0 DIP 90 90 90 10.031 18.808 18.355 Pbcn

0.50 mmol 3

formic acid

8.69 mmol N0333 FeCI₂-4H₂0 DBF 90 90 90 45.275 23.861 12.441 Cm cm 0.50 mmol 4

formic acid

8.69 mmol

N0335 FeCI₂-4H₂0 CHF 90 91.372 90 11.596 10.187 14.945 P21/n

0.50 mmol 4

formic acid

8.69 mmol

N0336 FeCI₂-4H₂0 MFA 90 90 90 11.794 48.843 8.4136 Pbcm

0.50 mmol 5

formic acid

8.69 mmol

N013 Mn(Ac)₂-4H₂0 ethanol 90 90 90 18.66 11.762 9.418 Pbcn

0.46 mmol

benzoic acid

0.92 mmol

bipyridine

0.46 mmol

N029 Mn(Ac)₂-4H₂0 DMF 120 90 90 14.16 33.521 33.521 P-1 MOF-0 0.46 mmol

similar H₃BTC

0.69 mmol

Mn(hfac)₂ Mn(Ac)₂-4H₂0 ether 90 95.32 90 9.572 17.162 14.041 C2/c (0₂CC₆H₅) 0.46 mmol

Hfac

0.92 mmol

bipyridine

0.46 mmol

BPR43G2 Zn(N0₃)₂-6H₂0 DMF 90 91.37 90 17.96 6.38 7.19 C2/c

0.0288 mmol CH₃CN

H₂BDC

0.0072 mmol

BPR48A2 Zn(N0₃)₂ 6H₂0 DMSO 90 90 90 14.5 17.04 18.02 Pbca

0.012 mmol toluene

H₂BDC

0.012 mmol

BPR49B1 Zn(N0₃)₂ 6H₂0 DMSO 90 91.172 90 33.181 9.824 17.884 C2/c

0.024 mmol methanol

H₂BDC

0.048 mmol

BPR56E1 Zn(N0₃)₂ 6H₂0 DMSO 90 90.096 90 14.587 14.153 17.183 P2(1 )/n

0.012 mmol n-propanol 3

H₂BDC

0.024 mmol

BPR68D10 Zn(N0₃)₂ 6H₂0 DMSO 90 95.316 90 10.062 10.17 16.413 P2(1 )/c

0.0016 mmol benzene 7

H₃BTC

0.0064 mmol

BPR69B1 Cd(N0₃)₂4H₂0 DMSO 90 98.76 90 14.16 15.72 17.66 Cc

0.0212 mmol

H₂BDC 0.0428 mmol

BPR73E4 Cd(N0₃)₂4H₂0 DMSO 90 92.324 90 8.7231 7.0568 18.438 P2(1 )/n

0.006 mmol toluene

H₂BDC

0.003 mmol

BPR76D5 Zn(N0₃)₂ 6H₂0 DMSO 90 104.17 90 14.4191 6.2599 7.0611 Pc

0.0009 mmol

H₂BzPDC

0.0036 mmol

BPR80B5 Cd(N0₃)₂-4H₂0 DMF 90 115.11 90 28.049 9.184 17.837 C2/c

0.018 mmol

H₂BDC

0.036 mmol

BPR80H5 Cd(N0₃)₂4H₂0 DMF 90 119.06 90 11.4746 6.2151 17.268 P2/c

0.027 mmol

H₂BDC

0.027 mmol

BPR82C6 Cd(N0₃)₂4H₂0 DMF 90 90 90 9.7721 21.142 27.77 Fdd2

0.0068 mmol

H₂BDC

0.202 mmol

BPR86C3 Co(N0₃)₂ 6H₂0 DMF 90 90 90 18.3449 10.031 17.983 Pca2(1 )

0.0025 mmol

H₂BDC

0.075 mmol

BPR86H6 Cd(N0₃)₂-6H₂0 DMF 80.98 89.69 83.41 9.8752 10.263 15.362 P-1

0.010 mmol 2

H₂BDC

0.010 mmol

Co(N0₃)₂ 6H₂0 NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1

BPR95A2 Zn(N0₃)₂ 6H₂0 NMP 90 102.9 90 7.4502 13.767 12.713 P2(1 )/c

0.012 mmol

H₂BDC

0.012 mmol

CuC₆F₄0₄ Cu(N0₃)₂-2.5H₂0 DMF 90 98.834 90 10.9675 24.43 22.553 P2(1 )/n

0.370 mmol chloro- H₂BDC(OH) ₂ benzene

0.37 mmol

Fe Formic FeCI₂-4H₂0 DMF 90 91.543 90 11.495 9.963 14.48 P2(1 )/n

0.370 mmol

formic acid

0.37 mmol

Mg Formic Mg(N0₃)₂-6H₂0 DMF 90 91.359 90 11.383 9.932 14.656 P2(1 )/n

0.370 mmol

formic acid

0.37 mmol

MgC₆H₄0₆ Mg(N0₃)₂-6H₂0 DMF 90 96.624 90 17.245 9.943 9.273 C2/c 0.370 mmol

H₂BDC(OH) ₂

0.37 mmol

Zn C₂H₄BDC ZnCI₂ DMF 90 94.714 90 7.3386 16.834 12.52 P2(1 )/n MOF-38 0.44 mmol

CBBDC

0.261 mmol

MOF-49 ZnCI₂ DMF 90 93.459 90 13.509 1 1.984 27.039 P2/c

0.44 mmol CH₃CN

m-BDC

0.261 mmol

MOF-26 Cu(N0₃)₂-5H₂0 DMF 90 95.607 90 20.8797 16.017 26.176 P2(1 )/n

0.084 mmol

DCPE

0.085 mmol

MOF-112 Cu(N0₃)₂-2.5H₂0 DMF 90 107.49 90 29.3241 21.297 18.069 C2/c

0.084 mmol ethanol

o-Br-m-BDC

0.085 mmol

MOF-109 Cu(N0₃)₂-2.5H₂0 DMF 90 1 1 1.98 90 23.8801 16.834 18.389 P2(1 )/c

0.084 mmol

KDB

0.085 mmol

MOF-11 1 Cu(N0₃)₂-2.5H₂0 DMF 90 102.16 90 10.6767 18.781 21.052 C2/c

0.084 mmol ethanol

o-BrBDC

0.085 mmol

MOF-110 Cu(N0₃)₂-2.5H₂0 DMF 90 90 120 20.0652 20.065 20.747 R-3/m

0.084 mmol

thiophene

dicarboxylic acid

0.085 mmol

MOF-107 Cu(N0₃)₂-2.5H₂0 DEF 104.8 97.075 95.20 1 1.032 18.067 18.452 P-1

0.084 mmol 6

thiophene

dicarboxylic acid.

0.085 mmol

MOF-108 Cu(N03)2-2.5H20 DBF/ 90 1 13.63 90 15.4747 14.514 14.032 C2/c

0.084 mmol methanol

thiophene

dicarboxylic acid

0.085 mmol

MOF-102 Cu(N03)2-2.5H20 DMF 91.63 106.24 1 12.0 9.3845 10.794 10.831 P-1

0.084 mmol 1

H2(BDCCI2)

0.085 mmol

Clbdd Cu(N03)2-2.5H20 DEF 90 105.56 90 14.91 1 15.622 18.413 P-1

0.084 mmol

H2(BDCCI2)

0.085 mmol

Cu(NMOP) Cu(N03)2-2.5H20 DMF 90 102.37 90 14.9238 18.727 15.529 P2(1 )/m

0.084 mmol

NBDC

0.085 mmol Tb(BTC) Tb(N03)3-5H20 DMF 90 106.02 90 18.6986 11.368 19.721 0.033 mmol

H3BTC

0.033 mmol

Zn3(BTC)2 ZnCI2 DMF 90 90 90 26.572 26.572 26.572 Fm-3m

Honk 0.033 mmol ethanol

H3BTC

0.033 mmol

Zn40(NDC) Zn(N03)2-4H20 DMF 90 90 90 41.5594 18.818 17.574 aba2

0.066 mmol ethanol

14NDC

0.066 mmol

CdTDC Cd(N03)2-4H20 DMF 90 90 90 12.173 10.485 7.33 Pmma

0.014 mmol H20

thiophene

0.040 mmol

DABCO

0.020 mmol

IRMOF-2 Zn(N03)2-4H20 DEF 90 90 90 25.772 25.772 25.772 Fm-3m

0.160 mmol

o-Br-BDC

0.60 mmol

IRMOF-3 Zn(N03)2-4H20 DEF 90 90 90 25.747 25.747 25.747 Fm-3m

0.20 mmol ethanol

H2N-BDC

0.60 mmol

IRMOF-4 Zn(N03)2-4H20 DEF 90 90 90 25.849 25.849 25.849 Fm-3m

0.11 mmol

[C3H70]2-BDC

0.48 mmol

IRMOF-5 Zn(N03)2-4H20 DEF 90 90 90 12.882 12.882 12.882 Pm-3m

0.13 mmol

[C5H110]2-BDC

0.50 mmol

IRMOF-6 Zn(N03)2-4H20 DEF 90 90 90 25.842 25.842 25.842 Fm-3m

0.20 mmol

[C2H4]-BDC

0.60 mmol

IRMOF-7 Zn(N03)2-4H20 DEF 90 90 90 12.914 12.914 12.914 Pm-3m

0.07 mmol

1.4NDC

0.20 mmol

IRMOF-8 Zn(N03)2-4H20 DEF 90 90 90 30.092 30.092 30.092 Fm-3m

0.55 mmol

2,6NDC

0.42 mmol

IRMOF-9 Zn(N03)2-4H20 DEF 90 90 90 17.147 23.322 25.255 Pnnm

0.05 mmol

BPDC

0.42 mmol

IRMOF-10 Zn(N03)2-4H20 DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.02 mmol

BPDC

0.012 mmol

IRMOF-11 Zn(N03)2-4H20 DEF 90 90 90 24.822 24.822 56.734 R-3m

0.05 mmol

HPDC

0.20 mmol

IRMOF-12 Zn(N03)2-4H20 DEF 90 90 90 34.281 34.281 34.281 Fm-3m

0.017 mmol

HPDC

0.12 mmol

ADC acetylenedicarboxylic acid

NDC naphthalenedicarboxylic acid

BDC benzenedicarboxylic acid

ATC adamantanetetracarboxylic acid

BTC benzenetricarboxylic acid

BTB benzenetribenzoic acid

MTB methanetetrabenzoic acid

ATB adamantanetetrabenzoic acid

ADB adamantanedibenzoic acid

Further metal-organic frameworks are MOF-2 to 4, MOF-9, MOF-31 to 36, MOF-39, MOF-69 to 80, MOF103 to 106, MOF-122, MOF-125, MOF-150, MOF-177, MOF-178, MOF-235, MOF-236, MOF-500, MOF-501 , MOF-502, MOF-505, I RMOF-1 , I RMOF-61 , IRMOP-13, I RMOP-51 , MIL-17, MIL-45, MIL-47, MI L-53, MIL-59, MIL-60, MI L-61 , MIL- 63, MI L-68, MI L-79, MI L-80, MIL-83, MIL-85, CPL-1 to 2, SZL-1 , which are described in the literature.

Particularly preferred metal-organic frameworks are MIL-53, Zn-tBu-isophthalic acid, AI-BDC, MOF-5, MOF-177, MOF-505, I RMOF-8, I RMOF-1 1 , Cu-BTC, AI-NDC, AI-aminoBDC, Cu-BDC-TEDA, Zn-BDC-TEDA, AI-BTC, Cu-BTC, AI-NDC, Mg-NDC, Al- fumarate, Zn-2-methylimidazolate, Zn-2-aminoimidazolate, Cu-biphenyldicarboxylate- TEDA, MOF-74, Cu-BPP, Sc-terephthalate. Greater preference is given to Sc- terephthalate, AI-BDC and AI-BTC. In particular, however, preference is given to Mg- formate, Mg-acetate and mixtures thereof because of their environmental friendliness. Aluminum-fumarate is particularly preferred.

The layer of the porous metal-organic framework preferably has a mass in the range from 0.1 g/m² to 100 g/m², more preferably from 1 g/m² to 80 g/m², even more preferably from 3 g/m² to 50 g/m².

Examples

The following examples indicate various methods of coating filter paper with aluminum- fumarate MOF by means of direct synthesis.

For all examples, two solutions were produced as described below:

Solution 1 : Deionized water (72.7 g) was placed in a vessel and AI₂(S04)₃x18H₂0 (16.9 g, 25.5 mmol) was dissolved therein with stirring.

Solution 2: Deionized water (87.3 g) was placed in a vessel and NaOH (6.1 g, 152.7 mmol) was dissolved therein with stirring. Fumaric acid (5.9 g, 50.9 mmol) was subsequently added while stirring and the mixture was stirred until a clear solution was formed. For example 1 , filters from Macherey-Nagel (d = 150 mm) were used. Filter papers from Schleicher & Schuell (d = 90-1 10 mm) were used for example 2. The surface area of the untreated filter papers is -1 -2 m²/g (specific surface area determined by the Langmuir method (LSA)). The surface areas of the coated papers were determined using a small sample of the filters (~ 100 mg).

In all examples, room temperature is 22°C. Example 1 : Coating of filter papers by spraying-on the solutions in a rotating spraying drum at room temperature

Experimental method:

The filter paper was fixed in the spraying drum by means of adhesive tape and sprayed with solution 1 by means of a pump having a spray head at room temperature and rotation of the drum. After brief drying or in the moist state, solution 2 was sprayed on at room temperature by means of the pump. The filter paper was subsequently dried at room temperature in a jet of compressed air in the rotating drum. Uniform coating with a few flakes at the edge was obtained. The increase in mass of the filters was 1 .2-2.3 g. The dried papers were washed 4 times with 10 ml each time of H₂0 on a suction filter under a slight water pump vacuum and dried again at room temperature. The filters obtained were activated at 150°C in a vacuum drying oven for 16 hours. XRD analysis of a selected sample displayed, in addition to Ibeta cellulose, a weak peak at 10 2-theta which can be assigned to the aluminum-fumarate MOF. The corresponding surface area was 51 m²/g LSA.

Example 2: Coating of filter paper by simultaneous spraying-on of the solutions 1 and 2

Experimental method:

The filter paper was suspended and simultaneously sprayed with up to 1 ml of the two solutions (Eco-Spray sprayer and Desaga SG-1 sprayer). The treated filter paper was dried in air at room temperature while suspended. Homogeneous layers having a few small flakes were obtained. The increasing mass of the filters was 80-290 mg. The paper was subsequently washed 4 times with 10 ml each time of H₂0 and dried at 100°C in a convection drying oven for 16 hours. 31 -279 mg were then detected on the filter papers. This corresponds to from 4.9 to 42 g/m². XRD analysis of a selected sample displayed, in addition to Ibeta cellulose, a strong peak at 10 2-theta (crystallinity -3000) which can be assigned to the aluminum-fumarate MOF.

Example 3: Coating of further support surfaces

10 x 10 cm pieces of a teatowel (90% cotton, 10% linen) A, a cotton glove B, cellulose cloths (Zewa®) C, bandaging waste (viscose) D and Basotect E (melamine resin foam) were treated in the same way as the filter paper in example 2. The mass taken up after spraying and drying was 770-500 mg. After washing of the samples A to D with water and subsequent drying at room temperature, coatings of 440-580 mg were obtained. This corresponds to from 4.4 to 5.8 g/m². Analysis of all samples displayed, in addition to the signals of the respective material, a peak at 10° (2-theta), which can be assigned to the aluminum-fumarate MOF. The surface areas of the treated materials were 17-22 m²/g LSA.

Claims

A process for coating at least part of a surface of a support with a porous metal- organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion, which comprises the steps

The process according to claim 1 , wherein the layer is dried.

The process according to claim 2, wherein the layer is dried at at least 150°C.

The process according to any of claims 1 to 3, wherein the spraying with the first, the second or with both solutions is carried out in a spraying drum.

The process according to any of claims 1 to 4, wherein the first, the second or both solutions are at room temperature.

The process according to any of claims 1 to 5, wherein the first, the second or both solutions are aqueous solutions.

The process according to any of claims 1 to 6, wherein the support surface is a fibrous or foam surface.

The process according to any of claims 1 to 7, wherein the at least one metal ion is selected from the group of metals consisting of Mg, Ca, Al and Zn.

The process according to any of claims 1 to 8, wherein the at least one at least bidentate organic compound is derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid.

The process according to any of claims 1 to 9, wherein the layer of the porous metal-organic framework has a mass in the range from 0.1 g/m² to 100 g/m².