CA2818825A1

CA2818825A1 - Process for coating support surface with porous metal-organic framework

Info

Publication number: CA2818825A1
Application number: CA2818825A
Authority: CA
Inventors: Manuela Gaab; Andrea Weber; Milan Kostur; Ulrich Mueller
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-12-07
Filing date: 2011-12-05
Publication date: 2012-06-14
Also published as: KR20130135882A; WO2012077030A1; MX2013006021A; CN103249738A; AU2011340166A1; EP2649081A4; JP2014500143A; BR112013012870A2; RU2013130865A; EP2649081A1

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.
W02009/056184 Al describes, for example, spraying a suspension comprising a metal-organic framework onto materials such as nonwovens.
DE 10 2006 031 311 Al 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.

(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; 0. Shekhah et al., J.
Am.
Chem. Soc. 129 (2007), 15118-15119; A. Schroedel et al., Angew. Chem. Int. Ed.

(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 113 (2008), 132-138 and A. Demessence et al., Chem. Commun. 2009, 7149-7151 and P. Kusgen et al., Advanced Engineering Materials 11 (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 (MOP) 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 111, B. Chen et al., Science 291, (2001), pages 1021 to 1023, DE-A-101 11230, DE-A 10 2005 053430, WO-A2007/054581, WO-A2005/049892 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), 7110-7118, 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 and/or DIN 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, Ila, IIla, IVa to Villa and lb to Vlb. 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 Mg", Ca", Sr2+, Ba2+, Sc3+, Y3+, Ln", Ti4+, zr4+, Hf4+, v4+, v3+, v2+, Nb3+, Ta3+, Cr", Mo", W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os", Os", Co", Co", Rh", Rh, Ir", Ir+, Ni2+, Ni, Pd2+, Pd, Pt2+, Pt, Cu2+, Cu, Ag+, Au, Zn2+, Cd2+, Hg2+, Al3+, Ga3+, In3+, TI3+, si4+, si2+, Ge4+, Ge2+, sn4+, sn2+, pb4+, Pb 2, AS5+, As3+, Ask, 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:
-CO2H, -CS2H, -NO2, -6(OH)2, -503H, -Si(OH)3, -Ge(OH)3, -Sn(OH)3, -Si(SH)4, -Ge(SH)4, -Sn(SH)3, -P03H, -AsO3H, -AsatH, -P(SH)3, -As(SH)3, -CH(RSH)2, -C(RSH)3 -CH(RNH2)2 -C(RNH2)3, -CH(ROH)2, -C(ROH)3, -CH(RCN)2, -C(RCN)3, where R 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 06 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, 0 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 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 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, 0, S, B, P, Si, Al, preferably N, 0 and/or S. The aromatic compound or the aromatic part of the both aromatic and aliphatic compound more preferably comprises one or two 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-1,11-biphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobipheny1-3,3'-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)pheny1-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzy1-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexane-dicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzy1-2-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-dimethy1-2,3-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-terpheny1-4,4"-dicarboxylic acid, (diphenyl ether)-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-buty1-1,3-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-methy1-9,10-d ioxo-9,10-d ihydroanth racene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,11-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-benzy1-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-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-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoy1-6-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-d ioxidoperylo[1,12-BCD]th iophene-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 ,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-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:

1 \. il\) & I N
N N N N
H H H H
,N N
_...., _ H H H H H
I \ 1 \ 1$ I \ NU
NN
it"----N N -----1\1 N'e----N N-----I\I
H H H H H
H
O
i-N
0 /-N 0 N-N ,N, N 0 N N 3 N N N N Nc) -..,.......N -......,.....,..NH
H H H H H

\NiN 0,IW N i N \

N N
el N/

H
H
lei NO el N NH

Very particular preference is given to using optionally at least monosubstituted aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids which can have one, two, 5 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-10 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, 0, S, B, P, and preferred heteroatoms are N, S and/or 0.
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(=O)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 11230.
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 a, 13 and y 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 a b c Space molar ratio s group M+L
MOF-0 Zn(NO3)2.6H20 ethanol 90 90 120 16.711 16.711 14.189 P6(3)/
H3(BTC) Mcm MOF-2 Zn(NO3)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) Zn(NO3)2.6H20 DMF 99.72 111.11 108.4 9.726 9.911 10.45 P-1 (1.89 mmol) Me0H
H2(BDC) (1.93 mmol) MOF-4 Zn(NO3)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(NO3)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(NO3)2.6H20 DMF 90 90 90 20.657 20.657 17.84 .. 14cm (0.27 mmol) chloro-H3(BTC) benzene (0.15 mmol) MOF-31 Zn(NO3)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(NO3)2.6H20 ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn2(ATC) 0.3 mmol NATO) 0.15 mmol MOF-20 Zn(NO3)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(NO3)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(NO3)3.5H20 DMSO 90 115.7 90 19.83 9.822 19.183 02/c Tb2 (ADC) 0.10 mmol Me0H

0.20 mmol MOF-9 Tb(NO3)3.5H20 DMSO 90 102.09 90 27.056 16.795 28.139 02/c Tb2 (ADC) 0.08 mmol 0.12 mmol MOF-6 Tb(NO3)3.5H20 DMF 90 91.28 90 17.599 19.996 10.545 P21/c 0.30 mmol Me0H
H2 (BDC) 0.30 mmol MOF-7 Tb(NO3)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(NO3)2.6H20 DEF 90 111.6 90 23.12 20.92 12 02/c 0.083 mmol H202 4,413PDC MeNH2 0.041 mmol MOF-69B Zn(NO3)2.6H20 DEF 90 95.3 90 20.17 18.55 12.16 02/c 0.083 mmol H202 2,6-NOD MeNH2 0.041 mmol MOF-11 Cu(NO3)2.2.5H20 H20 90 93.86 90 12.987 11.22 11.336 02/c 0u2(ATC) 0.47 mmol 0.22 mmol MOF-11 90 90 90 8.4671 8.4671 14.44 P42/

cu2(ATc) mmc dehydr.
MOF-14 Cu(NO3)2.2.5H20 H20 90 90 90 26.946 26.946 26.946 .. Im-3 Cu3 (BTB) 0.28 mmol DMF
H3BTB Et0H
0.052 mmol MOF-32 Cd(NO3)2.4H20 H20 90 90 90 13.468 13.468 13.468 P(-4)3m Cd(ATC) 0.24 mmol NaOH
HATO
0.10 mmol MOF-33 ZnCl2 H20 90 90 90 19.561 15.255 23.404 Imma Zn2 (ATB) 0.15 mmol DMF
H4ATB Et0H
0.02 mmol MOF-34 Ni(NO3)2.6H20 H20 90 90 90 10.066 11.163 19.201 P212121 Ni(ATC) 0.24 mmol NaOH
HATO
0.10 mmol MOF-36 Zn(NO3)2.4H20 H20 90 90 90 15.745 16.907 18.167 Pbca Zn2 (MTB) 0.20 mmol DMF

0.04 mmol MOF-39 Zn(NO3)2 41120 H20 90 90 90 17.158 21.591 25.308 Pnma Zn30(HBTB) 0.27 mmol DMF
H3BTB Et0H
0.07 mmol N0305 FeC12=4H20 DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol formic acid 86.90 mmol N0306A FeC12=4H20 DEF 90 90 90 9.9364 18.374 18.374 Pbcn 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(NO3)2 61120 DMSO 90 90 90 14.5 17.04 18.02 Pbca A2 0.012 mmol toluene 0.012 mmol BPR69 Cd(NO3)2 41120 DMSO 90 98.76 90 14.16 15.72 17.66 Cc B1 0.0212 mmol 0.0428 mmol BPR92 Co(NO3)2.6H20 NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1 A2 0.018 mmol 0.018 mmol BPR95 Cd(NO3)2 4H20 NMP 90 112.8 90 14.460 11.085 15.829 P2(1)/n 05 0.012 mmol 0.36 mmol Cu C6H406 Cu(NO3)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(SO4) H20 DMF like MOF-0 MOF-0 0.055 mmol similar H3BTC
0.037 mmol Tb(C6H406) Tb(NO3)3.5H20 DMF 104.6 107.9 97.147 10.491 10.981 12.541 0.370 mmol chloro-H2(C6H406) benzene 0.56 mmol Zn (0204) ZnCl2 DMF 90 120 90 9.4168 9.4168 8.464 P(-3)1m 0.370 mmol chloro-oxalic acid benzene 0.37 mmol Co(CHO) Co(NO3)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(NO3)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(NO3)2.2.5H20 DMF 90 90 90 8.366 8.366 11.919 P43 0.043 mmol malonic acid 0.192 mmol Zn6 (NDC)6 Zn(NO3)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 FI202 MOF-47 Zn(NO3)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(NO3)2.2.5H20 DMF 90 112.0 90 23.880 16.834 18.389 P2(1)/c 0.084 mmol BPhDC
0.085 mmol Cu-Thio Cu(NO3)2.2.5H20 DEF 90 113.6 90 15.474 14.514 14.032 P2(1)/c 0.084 mmol 7 thiophene dicarboxylic acid 0.085 mmol CIBDC1 Cu(NO3)2.2.5H200. DMF 90 105.6 90 14.911 15.622 18.413 02/c 084 mmol H2(BDCCI2) 0.085 mmol MOF-101 Cu(NO3)2.2.5H20 DMF 90 90 90 21.607 20.607 20.073 Fm3m 0.084 mmol BrBDC
0.085 mmol Zn3(BTC)2 Zn0I2 DMF 90 90 90 26.572 26.572 26.572 Fm-3m 0.033 mmol Et0H
H3BTC Base 0.033 mmol added MOF-j CO (C H3CO2)24 H2 H20 90 112.0 90 17.482 12.963 6.559 02 (1.65 mmol) H3(BZC) (0.95 mmol) MOF-n Zn(NO3)2.6H20 ethanol 90 90 120 16.711 16.711 14.189 P6(3)/mcm H3 (BTC) PbBDC Pb(NO3)2 DMF 90 102.7 90 8.3639 17.991 9.9617 P2(1)/n (0.181 mmol) ethanol H2(BDC) (0.181 mmol) Znhex Zn(NO3)2.6H20 DMF 90 90 120 37.116 37.117 30.019 P3(1)c (0.171 mmol) p-xylene 5 H3BTB ethanol (0.114 mmol) AS16 FeBr2 DMF 90 90.13 90 7.2595 8.7894 19.484 P2(1)c 0.927 mmol anhydr.
H2(BDC) 0.927 mmol AS27-2 FeBr2 DMF 90 90 90 26.735 26.735 26.735 .. Fm3m 0.927 mmol anhydr.
H3(BDC) 0.464 mmol AS32 Fe013 DMF 90 90 120 12.535 12.535 18.479 P6(2)c 1.23 mmol anhydr.
H2(BDC) ethanol 1.23 mmol AS54-3 FeBr2 DMF 90 109.98 90 12.019 15.286 14.399 02 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 Pca21 0.927 mmol anhydr. 7 m-BDC pyridine 1.204 mmol Zn(ADC) Zn(NO3)2.6H20 DMF 90 99.85 90 16.764 9.349 9.635 02/c 0.37 mmol chloro-H2(ADC) benzene 0.36 mmol MOF-12 Zn(NO3)2.6H20 ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn2 (ATC) 0.30 mmol NATO) 0.15 mmol MOF-20 Zn(NO3)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(NO3)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(NO3)2.6H20 DMSO 68.08 75.33 88.31 8.631 10.207 13.114 P-1 (DMSO) H2NDC
Zn(NDC) Zn(NO3)2.6H20 90 99.2 90 19.289 17.628 15.052 02/c Zn(HPDC) Zn(NO3)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(NO3)2.6H20 DMF 90 97.69 90 29.677 9.63 7.981 02/c 0.21 mmol H20/
H2 (HPDC) ethanol 0.06 mmol Zn3(PDC)2.5 Zn(NO3)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(NO3)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(NO3)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(NO3)2.6H20 Me0H 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`13PDC

0.005 mmol CdBDC Cd(NO3)2.4H20 DMF 90 95.85 90 11.2 11.11 16.71 P21/n 0.100 mmol Na2SiO3 H2(BDC) (aq) 0.401 mmol Cd-mBDC Cd(NO3)2.4H20 DMF 90 101.1 90 13.69 18.25 14.91 02/c 0.009 mmol MeN H2 H2(mBDC) 0.018 mmol Zn4OBND Zn(NO3)2.6H20 DEF 90 90 90 22.35 26.05 59.56 Fmmm 0.041 mmol MeNH2 Eu(TCA) Eu(NO3)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(NO3)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(NO3)3.6H20 H20 90 90 120 10.668 10.667 4.107 R-3m 0.138 mmol ethanol formic acid 0.43 mmol Fe012=4H20 DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol formic acid 86.90 mmol Fe012=4H20 DEF 90 90 90 9.9364 18.374 18.374 Pbcn 5.03 mmol formic acid 86.90 mmol Fe012=4H20 DEF 90 90 90 8.335 8.335 13.34 P-31c 5.03 mmol formic acid 86.90 mmol N0330 Fe012=4H20 form- 90 90 90 8.7749 11.655 8.3297 Pnna 0.50 mmol amide formic acid 8.69 mmol N0332 Fe012=4H20 DIP 90 90 90 10.031 18.808 18.355 Pbcn 0.50 mmol 3 formic acid 8.69 mmol N0333 FeC12=4H20 DBF 90 90 90 45.275 23.861 12.441 Cmcm 0.50 mmol 4 formic acid 8.69 mmol N0335 FeC12=4H20 CHF 90 91.372 90 11.596 10.187 14.945 P21/n 0.50 mmol 4 formic acid 8.69 mmol N0336 FeC12=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 02/c (02006H5) 0.46 mmol Hfac 0.92 mmol bipyridine 0.46 mmol BPR43G2 Zn(NO3)2.6H20 DMF 90 91.37 90 17.96 6.38 7.19 02/c 0.0288 mmol CH3CN

0.0072 mmol BPR48A2 Zn(NO3)2 6H20 DMSO 90 90 90 14.5 17.04 18.02 Pbca 0.012 mmol toluene 0.012 mmol BPR49B1 Zn(NO3)2 6H20 DMSO 90 91.172 90 33.181 9.824 17.884 02/c 0.024 mmol methanol 0.048 mmol BPR56E1 Zn(NO3)2 6H20 DMSO 90 90.096 90 14.587 14.153 17.183 P2(1)/n 0.012 mmol n-propanol 3 0.024 mmol BPR68D10 Zn(NO3)2 6H20 DMSO 90 95.316 90 10.062 10.17 16.413 P2(1)/c 0.0016 mmol benzene 7 0.0064 mmol BPR69B1 Cd(NO3)2 4H20 DMSO 90 98.76 90 14.16 15.72 17.66 Cc 0.0212 mmol 0.0428 mmol BPR73E4 Cd (NO3)2 4H20 DMSO 90 92.324 90 8.7231 7.0568 18.438 P2(1)/n 0.006 mmol toluene 0.003 mmol BPR76D5 Zn(NO3)2 6H20 DMSO 90 104.17 90 14.4191 6.2599 7.0611 Pc 0.0009 mmol H2BzPDC
0.0036 mmol BPR80B5 Cd(NO3)2.4H20 DMF 90 115.11 90 28.049 9.184 17.837 02/c 0.018 mmol 0.036 mmol BPR8OH5 Cd(NO3)2 4H20 DMF 90 119.06 90 11.4746 6.2151 17.268 P2/c 0.027 mmol 0.027 mmol BPR8206 Cd(NO3)2 4H20 DMF 90 90 90 9.7721 21.142 27.77 Fdd2 0.0068 mmol 0.202 mmol BPR8603 Co(NO3)2 6H20 DMF 90 90 90 18.3449 10.031 17.983 Pca2(1) 0.0025 mmol 0.075 mmol BPR86H6 Cd(NO3)2.6H20 DMF 80.98 89.69 83.41 9.8752 10.263 15.362 P-1 0.010 mmol 2 0.010 mmol Co(NO3)2 6H20 NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1 BPR95A2 Zn(NO3)2 6H20 NMP 90 102.9 90 7.4502 13.767 12.713 P2(1)/c 0.012 mmol 0.012 mmol CuC6F404 Cu(NO3)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 Fe012=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(NO3)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(NO3)2.6H20 DMF 90 96.624 90 17.245 9.943 9.273 02/c 0.370 mmol H2BDC(OH) 2 0.37 mmol Zn C2H4BDC ZnCl2 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 ZnCl2 DMF 90 93.459 90 13.509 11.984 27.039 .. P2/c 0.44 mmol CH3CN
m-BDC
0.261 mmol MOF-26 Cu(NO3)2.5H20 DMF 90 95.607 90 20.8797 16.017 26.176 P2(1)/n 0.084 mmol DOPE
0.085 mmol MOF-112 Cu(NO3)2.2.5H20 DMF 90 107.49 90 29.3241 21.297 18.069 02/c 0.084 mmol ethanol o-Br-m-BDC
0.085 mmol MOF-109 Cu(NO3)2.2.5H20 DMF 90 111.98 90 23.8801 16.834 18.389 P2(1)/c 0.084 mmol KDB
0.085 mmol MOF-111 Cu(NO3)2.2.5H20 DMF 90 102.16 90 10.6767 18.781 21.052 02/c 0.084 mmol ethanol o-BrBDC
0.085 mmol MOF-110 Cu(NO3)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(NO3)2.2.5H20 DEF 104.8 97.075 95.20 11.032 18.067 18.452 P-1 0.084 mmol 6 thiophene dicarboxylic acid.
0.085 mmol MOF-108 Cu(NO3)2.2.5H20 DBF/ 90 113.63 90 15.4747 14.514 14.032 02/c 0.084 mmol methanol thiophene dicarboxylic acid 0.085 mmol MOF-102 Cu(NO3)2.2.5H20 DMF 91.63 106.24 112.0 9.3845 10.794 10.831 P-1 0.084 mmol 1 H2(BDCCI2) 0.085 mmol Clbdcl Cu(NO3)2.2.5H20 DEF 90 105.56 90 14.911 15.622 18.413 P-1 0.084 mmol H2(BDCCI2) 0.085 mmol Cu(NMOP) Cu(NO3)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(NO3)3.5H20 DMF 90 106.02 90 18.6986 11.368 19.721 0.033 mmol 0.033 mmol Zn3(BTC)2 ZnCl2 DMF 90 90 90 26.572 26.572 26.572 Fm-3m Honk 0.033 mmol ethanol 0.033 mmol Zn40(NDC) Zn(NO3)2.4H20 DMF 90 90 90 41.5594 18.818 17.574 aba2 0.066 mmol ethanol 0.066 mmol CdTDC Cd(NO3)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(NO3)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(NO3)2.4H20 DEF 90 90 90 25.747 25.747 25.747 Fm-3m 0.20 mmol ethanol 0.60 mmol IRMOF-4 Zn(NO3)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(NO3)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(NO3)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(NO3)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(NO3)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(NO3)2.4H20 DEF 90 90 90 17.147 23.322 25.255 Pnnm 0.05 mmol BPDC
0.42 mmol IRMOF-10 Zn(NO3)2.4H20 DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.02 mmol BPDC
0.012 mmol IRMOF-11 Zn(NO3)2.4H20 DEF 90 90 90 24.822 24.822 56.734 R-3m 0.05 mmol HPDC
0.20 mmol IRMOF-12 Zn(NO3)2.4H20 DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.017 mmol HPDC
0.12 mmol IRMOF-13 Zn(NO3)2.4H20 DEF 90 90 90 24.822 24.822 56.734 R-3m 0.048 mmol PDC
0.31 mmol IRMOF-14 Zn(NO3)2.4H20 DEF 90 90 90 34.381 34.381 34.381 Fm-3m 0.17 mmol PDC
0.12 mmol IRMOF-15 Zn(NO3)2.4H20 DEF 90 90 90 21.459 21.459 21.459 Im-3m 0.063 mmol TPDC
0.025 mmol IRMOF-16 Zn(NO3)2.4H20 DEF 90 90 90 21.49 21.49 21.49 Pm-3m 0.0126 mmol NMP
TPDC
0.05 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, IRMOF-1, IRMOF-61, IRMOP-13, IRMOP-51, MIL-17, MIL-45, MIL-47, MIL-53, MIL-59, MIL-60, MIL-61, MIL-63, MIL-68, MIL-79, MIL-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, Al-BDC, MOF-5, MOF-177, MOF-505, IRMOF-8, IRMOF-11, Cu-BTC, Al-NDC, Al-aminoBDC, Cu-BDC-TEDA, Zn-BDC-TEDA, Al-BTC, Cu-BTC, Al-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, Al-BDC and Al-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 Al2(SO4)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 = 90-110 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:
5 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 10 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 lbeta cellulose, a weak peak at 15 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 20 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 25 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 lbeta 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 x 10 cm pieces of a teatowel (90% cotton, 10% linen) A, a cotton glove B, cellulose cloths (ZewaO) C, bandaging waste (viscose) D and Basotect E (melamine resin foam) 5 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 100 (2-theta), which can be assigned 10 to the aluminum-fumarate MOF. The surface areas of the treated materials were 17-22 m2/g LSA.

Claims

1. 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.

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

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

4. 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.

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

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

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

8. 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.

9. 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.

10. 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.