AU2011298030A1 - Process for producing carbon-comprising composite - Google Patents

Abstract

A process for producing a carbon-comprising composite is provided, wherein a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion is pyrolyzed under a protective gas atmosphere and the at least one at least bidentate organic compound is nitrogen-free. Composites which can be obtained in this way and sulfur electrodes comprising these and also their uses are further provided.

Description

WO 2012/028989 PCT/IB2011/053646 PROCESS FOR PRODUCING CARBON-COMPRISING COMPOSITE Description 5 The present invention relates to a process for producing a carbon-comprising composite. The invention further relates to composites which can be obtained in this way and sulfur electrodes comprising these and also their uses. Composites are materials which comprise two or more bonded materials. Their precise 10 chemical composition is frequently unknown, so that they usually have to be characterized by the process for producing them and also the starting materials. These materials can have properties which cannot be expected to the same extent, if at all, from their starting materials. 15 An example is a composite produced from a porous metal-organic framework made up of cobalt ions and a nitrogen-comprising ligand (1,3,5-triazine-2,4,6-triyltrisglycine, TTG). This composite is produced by pyrolysis and, owing to its nitrogen content, has good separation properties for the separation of C0 2

/CH

4 (Y. Shen et al., Chem. 20 Commun. 46 (2010), 1308-1310). Despite the composites known in the prior art, there is a need for further materials. It is therefore an object of the present invention to provide such materials and 25 processes for producing them. The object is achieved by a process for producing a carbon-comprising composite, which comprises the step 30 (a) Pyrolysis of a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion under a protective gas atmosphere, where the at least one at least bidentate organic compound is nitrogen-free. The process of the invention can comprise a further step (b). Here, an at least partial 35 removal of one or more metal components from the composite obtained in step (a) is carried out. This metal component or these metal components result from the transformation of the at least one metal ion comprised in the porous metal-organic framework. 40 WO 2012/028989 PCT/IB2011/053646 2 Furthermore, the process of the invention can comprise a step (c) in which the composite obtained from step (a) or (b) is impregnated with sulfur. The pyrolysis can be carried out by processes known in the prior art. 5 The pyrolysis in step (a) is preferably carried out at a temperature of at least 500'C, preferably at least 600'C. The pyrolysis is more preferably carried out in a temperature range from 600'C to 1000 C, even more preferably in the range from 600'C to 800'C. 10 Process step (a) is carried out under a protective gas atmosphere. The protective gas atmosphere is preferably an atmosphere of nitrogen. Other generally known protective gases such as noble gases are also possible. A porous metal-organic framework is used as starting material. This comprises at least 15 one at least bidentate organic compound coordinated to at least one metal ion, where the at least one at least bidentate organic compound is nitrogen-free. Such metal-organic frameworks (MOFs) are known in the prior art and are described, for example, in US 5,648,508, EP-A-0 790 253, M. O'Keeffe et al., J. Sol. State Chem., 20 152 (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 11 230, DE-A 10 2005 053430, WO-A 2007/054581, WO-A 2005/049892 and WO-A 2007/023134. 25 As a specific group of these metal-organic frameworks, the recent literature has described "limited" frameworks in which the network does not extend infinitely but rather with formation of polyhedra as a result of specific selection of the organic compound. A.C. Sudik, et al., J. Am. Chem. Soc. 127 (2005), 7110-7118, describe such specific frameworks. Here, these will be referred to as metal-organic polyhedra 30 (MOP) to distinguish them. 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 35 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 misopores can be checked by means of sorption measurements which determine the uptake capacity for nitrogen of the MOF at 77 kelvin in accordance with DIN 66131 and/or DIN 66134. 40 WO 2012/028989 PCT/IB2011/053646 3 The specific surface area, calculated according to the Langmuir model (DIN 66131, 66134) for an MOF in powder form is greater than 100 m 2 /g, more preferably above 300 m 2 /g, more preferably greater than 700 m 2 /g, even more preferably greater than 800 m 2 /g, even more preferably greater than 1000 m 2 /g and particularly preferably 5 greater than 1200 m 2 /g. Shaped bodies comprising metal-organic frameworks can have a relatively low active surface area, but this is preferably greater than 150 m 2 /g, more preferably greater than 300 m 2 /g, even more preferably greater than 700 m 2 /g. 10 The metal component in the framework according to the present invention is preferably selected from groups la, Ila, Illa, IVa to Villa 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 15 and Bi, where Ln denotes lanthanides. Lanthanides are La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, Yb. With regard to the ions of these elements, particular mention may be made of Mg 2 +, 20 Ca2+, Sr 2 +, Ba2+, Sc 3 +, y3+, Ln3+, Ti 4 *, Zr 4 *, Hf 4 *, V 4 *, V 3 +, V 2 +, Nb3+, Ta3+, Cr 3 +, Mo 3 +, W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru 3 +, Ru 2 +, Os3+, Os 2 +, C03+, C02+, Rh2+, Rh*, Ir 2 +, Ir*, Ni 2 +, Ni*, Pd2+, Pd*, Pt 2 +, Pt*, Cu 2 +, Cu*, Ag*, Au*, Zn2+, Cd2+, Hg 2 +, A13+, Ga 3 +, In 3 +, T13+, Si 4 *, Si 2 +, Ge 4 *, Ge2+, Sn 4 *, Sn2+, Pb 4 *, Pb2+, As 5 *, As 3 +, As+, Sb 5 , Sb3+, Sb*, Bi 5 +, Bi 3 + and Bit. 25 Mg, Al, Zr, Ti, V, Cr, Mo, Fe, Co, Cu, Ni, Zn are more particularly preferred. Greater preference is given to Al, Ti, Mg, Fe, Cu and Zn. Very particular preference is given to Mg, Al, Cu and Zn. 30 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. 35 As functional groups via which the abovementioned coordinate bonds can be formed, mention may be made by way of example of, in particular, the following functional groups: -CO 2 H, -CS 2 H, -NO 2 , -B(OH) 2 , -S0 3 H, -Si(OH) 3 , -Ge(OH) 3 , -Sn(OH) 3 , -Si(SH) 4 , -Ge(SH) 4 , -Sn(SH) 3 , -PO 3 H, -AsO 3 H, -AsO 4 H, -P(SH) 3 , -As(SH) 3 , -CH(RSH) 2 ,

-C(RSH)

3

-CH(ROH)

2 , -C(ROH) 3 , where R is, for example, preferably an alkylene group 40 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 WO 2012/028989 PCT/IB2011/053646 4 comprising 1 or 2 aromatic rings, for example 2 C6 rings, which may optionally be fused and may be appropriately substituted independently of one another by in each case at least one substituent and/or may comprise, independently of one another, in each case at least one heteroatom such as 0 and/or S. In likewise preferred embodiments, 5 mention may be made of functional groups in which the abovementioned radical R is not present. Such groups are, inter alia, CH(SH) 2 , -C(SH) 3 , -CH(OH) 2 , or -C(OH) 3 . 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 10 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. 15 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 20 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, adamantine, acetylene, ethylene or butadiene. 25 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 and/or with at least two rings being fused. 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 30 being particularly preferred. Each ring of the compound mentioned can also independently comprise at least one heteroatom such as 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 C6 rings, with the rings being present either separately or in a fused form. Particular mention may be made of 35 benzene, naphthalene and/or biphenyl 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 40 functional groups.

WO 2012/028989 PCT/IB2011/053646 5 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-hepta 5 decanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 1,3-butadiene-1,4 dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, thiophene-3,4-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9 dicarboxylic acid, perylenedicarboxylic acid, pluriol E 200-dicarboxylic acid, 3,6 10 dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octadicarboxylic acid, pentane-3,3-carboxylic acid, 1,1'-dinaphthyldicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3 dicarboxylic acid, phenylindanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 3,6,9 15 trioxaundecanedicarboxylic acid, hydroxybenzophenonedicarboxylic acid, pluriol E 300 dicarboxylic acid, pluriol E 400-dicarboxylic acid, pluriol E 600-dicarboxylic 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-sulfo-2,3 20 naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2',3'-diphenyl-p terphenyl-4,4"-dicarboxylic acid, (diphenyl ether)-4,4'-dicarboxylic acid, 4(1 H) oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 4 cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3 25 benzenedicarboxylic acid, 2,5-dihydroxy-1,4-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1 -nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4' dihydroxydiphenylmethane-3,3'-dicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7 30 dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid or camphordicarboxylic acid. The at least bidentate organic compound is even more preferably one of the dicarboxylic acids mentioned by way of example above as such. 35 The at least bidentate organic compound can, for example, be derived from a tricarboxylic acid such as 2-hydroxy-1,2,3-propanetricarboxylic acid, 1,2,3-, 1,2,4-benzenetricarboxylic acid, 40 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5 benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 5-acetyl-3-amino- WO 2012/028989 PCT/IB2011/053646 6 6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid or aurintricarboxylic acid. The at least bidentate organic compound is even more preferably one of the 5 tricarboxylic acids mentioned by way of example above as such. Examples of an at least bidentate organic compound derived from a tetracarboxylic acid are 10 1,1-dioxidoperylo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic 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 15 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, 1,2,9,1 0-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic acids such as 20 cyclopentane-1,2,3,4-tetracarboxylic acid. The at least bidentate organic compound is even more preferably one of the tetracarboxylic acids mentioned by way of example above as such. 25 Very particular preference is given to optionally at least monosubstituted aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids having one, two, three, four or more rings with each of the rings being able to comprise at least one heteroatom and two or more rings being able to comprise identical or different heteroatoms. Preference is given, for example, to monocyclic dicarboxylic acids, monocyclic tricarboxylic acids, 30 monocyclic tetracarboxylic acids, dicyclic dicarboxylic acids, dicyclic tricarboxylic acids, dicyclic tetracarboxylic acids, tricyclic dicarboxylic acids, tricyclic tricarboxylic acids, tricyclic tetracarboxylic acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and/or tetracyclic tetracarboxylic acids. Suitable heteroatoms are, for example, 0, S, B, P, and preferred heteroatoms among these are S and/or 0. As suitable 35 substituents, mention may be made of, inter alia, -OH, a nitro group, an alkyl or alkoxy group. Particular preference is given to using acetylenedicarboxylic acid (ADC), camphordicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids such 40 as phthalic acid, isophthalic acid, terephthalic acid (BDC), naphthalenedicarboxylic acids (NDC), biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), WO 2012/028989 PCT/IB2011/053646 7 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 5 or dihydroxyterephthalic acids such as 2,5-dihydroxyterephthalic acid (DHBDC), tetrahydropyrene-2,7-dicarboxylic acid (HPDC), biphenyltetracarboxylic acid (BPTC) as at least bidentate organic compounds. Very particular preference is given to, inter alia, phthalic acid, isophthalic acid, 10 terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4 benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5 benzenetetracarboxylic acid, fumaric acid, biphenyldicarboxylate, 1,5- and 2,6 naphthalenedicarboxylic acid, tert-butylisophthalic acid, dihydroxybenzoic acid, BTB, 15 HPDC,BPTC. 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, tricarboxylic or 20 tetracarboxylic acid. Apart from these at least bidentate organic compounds, the metal-organic framework can also comprise one or more monodentate ligands. 25 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 30 solvents for the preparation of MOF are described, inter alia in US-A 5,648,508 or DE-A 101 11 230. The pore size of the metal-organic framework can be controlled by selection of the suitable ligand and/or the at least bidentate organic compound. In general, the larger 35 the organic compound, the greater 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 name of the 40 framework, the metal and the at least bidentate ligand, the solvent and the cell WO 2012/028989 PCT/IB2011/053646 8 parameters (angles a, p and y and the spacings A, B and C in A) are indicated. The latter were determined by X-ray diffraction. MOF-n Constituents Solven a y a b c Space molar ratio t group M+L MOF-0 Zn(NO 3

)

2 -6H 2 0 Ethanol 90 90 120 16.71 16.71 14.18 P6(3)/

H

3 (BTC) 1 1 9 Mcm MOF-2 Zn(NO 3

)

2 -6H 2 0 DMF 90 102.8 90 6.718 15.49 12.43 P2(1)/n (0.246 mmol) toluene

H

2 (BDC) 0.241 mmol) MOF-3 Zn(NO 3

)

2 -6H 2 0 DMF 99.72 111.1 108.4 9.726 9.911 10.45 P-1 (1.89 mmol) MeOH 1

H

2 (BDC) (1.93mmol) MOF-4 Zn(NO 3

)

2 -6H 2 0 Ethanol 90 90 90 14.72 14.72 14.72 P2(1)3 (1.00 mmol) 8 8 8

H

3 (BTC) (0.5 mmol) MOF-5 Zn(NO 3

)

2 -6H 2 0 DMF 90 90 90 25.66 25.66 25.66 Fm-3m (2.22 mmol) Chlorob 9 9 9

H

2 (BDC) enzene (2.17 mmol) MOF-38 Zn(NO 3

)

2 -6H 2 0 DMF 90 90 90 20.65 20.65 17.84 14cm (0.27 mmol) Chlorob 7 7

H

3 (BTC) enzene (0.15 mmol) MOF-31 Zn(NO 3

)

2 -6H 2 0 Ethanol 90 90 90 10.82 10.82 10.82 Pn( Zn(ADC) 2 0.4 mmol 1 1 1 3)m

H

2 (ADC) 0.8 mmol MOF-12 Zn(NO 3

)

2 -6H 2 0 Ethanol 90 90 90 15.74 16.90 18.16 Pbca Zn 2 (ATC) 0.3 mmol 5 7 7

H

4 (AT C) 0.15 mmol MOF-20 Zn(NO 3

)

2 -6H 2 0 DMF 90 92.13 90 8.13 16.44 12.80 P2(1)/c ZnNDC 0.37 mmol Chlorob 4 7

H

2 NDC enzene 0.36 mmol MOF-37 Zn(NO 3

)

2 -6H 2 0 DEF 72.38 83.16 84.33 9.952 11.57 15.55 P-1 WO 2012/028989 PCT/IB2011/053646 9 0.2 mmol Chloro- 6 6

H

2 NDC benzen 0.2 mmol e MOF-8 Tb(NO 3

)

3 -5H 2 0 DMSO 90 115.7 90 19.83 9.822 19.18 C2/c Tb 2 (ADC) 0.10 mmol MeOH 3

H

2 ADC 0.20 mmol MOF-9 Tb(NO 3

)

3 -5H 2 0 DMSO 90 102.0 90 27.05 16.79 28.13 C2/c Tb 2 (ADC) 0.08 mmol 9 6 5 9

H

2 ADB 0.12 mmol MOF-6 Tb(NO 3

)

3 -5H 2 0 DMF 90 91.28 90 17.59 19.99 10.54 P21/c 0.30 mmol MeOH 9 6 5

H

2 (BDC) 0.30 mmol MOF-7 Tb(NO 3

)

3 -5H 2 0 H 2 0 102.3 91.12 101.5 6.142 10.06 10.09 P-1 0.15 mmol 9 6

H

2 (BDC) 0.15 mmol MOF-69A Zn(NO 3

)

2 -6H 2 0 DEF 90 111.6 90 23.12 20.92 12 C2/c 0.083 mmol H 2 0 2 4,4'BPDC MeNH 2 0.041 mmol MOF-69B Zn(NO 3

)

2 -6H 2 0 DEF 90 95.3 90 20.17 18.55 12.16 C2/c 0.083 mmol H 2 0 2 2,6-NDC MeNH 2 0.041 mmol MOF-11 Cu(NO 3

)

2 -2.5H 2

H

2 0 90 93.86 90 12.98 11.22 11.33 C2/c Cu 2 (ATC) 0 7 6 0.47 mmol

H

2 ATC 0.22 mmol MOF-11 90 90 90 8.467 8.467 14.44 P42/ Cu 2 (ATC) 1 1 mmc dehydr. I MOF-14 Cu(NO 3

)

2 -2.5H 2

H

2 0 90 90 90 26.94 26.94 26.94 Im-3 Cu 3 (BTB) 0 DMF 6 6 6 0.28 mmol EtOH

H

3 BTB 0.052 mmol WO 2012/028989 PCT/IB2011/053646 10 MOF-32 Cd(NO 3

)

2 -4H 2 0 H 2 0 90 90 90 13.46 13.46 13.46 P( Cd(ATC) 0.24 mmol NaOH 8 8 8 4)3m

H

4 ATC 0.10 mmol MOF-33 ZnCl 2

H

2 0 90 90 90 19.56 15.25 23.40 Imma Zn 2 (ATB) 0.15 mmol DMF 1 5 4

H

4 ATB EtOH 0.02 mmol MOF-34 Ni(NO 3

)

2 -6H 2 0 H 2 0 90 90 90 10.06 11.16 19.20 P2 1 2 1 2 1 Ni(ATC) 0.24 mmol NaOH 6 3 1

H

4 ATC 0.10 mmol MOF-36 Zn(NO 3

)

2 -4H 2 0 H 2 0 90 90 90 15.74 16.90 18.16 Pbca Zn 2 (MTB) 0.20 mmol DMF 5 7 7

H

4 MTB 0.04 mmol MOF-39 Zn(N0 3

)

2 4H 2 0 H 2 0 90 90 90 17.15 21.59 25.30 Pnma Zn 3 0(HBT 0.27 mmol DMF 8 1 8 B) H 3 BTB EtOH 0.07 mmol N0305 FeCl2-4H 2 0 DMF 90 90 120 8.269 8.269 63.56 R-3c 5.03 mmol 2 2 6 formic acid 86.90 mmol N0306A FeCl2-4H 2 0 DEF 90 90 90 9.936 18.37 18.37 Pbcn 5.03 mmol 4 4 4 formic acid 86.90 mmol N029 Mn(Ac) 2 -4H 2 0 DMF 120 90 90 14.16 33.52 33.52 P-1 MOF-0 0.46 mmol 1 1 similar H 3 BTC 0.69 mmol BPR48 Zn(N0 3

)

2 DMS 90 90 90 14.5 17.04 18.02 Pbca A2 6H 2 0 0 0.012 mmol toluen

H

2 BDC e 0.012 mmol BPR69 Cd(N0 3

)

2 DMS 90 98.76 90 14.16 15.72 17.66 Cc B1 4H 2 0 0 0.0212 mmol WO 2012/028989 PCT/IB2011/053646 11

H

2 BDC 0.0428 mmol BPR92 Co(NO 3

)

2 -6H 2 NMP 106.3 107.63 107.2 7.530 10.94 11.02 P1 A2 0 8 2 5 0.018 mmol

H

2 BDC 0.018 mmol BPR95 Cd(N0 3

)

2 NMP 90 112.8 90 14.46 11.08 15.82 P2(1)/n C5 4H 2 0 0 5 9 0.012 mmol

H

2 BDC 0.36 mmol Cu C 6

H

4 0 6 Cu(NO 3

)

2 -2.5 DMF 90 105.29 90 15.25 14.81 14.13 P2(1)/c

H

2 0 Chloro 9 6 0.370 mmol benze

H

2

BDC(OH)

2 ne 0.37 mmol M(BTC) Co(SO 4 ) H 2 0 DMF like MOF-0 MOF-0 0.055 mmol similar H 3 BTC 0.037 mmol Tb(C 6

H

4 0 6 Tb(NO 3

)

3 -5H 2 DMF 104.6 107.9 97.14 10.49 10.98 12.54 P-1 ) 0 Chloro 7 1 1 1 0.370 mmol benze

H

2

(C

6

H

4 0 6 ) ne 0.56 mmol Zn (C204) ZnCl 2 DMF 90 120 90 9.416 9.416 8.464 P(-3)lm 0.370 mmol Chloro 8 8 oxalic acid benze 0.37 mmol ne Co(CHO) Co(NO 3

)

2 -5H 2 DMF 90 91.32 90 11.32 10.04 14.85 P2(1)/n O 8 9 4 0.043 mmol formic acid 1.60 mmol Cd(CHO) Cd(N0 3

)

2 -4H 2 DMF 90 120 90 8.516 8.516 22.67 R-3c 0 0.185 mmol 8 8 4 formic acid 0.185 mmol Cu(C 3

H

2 0 Cu(N0 3

)

2 -2.5 DMF 90 90 90 8.366 8.366 11.91 P43 4) H 2 0 9 WO 2012/028989 PCT/IB2011/053646 12 0.043 mmol malonic acid 0.192 mmol Zn 6 Zn(NO 3

)

2 -6H 2 DMF 90 95.902 90 19.50 16.48 14.64 C2/m (N DC)5 0 0.097 mmol Chloro 4 2 MOF-48 14 NDC benze 0.069 mmol ne

H

2 0 2 MOF-47 Zn(N0 3

)

2 6H 2 0 DMF 90 92.55 90 11.30 16.02 17.53 P2(1)/c 0.185 mmol Chloro 3 9 5

H

2

(BDC[CH

3

]

4 ) benze 0.185 mmol ne

H

2 0 2 M025 Cu(NO 3

)

2 -2.5H 2 DMF 90 112.0 90 23.88 16.83 18.38 P2(1)/c O 0 4 9 0.084 mmol BPhDC 0.085 mmol Cu-Thio Cu(NO 3

)

2 -2.5H 2 DEF 90 113.6 90 15.47 14.51 14.03 P2(1)/c O 47 4 2 0.084 mmol thiophene docarboxylic acid 0.085 mmol CIBDC1 Cu(NO 3

)

2 -2.5H 2 DMF 90 105.6 90 14.91 15.62 18.41 C2/c O 0.084 mmol 1 2 3

H

2 (BDCCl 2 ) 0.085 mmol MOF- Cu(NO 3

)

2 -2.5H 2 DMF 90 90 90 21.60 20.60 20.07 Fm3m 101 0 7 7 3 0.084 mmol BrBDC 0.085 mmol Zn 3 (BTC ZnCl 2 DMF 90 90 90 26.57 26.57 26.57 Fm-3m )2 0.033 mmol EtOH 2 2 2

H

3 BTC Base 0.033 mmol added WO 2012/028989 PCT/IB2011/053646 13 MOF-j Co(CH 3

CO

2

)

2 -4 H 2 0 90 112.0 90 17.48 12.96 6.559 C2

H

2 0 2 3 (1.65 mmol)

H

3 (BZC) (0.95 mmol) MOF-n Zn(NO 3

)

2 -6H 2 0 Ethan 90 90 120 16.71 16.71 14.18 P6(3)/mc

H

3 (BTC) ol 1 1 9 m PbBDC Pb(N0 3

)

2 DMF 90 102.7 90 8.363 17.99 9.961 P2(1)/n (0.181 mmol) Ethan 9 1 7

H

2 (BDC) ol (0.181 mmol) Znhex Zn(NO 3

)

2 -6H 2 0 DMF 90 90 120 37.11 37.11 30.01 P3(1)c (0.171 mmol) p- 65 7 9

H

3 BTB xylene (0.114 mmol) Ethan ol AS16 FeBr 2 DMF 90 90.13 90 7.259 8.789 19.48 P2(1)c 0.927 mmol anhyd 5 4 4

H

2 (BDC) r. 0.927 mmol AS27-2 FeBr 2 DMF 90 90 90 26.73 26.73 26.73 Fm3m 0.927 mmol anhyd 5 5 5

H

3 (BDC) r. 0.464 mmol AS32 FeCl 3 DMF 90 90 120 12.53 12.53 18.47 P6(2)c 1.23 mmol anhyd 5 5 9

H

2 (BDC) r. 1.23 mmol Ethan ol AS54-3 FeBr 2 DMF 90 109.98 90 12.01 15.28 14.39 C2 0.927 anhyd 9 6 9 BPDC r. 0.927 mmol n Propa nol AS61-4 FeBr 2 Pyridi 90 90 120 13.01 13.01 14.89 P6(2)c 0.927 mmol ne 7 7 6 m-BDC anhyd 0.927 mmol r. AS68-7 FeBr 2 DMF 90 90 90 18.34 10.03 18.03 Pca2 1 WO 2012/028989 PCT/IB2011/053646 14 0.927 mmol anhyd 07 6 9 m-BDC r. 1.204 mmol Pyridi ne Zn(ADC) Zn(NO 3

)

2 -6H 2 0 DMF 90 99.85 90 16.76 9.349 9.635 C2/c 0.37 mmol Chlor 4

H

2 (ADC) obenz 0.36 mmol ene MOF-12 Zn(NO 3

)

2 -6H 2 0 Ethan 90 90 90 15.74 16.90 18.16 Pbca Zn 2 (ATC) 0.30 mmol ol 5 7 7

H

4 (AT C) 0.15 mmol MOF-20 Zn(NO 3

)

2 -6H 2 0 DMF 90 92.13 90 8.13 16.44 12.80 P2(1)/c ZnNDC 0.37 mmol Chlor 4 7

H

2 NDC obenz 0.36 mmol ene MOF-37 Zn(NO 3

)

2 -6H 2 0 DEF 72.38 83.16 84.33 9.952 11.57 15.55 P-1 0.20 mmol Chlor 6 6

H

2 NDC obenz 0.20 mmol ene Zn(NDC) Zn(NO 3

)

2 -6H 2 0 DMS 68.08 75.33 88.31 8.631 10.20 13.11 P-1 (DMSO) H 2 NDC 0 7 4 Zn(NDC) Zn(NO 3

)

2 -6H 2 0 90 99.2 90 19.28 17.62 15.05 C2/c

H

2 NDC 9 8 2 Zn(HPDC) Zn(NO 3

)

2 -4H 2 0 DMF 107.9 105.06 94.4 8.326 12.08 13.76 P-1 0.23 mmol H 2 0 5 7

H

2 (HPDC) 0.05 mmol Co(HPDC) Co(NO 3

)

2 -6H 2 DMF 90 97.69 90 29.67 9.63 7.981 C2/c o H 2 0/ 7 0.21 mmol Ethan

H

2 (HPDC) ol 0.06 mmol Zn 3 (PDC)2 Zn(NO 3

)

2 -4H 2 0 DMF/ 79.34 80.8 85.83 8.564 14.04 26.42 P-1 .5 0.17 mmol CIBz 6 8

H

2 (HPDC) H 2 0/ 0.05 mmol TEA Cd 2 Cd(NO 3

)

2 -4H 2 Metha 70.59 72.75 87.14 10.10 14.41 14.96 P-1 (TPDC)2 0 nol/ 2 2 4 0.06 mmol CHP

H

2 (HPDC) H 2 0 WO 2012/028989 PCT/IB2011/053646 15 0.06 mmol Tb(PDC)1. Tb(NO 3

)

3 -5H 2 0 DMF 109.8 103.61 100.1 9.829 12.11 14.62 P-1 5 0.21 mmol H 2 0/ 4 8

H

2 (PDC) Ethan 0.034 mmol ol ZnDBP Zn(NO 3

)

2 -6H 2 0 MeOH 90 93.67 90 9.254 10.76 27.93 P2/n 0.05 mmol 2 Dibenzyl phosphate 0.10 mmol Zn 3 (BPD ZnBr 2 DMF 90 102.76 90 11.49 14.79 19.18 P21/n C) 0.021 mmol 4,4'BPDC 0.005 mmol CdBDC Cd(NO 3

)

2 -4H 2 0 DMF 90 95.85 90 11.2 11.11 16.71 P21/n 0.100 mmol Na 2 Si

H

2 (BDC) 03 0.401 mmol (aq) Cd- Cd(NO 3

)

2 -4H 2 0 DMF 90 101.1 90 13.69 18.25 14.91 C2/c mBDC 0.009 mmol MeNH

H

2 (mBDC) 2 0.018 mmol Zn 4 0BN Zn(NO 3

)

2 -6H 2 0 DEF 90 90 90 22.35 26.05 59.56 Fmmm DC 0.041 mmol MeNH BNDC 2

H

2 0 2 Formate Ce(N0 3

)

3 -6H 2 0 H 2 0 90 90 120 10.66 10.66 4.107 R-3m 0.138 mmol Ethan 8 7 formic acid ol 0.43 mmol FeCl2-4H 2 0 DMF 90 90 120 8.269 8.269 63.56 R-3c 5.03 mmol 2 2 6 formic acid 86.90 mmol FeCl2-4H 2 0 DEF 90 90 90 9.936 18.37 18.37 Pbcn 5.03 mmol 4 4 4 formic acid 86.90 mmol FeCl2-4H 2 0 DEF 90 90 90 8.335 8.335 13.34 P-31c 5.03 mmol WO 2012/028989 PCT/IB2011/053646 16 formic acid 86.90 mmol N0330 FeCl2-4H 2 0 Form- 90 90 90 8.774 11.65 8.329 Pnna 0.50 mmol amide 9 5 7 formic acid 8.69 mmol N0332 FeCl2-4H 2 0 DIP 90 90 90 10.03 18.80 18.35 Pbcn 0.50 mmol 13 8 5 formic acid 8.69 mmol N0333 FeCl2-4H20 DBF 90 90 90 45.27 23.86 12.44 Cmcm 0.50 mmol 54 1 1 formic acid 8.69 mmol N0335 FeCl2-4H 2 0 CHF 90 91.372 90 11.59 10.18 14.94 P21/n 0.50 mmol 64 7 5 formic acid 8.69 mmol N0336 FeCl2-4H 2 0 MFA 90 90 90 11.79 48.84 8.413 Pbcm 0.50 mmol 45 3 6 formic acid 8.69 mmol N029 Mn(Ac) 2 -4H 2 0 DMF 120 90 90 14.16 33.52 33.52 P-1 MOF-0 0.46 mmol 1 1 similar H 3 BTC 0.69 mmol Mn(hfac) Mn(Ac) 2 -4H 2 0 Ether 90 95.32 90 9.572 17.16 14.04 C2/c 2 0.46 mmol 2 1

(O

2

CC

6 H Hfac 5) 0.92 mmol Bipyridine 0.46 mmol BPR43G Zn(NO 3

)

2 -6H 2 0 DMF 90 91.37 90 17.96 6.38 7.19 C2/c 2 0.0288 mmol CH 3 C

H

2 BDC N 0.0072 mmol BPR48A Zn(N0 3

)

2 6H 2 0 DMS 90 90 90 14.5 17.04 18.02 Pbca 2 0.012 mmol 0

H

2 BDC toluen WO 2012/028989 PCT/IB2011/053646 17 0.012 mmol e BPR49B Zn(N0 3

)

2 6H 2 0 DMS 90 91.172 90 33.18 9.824 17.88 C2/c 1 0.024 mmol 0 1 4

H

2 BDC Metha 0.048 mmol nol BPR56E Zn(N0 3

)

2 6H 2 0 DMS 90 90.096 90 14.58 14.15 17.18 P2(1)/n 1 0.012 mmol 0 73 3 3

H

2 BDC n 0.024 mmol Propa nol BPR68D Zn(N0 3

)

2 6H 2 0 DMS 90 95.316 90 10.06 10.17 16.41 P2(1)/c 10 0.0016 mmol 0 27 3

H

3 BTC Benze 0.0064 mmol ne BPR69B Cd(N0 3

)

2 4H 2 0 DMS 90 98.76 90 14.16 15.72 17.66 Cc 1 0.0212 mmol 0

H

2 BDC 0.0428 mmol BPR73E4 Cd(N0 3

)

2 DMSO 90 92.324 90 8.723 7.056 18.43 P2(1)/n 4H 2 0 toluene 1 8 8 0.006 mmol

H

2 BDC 0.003 mmol BPR76D5 Zn(N0 3

)

2 6H 2 0 DMSO 90 104.17 90 14.41 6.259 7.061 Pc 0.0009 mmol 91 9 1

H

2 BzPDC 0.0036 mmol BPR80B5 Cd(NO 3

)

2 -4H 2 DMF 90 115.11 90 28.04 9.184 17.83 C2/c O 9 7 0.018 mmol

H

2 BDC 0.036 mmol BPR80H5 Cd(N0 3

)

2 DMF 90 119.06 90 11.47 6.215 17.26 P2/c 4H 2 0 46 1 8 0.027 mmol

H

2 BDC 0.027 mmol BPR82C6 Cd(N0 3

)

2 DMF 90 90 90 9.772 21.14 27.77 Fdd2 4H 2 0 1 2 0.0068 mmol WO 2012/028989 PCT/IB2011/053646 18

H

2 BDC 0.202 mmol BPR86C3 Co(NO 3

)

2 DMF 90 90 90 18.34 10.03 17.98 Pca2(1) 6H 2 0 49 1 3 0.0025 mmol

H

2 BDC 0.075 mmol BPR86H6 Cd(NO 3

)

2 -6H 2 DMF 80.98 89.69 83.4 9.875 10.26 15.36 P-1 0 12 2 3 2 0.010 mmol

H

2 BDC 0.010 mmol Co(NO 3

)

2 NMP 106.3 107.63 107. 7.530 10.94 11.02 P1 6H 2 0 2 8 2 5 BPR95A2 Zn(N0 3

)

2 6H 2 0 NMP 90 102.9 90 7.450 13.76 12.71 P2(1)/c 0.012 mmol 2 7 3

H

2 BDC 0.012 mmol CuC 6

F

4 0 4 Cu(NO 3

)

2 -2.5H DMF 90 98.834 90 10.96 24.43 22.55 P2(1)/n 20 Chloro- 75 3 0.370 mmol benzen

H

2

BDC(OH)

2 e 0.37 mmol Fe Formic FeCl2-4H 2 0 DMF 90 91.543 90 11.49 9.963 14.48 P2(1)/n 0.370 mmol 5 formic acid 0.37 mmol Mg Formic Mg(N0 3

)

2 -6H 2 DMF 90 91.359 90 11.38 9.932 14.65 P2(1)/n O 3 6 0.370 mmol formic acid 0.37 mmol MgC 6

H

4 0 6 Mg(N0 3

)

2 -6H 2 DMF 90 96.624 90 17.24 9.943 9.273 C2/c o 5 0.370 mmol

H

2

BDC(OH)

2 0.37 mmol Zn ZnCl 2 DMF 90 94.714 90 7.338 16.83 12.52 P2(1)/n

C

2

H

4 BDC 0.44 mmol 6 4 MOF-38 CBBDC 0.261 mmol WO 2012/028989 PCT/IB2011/053646 19 MOF-49 ZnCl 2 DMF 90 93.459 90 13.50 11.98 27.03 P2/c 0.44 mmol CH 3 CN 9 4 9 m-BDC 0.261 mmol MOF-112 Cu(NO 3

)

2 -2.5H DMF 90 107.49 90 29.32 21.29 18.06 C2/c 20 Ethanol 41 7 9 0.084 mmol o-Br-m-BDC 0.085 mmol MOF-109 Cu(NO 3

)

2 -2.5H DMF 90 111.98 90 23.88 16.83 18.38 P2(1)/c 20 01 4 9 0.084 mmol KDB 0.085 mmol MOF-111 Cu(NO 3

)

2 -2.5H DMF 90 102.16 90 10.67 18.78 21.05 C2/c 20 Ethanol 67 1 2 0.084 mmol o-BrBDC 0.085 mmol MOF-110 Cu(NO 3

)

2 -2.5H DMF 90 90 120 20.06 20.06 20.74 R-3/m 20 52 5 7 0.084 mmol thiophene dicarboxylic acid 0.085 mmol MOF-107 Cu(N0 3

)

2 -2.5H DEF 104.8 97.075 95.2 11.03 18.06 18.45 P-1 20 06 2 7 2 0.084 mmol thiophene dicarboxylic acid 0.085 mmol MOF-108 Cu(N03)2-2.5 DBF/ 90 113.63 90 15.47 14.51 14.03 C2/c H20 Methan 47 4 2 0.084 mmol ol thiophene dicarboxylic acid 0.085 mmol MOF-102 Cu(N03)2-2.5 DMF 91.63 106.24 112. 9.384 10.79 10.83 P-1 WO 2012/028989 PCT/IB2011/053646 20 H20 01 5 4 1 0.084 mmol H2(BDCCl2) 0.085 mmol Clbdcl Cu(NO3)2-2.5 DEF 90 105.56 90 14.91 15.62 18.41 P-1 H20 1 2 3 0.084 mmol H2(BDCCl2) 0.085 mmol Tb(BTC) Tb(NO3)3-5H2 DMF 90 106.02 90 18.69 11.36 19.72 O 86 8 1 0.033 mmol H3BTC 0.033 mmol Zn3(BTC)2 ZnCl2 DMF 90 90 90 26.57 26.57 26.57 Fm-3m Honk 0.033 mmol Ethanol 2 2 2 H3BTC 0.033 mmol Zn40(NDC) Zn(NO3)2-4H2 DMF 90 90 90 41.55 18.81 17.57 aba2 O Ethanol 94 8 4 0.066 mmol 14NDC 0.066 mmol IRMOF-2 Zn(NO3)2-4H2 DEF 90 90 90 25.77 25.77 25.77 Fm-3m O 2 2 2 0.160 mmol o-Br-BDC 0.60 mmol IRMOF-4 Zn(NO3)2-4H2 DEF 90 90 90 25.84 25.84 25.84 Fm-3m O 9 9 9 0.11 mmol [C3H70]2 BDC 0.48 mmol IRMOF-5 Zn(NO3)2-4H2 DEF 90 90 90 12.88 12.88 12.88 Pm-3m O 2 2 2 0.13 mmol [C5H 110]2 BDC 0.50 mmol IRMOF-6 Zn(NO3)2-4H2 DEF 90 90 90 25.84 25.84 25.84 Fm-3m WO 2012/028989 PCT/IB2011/053646 21 0 2 2 2 0.20 mmol [C2H4]-BDC 0.60 mmol IRMOF-7 Zn(NO3)2-4H2 DEF 90 90 90 12.91 12.91 12.91 Pm-3m O 4 4 4 0.07 mmol 1,4NDC 0.20 mmol IRMOF-8 Zn(NO3)2-4H2 DEF 90 90 90 30.09 30.09 30.09 Fm-3m O 2 2 2 0.55 mmol 2,6NDC 0.42 mmol IRMOF-9 Zn(NO3)2-4H2 DEF 90 90 90 17.14 23.32 25.25 Pnnm o 7 2 5 0.05 mmol BPDC 0.42 mmol IRMOF-10 Zn(NO3)2-4H2 DEF 90 90 90 34.28 34.28 34.28 Fm-3m O 1 1 1 0.02 mmol BPDC 0.012 mmol IRMOF-11 Zn(NO3)2-4H2 DEF 90 90 90 24.82 24.82 56.73 R-3m O 2 2 4 0.05 mmol HPDC 0.20 mmol IRMOF-12 Zn(NO3)2-4H2 DEF 90 90 90 34.28 34.28 34.28 Fm-3m O 1 1 1 0.017 mmol HPDC 0.12 mmol IRMOF- Zn(NO 3

)

2 -4H 2 0 DEF 90 90 90 24.82 24.82 56.73 R-3m 13 0.048 mmol 2 2 4 PDC 0.31 mmol IRMOF- Zn(NO 3

)

2 -4H 2 0 DEF 90 90 90 34.38 34.38 34.38 Fm-3m 14 0.17 mmol 1 1 1 WO 2012/028989 PCT/IB2011/053646 22 PDC 0.12 mmol IRMOF- Zn(NO 3

)

2 -4H 2 0 DEF 90 90 90 21.45 21.45 21.45 Im-3m 15 0.063 mmol 9 9 9 TPDC 0.025 mmol IRMOF- Zn(NO 3

)

2 -4H 2 0 DEF 90 90 90 21.49 21.49 21.49 Pm-3m 16 0.0126 mmol NMP TPDC 0.05 mmol ADC Acetylenedicarboxylic acid NDC Naphthalenedicarboxylic acid BDC Benzenedicarboxylic acid 5 ATC Adamantanetetracarboxylic acid BTC Benzenetricarboxylic acid BTB Benzenetribenzoic acid MTB Methanetetrabenzoic acid ATB Adamantanetetrabenzoic acid 10 ADB Adamanetandibenzoic acid Further metal-organic frameworks are MOF-69 to 80, MOF1 03 to 106, MOF-1 77, MOF 235, MOF-236, MOF-501, MOF-502, MOF-505, IRMOF-1, IRMOF-61, IRMOP-51, MIL 45, MIL-47, MIL-53, MIL-59, MIL-60, MIL-61, MIL-63, MIL-68, MIL-85, which are 15 described in the literature. Particularly preferred metal-organic frameworks are MIL-53, Zn-tBu-isophthalic acid, AI-BDC, MOF-5, MOF-177, MOF-505, IRMOF-8, IRMOF-11, Cu-BTC, A-NDC, A-BTC, Cu-BTC, AI-NDC, Mg-NDC, Al-fumarate, MOF-74, Sc-terephthalate. Even greater 20 preference is given to AI-BDC, Al-fumarate, Al-NDC, AI-BTC and Cu-BTC. The nitrogen-free at least one at least bidentate organic compound is preferably derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid. 25 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, as far as the carboxy functions are concerned. Furthermore, the term "derived" means that the at least one at least bidentate organic compound can have further substituents. Thus, one or, independently of one another, more substituents such as 30 hydroxyl, methoxy, halogen or methyl groups can be present in addition to the carboxylic acid function. It is preferred that no further substituent, or only F WO 2012/028989 PCT/IB2011/053646 23 substituents, is/are present. For the purposes of the present invention, the term "derived" also means that the carboxylic acid function can be present as sulfur analogues. Sulfur analogues are -C(=O)SH and the tautomer thereof and -C(S)SH. Preference is given to no sulfur analogues being present. 5 Apart from the conventional method of preparing the MOFs, as is described, for example, in US 5,648,508, these can also be prepared by an electrochemical route. In this respect, reference may be made to DE-A 103 55 087 and WO-A 2005/049892. 10 In step (b), an at least partial removal of one or more metal components is carried out. It is preferred that this or these comprise at least one metal oxide. The at least partial removal is preferably carried out by washing out by means of an alkaline liquid. Other methods known in the prior art can also be used. A suitable 15 alkaline liquid is, for example, an aqueous NaOH solution. Other alkali metal hydroxides are also suitable. Depending on the metal compound, an acid treatment is also possible. In step (c), an impregnation of the composite obtained from step (a) or (b) is carried 20 out. Impregnation with chemicals is known and can be carried out as in the impregnation of porous metal-organic frameworks. This is described, for example, in the international patent application PCT/EP2010/053530. The impregnation is preferably effected by mixing and subsequent heating. The 25 impregnation is preferably carried out by mechanical mixing. Sulfur can be introduced as a solid or from a suspension or solution, in particular an organic solution such as a toluene-comprising solution, in particular a toluene solution. The present invention further provides a composite which can be obtained by a 30 process according to the present invention. The present invention further provides for the use of a composite material according to the invention which can be obtained by a process according to the invention for absorption of at least one material for the purposes of storage, removal, controlled 35 release, chemical reaction of the material or as support. The at least one material is preferably a gas or gas mixture. Storage processes using metal-organic frameworks in general are described in 40 WO-A 2005/003622, WO-A 2003/064030, WO-A 2005/049484, WO-A 2006/089908 WO 2012/028989 PCT/IB2011/053646 24 and DE-A 10 2005 012 087. The processes described there can also be used for the composite of the invention. Separation or purification processes using metal-organic frameworks in general are 5 described in EP-A 1 674 555, DE-A 10 2005 000938 and in DE-A 10 2005 022 844. The processes described there can also be used for the composite of the invention. If the composite of the invention is used for storage, this is preferably carried out in a temperature range from -200'C to +80'C. A temperature range of from -400C to +800C 10 is more preferred. For the purposes of the present invention, the terms "gas" and "liquid" will be used in the interests of simplicity, but gas mixtures and liquid mixtures or liquid solutions are also encompassed by the term "gas" or "liquid". 15 Preferred gases are hydrogen, natural gas, town gas, hydrocarbons, in particular methane, ethane, ethyne, acetylene, propane, n-butane and also i-butane, carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, sulfur oxides, halogens, halogenated hydrocarbons, NF 3 , SF 6 , ammonia, boranes, phosphanes, hydrogen 20 sulfide, amines, formaldehyde, noble gases, in particular helium, neon, argon, krypton and xenon. The gas is particularly preferably carbon dioxide which is separated off from a gas mixture comprising carbon dioxide. The gas mixture preferably comprises carbon 25 dioxide together with at least H 2 , CH 4 or carbon monoxide. In particular, the gas mixture comprises carbon monoxide in addition to carbon dioxide. Very particular preference is given to mixtures which comprise at least 10 and not more than 45% by volume of carbon dioxide and at least 30 and not more than 90% by volume of carbon monoxide. 30 A preferred embodiment is pressure swing adsorption using a plurality of parallel adsorber reactors, with the adsorbent charge consisting entirely or partly of the material according to the invention. The adsorption phase for the C02/CO separation preferably takes place at a C02 partial pressure of from 0.6 to 3 bar and a temperature of at least 35 200C but not more than 700C. To desorb the adsorbed carbon dioxide, the total pressure in the adsorber reactor concerned is usually reduced to values in the range from 100 mbar to 1 bar. Preference is also given to the use of the framework of the invention for storing a gas 40 at a minimum pressure of 100 bar (absolute). The minimum pressure is more WO 2012/028989 PCT/IB2011/053646 25 preferably 200 bar (absolute), in particular 300 bar (absolute). The gas is particularly preferably hydrogen or methane. However, the at least one material can also be a liquid. Examples of such liquids are 5 disinfectants, inorganic or organic solvents, fuels, in particular gasoline or diesel, hydraulic fluid, radiator fluid, brake fluid or an oil, in particular machine oil. Furthermore, the liquid can be a halogenated aliphatic or aromatic, cyclic or acyclic hydrocarbon or a mixture thereof. In particular, the liquid can be acetone, acetonitrile, aniline, anisole, benzene, benzonitrile, bromobenzene, butanol, tert-butanol, quinoline, chlorobenzene, 10 chloroform, cyclohexane, diethylene glycol, diethyl ether, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dioxane, glacial acetic acid, acetic anhydride, ethyl acetate, ethanol, ethylene carbonate, ethylene dichloride, ethylene glycol, ethylene glycol dimethyl ether, formamide, hexane, isopropanol, methanol, methoxypropanol, 3-methyl-1-butanol, methylene chloride, methyl ethyl ketone, N 15 methylformamide, N-methylpyrrolidone, nitrobenzene, nitromethane, piperidine, propanol, propylene carbonate, pyridine, carbon disulfide, sulfolane, tetrachloroethene, carbon tetrachloride, tetrahydrofuran, toluene, 1,1,1-trichloroethane, trichloroethylene, triethylamine, triethylene glycol, triglyme, water or mixtures thereof. 20 Furthermore, the at least one material can be an odorous substance. The odorous substance is preferably a volatile organic or inorganic compound which comprises at least one of the elements nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine or iodine, or is an unsaturated or aromatic hydrocarbon or a 25 saturated or unsaturated aldehyde or a ketone. More preferred elements are nitrogen, oxygen, phosphorus, sulfur, chlorine, bromine; particular preference is given to nitrogen, oxygen, phosphorus and sulfur. In particular, the odorous substance is ammonia, hydrogen sulfide, sulfur oxides, 30 nitrogen oxides, ozone, cyclic or acyclic amines, thiols, thioethers and also aldehydes, ketones, esters, ethers, acids or alcohols. Particular preference is given to ammonia, hydrogen sulfide, organic acids (preferably acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, heptanoic acid, lauric acid, pelargonic acid) and also cyclic or acyclic hydrocarbons comprising nitrogen or sulfur 35 and also saturated or unsaturated aldehydes such as hexanal, heptanal, octanal, nonanal, decanal, octenal or nonenal and in particular volatile aldehydes such as butyraldehyde, propionaldehyde, acetaldehyde and formaldehyde and additionally fuels such as gasoline, diesel (constituents). 40 The odorous substances can also be fragrances which are used, for example, for producing perfumes. As fragrances or oils which liberate such fragrances, mention may WO 2012/028989 PCT/IB2011/053646 26 be made by way of example of: essential oils, basil oil, geranium oil, mint oil, cananga tree oil, cardamom oil, lavender oil, peppermint oil, nutmeg oil, chamomile oil, eucalyptus oil, rosemary oil, lemon oil, lime oil, orange oil, bergamot oil, muscat sage oil, coriander oil, cypress oil, 1,1-dimethoxy-2-phenylethane, 2,4-dimethyl-4 5 phenyltetrahyd rofu ran, dimethyltetrahydrobenzaldehyde, 2,6-dimethyl-7-octen-2-ol, 1,2-diethoxy-3,7-dimethyl-2,6-octadiene, phenylacetaldehyde, rose oxide, ethyl-2 methylpentanoate, 1-(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-2-buten-1 -one, ethylvanillin, 2,6-dimethyl-2-octenol, 3,7-dimethyl-2-octenol, tert-butylcyclohexyl acetate, anisyl acetate, allylcyclohexyloxy acetate, ethyl linalool, eugenol, coumarin, 10 ethyl acetoacetate, 4-phenyl-2,4,6-trimethyl-1,3-dioxane, 4-methylene-3,5,6,6 tetramethyl-2-heptanone, ethyl tetrahydrosafranate, geranyl nitrile, cis-3-hexen-1-ol, cis-3-hexenyl acetate, cis-3-hexenyl methyl carbonate, 2,6-dimethyl-5-hepten-1-al, 4 (tricyclo[5.2.1.0]decylidene)-8-butanal, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3 methylpentan-2-ol, p-tert-butyl alpha-methylhydrocinnamaldehyde, ethyl 15 [5.2.1.0]tricyclodecanecarboxylate, geraniol, citronellol, citral, linalool, linalyl acetate, ionones, phenylethanol or mixtures thereof. For the purposes of the present invention, a volatile odorous substance preferably has a boiling point or boiling point range of less than 300'C. The odorous substance is 20 more preferably a readily volatile compound or mixture. The odorous substance particularly preferably has a boiling point or boiling range of less than 250'C, more preferably less than 230'C, particularly preferably less than 200'C. Preference is likewise given to odorous substances which have a high volatility. The 25 vapor pressure can be employed as a measure of the volatility. For the purposes of the present invention, a volatile odorous substance preferably has a vapor pressure of more than 0.001 kPa (20'C). The odorous substance is more preferably a readily volatile compound or mixture. The odorous substance particularly preferably has a vapor pressure of more than 0.01 kPa (20'C), more preferably a vapor pressure of 30 more than 0.05 kPa (20'C). The odorous substances particularly preferably have a vapor pressure of more than 0.1 kPa (20'C). Examples in which a chemical reaction can take place in the presence of the metal organic framework of the invention are the alkoxylation of monools and polyols. The 35 method of carrying out such alkoxylations is described in WO-A 03/035717 and WO-A 2005/03069. Likewise, the porous metal-organic framework of the invention can be used for the epoxydation and also preparation of polyalkylene carbonates and hydrogen peroxide. Such reactions are described in WO-A 03/101975, WO-A 2004/037895 and US-A 2004/081611. 40 Particular preference is given to catalytic reactions.

WO 2012/028989 PCT/IB2011/053646 27 In addition, the metal-organic framework of the invention can serve as support, in particular as support for a catalyst. 5 The sulfur-impregnated composites of the present invention, in particular, are suitable as sulfur electrode. The present invention therefore further provides a sulfur electrode comprising such a composite according to the invention. 10 The present invention further provides for the use of a sulfur electrode according to the invention in an Li-sulfur battery and also provides an Li-sulfur battery comprising such a sulfur electrode. 15 Examples Example 1: Pyrolysis of Al-terephthalic acid MOF Experimental method: 20 20 g of Al-MOF (Al-terephthalic acid MOF: 1100 m 2 /g determined by the Langmuir method) are introduced into a fused silica tube. This is placed in a tube furnace and flushed overnight with nitrogen. The tube is subsequently heated over a period of 2 hours to 6000C in a stream of nitrogen. During this procedure, the tube is rotated slowly (45 rpm). The powder is pyrolyzed at 6000C for 1 hour. After cooling (about 1.5 hours), 25 the black powder is removed from the tube. Weight obtained: 8.7g Analysis: Surface area: 387 m 2 /g determined by the Langmuir method Elemental analysis: Al 30% by weight 30 Example 2: NaOH washing of the pyrolyzed Al-terephthalate Starting materials: 6.47 g of pyrolized material from Example 1 100 g of sodium hydroxide solution, 10% strength 35 Experimental procedure a) Synthesis: Pyrolyzed material from Example 1 is stirred with the sodium hydroxide solution at 800C in a 250 ml four-neck flask for 10 hours. b) Work-up: The solid is filtered off on a glass frit No. 4 at room temperature, stirred 3 times with 50 ml each time of deionized water, allowed to stand for 5 minutes, filtered 40 off; washed 7 times with 50 ml each time of deionized water. Finally, it is stirred with 25 ml of acetone and sucked dry.

WO 2012/028989 PCT/IB2011/053646 28 c) Drying: 16 hours at 1000C in a vacuum drying oven Color: black Yield: 2.61 g Analysis: Bulk density: 186 g/l 5 Surface area 1620 m 2 /g determined by the Langmuir method Elemental analysis: Al 0.1% by weight; Na 0.61% by weight Example 3: Loading of the material from Example 1 with sulfur. 10 1.0 g of material from Example 1 and 6 g of sulfur are homogeneously mixed and heated at 180'C in an open apparatus for 6 hours. This gives 5.3 g of a solid dark gray substance which was milled to a fine powder by means of a ball mill. Elemental analysis: 15 C = 6.6% by weight S = 83% by weight Example 4: Loading of the material from Example 2 with sulfur. 20 1.0 g of material from Example 2 and 6 g of sulfur are homogeneously mixed and heated at 180'C in an open apparatus for 6 hours. This gives 5.7 g of a porous dark gray substance which was milled to a fine powder by means of a ball mill. 25 Elemental analysis: C = 12.5% by weight S = 86% by weight Example 5: Production of an electrochemical cell according to the invention 30 (electrode) 2.30 g of material from Example 3 or 4, 0.80 g of Super P, 0.11 g of KS 6, 0.15 g of Celvol binder are mixed together. The mixture is dispersed in a solvent mixture of 65% of H 2 0, 30% of isopropanol, 5% of 1-methoxy-2-propanol. The dispersion was stirred 35 for 10 hours. The dispersion is applied by means of a doctor blade to Al foil and dried at 40'C under reduced pressure for 10 hours. Example 6: Production of a benchmark electrochemical cell 40 WO 2012/028989 PCT/IB2011/053646 29 3.310 g of sulfur, 2.39 g of Super P, 0.19 g of KS 6, 0.25 g of Celvol binder are mixed together. The mixture is dispersed in a solvent mixture of 65% of H 2 0, 30% of isopropanol, 5% of 1-methoxy-2-propanol. The dispersion is stirred for 10 hours. 5 Example 7: Testing of the electrochemical cell according to the invention For the electrochemical characterization of the composite, an electrochemical cell is built. Anode: Li foil 50 pm thick, separator Tonen 15 pm thick, cathode with composite material as described above. Electrolyte: 8% by weight of LiTFSI (LiN(SO 2

CF

3

)

2 ), 4% 10 by weight of LiNO 3 , 44% by weight of dioxolane and 44% by weight of dimethoxyethane. Charging and discharging of the cell is carried out at a current of 7.50 mA in the potential range 1.8-2.5. The cell capacity was 75.1 mAh. Results are summarized n Table 1. 15 Table 1 Sample Capacity Capacity 5th cycle [mAh/g S] 50th cycle [mAh/g S] Example 6 850 800 Example 5 1120 950 (material from Example 3) Example 5 1130 950 (material from Example 4)

Claims (15)

1. A process for producing a carbon-comprising composite, which comprises the step 5 (a) pyrolysis of a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion under a protective gas atmosphere, where the at least one at least biden tate organic compound is nitrogen-free. 10

2. The process according to claim 1, wherein the pyrolysis is carried out at at least 5000C.

3. The process according to claim 1 or 2, wherein the protective gas atmosphere 15 comprises nitrogen.

4. The process according to any of claims 1 to 3, wherein the at least one metal ion is an ion selected from the group of metals consisting of Mg, Al, Zr, Ti, V, Cr, Mo, Fe, Co, Cu, Ni and Zn. 20

5. The process according to any of claims 1 to 4, wherein the nitrogen-free at least one at least bidentate organic compound is derived from a dicarboxylic, tricar boxylic or tetracarboxylic acid. 25

6. The process according to any of claims 1 to 5, which comprises the further step (b) at least partial removal of one or more metal components from the com posite obtained in step (a). 30

7. The process according to claim 6, wherein the one or more metal components comprise at least one metal oxide.

8. The process according to claim 6 or 7, wherein the at least partial removal is carried out by washing out by means of an alkaline or acidic liquid. 35

9. The process according to any of claims 1 to 8, which comprises the further step (c) impregnation of the composite obtained from step (a) or (b) with sulfur. WO 2012/028989 PCT/IB2011/053646 31

10. The process according to claim 9, wherein the impregnation is carried out by mixing and subsequent heating.

11. The process according to claim 9 or 10, wherein the sulfur is used as solid or in 5 solution.

12. A composite which can be obtained by a process according to any of claims 1 to 11. 10

13. The use of a composite which can be obtained by a process according to any of claims 1 to 11 for the absorption of at least one material for the purpose of sto rage, removal, controlled release, chemical reaction of the at least one material or as support. 15

14. A sulfur electrode comprising a composite which can be obtained by a process according to any of claims 9 to 11.

15. The use of a sulfur electrode according to claim 14 in an Li-sulfur battery.