Note: Descriptions are shown in the official language in which they were submitted.
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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.
127
(2005), 13744-13745 (see also S. Hermes et al. Chem. Mater. 19 (2007), 2168-
2173;
D. Zacher et al., J. Mater. Chem. 17 (2007), 2785-2792; 0. Shekhah et al., J.
Am.
Chem. Soc. 129 (2007), 15118-15119; A. Schroedel et al., Angew. Chem. Int. Ed.
49
(2010), 7225-7228).
MOF layers on silicone supports are described by G. Lu, J. Am. Chem. Soc. 132
(2010), 7832-7833.
MOF layers on polyacrylonitrile supports are described by A. Centrone et al.,
J. Am.
Chem. Soc. 132 (2010), 15687-15691.
Copper-benzenetricarboxylate MOF on copper membranes is described by H. Guo et
al., J. Am. Chem. Soc. 131 (2009), 1646-1647.
The production of an MOF layer on an aluminum support by dipping and crystal
growing is described by Y.-S. Li et al., Angew. Chem. Int. Ed. 49 (2010), 548-
551.
Similar subject matter is described by J. Gascon et al., Microporous and
Mesoporous
Materials 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.
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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
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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).
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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.
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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
DIN 66131
and/or DIN 66134.
5
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
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-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
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the both aromatic and aliphatic compound more preferably comprises one or two
06
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'-
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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-
1H-
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-
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9
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:
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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
1 1 1
N N N N Nc) -..,.......N -......,.....,..NH
H H H H H
0
\NiN 0,IW N i N \
401 /N
N N
el N/
H H H N 0
H
H
lei NO el
N NH
0
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
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(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
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12
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)
MOF-3
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)
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13
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
H2ADC
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
H2ADB
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
H2ATC
0.22 mmol
MOF-11 90 90 90 8.4671
8.4671 14.44 P42/
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14
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
H4MTB
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
H213DC
0.012 mmol
BPR69 Cd(NO3)2 41120 DMSO 90 98.76 90 14.16
15.72 17.66 Cc
B1 0.0212 mmol
H213DC
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
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H2BDC
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
H2BDC
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
P-1
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
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16
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
0
(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
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17
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
H2NDC
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
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18
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
BNDC H202
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
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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
H2BDC
0.0072 mmol
BPR48A2 Zn(NO3)2 6H20 DMSO 90 90 90 14.5 17.04
18.02 Pbca
0.012 mmol toluene
H2BDC
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
H2BDC
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
H2BDC
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
H3BTC
0.0064 mmol
BPR69B1 Cd(NO3)2 4H20 DMSO 90 98.76 90
14.16 15.72 17.66 Cc
0.0212 mmol
H2BDC
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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
H2BDC
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
H2BDC
0.036 mmol
BPR8OH5 Cd(NO3)2 4H20 DMF 90 119.06 90 11.4746
6.2151 17.268 P2/c
0.027 mmol
H2BDC
0.027 mmol
BPR8206 Cd(NO3)2 4H20 DMF 90 90 90 9.7721
21.142 27.77 Fdd2
0.0068 mmol
H2BDC
0.202 mmol
BPR8603 Co(NO3)2 6H20 DMF 90 90 90 18.3449
10.031 17.983 Pca2(1)
0.0025 mmol
H2BDC
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
H2BDC
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
H2BDC
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
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21
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
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Tb(BTC) Tb(NO3)3.5H20 DMF 90 106.02
90 18.6986 11.368 19.721
0.033 mmol
H3BTC
0.033 mmol
Zn3(BTC)2 ZnCl2 DMF 90 90 90 26.572
26.572 26.572 Fm-3m
Honk 0.033 mmol ethanol
H3BTC
0.033 mmol
Zn40(NDC) Zn(NO3)2.4H20 DMF 90 90 90 41.5594 18.818
17.574 aba2
0.066 mmol ethanol
14NDC
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
H2N-BDC
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
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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-
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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.
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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
2
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.
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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.
