Metal–organic frameworks—prospective industrial applications{ U. Mueller,* M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt and J. Pastre ´ Received 22nd August 2005, Accepted 26th October 2005 First published as an Advance Article on the web 23rd November 2005 DOI: 10.1039/b511962f The generation of metal–organic framework (MOF) coordination polymers enables the tailoring of novel solids with regular porosity from the micro to nanopore scale. Since the discovery of this new family of nanoporous materials and the concept of so called ‘reticular design’, nowadays several hundred different types of MOF are known. The self assembly of metal ions, which act as coordination centres, linked together with a variety of polyatomic organic bridging ligands, results in tailorable nanoporous host materials as robust solids with high thermal and mechanical stability. Describing examples of different zinc-containing structures, e.g. MOF-2, MOF-5 and IRMOF- 8 verified synthesis methods will be given, as well as a totally novel electrochemical approach for transition metal based MOFs will be presented for the first time. With sufficient amounts of sample now being available, the testing of metal–organic frameworks in fields of catalysis and gas processing is exemplified. Report is given on the catalytic activation of alkynes (formation of methoxypropene from propyne, vinylester synthesis from acetylene). Removal of impurities in natural gas (traces of tetrahydrothiophene in methane), pressure swing separation of rare gases (krypton and xenon) and storage of hydrogen (3.3 wt% at 2.0 MPa/77 K on Cu-BTC-MOF) will underline the prospective future industrial use of metal– organic frameworks in gas processing. Whenever possible, comparison is made to state-of-art applications in order to outline possibilities which might be superior by using MOFs. 1. Introduction As early as 1965 a first publication by Tomic 1 on novel solids was introduced which, nowadays, would be categorized and addressed as metal–organic frameworks, coordination poly- mers or supramolecular structures. Already in the aforemen- tioned contribution simple syntheses of coordination polymers based on metals like zinc, nickel, iron, aluminium (but also on thorium and uranium) employing bi- to tetravalent aromatic carboxylic acids are described . Interesting features of these compounds such as high thermal stability and high metal content were already investigated. However, decades later interest in the field was stimulated by the group of O. M. Yaghi, which published the structure of MOF-5 in late 1999, 2 and the concept of reticular design, with totally different carboxylate linkers, in 2002. 3–5 Meanwhile, numerous reviews have addressed this fast growing research efforts, the most comprehensive ones given by Kitagawa 6 and Yaghi. 7 Structures, properties and possible applications as BASF Aktiengesellschaft, Chemicals Research & Engineering, D-67056, Ludwigshafen, Germany. E-mail: [email protected]{ Presented at Symposium T: Porous materials for emerging applica- tions, International Conference on Materials for Advanced Technologies (ICMAT 2005), Singapore, 3–8 July 2005. Ulrich Mueller, born 1957 in Katzenelnbogen, Germany. 1977: studied chemistry in Mainz (thesis on the synthesis of large zeolite crystals and sorption properties) and recieved his PhD in the group of Prof. K.K. Unger; research activities at CNRS ‘Tian&Calvet’, Marseille, ILL Grenoble, and with G.T. Kokotailo, Univ. Pennsylvania. 1989: Ammonia Laboratory BASF: zeolite synthesis and application in catalysis and adsorption. 1999: Senior Scientist, zeolite catalysis: CFC-free polyurethane foams, catalysts for crop protection agents, chemical intermediates, sorptive olefin feedstream purification, piloting of pro- pylene epoxidation catalysts. 1999: Synthesis, scale-up, modification and testing of various metal–organic frame- work compositions. 2005: BASF Research Director. Markus M. Schubert, born 1971 in Munich, Germany. 1991: study of chemistry in Ulm and PhD in group of Prof. Behm on catalysis and surface chemistry. 2000: Postdoc at ETH Zu ¨rich with Prof. Baiker. 2001: Ammonia Laboratory BASF: catalysts carriers, acid–base catalysis. 2004: Scale-up and piloting of metal–organic frameworks for gas processing. APPLICATION www.rsc.org/materials | Journal of Materials Chemistry 626 | J. Mater. Chem., 2006, 16, 626–636 This journal is ß The Royal Society of Chemistry 2006 Downloaded by Imperial College London Library on 24 January 2013 Published on 23 November 2005 on http://pubs.rsc.org | doi:10.1039/B511962F View Article Online / Journal Homepage / Table of Contents for this issue
Describing examples of different zinc-containing structures, e.g. MOF-2, MOF-5 and IRMOF- 8 verified synthesis methods will be given, as well as a totally novel electrochemical approach for transition metal based MOFs will be presented for the first time. With sufficient amounts of sample now being available, the testing of metal–organic frameworks in fields of catalysis and gas processing is exemplified. Report is given on the catalytic activation of alkynes (formation of methoxypropene from propyne, vinylester synthesis from acetylene). Removal of impurities in natural gas (traces of tetrahydrothiophene in methane), pressure swing separation of rare gases (krypton and xenon) and storage of hydrogen (3.3 wt% at 2.0 MPa/77 K on Cu-BTC-MOF) will underline the prospective future industrial use of metal– organic frameworks in gas processing. Whenever possible, comparison is made to state-of-art applications in order to outline possibilities which might be superior by using MOFs.
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U. Mueller,* M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt and J. Pastre
Received 22nd August 2005, Accepted 26th October 2005
First published as an Advance Article on the web 23rd November 2005
DOI: 10.1039/b511962f
The generation of metal–organic framework (MOF) coordination polymers enables the tailoring
of novel solids with regular porosity from the micro to nanopore scale. Since the discovery of
this new family of nanoporous materials and the concept of so called ‘reticular design’, nowadays
several hundred different types of MOF are known. The self assembly of metal ions, which act
as coordination centres, linked together with a variety of polyatomic organic bridging ligands,
results in tailorable nanoporous host materials as robust solids with high thermal and
mechanical stability.
Describing examples of different zinc-containing structures, e.g. MOF-2, MOF-5 and IRMOF-
8 verified synthesis methods will be given, as well as a totally novel electrochemical approach for
transition metal based MOFs will be presented for the first time.
With sufficient amounts of sample now being available, the testing of metal–organic
frameworks in fields of catalysis and gas processing is exemplified. Report is given on the catalytic
activation of alkynes (formation of methoxypropene from propyne, vinylester synthesis from
acetylene). Removal of impurities in natural gas (traces of tetrahydrothiophene in methane),
pressure swing separation of rare gases (krypton and xenon) and storage of hydrogen (3.3 wt% at
2.0 MPa/77 K on Cu-BTC-MOF) will underline the prospective future industrial use of metal–
organic frameworks in gas processing. Whenever possible, comparison is made to state-of-art
applications in order to outline possibilities which might be superior by using MOFs.
1. Introduction
As early as 1965 a first publication by Tomic1 on novel solids
was introduced which, nowadays, would be categorized and
addressed as metal–organic frameworks, coordination poly-
mers or supramolecular structures. Already in the aforemen-
tioned contribution simple syntheses of coordination polymers
based on metals like zinc, nickel, iron, aluminium (but also on
thorium and uranium) employing bi- to tetravalent aromatic
carboxylic acids are described . Interesting features of these
compounds such as high thermal stability and high metal
content were already investigated.
However, decades later interest in the field was stimulated
by the group of O. M. Yaghi, which published the structure of
MOF-5 in late 1999,2 and the concept of reticular design, with
totally different carboxylate linkers, in 2002.3–5 Meanwhile,
numerous reviews have addressed this fast growing research
efforts, the most comprehensive ones given by Kitagawa6 and
Yaghi.7 Structures, properties and possible applications as
BASF Aktiengesellschaft, Chemicals Research & Engineering, D-67056,Ludwigshafen, Germany. E-mail: [email protected]{ Presented at Symposium T: Porous materials for emerging applica-tions, International Conference on Materials for AdvancedTechnologies (ICMAT 2005), Singapore, 3–8 July 2005.
Ulrich Mueller, born 1957 inKatzenelnbogen, Germany.1977: studied chemistry inMainz (thesis on the synthesisof large zeolite crystals andsorption properties) andrecieved his PhD in the groupof Prof. K.K. Unger; researcha c t i v i t i e s a t C N R S‘Tian&Calvet’, Marseille, ILLGrenoble, and with G.T.K o k o t a i l o , U n i v .Pennsylvania. 1989: AmmoniaLaboratory BASF: zeolitesynthesis and application in
catalysis and adsorption. 1999: Senior Scientist, zeolite catalysis:CFC-free polyurethane foams, catalysts for crop protectionagents, chemical intermediates, sorptive olefin feedstream
purification, piloting of pro-pylene epoxidation catalysts.1999: Synthesis, scale-up,modification and testing ofvarious metal–organic frame-work compositions. 2005:BASF Research Director.
Markus M. Schubert, born1971 in Munich, Germany.1991: study of chemistry inUlm and PhD in group ofProf. Behm on catalysis andsurface chemistry. 2000:Postdoc at ETH Zurich with
Prof. Baiker. 2001: Ammonia Laboratory BASF: catalystscarriers, acid–base catalysis. 2004: Scale-up and piloting ofmetal–organic frameworks for gas processing.
APPLICATION www.rsc.org/materials | Journal of Materials Chemistry
626 | J. Mater. Chem., 2006, 16, 626–636 This journal is � The Royal Society of Chemistry 2006
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storage media were again studied by Rowsell, from Yaghi’s
group.7,8 Comparisons with oxides, molecular sieves, porous
carbon and heteropolyanion salts has been filed by Barton
and coauthors.9 Nowadays several hundred different MOFs
are known. The self assembly of metal ions, which act as
coordination centres, linked together with a variety of
polyatomic organic bridging ligands, results in tailored
nanoporous host materials as robust solids with high thermal
and mechanical stability (Fig. 1). Interestingly, unlike other
solid matter, e.g. zeolites, carbons and oxides, a number of
coordination compounds are known to exhibit high frame-
work flexibility and shrinkage/expansion due to interaction
with guest molecules.6 The most striking difference to state-of-
art materials is probably the total lack of non-accessible bulk
volume in metal–organic framework structures. Although high
surface areas are already known from activated carbons and
zeolites as well, it is the absence of any dead volume in MOFs
which principally gives them (on a weight-specific basis) the
highest porosities and world record surface areas (Fig. 2),
especially with MOF-177, for which values of 4500 m2 g21 are
reported.5 Of course, properties like the drastically increased
velocity of molecular traffic through these open structures
are closely related to the regularity of pores in nanometer size
as well.
Thus the combination of so far unreached porosity, surface
area, pore size and wide chemical inorganic–organic composi-
tion recently brought these materials to the attention of many
researchers in both academia and industry, with about 1000
publications on ‘coordination polymers’ per annum.6
This paper, however, aims to describe how MOF-materials
can be synthesized using verified synthetic methods as well as
by a totally novel electrochemical approach.10
With a large range of samples now available, the testing of
metal–organic frameworks in fields of catalysis and gas
processing is enabled. A report is given on the catalytic
activation of alkynes (the formation of methoxypropene
from propyne, vinylester synthesis from acetylene).11 Further
examples like olefin polymerization, Diels–Alder reaction,
transesterification6 or cyanosilylation12 are referenced in the
literature.
The removal of impurities in natural gas (i.e. traces of
tetrahydrothiophene in methane), pressure swing separation of
Friedhelm Teich, born 1955 inTrier, Germany. 1973: studyof Chemical Engineeringat Karlsruhe (PhD on gasprocessing). 1986: Dyestuff &Pigments laboratory BASF.2 0 0 4 : B A S F C h e m i c a l sResearch & Engineering,20 years experience in design-ing and developing processesfor the production of pigmentsand fine chemicals. 2004:process simulation for applica-tion of metal–organic frame-work materials.
Hermann Putter, born 1944 in Duesseldorf, Germany. 1951–1964: school in Duesseldorf. 1964–1972: study of chemistry inWuerzburg (thesis on the preparation and elucidation of theelectrochemical properties of squaric acid derivatives). 1969:summer/autumn: electroanalytical studies at the HeyrovskyInstitute in Prague. 1973–1985: Main Laboratory BASF,
Ludwigshafen, development ofdirect and indirect organicelectrosyntheses, commerciali-sation of the first electro-dialysis processes in ourcompany. 1985–1992: plantmanager of a chloralkali plantin Ludwigshafen. 1990: estab-lishment of the first chlorineb a s e d ‘ ‘ c h e m i s t r e e ’ ’ o fGermany for VCI. During thistime: papers, public discussionsand lectures on chlorinec h e m i s t r y . S i n c e 1 9 9 3 :Manager of R&D activities on
all electrochemical processes of our company. Since 1994:lectures on environmental and sustainability aspects of chemistry.1999: BASF innovation award for the first technical pairedelectrosynthesis, a process with high atom efficiency that avoidsemissions and halves the energy demand of an electrosynthesis.2001: BASF Research Fellow. 2003, Synthesis of metal–organicframeworks using electrochemistry.
Kerstin Schierle-Arndt, born1971 in Koln, Germany. 1990:study of chemistry in Bonn;PhD in organic electro-chemistry. 1998: AmmoniaLaboratory BASF: electro-chemical research. 2003:C h e m i c a l s R e s e a r c h &E n g i n e e r i n g , H e a d o fContro l l ing . 2005: NewBusiness development atBASF’s Inorganic Specialties.
Joerg Pastre, born 1970, inGroß-Gerau, Germany. 1977:s t u d y o f c h e m i s t r y i nDarmstadt. 2000: PhD onChemical Engineering at ETHZu r ich. 2000: Ammonialaboratory BASF: processdeve lopment department.2005: New business develop-ment at BASF InorganicSpecialties.
This journal is � The Royal Society of Chemistry 2006 J. Mater. Chem., 2006, 16, 626–636 | 627
in principle, many interesting and promising features over
prior art, viz.
N world records in surface area
N ultimate porosity with absence of blocked volume in solid
matter
N combined flexible and robust frameworks
N full exposure of metal sites
N high mobility of guest species in regular framework
nanopores
N fast growing number of novel inorganic–organic chemical
compositions.
Obviously, many applications might (and surely will) be
tested once verified synthesis recipes of MOFs are available.
The recipes given in the Experimental section will allow the
reader to prepare these new compounds in laboratory-scale
amounts. However, industrial synthesis at BASF is understood
to be far more advanced, already into barrel-size pilot scale,
and additional issues need to be taken into account during the
manufacturing procedures, which of course are beyond the
scope of this paper.
Unlike many other novel materials, e.g. carbon polymorphs,
fullerenes, bucky-balls, CNT, the metal–organic framework
materials’ preparation and fabrication does not necessarily
need additional capital investment into a totally new synthesis
technology. Simply adaptation of conventionally available
precipitation and crystallisation manufacturing methods needs
to be done. Shaping of metal–organic framework powders
into industrially widespread geometries of mm-sized tablets,
extrudates, honeycombs, etc. can be performed on MOFs as
well without any major obstacle.
The examples which we gave for catalysis as well as for gas
processing and storage already indicate that there is much
room left for many future research efforts (viz. storage of
alternative energy carriers like small hydrocarbons, odour
removal in both stationary—e.g. household—as well as
mobile (bus, train, subway, ship) environments or the adverse
odorization in carrying perfumes, etc. Pick-up of liquids
without swelling of solids could be of interest as well, e.g. for
food packaging or removal of hazard liquids like organic
solvents, oils, brake fluids and the like).
It is worthwhile to mention that, unlike state-of-art
heterogeneous catalysts, the metal sites in MOFs are usually
fully exposed, therefore giving an ultimately high degree of
metal-dispersion. From supplementary work we already
know that these metal sites usually behave differently from
bulk metals. Compared to zeolites the amount of metals in
MOFs are by almost a factor of ten higher and many of the
metal species belong for chemists to the interesting class of
transition metals.
In summary and perspective, all this might lead to a fast
growing, prosperous and widespread innovation in materials
science, both in academia and industry. However, one
certainly has to keep attention to find superior performance
by applying MOFs over state-of-art technologies. It will
never be sufficient just to find a ‘me-too’ solution instead
of looking for considerable improvement of the best existing
one. Only the latter approach will finally contribute to true
innovation and value-added growth of industrial companies
and society.
Acknowledgements
Technical assistance of Dr O. Metelkina-Schubert, Dr Cox,
S. Lutter, W. Kippenberger, U. Diehlmann, R. Hess, R. Ruetz,
I. Schwabauer, R. Senk, and H. Sichler is gratefully acknowl-
edged. U.M. thanks O.M. Yaghi and S. Kitagawa for many
stimulating discussions on metal–organic frameworks (MOFs)
and coordination polymers (CPLs).
References
1 E. A. Tomic, J. Appl. Polym. Sci., 1965, 9, 3745–3752.2 H. Li, M. Eddaoudi, M. O’Keeffe and O. M. Yaghi, Nature, 1999,
402, 276–279.3 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keefe
and O. M. Yaghi, Science, 2002, 295, 469–472.4 O. M. Yaghi, M. Eddaoudi, H. Li, J. Kim and N. Rosi, WO 2002/
088148, 2002, University of Michigan.5 H. K. Chae, D. Y. Siberio-Perez, J. Kim, Y. B. Go, M. Eddaoudi,
A. J. Matzger, M. O’Keeffe and O. M. Yaghi, Nature, 2004, 427,523–527.
6 S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem., Int. Ed.,2004, 43, 2334–2375.
7 J. L. C. Rowsell and O.M. Yaghi, Microporous MesoporousMater., 2004, 73, 3–14.
8 J. L. C. Rowsell and O. M. Yaghi, Angew. Chem., 2005, 117,4748–4758.
9 T. J. Barton, L. M. Bull, W. G. Klemperer, D. A. Loy,B. McEnaney, M. Misono, P. A. Monson, G. Pez, G. W. Scherer,J. C. Vartuli and O. M. Yaghi, Chem. Mater., 1999, 11, 2633–2656.
10 U. Mueller, H. Puetter, M. Hesse and H. Wessel, WO 2005/049892,2005, BASF Aktiengesellschaft.
11 U. Mueller, M. Hesse, L. Lobree, M. Hoelzle, J. D. Arndt andP. Rudolf, WO 2002/070526, 2002, BASF Aktiengesellschaft.
12 K. Schlichte, T. Kratzke and S. Kaskel, Microporous MesoporousMater., 2004, 73, 81–88.
13 Q. M. Wang, D. Shen, M. Buelow, M. L. Lau, F. R. Fitch andS. Deng, US Pat. 6 491 740, 2002, The BOC Group, Inc.
14 S. S.-Y. Chui, S. M.-F. Lo, J. P. H. Charmant, A. G. Orpen andI. D. Williams, Science, 1999, 283, 1148–1150.
15 F. Stallmach, S. Groeger, V. Kuenzel, J. Kaerger, O. M. Yaghi,M. Hesse and U. Mueller, Angew. Chem., Int. Ed. (submitted).
16 M. Eddaoudi, H. Li and O.M. Yaghi, J. Am. Chem. Soc., 2000,122, 1391–1397.
17 U. Mueller, G. Luinstra and O. M. Yaghi, US Pat. 6 617 467,2004, BASF Aktiengesellschaft.
18 R. Eberhardt, M. Allmendiger, M. Zintl, C. Troll, G. A. Luinstraand B. Rieger, Macromol. Chem. Phys., 2004, 205, 42–47.
19 Chuan-De Wu, A. Hu, L. Zhang and W. Lin, J. Am. Chem. Soc.,2005, 127, 8940.
20 J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon andK. Kim, Nature, 2000, 404, 982–986.
21 Ch. Miller, P. Rudolf and H. J. Teles, WO 2004/009523, 2004,BASF Aktiengesellschaft.
22 K. Seki and W. Mori, J. Phys. Chem. B, 2002, 106, 1380–1385.23 O. M. Yaghi, US Pat. 5 648 508, 1997, Nalco Chemical Company.24 U. Mueller, K. Harth, M. Hoelzle, M. Hesse, L. Lobree, W. Harder
and O. M. Yaghi, WO 2003/064030, 07.08.2003, BASFAktiengesellschaft.
25 S. Barrett, Fuel Cells Bull., 2005, 12–19.26 G. Ferey, M. Latroche, C. Serre, F. Millange, T. Loiseau and
A. Percheron-Guegan, Chem. Commun., 2003, 2976–2977.27 D. N. Dybtsev, H. Chun and K. Kim, Angew. Chem., 2004, 116,
5143–5146.28 B. Chen, N. W. Ockwig, A. R. Millward, D. S. Contreras and
O. M. Yaghi, Angew. Chem., 2005, 117, 4823–4827.29 E. Y. Lee, S. Y. Jang and M. P. Suh, J. Am. Chem. Soc., 2005, 127,
6374–6381.30 D. N. Dybtsev, H. Chun, S. H. Yoon, D. Kim and K. Kim, J. Am.
Chem. Soc., 2004, 126, 32–33.31 Q. Yang and Ch. Zhong, J. Phys. Chem. B, 2005, 109, 24, 11862–4.32 G. Ferey, C. Serre, C. Mellot-Draznieks, F. Millange, S. Surble,
J. Dutour and I. Margiolaki, Angew. Chem., 2004, 116, 6456–6461.
This journal is � The Royal Society of Chemistry 2006 J. Mater. Chem., 2006, 16, 626–636 | 635
33 R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota,R. V. Belosludov, T. C. Kobayashi, H. Sakamoto, T. Chiba,M. Takata, Y. Kawazoe and Y. Mita, Nature, 2005, 436, 238–241.
34 C. Serre, F. Millange, S. Surble and G. Ferey, Angew. Chem., 2004,116, 6446–6449.
35 E. Choi, K. Park, C. Yang, H. Kim, J. Son, S. W. Lee,Y. H. Lee, D. Min and Y. Kwon, Chem.—Eur. J., 2004, 10,5535–5540.
36 Q. Fang, G. Zhu, M. Xue, J. Sun, Y. Wei, S. Qiu and R. Xu,Angew. Chem., 2005, 117, 3913–3916.
636 | J. Mater. Chem., 2006, 16, 626–636 This journal is � The Royal Society of Chemistry 2006