Metal Organic Framework (MOF)
CH-103
B.Tech. Chemistry course
Indian Institute of Technology Indore
Zeolite
Aluminosilicate Na2Al2Si3O10·2H2O
Zeolites have a porous structure that can
accommodate a wide variety of cations,
such as Na+, K+, Ca2+, Mg2+ and others.
Historical background of MOF
1897 Hofmann synthesized
Ni(CN)2(NH3)·C6H6 (Hofmann
complex) by slow diffusion of C6H6
into an NH3 solution of Ni(CN)2
1927/1944 Pfeiffer & Feigl
posulated the structure of Hofmann
complex as [Ni(CN)2(NH3)(η6-C6H6)]
1954 Powell characterize the
structure of Hofmann complex by
X-ray (as shown here). The
structure can be briefly explained
as “2D Square network bridged by
CN groups are stacked parallel to
each other with the help of NH3,
and the generated channel
encapsulating the benzene
molecule”
Variation of the Hofmann complex and the development of MOF
Hofmann complex can be better
represented as
M1M2(NH3)2(CN)4·2G (G = Guest
molecules)
Cu-Ni MOF
Cu(NH3)2Ni(CN)4·2C6H6
Replacing NH3 with a proper
bridging ligand ethylene diamine
(en) or 4,4’-bipyridine give more
stability to the MOF.
Cd-Ni MOF
Cd(en)Ni(CN)4·2C6H6
3-D infinite framework CuI[C(C6H4CN)4]n
Bidentate linear organic molecules can be Robson’s work shed the light of
replaced by other multidentate organic linkers, controlling the cavity size of
such as MOFs with predetermined size
4,4′,4′′,4′′′-tetracyanotetraphenylmethane was and shape of inorganic nodes,
first applied by Robson’s group to yield and organic linkers.
3-dimensional infinite framework
CuI[C(C6H4CN)4]n. with a large unit cell volume
of 4200 Å , in which about two-thirds of the
volume is occupied by removable solvents
molecules.
3-D infinite framework CuI[C(C6H4CN)4]n
Morphologies in MOF
2D morphologies in MOF with BDC
MOF-2
Metal-carboxylate cluster (square paddlewheel)
Inorganic molecular units
Inorganic molecules-subunits which provide thermal and mechanical stability
and optical and electronic properties, plays major role along with the organic
linkers to offer tuneable properties by controlling the shape (ligand
coordination angles), size (expansion of ligands, long organic linkers), and
functionality (decoration of organic ligands).
Molecular Building Blocks (MBB) are used to tune and design MOF of desired
topology for specific application.
3D morphologies in MOF with Benzenedicarboxylate (BDC)
reported by Yaghi
Square paddle wheel
Square paddle wheel
MOF-5 have very high pore volume than Zeolite
(may be equivalent to a soccer field)
Surface area = 2900 m2/g
Changing the organic linker may
increase the Pore size, without
changing the structural
morphology
Changing the
organic linker may
increase the Pore
size
Very large pore size
that can encapsulate
a large protein
molecule
Popular organic linker
HKUST-1
Some other popular MOF with different metal or organic ligands
Comparative surface area of various MOFs
Functionalized MOF
By functionalizing the organic linker
It may help to anchor a suitable metal ion for catalysis or
for selective binging of an organic molecule
It may act as a tool for pore fictionalization
Porous MOF as catalytic systems
Mesoporous Metal-Organic Frameworks with
Ultrahigh Stability as a Biomimetic Catalyst
Selective Gas sorption properties of MOF
Based on pore volume or pore size or the nature of
the pore (hydrophobic or hydrophilic): pore
fictionalization
Detection of explosive
MOF is capable of very fast and reversible detection of the vapors of
the nitroaromatic explosive 2,4-dinitrotoluene and the plastic
explosive taggant 2,3-dimethyl-2,3-dinitrobutane, through redox
fluorescence quenching with unprecedented sensitivity
Gas sorption properties of MOF
Tuning the Gas sorption properties of MOF
By encapsulating a guest (here Mg) that can enhance
the H2 sorption because of its affinity towards H2
Tuning the Gas sorption properties of MOF
By encapsulating a guest (here Li) that can enhance
the H2 sorption because of its affinity towards H2
Efficient and tunable white-light emission of metal–organic
frameworks by iridium-complex encapsulation
Acknowledgements
The content used in this presentation is mostly collected from the World
Wide Web (WWW), and the popular research articles of Prof. O.M. Yaghi
published in Science and ACS journals.
Books for further reading:
Metal-Organic Frameworks: Design and Application
by L. R. MacGillivary
Metal-Organic Frameworks: Applications from Catalysis to Gas storage
by D. Farrusseng
This presentation is solely for teaching purpose at undergraduate level
