Forum Article
pubs.acs.org/IC
Preface for the Forum on Metal−Organic Frameworks for Energy
Applications
Wenbin Lin*,† and Jeffrey R. Long*,‡,§
†
Department of Chemistry, University of Chicago, 929 East 56th Street, Chicago, Illinois 60637, United States
‡
Department of Chemistry and Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United
States
§
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
M etal−organic frameworks (MOFs) have emerged as a
promising new class of porous materials with widely
varying, and sometimes tunable, structures and properties.1
Although earlier concepts of extended coordination networks
were advanced by Robson and co-workers in the late 1980s,2
the field of MOFs did not catch the imagination of the broader
scientific community until the mid-1990s, when seminal
contributions from Yaghi,3 Kitagawa,4 Ferey,5 and others6
demonstrated that such structures could exhibit permanent
porosity and possess interesting functionalities. The initial
excitement about MOFs was mainly driven by their enormous
internal surface areas and their potential for storing hydrogen at
high densities, a critical need for hydrogen-based clean energy
technologies.7 Extensive efforts over the past 2 decades have led
to the synthesis of a large number of highly porous MOFs, and
many of these materials have been examined for the storage of
key gaseous molecules, including hydrogen, methane, and
carbon dioxide.8 In addition, the ability to achieve selective
adsorption by adjusting the surface chemistry has raised the
possibility of employing MOFs to improve the efficiency of
some energy-intensive separation processes, including the
removal of carbon dioxide from flue gases9 and the separation
of hydrocarbon mixtures.10 More recently, by taking advantage
of the extraordinary tunability of both the organic and inorganic
building units, a number of designer MOFs have been
examined for other clean energy applications, such as using
MOFs as model structures for studying essential steps in solar
energy utilization, including energy transfer, light-harvesting,
water oxidation, and proton reduction.11 This Forum features a
collection of articles that encompass many aspects of MOF
research relating to the possible development of new clean
energy technologies.
A number of articles address the design and modification of
MOF architectures. Serre, Devic, and co-workers describe the
design and synthesis of four crystalline titanium(IV) carbox-
yphenolate MOFs synthesized using the 2,5-dihydroxytereph-
thalic acid (H4dobdc) linker.12 Because of the strong
coordination ability of the α-hydroxycarboxylate moieties,
these MOFs feature extended network structures built from
single Ti4+-ion metal-connecting points that are connected
solely by the dobdc4− ligands. As a result of the ligand-to-metal
charge transfer arising from Ti−phenolate bonds, these MOFs
strongly absorb visible light. Titanium MOFs also mediate
hydrogen evolution in the presence of trimethylamine under
UV irradiation.
Banerjee and co-workers synthesized manganese, cobalt, and
cadmium MOFs based on linkers derived from 3-fluoro-4-
© 2016 American Chemical Society
pyridinecarboxylic acid and trans-3-fluoro-4-pyridineacrylic
acid.13 They studied the effects of partial fluorination and
isoreticulation of MOF structures and measured the resulting
hydrogen adsorption capacities, observing no clear trend.
Senkovska and co-workers systematically studied the inner-
surface functionalization of DUT-67, a zirconium-based MOF
featuring Zr6O6(OH)2 nodes and 2,5-thiophenedicarboxylate
bridging ligands.14 The coordinating acetate modulators were
exchanged postsynthetically with a series of carboxylic acids of
varying hydrophobicity. Such simple modulator exchanges
systematically tune the hydrophobicity of the MOF inner
surfaces and can help to stabilize the MOFs toward water
removal compared to the parent DUT-67 material.
Investigations of new MOFs intended for the storage or
purification of small molecules provide the topic for four of the
articles. Qian, Chen, and co-workers report the synthesis of
ZJU-40, a copper MOF incorporating the 5,5′-(pyrazine-2,5-
diyl)diisophthalic acid linker.15 Because of its high porosity,
moderate pore size, and noncoordinated Lewis basic nitrogen
sites, this MOF exhibits a high acetylene uptake capacity. The
nitrogen sites, however, have almost no effect on the CO2
uptake. Consequently, ZJU-40 displays a high adsorption
selectivity of 12−17 for C2H2/CO2 separations at ambient
temperature.
Ibarra, Schröder, Zou, and co-workers detail a study of the
competitive CO2/N2 adsorption in two scandium MOFs based
on biphenyl-3,3′,5,5′-tetracarboxylate and thiophene-2,5-dicar-
boxylate ligands.16 Canonical Monte Carlo and density
functional theory (DFT) computational analyses of CO2 and
hydrocarbon uptake in both MOFs reveal preferential
adsorption sites due to supramolecular interactions between
the framework and adsorbate.
Liu, Cui, and co-workers report the synthesis of chiral,
porous zinc and cadmium MOFs incorporating enantiopure
(R)-2,3-dihydroimidazo[1,2-a]pyridine ligands, together with
an examination of their enantioselective adsorption properties
toward chiral sulfoxides.17 The zinc MOF exhibits a modest
enantioselectivity of 12−47 in adsorbing either R or S
enantiomers from racemic sulfoxide mixtures.
Allendorf and co-workers highlight their efforts on using
MOF−guest interactions to study the fundamental aspects of
energy applications.18 They describe efforts toward hydrogen
Special Issue: Metal-Organic Frameworks for Energy Applications
Received: July 13, 2016
Published: August 1, 2016
7189 DOI: 10.1021/acs.inorgchem.6b01680
Inorg. Chem. 2016, 55, 7189−7191
Inorganic Chemistry
and noble gas storage, hydrogenolysis of biomass, light
harvesting, and conductive materials. In particular, they show
how, by treating guest molecules as integral design elements for
guest@MOF constructs, interesting insights can be gained in
the development of clean energy technologies.
Luminescence, energy transfer, and electron transport are
also important topics for potential energy applications of
MOFs. Li and co-workers discuss the use of fluorescent MOFs
as energy-efficient and lanthanide metal-free lighting phos-
phors.19 They report the design and synthesis of a series of
highly fluorescent zinc MOFs based on 1,1,2,2-tetrakis[4-(4-
carboxyphenyl)phenyl]ethene and 1,1,2,2-tetrakis[4-(pyridin-4-
yl)phenyl]ethene ligands, demonstrating greater than 75%
fluorescence quantum yields for many of the materials. The
enhanced quantum efficiency and thermal stability of
luminescent MOFs over the organic ligands are attributed to
chromophore rigidification in the MOFs. The luminescence
properties of these MOFs can be further tuned through the
choice of coligands. MOFs thus provide an interesting platform
for the design of lanthanide metal-free phosphors for energy-
efficient solid-state lighting applications.
Shustova and co-workers discuss recent advances in efficient
multiple-chromophore coupling in structurally defined
MOFs.20 In particular, because of their structural regularity
and synthetic tunability, MOFs offer an excellent platform for
engineering molecular assemblies that mimic protein systems
with exceptionally high energy-transfer efficiency. These
authors also report the synthesis of 16 dye molecules based
on the benzylidene imidazolinone core that can be encapsu-
lated inside the rigid scaffold of Zn3(BTC)2 to lead to novel
noncoordinative MOF mimics of protein β-barrels.
Hendon, Walsh, and Dincă describe a potentially promising
approach to the design of porous and conductive MOFs based
on DFT calculations.21 They propose the possibility of
overcoming the poor electronic communication between
metal clusters and the organic ligands in MOFs by extending
the dimensionality of the inorganic components. The
calculations indicate that the alkaline-earth oxides SrO and
BaO can be transformed to form porous solids with acetate and
trifluoroacetate ligands, leading to changes in the frontier
crystalline orbital composition, band dispersion, and dielectric
constants. The insights gained from such DFT analyses could
prove instructive in the design of hybrid solids with tunable
band structures.
Baldansuren, D’Alessandro, and co-workers report the
electrochemical properties of the redox-active tris[4-(pyridine-
4-yl)phenyl]amine (NPy3) ligand and a zinc-containing MOF
based on this ligand.22 Through comprehensive in situ UV/vis/
near-IR, electron paramagnetic resonance, and fluorescence
spectroelectrochemical experiments, they determined that NPy3
forms a highly delocalized radical cation upon one-electron
oxidation both in solution and in the MOF framework.
Significantly, the authors establish the utility of in situ
spectroelectrochemical methods in the study of electroactive
MOFs.
The remainder of the articles deal with one of the most
challenging potential applications of MOFs: combining their
porosity and functionalities to effect molecular transformations
that are of importance to energy conversion and utilization.
Cohen and co-workers discuss the use of MOFs as single-site
metal catalysts for small-molecule transformations.23 They
introduce the general aspects of the design of catalytic MOFs,
survey common molecular metal catalysts in MOFs, and
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highlight molecular MOF catalysts for hydrogen evolution and
CO2 reduction. Finally, they report their original research on
the design of new MOFs based on squaramide ligands that can
provide second-sphere interactions with the metal center,
position substrates through hydrogen bonding, or even perform
a complementary (i.e., tandem) organocatalytic reaction.
Ma and co-workers report their research on the synthesis of a
Zn-(Zn-porphyrin) MOF of pcu topology.24 The MOF adopts
4-fold interpenetration due to the highly elongated nature of
the porphyrin ligand. The Zn-porphyrin moieties provide Lewis
acidic sites for catalysis of the reaction of CO2 with epoxides to
form cyclic carbonates.
Wu and co-workers report the synthesis of a metal-
loporphyrin−polyoxometalate (POM) hybrid material for the
synergistic activation of O2.25 Specifically, they demonstrate a
turnover frequency of 6 s−1 together with an exceptionally high
turnover number of 220000 for the metalloporphyrin−POM
hybrid in the epoxidation of styrene using isobutyraldehyde and
O2.
Finally, Kobayashi, Mitsuka, and Kitagawa highlight their
research efforts on the synthesis and applications of hybrid
materials composed of metal nanoparticles and MOFs.26 The
synthetic strategies for several metal@MOF systems are
surveyed, including Pd@HKUST-1, Pd−Au@ ZIF-8, and
Cu@MIL-100-Cr. They also discuss hydrogen storage in
Pd@HKUST-1, alcohol oxidation by Pd−Au@ ZIF-8, and
CO2 reduction to methanol by Cu@MIL-100-Cr, while further
reporting their original research on the one-pot synthesis of the
new composite materials Pd/ZIF-8 and Ni@MOF-74.
As illustrated in the Forum Articles, the design and synthesis
of MOFs with extraordinarily high porosity has witnessed
significant advancement in the past 2 decades. The practical
application of MOFs in the storage of gases such as hydrogen
and methane still faces some critical challenges, including
limitations in volumetric capacity at ambient temperatures,
tolerance toward impurities, and potentially a relatively high
cost. On the other hand, the implementation of MOFs in
replacing energy-intensive gas separations may be closer to
reality, owing to some significant potential advantages over
other solid adsorbents and absorptive solutions.27 The studies
of MOFs in energy-efficient lighting, energy conversion, energy
storage, and small-molecule activation all benefit from the
synthetic tunability of MOFs, a unique advantage of MOFs
over other crystalline solid-state materials. Such synthetic
versatility can be leveraged to design MOF materials for other
important applications, including chemical sensing,28 earth-
abundant element catalysis,29 and disease diagnosis and
treatment.30
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: wenbinlin@uchicago.edu.
*E-mail: jrlong@berkeley.edu.
Notes
Views expressed in this editorial are those of the author and not
necessarily the views of the ACS.
■
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7191 DOI: 10.1021/acs.inorgchem.6b01680

Inorg. Chem. 2016, 55, 7189−7191