Journal of the American Chemical Society
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MOFs such as HKUST-1 (17.4 %)19, Al-soc-MOF-1 (62.8 %)20,
PCN-14 (16.6 %)21, MOF-520 (38.7 %)22 and MOF-905 (44.6
%)23 supports and affirms the high degree of CH4 packing in
the pbz-MOF-1 between 35 and 65 bar. The gravimetric and
volumetric working capacity between 5-80 bar and 298 K is
estimated to be 22.7 wt% and 180 cm3.cm-3, respectively. In-
terestingly, in contrast to other MOFs with intermediate
porosity such as PCN-1421, HKUST-119, Ni-MOF-7419 and
UTSA-2024, the decrease of the storage temperature to 273 K
led to an increase in the CH4 working capacity. For instance,
in the case HKUST-1 and when going from 298 K to 273 K,
the volumetric working capacity between 5-65 bar decreased
from 190 cm3 cm-3 to 155 cm3 cm-3. Whereas for pbz-MOF-1,
under the same conditions, the opposite occurred and an
increase from 162 cm3 cm-3 to 185 cm3 cm-3 was observed. This
manifest unique feature in the microporous pbz-MOF-1
could be attributed to the favorable synergistic effect be-
tween the pore system dimensions and the localized high
density of aromatic rings per accessible unit volume.
In summary, we have demonstrated for the first time the
successful use of reticular chemistry and the MMB approach
for the construction of a highly connected Zr-based MOF
with the intricate pbz topology. The synthesis of the pbz-
MOF-1, constructed from 6-connected hexagonal Zr6 clusters
and bridged by a novel nanosized hexatopic linker, repre-
sents the first example of a crystalline solid-state material
displaying the 6-c pbz net. High pressure CH4 adsorption
measurements on the highly porous pbz-MOF-1 revealed a
high storage capacity of 0.23 g g-1 and 210.4 cm3(STP) cm-3 at
80 bar. Moreover, pbz-MOF-1 exhibits one of the highest
enhancement in the adsorbed phase density when going
from 35 to 65 bar. The successful synthesis of the first pbz-
MOF paves the way to expand this approach to other ligands
and inorganic building blocks with the aim to tune the pore
system and functionality.
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ASSOCIATED CONTENT
Supporting Information
Synthesis, NMR, PXRD, TGA, and additional sorption data.
This material is available free of charge via the Internet at
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AUTHOR INFORMATION
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Corresponding Author
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N. W.; DelgadoꢁFriedrichs, O.; O'Keeffe, M.; Yaghi, O. M., Acc.
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ACKNOWLEDGMENT
This research has been co-financed by the European Union
and Greek national funds through the Operational Program
"Education and Lifelong Learning" of the National Strategic
Reference Framework (NSRF) - Research Funding Program:
ARISTEIA II – 4862. Financial support by King Abdullah
University of Science and Technology (KAUST) is gratefully
acknowledged.
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Maspero, A.; Barea, E.; Navarro, J. A. R., Angew. Chem. Int. Ed.
2010, 49 (40), 7308ꢁ7311.
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Inorg. Chem. 2009, 48 (11), 4655ꢁ4657.
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Ouellette, W.; Liu, H. X.; O'Connor, C. J.; Zubieta, J.,
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Spek, A. L., Acta Crystallogr. Sect. D. 2009, 65, 148ꢁ
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