C O M M U N I C A T I O N S
Table 1. Surface Areas, Pore Volumes, and Porosities of Selected
curves, XRPD patterns, SEM images, figures for PCN-66, and complete
ref 9c. This material is available free of charge via the Internet at http://
pubs.acs.org.
MOFs
surface area (m2 g-1
)
pore volume (cm3 g-1
(exptl/calcda)
)
porosity
(%)a
material
(Langmuir/BET/calcda)
MOF-5b
4400/3800/3110
4593/4024/3125
5640/4746/3654
5900/4100/3252
3500/3000/3455
4600/4000/3935
1.04/1.31
1.53/1.58
1.59/1.87
2.00/1.95
1.36/1.37
1.63/1.75
77.9
80.9
80.0
82.0
77.0
78.1
References
IRMOF-20c
MOF-177d
MIL-101e
PCN-61
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PCN-66
a Calculated using Material Studio 4.4. b Data from refs 1a and 11.
c Data from ref 12. d Data from refs 4 and 12a. e Data from ref 9a.
different-sized cavities discussed above (Figure 3b). Although its
validity in microporous materials has been questioned, the
Brunauer-Emmett-Teller (BET) method is still widely used to
estimate the surface areas of MOFs.10 The two criteria discussed
in the literature have been strictly followed to decide the pressure
range for applying the BET analysis.5a With the BET model, an
activated PCN-61 sample was estimated to have a specific surface
area of 3000 m2 g-1, and the Langmuir surface area was 3500 m2
g-1 assuming monolayer coverage. For PCN-66, where the larger
ligand was used, there was a remarkable increase in surface area
(BET, 4000 m2 g-1; Langmuir, 4600 m2 g-1), which supports our
hypothesis that the expansion of the ligand leads to increased surface
area. To the best of our knowledge, PCN-66 possesses the highest
surface area reported to date for MOFs based on paddlewheel
clusters, and it is also among the highest reported (Table 1). It can
be extrapolated that use of even larger hexatopic carboxylate ligands
may lead to stable MOFs with even higher surface areas.
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cavities with microwindows were synthesized. The stabilities of
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cuboctahedra building units, which limit the open window sizes of
the mesocavities. The surface area of the activated MOF was
increased remarkably by ligand extension, presumably as a result
of the increased size of the mesocavities. The combination of the
(3,24)-connected network topology with the larger ligand demon-
strated that the incorporation of mescocavities with microwindows
may serve as a general approach toward stable MOFs with higher
surface areas. Work along this line is currently underway in our
laboratory and will be reported soon.
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Acknowledgment. This work was supported by the U.S.
Department of Energy (DE-FC36-07GO17033), the U.S. Defense
Logistics Agency (N00164-07-P-1300), and the U.S. National
Science Foundation (CHE-0449634). The microcrystal diffraction
was carried out at the Advanced Photon Source on beamline 15ID-C
with the kind assistance of Yu-Sheng Chen at Argonne National
Laboratory (CHE-0535644, DEAC02-06CH11357). We acknowl-
edge Dr. Shuisong Ni, Dr. Shengqian Ma, and Dr. Xi-Sen Wang
for their help with the X-ray crystallography and gas-sorption
measurements.
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Supporting Information Available: Crystallographic data for PCN-
60, -61, and -66 (CIF), experimental details, thermogravimetric analysis
JA901109T
9
9188 J. AM. CHEM. SOC. VOL. 131, NO. 26, 2009