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DOI: 10.1039/C7CC03354K
COMMUNICATION
Journal Name
BPDC-(NO ) are intimately mixed in CuNbO-1 and do not melt 0001). K.A.M acknowledges the National Science Foundation
2 4
before framework destruction, they can react more efficiently Graduate Research Fellowship Program and Dr. John Mansfield
during the thermal decomposition to form the characteristic for collecting TEM images. J.K. acknowledges financial support
carbon composites. Furthermore, the intimate mixing of these from the Mid-Career Researcher Program of the National
components in CuNbO-1 leads to a morphologically distinct Research Foundation of Korea funded by the Ministry of
carbon support that originates from a thermal initiation point, Science,
ICT,
and
Future
Planning
(NRF-
which propagates through the crystal leading to the formation 2014R1A2A1A11054190) and Pohang Accelerator Laboratory
of fibrous metal-carbon composites.
in S. Korea for X-ray data collection at the 2D-SMC beamline.
To demonstrate the extension of this type of
decomposition to other MOFs containing similar nitrated
Notes and references
aromatic
Cu(dnpdc)(H
by a modified procedure: dnpdc = 2,2′-dinitrobiphenyl-4,4′- the effects of coordination polymerization on the properties of
linkers,
a
recently
reported
MOF,
[
2
O)] (DMA)
n
4 2 2
(H O) was selected and synthesized † There are examples of structure-property relationships where
1
1
nitrogen-rich energetic heterocycles have been elucidated.
Typically thermolysis/pyrolysis of MOFs leads to carbon
supports that are morphologically similar to the parent MOF.
For the catalytic effect of metals on decomposition products of
CuNbO-2 has been formulated as endothermic compounds see ref: J. Am. Chem. Soc., Vol. 121,
dicarboxylate or BPDC-(NO
(
2
)
2
.
Similar to CuNbO-1, this MOF
paddlewheels as
NbO-topology but doubly-
‡
hereafter, CuNbO-2) is composed of Cu
2
vertices
interpenetrated;
and 1a,7exhibits
§
[Cu(BPDC-(NO
2
)
4
)(DMA)]
n
with DMA as an axial ligand based No. 44, 1999.
1
(a) K. A. McDonald, S. Seth and A. J. Matzger, Cryst. Growth.
Des., 2015, 15, 5963; (b) S. Zhang, Q. Yang, X. Liu, X. Qu, Q.
Wei, G. Xie, S. Chen, S. Gao, Coord. Chem. Rev., 2016, 307
92; (c) Q. Zhang, J. M. Shreeve, Angew. Chem., Int. Ed. 2014,
53, 2540.
on a single-crystal X-ray diffraction analysis (Table S2). We
were able to show that the thermal decomposition pathway of
CuNbO-2 is similar to that of CuNbO-1 in spite of differences in
the sort of the axial ligand, degree of interpenetration, and
extent of linker nitration. Moreover, an analysis of the
decomposition product revealed that the morphology and
structure of the resulting carbon are the same (Section VI in
the ESI) suggesting possible generality for the decomposition
paths observed here. However, other MOFs composed of
hydroxo-bridged multi-nuclear copper clusters and BPDC-
,
2
2
3
(a) T. M. Klapötke, Chemistry of High-Energy Materials,
Walter de Gruyter, Berlin/Boston, 2012, p. 83-85; (b) R.
Meyer and J. K ̈ohler and A. Homburg, Explosives, Wiley-VCH,
Weinheim, 2007, p. 131.
(a) S. J Yang, T. Kim, J. H. Im, Y. S. Kim, K. Lee, H. Jung and C.
R. Park, Chem. Mater., 2012, 24, 464; (b) J. A. Carrasco, J.
Romero, G. Abellán, J. Hernández-Saz, S. I. Molina, C. Martí-
Gastaldo and E. Coronado, Chem. Commun., 2016, 52, 9141;
(c) R. R. Salunkhe, Y. V. Kaneti, J. Kim, J. H. Kim and Y.
Yamauchi, Acc. Chem. Res., 2016, 49, 2796.
(
NO
described herein based on their reported TGA curves.
Moreover, Gd-MOF formulated as {[Gd(BPDC-
NO O) ](S)(H O)} (S = ethyl 3-oxobutanoate)
2 2
) do not seem to show the sort of decomposition
1
1,12
a
4
(a) H. Furukawa, J. Kim, N. W. Ockwig, M. O'Keeffe and O. M.
Yaghi, J. Am. Chem. Soc., 2008, 130, 11650; (b) K. S. Jeong, Y.
B. Go, S. M. Shin, S. J. Lee, J. Kim, O. M. Yaghi and N. Jeong,
(
2
)
4
)
1.5(DMF)
2
(H
2
2
2
n
1
3
does not show abrupt thermal decompostion. Therefore,
these observations imply that the unique decomposition
Chem. Sci., 2011,
P. K. Chu and L. Li, Materials Chemistry and Physics, 2006, 96
53.
(a) A. C. Ferrari and J. Robertson, Phys. Rev. B, 2000, 61
2, 877.
5
6
,
pathways
Cu(dnpdc)(H
as
O)]
found in
CuNbO-1
and
2
[
2
n
(DMA) (H O) can be achieved only when
4
2
2
,
particular metal clusters and nitrated aromatic linkers are
properly combined.
14095; (b) A. Sadezky, H. Muckenhuber, H. Grothe, R.
Niessner and U. Pöschl, Carbon, 2005, 43, 1731; (c) C. T. J.
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Hussain, Carbon, 2013, 54, 1.
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Nature, 2007, 448, 457; (b) S. Park, J. An, I. Jung, R. D. Piner,
S. J. An, X. Li, A. Velamakanni and R. S. Ruoff, Nano Lett.,
In conclusion, the decomposition pathway of CPs
containing nitrated aromatic energetic linkers differs from
those containing nitrogen-rich heterocycles in that
deflagration leads to anisotropic decomposition forming
metal-carbon composites. The decomposition under air,
vacuum, or nitrogen highlights the effect of trapped gasses
inside the pores of the MOFs (CuNbO-1 and -2), which act as
blowing agents during decomposition. This behavior differs
dramatically from the energetic linker alone. Thus, it is
necessary to achieve mixing at the molecular level between
the linkers and copper ions through MOF formation, which
induces metal-catalyzed decomposition in the carbonization
process. The extremely high level of metal dispersion in a
similar way as in GICs suggests future applications of this
7
2
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Chem. C, 2014, 118, 6972.
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9
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synthetic approach in producing catalysts and conducting or 11 N. Zhang, J.-Y. Zhang, Q.-X. Jia, W. Deng and E.-Q. Gao, RSC
energy storage materials where metal-carbon composites are
vital to function.
A.J.M, K.A.M, and J.C.B gratefully acknowledge the support of
the Defense Threat Reduction Agency (Award # HDTRA1-15-1-
Adv., 2015, 5, 70772.
2 T. Qin, J. Gong, J. Ma, X. Wang, Y. Wang, Y. Xu, X. Shen and D.
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| J. Name., 2012, 00, 1-3
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