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ChemComm
Ministry of Education, Culture, Sports, Science and
DOI: 10.1039/C4CC07562E
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Material Sciences (iCeMS) is supported by the World
Premier International Research Initiative (WPI).
Notes and references
a
Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto
University, Yoshida Ushinomiyacho, Sakyo-ku, Kyoto 606-8501, Japan.
E-mail: kitagawa@icems.kyoto-u.ac.jp
Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho,
5
5
0
5
b
Fig. 3. Crystal size-dependence map for the four PCP/MOF
catalysts discussed in this paper. The catalytic reaction is as
follows: (MOF-76(Yb)), esterification reaction; (MOF-74(Co)),
Kawaguchi, Saitama 332-0012, Japan.
c
Shoei Chemical Inc., 5 Azawakasa, Fujikicho, Tosu, Saga 841-0048,
Japan. E-mail: k-nagashima@shoeichem.co.jp.
d
Department of Synthetic Chemistry and Biological Chemistry,
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1
cycloaddition of CO
2
to styrene oxide ; (UiO-66), cyclization of
Graduate School of Engineering, Kyoto University, Kyoto-daigaku
Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
†Electronic Supplementary Information (ESI) available: Experimental
procedures and characterization. See DOI: 10.1039/b000000x/
9
(
+)-citronellal ; and (MIL-101(Cr)), oxidation of diphenyl
8
methane .
In contrast, the significant changes in size of the MOF-
60
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7
6(Yb) samples enhanced the catalytic performance during
1
the esterification reaction, although 1a and 1b were identical
III
in terms of their structure and acidity of the Yb cations, as
1
5
2
evidenced by the XRPD, N adsorption, and IR data using
6
7
7
8
8
9
5
0
5
0
5
0
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acetone as a probe molecule. A decrease in 1-D channel
length would increase the number of OMSs functionalizing
as catalytic sites inside the pores of the MOF-76(Yb).
Quantitatively, the functionalizing OMS of 1a was
calculated to be about three times that of 1b from the TOF
5
. J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon and K. Kim,
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1
2
2
3
3
4
0
5
0
5
0
5
0
–
1
–1
for 1a (2.6 h ) and 1b (0.8 h ). This indicates that all the
OMSs in the 1-D channels of 1a are fully utilized as
catalytic sites, whereas the number of practically
functionalizing OMSs in 1b is reduced by about one-sixth
from the aperture window of the 1-D channels. On the other
hand, in the case of the isomerization reaction, the
significantly enhanced diffusion on the substrate driven by
the high-temperature condition presumably leads to the non-
dependence on the crystal size. From these results, we can
conclude that heterogeneous PCP/MOF catalysts in the
submicrometer region can offer better catalytic performance
than in the micrometer region, but this depends on the
diffusion rate of the substrate and the products of the target
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In conclusion, submicrosized MOF-76(Yb) (1a) was
prepared at room temperature. The structure and acidity of
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1
7
a were found to be identical to those of microsized MOF-
6(Yb) (1b). Compound 1a exhibits higher catalytic
performance for esterification than 1b, whereas there was no
difference between these compounds for the isomerization 95 18. M. Higuchi, K. Nakamura, S. Horike, Y. Hijikata, N. Yanai, T.
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reaction studied. Thus, control of the crystal size of
heterogeneous porous catalysts, such as PCP/MOFs, offers a
promising approach to high-performance catalysts based on
the large number of practically functionalizing OMSs.
This research was supported by the New Energy and
Industrial Technology Development Organization, Japan
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(
NEDO), the PRESTO Program of the Japan Science and
1
Technology Agency (JST), the Advanced Catalytic
Transformation Program for Carbon Utilization (ACT-C),
the MEXT Project for Developing Innovation Systems
Regional Innovation Strategy Support Program Kyoto Next-
Generation Energy System Creation Strategy (MEXT = the
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1
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