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COMMUNICATION
Journal Name
stabilized in the MOF matrix during the catalytic process under
the reaction conditions (ESI, Fig. S9). In addition, no further
Notes and references
DOI: 10.1039/C6CC06076E
1
(a) A. Corma, H. García and F. X. Llabrés i Xamena, Chem. Rev.,
hydrogenation occurred after removal of
system (Fig. 4).
2 from the reaction
2
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For confirmation of the encapsulated Cu(0) NPs being
responsible for the catalytic activity, a series of control
experiments were performed. When the reaction was carried
2
(a) A. Dhakshinamoorthy, H. Garcia, Chem. Soc. Rev., 2012,
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2 2
out using Cu(OAc) , UiO-66-NH or 1 as the catalyst under the
same reaction conditions, the corresponding yields for
ethylbenzene are 59, 18 and 57 %, respectively. Only 9 % of
ethylbenzene was obtained when styrene hydrogenation was
performed without any catalyst (ESI, Fig. S10). So the loaded
Cu(0) NPs in UiO-66-MOF matrix is responsible for the catalytic
activity.
3
4
5
N. C. Thacker, Z. Lin, T. Zhang, J. C. Gilhula, C. W. Abney, W.
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8 %
98 %
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2
3
4
5
6
7
8
9
,
4
Cl
8
(a) K. J. Gagnon, C. M. Beavers, A. Clearfield, J. Am. Chem.
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9
7 %
O
85 %
63 %
50 %
Cl
94 %
9
1
1
1
1
1
Cl
9
9
6 %
4 %
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a
Determined by GC.
After that, we investigated the catalytic activity of
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2 for
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1
6
(
2
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excellent conversions toward nine-atom mono-substituted
vinyl benzenes (entries 1-6, yields, 94-98 %) regardless of the
electron-donating or electron-withdrawing groups and
positions of the substituents. On the other hand, the
hydrogenating yields for ten-atom substrates (entries 7 and 8,
yields, 63-85 %) or 1.1-disubstituted styrene (entry 9, yield,
1
7 K. Manna, T. Zhang, M. l. Carboni, C. W. Abney, W. Lin, J. Am.
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3
1
2
3
5
0 %) are low, which might be explained by the stereo-
hindrance effect.
In conclusion, two base metal loaded MOF catalysts
Cu(II)@UiO-66-NH (1) and Cu(0)@UiO-66-NH (2) have been
2 2
obtained and studied. The main feature of these new materials
is their high catalytic activity for olefin oxidation and
hydrogenation under mild conditions. This makes them the
real candidates to provide an alternative to conventional noble
metal-based corresponding catalysts.
7
2
2 T. Zhang, K. Manna, W. Lin, J. Am. Chem. Soc., 2016, 138,
3
241−3249.
2
3 N. C. Thacker, Z. Lin, T. Zhang, J. C. Gilhula, C. W. Abney, W.
Lin, J. Am. Chem. Soc., 2016, 138, 3501−3509.
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Catal., 2009, 351, 2271 – 2276.
2
5 P. Garca-Garca, M. Muller, A. Corma, Chem. Sci., 2014,
979–3007.
5,
2
We are grateful for financial support from NSFC (Grant Nos.
2
2
1671122, 21475078 and 21271120), 973 Program (Grant No.
013CB933800) and Taishan Scholar’s Construction Project.
4
| J. Name., 2012, 00, 1-3
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