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decreased from 71% to 44% due to the migration and sintering of
Pd NPs during the repeated cycles (Figure S23e−h). Evidently,
the core−shell Pd@IRMOF-3 nanocomposites are highly stable
against the migration and sintering of Pd NPs and exhibit
excellent activity, selectivity, and stability for the cascade
reactions with respect to the conventional Pd/IRMOF-3.
In summary, the multifunctional core−shell Pd@IRMOF-3
nanocatalysts, for which a Pd NP core is coated with uniform
amino-functionalized IRMOF-3 shell, can be readily prepared by
a facile mixed solvent method. Impressively, the core−shell
nanocomposites could effectively and efficiently realize the
cascade catalysis of Knoevenagel condensation of A and
malononitrile to form B via the alkaline IRMOF-3 shells coupled
with subsequent hydrogenation of the intermediate product B
using the Pd NP cores. Compared with the conventional
supported Pd/IRMOF-3 catalysts, the core−shell Pd@IRMOF-
3 nanostructures show preferential selective hydrogenation of
−NO2 groups of the intermediate products B, thus considerably
improving the yield of the target products C. The corresponding
DFT calculations and experimental evidence disclose that the
characteristic core−shell structures are the origin to improve the
selectivity of the cascade reactions. Furthermore, the core−shell
Pd@IRMOF-3 hybrids are easily recoverable and can be recycled
without loss of catalytic activity in the repetitive reuse cycles.
Such a rational design on the nanocomposites of the noble metal
NPs and MOFs will open up opportunities for design and
fabrication of high-performance multifunctional catalysts.
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ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental and theoretical calculation details and additional
figures. This material is available free of charge via the Internet at
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H. Angew. Chem., Int. Ed. 2012, 51, 4872.
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AUTHOR INFORMATION
Corresponding Authors
■
Notes
(11) (a) Tirelli, N.; Altomare, A.; Solaro, R.; Ciardelli, F.; Meier, U.;
The authors declare no competing financial interest.
Bosshard, C.; Gunter, P. J. Prakt. Chem. 1998, 340, 122. (b) Sato, N.;
Yuki, Y.; Shinohara, H.; Takeji, Y.; Ito, K.; Michikami, D.; Hino, K.;
̈
Yamazaki, H. Patent US 2012/0022077.
ACKNOWLEDGMENTS
■
(12) (a) Zhang, N.; Fu, X.; Xu, Y.-J. J. Mater. Chem. 2011, 21, 8152.
(b) He, L.; Liu, Y.; Liu, J.; Xiong, Y.; Zheng, J.; Liu, Y.; Tang, Z. Angew.
Chem., Int. Ed. 2013, 52, 3741.
(13) Surble, S.; Millange, F.; Serre, C.; Ferey, G.; Walton, R. I. Chem.
Commun. 2006, 14, 1518.
(14) (a) Guerrero-Martínez, A.; Perez-Juste, J.; Liz-Marzan, L. M. Adv.
́ ́
Mater. 2010, 22, 1182. (b) Yu, L.; Zhang, G.; Yuan, C.; Lou, X. W. Chem.
Commun. 2013, 49, 137.
This work was supported financially by National Research Fund
for Fundamental Key Project (2014CB931801, Z.Y.T.;
2012CB933001, K.D.), National Natural Science Foundation
for Distinguished Youth Scholars of China (21025310, Z.Y.T.),
National Natural Science Foundation of China (91027011,
Z.Y.T.; 21303029, G.D.L.; 20933008, K.D.).
(15) Nguyen, L. T. L.; Le, K. K. A.; Truong, H. X.; Phan, N. T. S. Catal.
Sci. Technol. 2012, 2, 521.
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