Dalton Transactions
DOI: 10.1039/C5DT01191D
Blank experiments conducted in the presence of citrateꢀcapped
Fe O nanoparticles showed no detectable amounts of
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4
Knoevenagel or cycloaddition products and confirmed that both
reactions were catalyzed by ZIFꢀ8 materials associated to Fe O .
3
4
3
4
5
0
5
We also examined the leaching behaviour of Fe O @ZIFꢀ8
60
3
4
particles in Knoevenagel and Huisgen reactions. The Fe and Zn
contents were determined in the crude reaction products using
Inductively Coupled PlasmaꢀOptical Emission Spectrometry
5
(ICPꢀOES). Low levels for Fe leaching (207 and 39 µg/L in
6
7
7
8
8
9
9
5
0
5
0
5
0
5
1
Huisgen and Knoevenagel products, respectively) and Zn
leaching (234 and 107 µg/L in Huisgen and Knoevenagel
products, respectively) were obtained. These results show that
ZIFꢀ8 crystals provide enough binding sites on the surface of
Fe O particles to minimize deterioration and leaching and thus to
6
7
8
9
1
3
4
1
facilitate efficient catalyst recycling. Finally, the XRD patterns of
Fe O @ZIFꢀ8 and Fe O @Cu25%/ZIFꢀ8 catalysts exhibit no
3
4
3
4
0
significant changes in their crystallinity after five recyclings (Fig.
S6), which further confirms their high stability.
1
1
1
2
S. Sun and H. Zeng, J. Am. Chem. Soc., 2002, 124, 8204.
A. H. Latham and M. E. Williams, Acc. Chem. Res., 2008, 41,
4
11ꢀ420.
Conclusions
1
1
3
4
S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L. Vander
Elst and R. N. Muller, Chem. Res., 2008, 108, 2064ꢀ2110.
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H. ꢀH. Limbach, B. Chaudret and R. A. Fischer, J. Am. Chem.
Soc., 2008, 130, 6119ꢀ6130.
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To sum up, we have developed an aqueousꢀbased route for
incorporating ca 10 nmꢀsized Fe O nanoparticles inside ZIFꢀ8
3
4
crystals and used Fe O @ZIFꢀ8 particles as a heterogeneous
3
4
catalyst for Knoevenagel condensations between benzaldehyde
and malononitrile. The Fe O @ZIFꢀ8 catalyst is easily
15 R. J. T. Houk, B. W. Jacobs, F. E. Gabaly, N. N. Chang, A. A.
Talin, D. D. Graham, S. D. House, I. M. Robertson and M. D.
Allendorf, Nano Lett., 2009, 9, 3413ꢀ3418.
3
4
recoverable by magnetic separation and can be reused more than
ten times without any loss in the catalytic activity. Using the
1
6
H. ꢀL. Jiang, B. Liu, T. Akita, M. Haruta, H. Sakurai and Q.
Xu, J. Am. Chem. Soc., 2009, 131, 11302ꢀ11303.
2+
same approach, Fe O particles were also loaded into Cu ꢀdoped
3
4
17 H. Liu, Y. Liu, Y. Li, Z. Tang and H. Jiang, J. Phys. Chem. C,
2010, 114, 13362ꢀ13369.
18 M. Meilikhov, K. Yusenko, D. Esken, S. Turner, G. Van
Tendeloo and R. A. Fischer, Eur. J. Inorg. Chem., 2010, 3701ꢀ
ZIFꢀ8 crystals and the particles obtained were successfully used
2
+
for Cu ꢀcatalyzed Huisgen cycloadditions. Results obtained in
this study open an avenue to the fabrication of highly efficient
and easily recoverable MOFs based nanocatalysts.
3
714.
19 T. T. Isimjan, H. Kazemian, S. Rohani and A. K. Ray, J.
Mater. Chem., 2010, 20, 10241ꢀ10245.
2
0
H. ꢀL. Jiang and Q. Xu, Chem. Commun., 2011, 47, 3351ꢀ
370.
Acknowledgements
3
This work was supported by ICCEL and MICA Carnot Institutes.
We thank Kevin Mozet (LRGP, UMR CNRS 7274, Université de
Lorraine) and Hervé Marmier (LIEC, UMR CNRS 7360,
Université de Lorraine) for BET and ICPꢀOES measurements,
respectively.
21 K. Sugikawa, Y. Furukawa and K. Sada, Chem. Mater., 2011,
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C. Wang, K. E. deKrafft and W. Lin, J. Am. Chem. Soc., 2012,
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2
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G. Lu, S. Li, Z. Guo, O.K. Farha, B.G. Hauser, X. Qi, Y.
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Notes and references
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Laboratoire Réactions et Génie des Procédés (LRGP), UMR CNRS
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45
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7274, Université de Lorraine, 1 rue Grandville 54001 Nancy, France. E-
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†
Electronic Supplementary Information (ESI) available: Synthetic
procedures, size distributions, TEM images of Fe nanoparticles,
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recycling performances of the catalysts, and XRD patterns of materials
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