ACS Catalysis
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NH . The size of those observed Pt NCs matches the
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E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R. Chem. Rev. 2012, 112, 724−
dimension of the octahedral cavities in UiO-66-NH , which
2
7
81.
indicates that the cavities restrict the growth of Pt NCs and
these Pt NCs are confined inside the cavities of the MOF. The
(
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1
(
1
(
confinement of Pt NCs inside the cavities of UiO-66-NH was
2
further confirmed by TEM observations under tilting, and by
measuring their activity in the hydrogenation of ethylene, 1-
hexene, and 1,3-cyclooctadiene. The benefit of confining Pt
1
NCs inside the cavities of UiO-66-NH is demonstrated by
2
their more than 90% chemoselectivity to cinnamyl alcohol in
the hydrogenation of cinnamaldhyde. Pt NCs supported on the
external surface of the MOF give less than 72% selectivity to
cinnamyl alcohol. More importantly, the MOF-confined Pt
NCs are very stable under the condition used for
cinnamaldehyde hydrogenation. The catalyst can be reused
̈
Lebedev, O. I.; Van Tendeloo, G.; Walaszek, B.; Buntkowsky, G.;
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0 times without any loss in activity and selectivity. We also
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carried out reaction kinetic studies on the MOF-confined Pt
NCs in cinnamaldehyde hydrogenation and confirmed the
catalyst stability during recycle runs. The stability of the MOF
structure and Pt NCs are confirmed by measuring the XRD
patterns and TEM images of used catalysts.
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(
7
(
̈
rfer, J.; Friedrich, M.; Miyajima, N.; Albuquerque,
ASSOCIATED CONTENT
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*
S
Supporting Information
1
DRIFT, EDX, TEM observation under tilting samples, nitrogen
sorption, and PXRD measurements; kinetic studies during
recycle; TEM images for the catalyst after reaction and a
control sample; leaching test experimental data; catalytic results
A. A.; Graham, D. D.; House, S. D.; Robertson, I. M.; Allendorf, M. D.
Nano Lett. 2009, 9, 3413−3418.
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(
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(
AUTHOR INFORMATION
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2
(
23) Zahmakiran, M. Dalton Trans. 2012, 41, 12690−12696.
Author Contributions
(24) Esken, D.; Turner, S.; Lebedev, O. I.; Van Tendeloo, G.;
§
Fischer, R. A. Chem. Mater. 2010, 22, 6393−6401.
Z.G. and C.X. contributed equally to this work.
̈
(25) Aijaz, A.; Karkamkar, A.; Choi, Y. J.; Tsumori, N.; Ronnebro, E.;
Notes
Autrey, T.; Shioyama, H.; Xu, Q. J. Am. Chem. Soc. 2012, 134, 13926−
3929.
26) Dhakshinamoorthy, A.; Opanasenko, M.; Cejka, J.; Garcia, H.
Catal. Sci. Technol. 2013, 3, 2509−2540.
27) Park, Y. K.; Choi, S. B.; Nam, H. J.; Jung, D.-Y.; Ahn, H. C.;
Choi, K.; Furukawa, H.; Kim, J. Chem. Commun. 2010, 46, 3086−3088.
28) Zlotea, C.; Campesi, R.; Cuevas, F.; Leroy, E.; Dibandjo, P.;
Volkringer, C.; Loiseau, T.; Ferey, G.; Latroche, M. J. Am. Chem. Soc.
The authors declare no competing financial interest.
1
(
ACKNOWLEDGMENTS
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(
We thank Ames Laboratory (Royalty Account) and Iowa State
University for startup funds. This work was also supported by
the Laboratory Research and Development Program of The
Ames Laboratory. The Ames Laboratory is operated for the
U.S. Department of Energy by Iowa State University under
Contract No. DE-AC02-07CH11358. We thank Gordon J.
Miller for use of his XRD, and Igor I. Slowing for use of his gas
adsorption analyzer and ICP-AES.
(
́
2010, 132, 2991−2997.
(29) Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.;
Bordiga, S.; Lillerud, K. P. J. Am. Chem. Soc. 2008, 130, 13850−13851.
(30) Schaate, A.; Roy, P.; Godt, A.; Lippke, J.; Waltz, F.; Wiebcke,
M.; Behrens, P. Chem.Eur. J. 2011, 17, 6643−6651.
(31) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater.
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dx.doi.org/10.1021/cs400982n | ACS Catal. 2014, 4, 1340−1348