10.1002/anie.201703938
Angewandte Chemie International Edition
COMMUNICATION
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aniline products than Pd/C and Pd/Beta (Figures 3C and E).
Even in the hydrogenation of nitroarenes with ortho-substituted
groups, such as 2-chloronitrobenzene, the Pd@Beta still
displays the selectivity to 2-aminochlorobenzene at over 99.5%,
much higher than that of 74.2% over the Pd/Beta (Table S8).
These data demonstrate the universality of the Pd@Beta for the
selective hydrogenation of various nitroarenes with substituted
groups at different positions (meta, ortho, and para), due to the
specific adsorption of nitro group of these molecules on the Pd
sites in the Pd@Beta (Table S8, Figure S25).
Recent works summarize typical metal-containing (e.g. Au,
Co, Pt, Fe and bimetallic hybrids) heterogeneous catalysts for
selective hydrogenation of nitroarenes with hydrogen,[5,6,7a] but it
is rarely achieved on heterogeneous monometallic Pd catalysts
with both high activity and excellent selectivity.[19] Here, fixing
metal nanoparticles inside of zeolite crystals open the way to
obtain a series of heterogeneous catalysts with high activity and
selectivity simultaneously, such as Pd@MOR (MOR is zeolite
mordenite), Ru@Beta, and Pt@Beta (Figure S26), all with
uniformly distributed metal nanoparticles, as confirmed by TEM
tomography images (Figures S27-S29). Significantly, the
Pd@MOR, Ru@Beta, and Pt@Beta catalysts all display
outstanding selectivities in the hydrogenation of various
substituted nitroarenes and chlorobenzaldehyde (Figure 3, see
Table S7 for detailed data and reaction conditions), and these
values are much greater than those of Pd/MOR, Ru/Beta, and
Pt/Beta obtained by impregnation methods (Figure S30). These
results taken together demonstrate the generality of the
synthesis and catalytic efficacy of metals@zeolites.
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In summary, we report a novel strategy to improve the
selectivity of Pd nanoparticles in the hydrogenation of
substituted nitroarenes by using a core-shell Pd@Beta catalyst
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This work is supported by National Natural Science Foundation
of China (91634201, 21403192 and 91645105).
Keywords: zeolite • heterogeneous catalyst • Pd nanoparticle •
selective hydrogenation
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