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ChemComm
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DOI: 10.1039/C7CC06530B
COMMUNICATION
Journal Name
(c) H.-X. Zhang, M. Liu, T. Wen and J. Zhang, Coord. Chem.
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Moreover, the size and morphology of CuNi NPs have no
significant change after 5 and even 20 runs , verifying the
favorable confinement effect of the porous MIL-101 (Fig. S3).
In reference to the previously reported CuNi/graphene
catalyst,9d the CuNi@MIL-101 with smaller CuNi NPs by a facile
synthesis exhibits significant improvement in both catalytic
activity and recyclability, probably due to the great pore
confinement effect in MIL-101. Moreover, CuNi/MIL-101
prepared by wet impregnation method instead of DSA can
maintain its activity in 4 consecutive cycles, and its activity
gradually decreases to 85%, 81% and 79% in the subsequent
5th-7th cycles, respectively, which might be explained by the
unstable CuNi NPs mainly stayed on MIL-101 (Fig. S4).
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In summary, a cascade process has been successfully
developed to enhance the catalytic reduction of nitroarene by
coupling with NH3BH3 dehydrogenation. CuNi@MIL-101
catalyst was facilely synthesized by rational incorporation of
Cu2+/Ni2+ ions into MIL-101 via DSA accompanied by in situ
reduction with NH3BH3. The resultant CuNi@MIL-101 exhibits
a superior catalytic activity for the cascade reaction of NH3BH3
dehydrogenation and the subsequent selective reduction of
nitroarenes. The excellent activity would be attributed that the
hydrogen, in situ generated from NH3BH3, is beneficial to its
sufficient contact with substrate, and thus accelerates the
nitroarene reduction. Various nitroarenes with different
substituents can be reduced to into the corresponding anlines
in 4-8 min with >99% yields. Moreover, the great stability and
recyclability of CuNi@MIL-101 catalyst can be unambiguously
demonstrated by five consecutive runs of the cascade
reaction. We believe the obtained cost-effective catalyst is
very promising for the nitroarene hydrogenation in the
presence of in situ generated hydrogen from ammonia borane,
and relative cascade reactions for industrial applications.
Research along this line is ongoing in our laboratory.
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This work is supported by the NSFC (21371162, 21673213,
and 21521001), the National Research Fund for Fundamental
Key Project (2014CB931803) and the Recruitment Program of
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4 | J. Name., 2012, 00, 1-3
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