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Issue 16, 2017
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Selective hydrogenation of unsaturated carbonyls by Ni–Fe-based alloy catalysts

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Abstract

Ni–Fe alloy catalysts prepared by a simple hydrothermal method and subsequent H2 treatment exhibited the greatest activity and selectivity for the hydrogenation of biomass-derived furfural to furfuryl alcohol among the examined second metals, such as Al, Ga, In, Co, and Ti. This work reveals that the alloying of Ni and Fe is a key factor in achieving highly selective hydrogenation of the C[double bond, length as m-dash]O moiety in unsaturated carbonyl substrates. We found that decreasing the temperature of H2 treatment (i.e. decreasing the crystallite size), e.g. Ni–Fe(2)HT-573 K (TOF = 952 h−1), increased the activity compared to that over Ni–Fe(2)HT-673 (TOF = 375 h−1) for furfural hydrogenation. This result suggests that a low-coordinated Ni–Fe alloy was imperative for the catalytic cycle. Moreover, the effect of the metal/support interface was critical; despite the high catalytic performance of Ni–Fe/TiO2, Ni–Fe/Al2O3, and Ni–Fe/CeO2, Ni–Fe supported on SiO2, taeniolite, and hydrotalcite catalysts were ineffective. Vibrational studies using FT-IR measurement confirmed that furfural was physically adsorbed on the surface of the Ni–Fe alloy catalyst via an η1(O) configuration. The synthetic scope of the Ni–Fe catalytic system was very broad; various types of unsaturated carbonyls, such as unsaturated aromatics, unconjugated aliphatics, and a large substituent, were selectively converted into the corresponding unsaturated alcohols.

Graphical abstract: Selective hydrogenation of unsaturated carbonyls by Ni–Fe-based alloy catalysts

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Publication details

The article was received on 12 May 2017, accepted on 20 Jul 2017 and first published on 21 Jul 2017


Article type: Paper
DOI: 10.1039/C7CY00945C
Citation: Catal. Sci. Technol., 2017,7, 3637-3646
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    Selective hydrogenation of unsaturated carbonyls by Ni–Fe-based alloy catalysts

    W. S. Putro, T. Kojima, T. Hara, N. Ichikuni and S. Shimazu, Catal. Sci. Technol., 2017, 7, 3637
    DOI: 10.1039/C7CY00945C

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