Catalytic activity of nanoscale borides: Co2B and Ni7B3 in the liquid-phase hydrogenation of citral

•First test of catalytic activity of new phase, Ni7B3.•Well-defined nanoscale borides for hydrogenation of citral.•Selective hydrogenation of CC or CO possible.

Metal borides are unconventional heterogeneous catalysts. Now, two compounds - the new phase Ni7B3 and well-known Co2B - were synthesized as well-defined, nanoscale material. After characterization (X-ray diffraction, scanning electron microscopy, nitrogen physisorption) they were tested for the liquid phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) in n-hexane at different temperatures. Hydrogenation products such as geraniol, nerol, citronellal and citronellol were analyzed. The Ni-free catalyst Co2B results in the formation of nerol and geraniol or citronellol selectively, depending on the reaction time. The new compound Ni7B3 yields citronellal or citronellol, depending on the temperature. Thus, the hydrogenation potential of borides - obtained as well-characterized, unsupported heterogeneous catalysts by a one-pot synthesis procedure and post-synthetic annealing - is demonstrated. The cobalt boride preferentially hydrogenates CO bonds, while the nickel boride is selective for CC double bonds.

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