Kinetic investigation into the chemoselective hydrogenation of α,β-unsaturated carbonyl compounds catalyzed by Ni(0) nanoparticles

Abstract

A series of Ni(0) nanocatalysts was prepared from a Ni(COD)₂ complex in the presence of different stabilizers (hexadecylamine, polyvinylpyrrolidone (PVP), PVP/triphenylphosphine, octanoic acid and stearic acid) for their evaluation in the selective hydrogenation reaction of α,β-unsaturated carbonyl compounds by H₂ under mild reaction conditions, i.e., low H₂ pressure, temperature and catalyst loading. All nanocatalysts were active in reducing only the CC bond and this chemoselectivity was attributed to the reduced nature of the Ni-NPs surface. Moreover, the hydrogenation reaction rate appeared to be sensitive to ligand type, with the carboxylic acid-stabilized systems showing the best performances. A full kinetic investigation into the t-chalcone chemoselective reduction of the CC bond, with the best catalyst (Ni-octanoic acid) revealed that the rate-determining step is the hydrogenation of the adsorbed substrate on the NPs surface, following a Horiuti–Polanyi type of mechanism. Regarding sustainable chemistry concerns, the best catalyst could be reused up to 10 times without significant loss of activity.