A range of Ni–SiO2 catalysts have been prepared by homogeneous precipitation–deposition and impregnation techniques and modified with aqueous solutions of R-(+)-tartaric acid (TA) to induce enantioselectivity in the asymmetric hydrogenation of a prochiral β-ketoester (methyl acetoacetate) to a β-hydroxyester ((R)-(−)-methyl 3-hydroxybutyrate). The effects of catalyst precursor preparation, nickel loading, and precalcination on the reduction of the precursor were examined and the nature of the resultant nickel particle size distribution is described. The influence of metal–support interactions on the uptake of TA was investigated and data on the corrosive metal leaching and the consequent changes in metal dispersion are presented. Modification of the catalysts with TA not only induced enantioselectivity, but also increased the turnover frequency by up to 15 times that observed for the unmodified surface. The amount of TA adsorbed and the fractional surface coverage by TA is related to the degree of enantiodifferentiation. The effects of variations in supported nickel metal particle sizes (in the overall range of 1.4–13.6 nm) on the reaction rate and enantioselectivity were examined; while the selectivity was independent of metal particle size, the rate of hydrogenation was found to be structure sensitive and a correlation between reaction rate sensitivity and particle size is presented.
Effect of initial nickel particle size on stability of nickel catalysts for aqueous phase reforming
