Selective Hydrogenolysis of Glycerol to Propylene Glycol on Cu-ZnO Composite Catalysts: Structural Requirements and Reaction Mechanism

Cu-ZnO catalysts were prepared by homogeneous coprecipitation with varying Cu/Zn atomic ratios (0.4-2:1). The catalysts were examined in selective hydrogenolysis of glycerol to propylene glycol. Although propylene glycol selectivities remained essentially constant (over 93%) on the different Cu-ZnO catalysts, the turnover frequencies changed markedly with the Cu/Zn ratio, and reached the greatest value at the ratio of 1:1. Such activity dependence on the Cu/Zn ratio was in parallel with the change in the interaction between Cu and ZnO and in the Cu microstrain, as a consequence of the effects on the crystalline phases of hydroxycarbonate precursors for the Cu-ZnO catalysts, reflecting the structural requirements for glycerol hydrogenolysis. The hydrogenolysis mechanism was also examined and apparently involves kinetically relevant glycerol dehydrogenation to glyceraldehyde on Cu-ZnO and subsequent glyceraldehyde dehydration and hydrogenation to propylene glycol. The mechanism is consistent with the observed superior activities of the more strained Cu particles, and the higher propylene glycol selectivities obtained at higher glycerol and hydrogen concentrations. These findings provide a rationale for the design of more effective Cu-based catalysts in selective hydrogenolysis of glycerol and other biomass-derived polyols, for example, by synthesis of highly strained Cu particles strongly interacting with ZnO or other oxide supports.