Study of the Glycerol Hydrogenolysis Reaction on Cu, Cu–Zn, and Cu–ZnO Clusters

Abstract

Quantum chemistry calculations have been performed to access the efficacy of Cu-based catalysts in various mechanistic steps of the glycerol hydrogenolysis reaction. Calculations are first performed for reactants in the gas phase (noncatalyzed system) and reactants in the gas phase with a 3-atom Cu cluster (catalyzed system). We demonstrate that the glycerol to ethylene glycol conversion is preferred in the noncatalyzed system but glycerol conversion to 1,2-propanediol via the 2-acetol intermediate is preferred in the catalyzed system. We next analyze the adsorption energies of the reactant and product species involved in the glycerol to 1,2-PDO reaction on an 8-atom Cu cluster and Cu cluster doped with a Zn atom or a ZnO molecule. Finally, we study the effects of Zn or ZnO doping on the activation barriers of the two steps of the glycerol to 1,2-PDO reaction.

CO2 and H2 Activation on Zinc‐Doped Copper Clusters

“…[44] Up to now only a few neutral Cu n Zn clusters were studied in the literature, [33,45] and these neutral clusters were considered catalysts only in glycerol hydrogenation. [46] We also extend the studies toward the cationic clusters, which are more likely realized in typical gas phase experimental studies. [44] Furthermore, some experimental and theoretical surface studies suggest that the Cu-based active sites for CO 2 hydrogenation to methanol are partially positively charged species, [47,48] while others attribute the catalytic activity to the fully reduced Cu 0 catalyst.…”

“…Following the work reported on the CO 2 activation mechanism on Cu 3 X (X=transition metal atom) neutral clusters, [23] we extended the investigation on the lowest energy isomers of Cu n Zn (n=4–6), which are within the accessible size‐range of cluster reactivity analysis using infrared multi‐photon experiments [44] . Up to now only a few neutral Cu n Zn clusters were studied in the literature, [33,45] and these neutral clusters were considered catalysts only in glycerol hydrogenation [46] . We also extend the studies toward the cationic clusters, which are more likely realized in typical gas phase experimental studies [44] .…”

Glycerol Hydrogenolysis to Bio-Propanol: Catalytic Activity and Kinetic Model for Ni/C Modified with Al(H2PO4)3

“…However, its reactivity makes it a raw material for the synthesis of other chemical compounds, which are currently obtained by petrochemical methods [4,5]. For example, the hydrogenolysis of glycerol leads to the formation of glycols and propanols [6][7][8].…”