Effect of the oxygen coordination environment of Ca-Mn oxides on the catalytic performance of Pd supported catalysts for aerobic oxidation of 5-hydroxymethyl-2-furfural

Four types of Ca-Mn oxides, CaMnO3, CaMn2O4, CaMn3O6 and Ca2Mn3O8, have been prepared and used as supports for Pd nanoparticles. The oxygen activation capacity of these oxides and the catalytic activity of the oxide supported Pd nanocatalysts have been investigated using the aerobic oxidation of 5-hydroxymethyl-2-furfural as a model reaction. It is found that the local coordination environment of lattice oxygen sites plays a crucial role on their redox properties and charge transfer ability from Pd nanoparticles to the support. In particular, the Ca-Mn oxide with lower oxygen coordination number, weaker metal-oxygen bonds and tunnel crystal structure, e.g. CaMn2O4, exhibits promoted oxygen activation capacity, and stronger electron transfer ability. Consequently, Pd/CaMn2O4 exhibits the highest catalytic activity among these catalysts, providing a promising yield of 2,5-furandicarboxylic acid. This work may shed light on future investigations on the design of local structure of active oxygen sites in oxides or oxide supported catalysts for redox reactions.