Electronically Coupled PtCo/MgAl Hydrotalcite Catalysts Display Tunable Selectivity Toward Glyceric Acid and Lactic Acid for Glycerol Conversion

Selective oxidation of glycerol is one of the most promising routes to produce value-added fine chemicals from biomass. However, achieving good selectivity towards glyceric and lactic acids still remains a grand challenge in this field. A series of unique electronically coupled PtCo catalysts, supported on layered double hydroxides via co-precipitation method, was reported in this work, as they display tunable selectivity toward glyceric acid and lactic acid during glycerol conversion. It is found that the unusual electronic transfer from MgAl hydrotalcite support to cobalt species, leading to high electron binding energy of PtCo sites on catalyst surface. The presence of cobalt components contributes to synergistic enhancement of oxidation activity at electron deficient Pt sites and more critically, weakened Pt–O strength during glycerol conversion. Such unique electronic reconfiguration, as characterized by XRD and XPS spectroscopy, induces two alternative reaction pathways under different reaction temperatures. While Pt–O bonding strength is significantly weakened by strong Co–O affinity at relatively higher reaction temperature (100 °C), such effect is almost negligible at 50 °C. As a result, lactic acid selectivity of 67% was obtained at 100 °C, while glyceric acid selectivity of 65% was achieved at 50 °C, over the bifunctional PtCo/MgAl hydrotalcite catalysts. The design principles reported in this work offer alternative approaches for manufacturing cost-effective catalytic materials for glycerol conversion to various value-added carboxylic acids and derivatives.