Metal-doped niobate pyrochlores and double-perovskites for glycerol valorization: structural and electronic properties and DFT calculations.

In this study, metal-doped niobates and perovskites were obtained by a solid-state reaction. The solids were evaluated in the esterification of glycerol in the presence of acetic acid to produce valuable esters of glycerol. The structural features of the solids indicated the ZnNb 2 O 6 , Pb 2.8 Nb 2 O 7.8 and CuNb 2 O 6 columbite main phases and La 2 MnFeO 6 double-perovskite. Density functional theory (DFT) studies of Pb 2.8 Nb 2 O 7.8 clearly confirmed the existence of a robust orthorhombic structure and its electronic properties were correlated with the Nb and Pb interactions. The morphological and elemental analyses also indicated that not all surface elements, as well as morphology, were crucial for catalytic properties. All solids were active and selective toward triacetin formation upon glycerol esterification with acetic acid. The catalytic performance depends mainly on the availability of the surface and its structural stability, as well as defects formation. Recyclability studies indicated that the La 2 MnFeO 6 double-perovskite was an efficient catalyst, achieving glycerol conversion of 68% and triacetin selectivity of 25% up to 4 cycles of use in the reaction. The structural defects near the Mn 4+ /Mn 3+ surface sites resulted in the diffusion of anions and an increased concentration of oxygen vacancies contributed to the stable performance of the solid in glycerol ester production.