Porous lanthanide oxides via a precursor method: morphology control through competitive interaction of lanthanide cations with oxalate anions and amino acids.

Porous lanthanide oxides were fabricated by a precursor-thermolysis method. The precursors were synthesized by a hydrothermal reaction with lanthanide (La, Ce, Pr and Nd) salts, sodium oxalate and asparagine (or glutamine). Under hydrothermal conditions asparagine and glutamine exhibited greatly different complexation abilities with lanthanide cations. The competitive interactions of lanthanide cations with oxalate anions and asparagine (or glutamine) gave rise to the formation of precursors with different structures and morphologies. ESI-MS detection further confirmed the different complexation abilities of asparagine or glutamine with lanthanide cations at the molecular level. Variation of oxalate anion concentration or the pH value of the reaction solution could tune the morphology of the products. After calcination, porous lanthanide oxides were obtained with the morphologies of their corresponding precursors. Our work suggests that the complexation ability of organic molecules with metal cations could be a crucial factor for morphological control of the precursors. Moreover, considering the diversity of organic additives and metal salts, other metal oxides with complex composition and morphology could be fabricated via this organic molecule-modified precursor method.