Stabilizing the B-site oxidation state in ABO3 perovskite nanoparticles

Abstract

The stabilization of the B-site oxidation state in ABO₃ perovskites using wet-chemical methods is a synthetic challenge, which is of fundamental and practical interest for energy storage and conversion devices. In this work, defect-controlled (Sr-deficiency and oxygen vacancies) strontium niobium(IV) oxide (Sr_1−xNbO_3−δ, SNO) metal oxide nanoparticles (NPs) were synthesized for the first time using a low-pressure wet-chemistry synthesis. The experiments were performed under reduced oxygen partial pressure to prevent by-product formation and with varying Sr/Nb molar ratio to favor the formation of Nb⁴⁺ pervoskites. At a critical Sr to Nb ratio (Sr/Nb = 1.3), a phase transition is observed forming an oxygen-deficient SrNbO₃ phase. Structural refinement on the resultant diffraction pattern shows that the SNO NPs consists of a near equal mixture of SrNbO₃ and Sr_0.7NbO_3−δ crystal phases. A combination of Rietveld refinement and X-ray photoelectron spectroscopy (XPS) confirmed the stabilization of the +4 oxidation state and the formation of oxygen vacancies. The Nb local site symmetry was extracted through Raman spectroscopy and modeled using DFT. As further confirmation, the particles demonstrate the expected absorption highlighting their restored optoelectronic properties. This low-pressure wet-chemical approach for stabilizing the oxidation state of a transition metal has the potential to be extended to other oxygen sensitive, low dimensional perovskite oxides with unique properties.