Hydrothermal Synthesis of a B-Site Magnetic Ruthenate Pyrochlore

Abstract

The pyrochlore oxide (CeIV0.67Na0.33)2RuIV2O7 crystallizes directly as a phase-pure sample, without the need for postsynthesis annealing, from aqueous solutions of Ru3+, Ce3+, and sodium hydroxide in the presence of hydrogen peroxide as oxidizing agent at less than 250 °C. The structure has been refined using powder neutron diffraction and is consistent with electron diffraction and EDXA analysis performed using transmission electron microscopy (cubic Fd3m with a = 10.1659(1) A). The pyrochlore phase is metastable and upon heating to ∼400 °C begins to phase separate to ultimately yield a mixture including Na2Ru4O9, RuO2, Ce2O3, and CeO2. Magnetization measurements confirm that the material is a new example of a B-site magnetic pyrochlore, analogous to the known phase Y2Ru2O7, but that show evidence for magnetic frustration at low temperatures. Heat capacity measurements and low-temperature neutron diffraction indicate the possibility of spin-glass-like behavior with no evidence of long-range magnetic ord...