Nanocrystalline CeO2-δ coated β-MnO2 nanorods with enhanced oxygen transfer property

Abstract

In this research, β-MnO2 nanorods were synthesized by a hydrothermal method, followed by a facile precipitation method to obtain nanocrystalline CeO2-δ coated β-MnO2 nanorods. The as-prepared samples were characterized by XRD, HRTEM, FESEM, XPS and in-situ high-temperature XRD. The HRTEM results show that well dispersed CeO2-δ nanocrystals sized about 5 nm were coated on the surface of β-MnO2 nanorods. The oxygen storage and transfer property of as-synthesized materials were evaluated using TGA under various atmospheres (air, pure N2, and 5%H2/95%Ar). The TGA results indicate that CeO2-δ modification could favour the reduction of Mn4+ to Mn3+ and/or Mn2+ at lower temperature as compared with pure β-MnO2 nanorods and the physically mixed CeO2-δ-β-MnO2 under low oxygen partial pressure conditions (i.e., pure N2, 5%H2/95%Ar). Specifically, CeO2-δ@β-MnO2 sample can exhibit 7.5 wt% weight loss between 100 and 400 °C under flowing N2 and 11.4 wt% weight loss between 100 and 350 °C under flowing 5%H2/95%Ar. During the reduction process under pure N2 or 5%H2/95%Ar condition, the oxygen ions in β-MnO2 nanorods are expected to be released to the surroundings in the form of O2 or H2O with the coated CeO2-δ nanocrystals acting as mediator as inferred from the synergistic effect between the well-interacted CeO2-δ nanocrystals and β-MnO2 nanorods.