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High-Pressure Synthesis of the Cobalt Pyrochlore Oxide Pb2Co2O7 with Large Cation Mixed Occupancy.

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The novel A2B2O7-type compound Pb2Co2O7 was synthesized at 8 GPa and 1673 K. Synchrotron X-ray diffraction shows a cubic pyrochlore structure with space group Fd3̅m. Rietveld structural analysis reveals a… Click to show full abstract

The novel A2B2O7-type compound Pb2Co2O7 was synthesized at 8 GPa and 1673 K. Synchrotron X-ray diffraction shows a cubic pyrochlore structure with space group Fd3̅m. Rietveld structural analysis reveals a large cation mixed occupancy at both A and B sites by about 40%, the greatest value found in the pyrochlore family. In combination with the X-ray absorption spectroscopy results, the specific chemical composition and charge states are determined to be (Co0.6Pb0.4)3+2(Pb0.6Co0.4)4+2O7, in which both the A-site Co3+ and the B-site Co4+ are low-spin. Due to the tetrahedral geometric frustration effects as well as the random Co4+ and Pb4+ distribution at the B site, spin glassy behavior is well observed following the conventional critical slowing down feature in Pb2Co2O7.

Keywords: large cation; cation mixed; mixed occupancy; pb2co2o7

Journal Title: Inorganic chemistry
Year Published: 2017

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