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

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Hu,  Zhiwei
Zhiwei Hu, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Yang, J., Dai, J., Liu, Z., Yu, R., Hojo, H., Hu, Z., et al. (2017). High-Pressure Synthesis of the Cobalt Pyrochlore Oxide Pb2Co2O7 with Large Cation Mixed Occupancy. Inorganic Chemistry, 56(19), 11676-11680. doi:10.1021/acs.inorgchem.7b01646.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002E-134B-A
Abstract
The novel A(2)B(4)O(7)-type compound Pb2Co2O7 was synthesized at 8 GPa and 1673 K. Synchrotron X-ray diffraction shows a cubic pyrochlore structure with space group Fd (3) over barm. 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)O-4+(2)7 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.