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Redox behaviour and solid solubility of cerium ortho-niobates

DOI: 10.1016/j.jssc.2018.12.042 DOI Help

Authors: Cassandra M. Harris (Imperial College London) , Stephen J. Skinner (Imperial College London)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of Solid State Chemistry , VOL 271 , PAGES 135 - 143

State: Published (Approved)
Published: March 2019
Diamond Proposal Number(s): 7943

Abstract: Using Ce LIII edge X-ray absorption near edge spectroscopy (XANES), it is shown that acceptor dopants introduced to cerium members of the rare earth ortho-niobate series, Ce1-xSrxNbO4±δ and Ce1-xCaxNbO4±δ, are charge compensated by the formation of holes on the cerium sublattice. These spectroscopic studies are complemented by structural studies, using X-ray and neutron powder diffraction, determining that the solubility limit of the strontium and calcium dopants within the CeNbO4+δ structure is ~10% and ~30% respectively. Under oxidising conditions, the Ce3+/Ce4+ redox couple facilitates reversible redox processes, and it is observed that the Ce1-xSrxNbO4±δ and Ce1-xCaxNbO4±δ materials form commensurate and incommensurately modulated oxygen hyperstoichiometric phases as a function of temperature. Under reducing atmospheres, this redox activity is suppressed, and charge-compensating Ce4+ holes are annihilated.

Keywords: XANES; Cerium niobate; SOFC; Rare-earth ortho-niobate; Redox

Subject Areas: Chemistry, Energy

Beamlines: B18-Core EXAFS