Journal
JOURNAL OF MATERIALS CHEMISTRY
Volume 20, Issue 20, Pages 4103-4115Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b926282b
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Funding
- Region Bretagne
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The chemical reduction of the K2NiF4-type oxides, Ln(2)Sr(2)CrNiO(8-delta) (Ln La, Nd) and Nd2.25Sr1.75CrNiO8-delta, has been investigated in situ under a dynamic hydrogen atmosphere at high temperature using neutron powder diffraction. The high count-rate and high resolution of the D20 diffractometer at ILL, Grenoble allowed real-time data collection and structure refinement by full-pattern Rietveld analysis with a temperature resolution of 1 degrees C. Excellent agreement was obtained with the results of thermogravimetric analysis of these materials, which are potential fuel-cell electrodes. The neutron study revealed that oxygen is lost only from the equatorial anion site; the reduction of La2Sr2CrNiO8-delta yields a pure Ni(II) phase, La2Sr2CrNiO7.5 en route to a mixed Ni(II, I) oxide, La2Sr2CrNiO7.40, whereas hydrogen reduction of Nd2Sr2CrNiO8-delta and Nd2.25Sr1.75CrNiO8-delta proceeds continuously from Ni(III) to an average oxidation state of 1.80 for the nickel ion. The data collected throughout a subsequent heating/cooling cycle in air indicated that the reduced phases intercalate oxygen reversibly into the equatorial vacancies of the K2NiF4-type structure. The retention of I4/mmm symmetry, along with the absence of the formation of any impurities throughout the heating/cooling cycles under reducing and oxidizing atmospheres, demonstrates both the reversibility and the strongly topotactic character of the oxygen deintercalation/intercalation chemical redox process and establishes the excellent structural stability of these layered mixed-metal oxides over a wide range of oxygen partial pressures.
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