In situ neutron diffraction study of the high-temperature redox chemistry of Ln(3-x)Sr(1+x)CrNiO(8-delta) (Ln = La, Nd) under hydrogen

摘要

The chemical reduction of the K2NiF4-type oxides, Ln2Sr2CrNiO8-δ (Ln = La, Nd) and Nd 2.25Sr1.75CrNiO8-δ, 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 °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-δ yields a pure Ni(ii) phase, La2Sr2CrNiO7.5en route to a mixed Ni(ii,i) oxide, La2Sr2CrNiO7.40, whereas hydrogen reduction of Nd2Sr2CrNiO8-δ and Nd2.25Sr1.75CrNiO8-δ 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. © 2010 The Royal Society of Chemistry.