Oxygen transport pathways in Ruddlesden-Popper structured oxides revealed via in situ neutron diffractionElectronic supplementary information (ESI) available. See DOI: 10.1039/c5ta04193g

Ruddlesden-Popper structured oxides, general form A n +1 B n O 3 n +1 , consist of n -layers of the perovskite structure stacked in between rock-salt layers, and have potential application in solid oxide electrochemical cells and ion transport membrane reactors. Three materials with constant Co/Fe ratio, LaSrCo 0.5 Fe 0.5 O 4− δ ( n = 1), La 0.3 Sr 2.7 CoFeO 7− δ ( n = 2), and LaSr 3 Co 1.5 Fe 1.5 O 10− δ ( n = 3) were synthesized and studied via in situ neutron powder diffraction between 765 K and 1070 K at a p O 2 of 10 −1 atm. The structures were fit to a tetragonal I 4/ mmm space group, and were found to have increased total oxygen vacancy concentration in the order La 0.3 Sr 2.7 CoFeO 7− δ > LaSr 3 Co 1.5 Fe 1.5 O 10− δ > LaSrCo 0.5 Fe 0.5 O 4− δ , following the trend predicted for charge compensation upon increasing Sr 2+ /La 3+ ratio. The oxygen vacancies within the material were almost exclusively located within the perovskite layers for all of the crystal structures with only minimal vacancy formation in the rock-salt layer. Analysis of the concentration of these vacancies at each distinct crystallographic site and the anisotropic atomic displacement parameters for the oxygen sites reveals potential preferred oxygen transport pathways through the perovskite layers. In situ neutron diffraction techniques were utilized to provide detailed information about the crystal structure of n = 1, n = 2, and n = 3 Ruddlesden-Popper structures focusing on the oxygen transport pathways created by localization of oxygen vacancies.