Mapping of chemical order in inorganic compounds
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Presentations of some of the possibilities of observing cation and anion order in perosvkite based structures in order to solve their structure or to solve other questions, when they could not be solved by bulk diffraction techniques. The examples include a (Pb,Bi)FeO3-d compound, a solid oxide fuel cell compound Sr(Nb,Co,Fe)O3-d and several brownmillerite related compounds, as well as a "relaxor ferromagnetic". This was an invited lecture given at the Spring meeting of the British Crystallographic Association in 2014.
Transcript of Mapping of chemical order in inorganic compounds
- 1.Mapping of chemical order in inorganic compounds Maria Batuk, Dmitry Batuk, Artem M. Abakumov, Joke Hadermann
2. 2 B-cation: transition metal (Fe3+, Ti4+, Zr4+, Nb5+, ) Perovskite structure Cubic structure Space group Pm3m Unit cell parameter ap 3.8 4.2 ABO3 A-cation: alkali, alkali-earth (Ba2+, Sr2+), rare-earth metals, Bi3+, Pb2+ 3. 3 SrCo0.8Fe0.2O3- highest flux among La1-xSrxCo1-yFeyO3- perovskites Brownmillerite structure at RT + Nb Reported disordered perovskite at RT Problem: 4. 4 p p SrCo0.7Fe0.2Nb0.1O2.72 Cubic perovskite 5. 5 HAADF-STEM of cubic perovskite 6. 6 SrCo0.7Fe0.2Nb0.1O2.72 7. 7 8. 8 9. 9 10. 10 Sr2Al0.78Mn1.22O5.2 SrCo0.7Fe0.2Nb0.1O2.72 11. 11 La0.25Sr0.75MnO2.38 La0.17Sr0.83MnO2.36 SrMnO2.22 12. 12 La0.1Sr0.9MnO2.32 13. 13 O A B ABF-STEM of cubic perovskite 14. 14 The structure of Pb0.65Bi0.31Fe1.04O2.68 Refined structure Annular Bright Field (ABF) STEM I ~ Z1/3 High Angle Annular Dark Field (HAADF) STEM I ~ Z1.6-1.9 15. 15 15 a 3.92 ap, c 51.52 13ap octahedra FeTi2: 0.63Fe + 0.37Ti pyramids FeTi1: 0.87Fe + 0.13Ti Pb6BiFe3TiO13Cl2 Cl PbBiO2 Cl Perovskite block Rietveld refinement: 16. 16 17. 17 5 nm La3Ni2SbO9 P.D. Battle et al., In. Chem. 52 (2013) 6648 18. 18 Cation order HR- EDX HR- EELS ABF- STEM HAADF- STEM Anion order 19. 19 La3Sb2NiO9 Peter Battle, Oxford University La0.25Sr0.75MnO2.38, La0.17Sr0.83MnO2.36 and SrMnO2.22 Edward Dixon and Michael Hayward, Oxford University Sr2Al0.78Mn1.22O5.2 Anna S. Kalyushnaya, Marina G. Rozova, Evgeny V. Antipov, Moscow State University SrCo0.7Fe0.2Nb0.1O2.72 Olga Yu. Podyacheva, Boreskov Institute of Catalysis EELS on SrCo0.7Fe0.2Nb0.1O2.72 Stuart Turner, EMAT 20. 20 These slides can also be found on Slideshare/johader 'Layered oxygen vacancy ordering in Nb-doped SrCo1-xFexO3-delta perovskite' S. Van Rompaey, W. Dachraoui, S. Turner, O.Y. Podyacheva, H.Y. Tan, J. Verbeeck, A.M. Abakumov, J. Hadermann Zeitschrift fur Kristallografie, 228 (2013) 28-34 'Synthesis,crystal structure and magnetic properties of the Sr2Al0.78Mn1.22O5.2 anion- deficient layered perovskite ' Hans DHondt, Joke Hadermann, Artem M.Abakumov, Anna S.Kalyuzhnaya, Marina G. Rozova, Alexander A. Tsirlin, Ramesh Nath, Haiyan Tan, Jo Verbeeck, Evgeny V. Antipov, Gustaaf Van Tendeloo Journal of Solid State Chemistry 182, 356363 (2009). 'Structures and Magnetism of La1xSrxMnO3(0.5+x)/2 (0.67 x 1) Phases ' E. Dixon, J. Hadermann, M. Hayward Chem. Mater. 2012, 24, 14861495 'Pb5Fe3TiO11Cl: a rare example of Ti(IV) in a square pyramidal oxygen coordination' Maria Batuk1,*, Dmitry Batuk1, Artem M. Abakumov1,2, Joke Hadermann1 Accepted by Journal of Solid State Chemistry Abakumov, A. M.; Batuk, D.; Hadermann, J.; Rozova, M. G.; Sheptyakov, D. V.; Tsirlin, A. A.; Niermann, D.; Waschkowski, F.; Hemberger, J.; Van Tendeloo, G.; Antipov, E. V. Antiferroelectric (Pb,Bi)1 xFe1+ xO3 y Perovskites Modulated by Crystallographic
