Heterobimetallic Ba–Co aminopolycarboxylate complexes as precursors for BaCoO3-δoxides; towards a one-stage-deposition of cobaltite filmsCCDC reference numbers 772915and 772916. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c0jm01012j

Autor: Ion Bulimestru, Olivier Mentré, Nathalie Tancret, Aurélie Rolle, Nora Djelal, Laurence Burylo, Nicoleta Cornei, Nelea Popa, Aurelian Gulea
Zdroj: Journal of Materials Chemistry; Nov2010, Vol. 20 Issue 47, p10724-10734, 11p
Abstrakt: Aminopolycarboxylate (APC) ligands have been selected to prepare seven new heterobimetallic barium-cobalt complexes as molecular precursors for BaCoO3-δoxide materials. The use of APC = nitrilotriacetate (nta3−), ethylenediaminetetraacetate (edta4−), cyclohexane-1,2-diaminetetraacetate (cdta4−) and diethylenetriaminepentaacetate (dtpa5−) polydentate chelating agents enables the possible incorporation of Ba and CoIIor CoIIIin a 1 : 1 ratio. The crystal structure of the new BaCoII(nta)CH3COO·2H2O and BaCo(cdta)·5H2O have been refined from single crystal X-ray diffraction data. Our choice for the barium-cobalt system is based on the existence of a number of distinct BaCoO3-δhexagonal perovskite polytypes, depending on the oxygen stoichiometry. It yields an easy probing of the cobalt oxidation state after thermal treatments. Temperature controlled X-ray diffraction (TCXRD) technique has been used to characterize the phases in competition upon thermal cycles of the precursors. The influences of the nature of ligands, initial cobalt oxidation state, temperature and working atmosphere on the process of formation of the mixed-oxide have been investigated. All the APC-precursors show appearance of a mixture of crystallized barium carbonate and Co3O4in various ratio during the degradation process under air or flowing oxygen at 350–450 °C. Further thermal treatment under flowing oxygen leads to pure submicronic 2H-BaCoO3-δabove 650 °C in the case of cdta complexes, i.e.in softer conditions compared to the solid state route performed under high oxygen pressure. No essential influence of the cobalt valence in the precuror complexes was observed regarding the target BaCoO3-δoxygen non stoichiometry. Finally, with a view to access porous electrodes for SOFCs, we demonstrated the possibility of one-stage-deposition of BaCoO3-δlayers on dense YSZ substrates, with a relatively good adherence, viathe high temperature degradation of these complexes. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index