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Analysis of oxidation decomposition reaction scheme and its kinetics of delafossite-type oxide CuLaO2 by thermogravimetry and high-temperature X-ray diffraction

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Abstract

The oxidation decomposition reaction and its reaction kinetics of delafossite-type oxide CuLaO2, which is a mother phase of new luminescent material, at various temperatures were investigated by thermogravimetry and high-temperature X-ray diffraction. It was clarified that CuLaO2 is not thermodynamically stable in air and reacts with O2, which is represented as the chemical reaction formula, 4CuLaO2 + O2 → 2CuLa2O4 + 2CuO, above 500 °C. It was also revealed that CuLaO2 transforms to a metastable CuLaO2.66 phase with a copper valence of 2.32+ and some phases with lower crystallinity below 500 °C. At 800 °C, a metastable defect perovskite Cu2La2O5 phase was generated at initial period of the decomposition, resulting in variation to mixture of CuLa2O4 and CuO as reaction proceeded. It was found that a first-order reaction model can be applied to the reaction kinetics of the oxidation decomposition reaction. The activation energy for the reaction was estimated to be 65 kJ mol−1 under air flow. It was concluded that CuLaO2 has lower kinetic stability than the other delafossite-type oxides such as CuAlO2 and CuGaO2.

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References

  1. Kawazoe H, Yasukawa M, Hyodo H, Kurita M, Yanagi H, Hosono H. P-type electrical conduction in transparent thin films of CuAlO2. Nature. 1997;389:939–42.

    Article  CAS  Google Scholar 

  2. Hoffman RL, Wager JF, Jayaraj MK, Tate J. Electrical characterization of transparent p-i-n heterojunction diodes. J Appl Phys. 2001;90:5763–7.

    Article  CAS  Google Scholar 

  3. Saadi S, Bouguelia A, Derbal A, Trari M. Hydrogen photoproduction over new catalyst CuLaO2. J Photochem Photobiology A Chem. 2007;187:97–104.

    Article  CAS  Google Scholar 

  4. Tsuboi N, Ohara H, Hoshino T, Kobayashi S, Kato K, Kaneko F. Luminescence properties of delafossite-type CuYO2 doped with calcium, oxygen or rare earth Tb. Jpn J Appl Phys. 2005;44:765–8.

    Article  CAS  Google Scholar 

  5. Katsui A, Takahashi Y, Matsushita H. Strong yellow-green luminescence in delafossite-type CuLaO2 doped with calcium or strontium. Jpn J Appl Phys. 2007;46:L546–8.

    Article  CAS  Google Scholar 

  6. Takahashi H, Motegi Y, Tsuchigane R, Hasegawa M. Pressure effect on the antiferromagnetic transition temperature in CuFeO2. J Magn Magn Mater. 2004;272:216–7.

    Article  Google Scholar 

  7. Fujishiro F, Murakami M, Hashimoto T, Takahashi M. Orange luminescence of Eu3+-doped CuLaO2 delafossite oxide. J Ceram Soc Jpn. 2010;118:1217–20.

    Article  CAS  Google Scholar 

  8. Fujishiro F, Sekimoto R, Hashimoto T. Optical properties of photoluminescent polycrystalline CuLa0.98Eu0.02O2 thin film prepared by pulsed laser deposition at room temperature. Mater Lett. 2011;65:2492–4.

    Article  CAS  Google Scholar 

  9. Kumekawa Y, Hirai M, Kobayashi Y, Endoh S, Oikawa E, Hashimoto T. Evaluation of thermodynamic and kinetic stability of CuAlO2 and CuGaO2. J Therm Anal Calorim. 2010;99:57–63.

    Article  CAS  Google Scholar 

  10. Bednorz JG, Müller KA. Possible high T c superconductivity in the Ba–La–Cu–O system. Z Phys B. 1986;64:189–93.

    Article  CAS  Google Scholar 

  11. Bringley JF, Scott BA, La Placa SJ, Boehme RF, Shaw TM, McElfresh MW, Trail SS, Cox DE. Synthesis of the defect perovskite series LaCuO3−δ with copper valence varying from 2+ to 3+. Nature. 1990;347:263–5.

    Article  CAS  Google Scholar 

  12. Darracq S, Largeteau A, Demazeau G, Scott BA, Bringley JF. Stability of the tetragonal and rhombohedral forms of LaCuO3 in relation to pressure. Eur J Solid State Inorg Chem. 1992;29:585–96.

    CAS  Google Scholar 

  13. Garlea O, Darie C, Bougerol C, Isnard O, Bordet P. Structure of LaCuO2.66: an oxidized delafossite compound containing hole-doped kagome planes of Cu2+ cations. Solid State Sci. 2003;5:1095–104.

    Article  CAS  Google Scholar 

  14. Shannon RD, Rogers DB, Prewitt CT. Chemistry of noble metal oxides. I. Syntheses and properties of ABO2 delafossite compounds. Inorg Chem. 1971;10:713–8.

    Article  CAS  Google Scholar 

  15. Cava RJ, Zandbergen HW, Ramirez AP, Takagi H, Chen CT, Krajewski JJ, Peck WF Jr, Waszczak JV, Meigs G, Roth RS, Schneemeyer LF. LaCuO2.5+x and YCuO2.5+x delafossites: materials with triangular Cu2+δ planes. J Solid State Chem. 1993;104:437–52.

    Article  CAS  Google Scholar 

  16. Khasanova NR, Izumi F, Hiroi Z, Takano M, Huang Q, Santoro A. Redetermination of the structure of La2Cu2O5 by neutron powder diffraction. Acta Cryst. 1996;C52:2381–4.

    CAS  Google Scholar 

  17. Izumi F, Kim YI, Muromachi ET, Kamiyama T. Neutron powder diffraction study of phase separation in La2CuO4+δ oxidized in KMnO4 solutions. Phys C. 1994;C235–240:841–2.

    Article  Google Scholar 

  18. Momma K, Izumi F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J Appl Crystallogra. 2011;44:1272–6.

    Article  CAS  Google Scholar 

  19. Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst. 1976;A32:751–67.

    Article  CAS  Google Scholar 

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Acknowledgements

The authors thank Prof. M. Murayama and Mr. T. Matsuzaki (Center for Advanced Marine Core Research, Kochi University) for the measurement of the particle size distribution using the laser diffraction particle size analyzer.

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Authors and Affiliations

  1. Department of Natural Science, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi, 780-8520, Japan

    Fumito Fujishiro & Sayo Takaichi

  2. Department of Integrated Sciences in Physics and Biology, College of Humanities and Sciences, Nihon University, 3-25-40 Sakurajosui, Setagaya-ku, Tokyo, 156-8550, Japan

    Kosuke Hirakawa

  3. Department of Physics, College of Humanities and Sciences, Nihon University, 3-25-40 Sakurajosui, Setagaya-ku, Tokyo, 156-8550, Japan

    Takuya Hashimoto

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  1. Fumito Fujishiro
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Correspondence to Fumito Fujishiro.

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Fujishiro, F., Takaichi, S., Hirakawa, K. et al. Analysis of oxidation decomposition reaction scheme and its kinetics of delafossite-type oxide CuLaO2 by thermogravimetry and high-temperature X-ray diffraction. J Therm Anal Calorim 123, 1833–1839 (2016). https://doi.org/10.1007/s10973-015-4723-9

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  • DOI: https://doi.org/10.1007/s10973-015-4723-9

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