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Phase Segregation in Cerium−Lanthanum Solid Solutions

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Inorganic Chemistry and Catalysis, Department of Chemistry, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht, The Netherlands, and Laboratoire de Physique des Solides, Université Paris-Sud, 91405 Orsay Cédex, France
Cite this: J. Phys. Chem. B 2006, 110, 20, 9984–9990
Publication Date (Web):May 3, 2006
https://doi.org/10.1021/jp060882+
Copyright © 2006 American Chemical Society
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    Abstract

    Electron energy-loss spectroscopy (EELS) in combination with scanning transmission electron microscopy (STEM) reveals that the La enrichment at the surface of cerium−lanthanum solid solutions is an averaged effect and that segregation occurs in a mixed oxide phase. This separation occurs within a crystalline particle, where the dopant-rich phase is located at the surface of the dopant-deficient phase. The limiting structure appears to be a solid solution with a La fraction of x = 0.6 in the bulk and x = 0.75 at the surface. Up to a La fraction of 0.6, this phase will coexist with a lanthanum-type structure in different proportions depending on the dopant amount. STEM-EELS appears to be a powerful technique to clarify the existence of a multiphase system, and it shows that XRF, XPS, and XRD measure averaged results and do not show the phase complexity of the solids.

    †

     Utrecht University.

    ‡

     Université Paris-Sud.

    *

     Corresponding author. Phone:  +31 30 253 4328; fax:  +31 30 251 1027; e-mail:  [email protected].

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    19. Md. Moniruzzaman, Taishi Kobayashi, Takayuki Sasaki. Phase transformation of mixed lanthanide oxides in an aqueous solution. Journal of Nuclear and Radiochemical Sciences 2021, 21 (0) , 15-27. https://doi.org/10.14494/jnrs.21.15
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    46. D. Horlait, F. Tocino, N. Clavier, N. Dacheux, S. Szenknect. Multiparametric study of Th1−xLnxO2−x/2 mixed oxides dissolution in nitric acid media. Journal of Nuclear Materials 2012, 429 (1-3) , 237-244. https://doi.org/10.1016/j.jnucmat.2012.05.047
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    48. Vyshnavi Narayanan, Petra Lommens, Klaartje De Buysser, Danny E. P. Vanpoucke, Ruben Huehne, Leopoldo Molina, Gustaaf Van Tendeloo, Pascal Van Der Voort, Isabel Van Driessche. Aqueous CSD approach for the growth of novel, lattice-tuned LaxCe1−xOδ epitaxial layers. Journal of Materials Chemistry 2012, 22 (17) , 8476. https://doi.org/10.1039/c2jm15752g
    49. Novica Paunović, Zorana Dohčević-Mitrović, Rareş Scurtu, Sonja Aškrabić, Marija Prekajski, Branko Matović, Zoran V. Popović. Suppression of inherent ferromagnetism in Pr-doped CeO2 nanocrystals. Nanoscale 2012, 4 (17) , 5469. https://doi.org/10.1039/c2nr30799e
    50. Wei-ping GONG, Rui ZHANG, Zhong-sheng CHEN. Thermodynamic modelling and applications of Ce–La–O phase diagram. Transactions of Nonferrous Metals Society of China 2011, 21 (12) , 2671-2676. https://doi.org/10.1016/S1003-6326(11)61109-6
    51. Shuang Liang, Esteban Broitman, Yanan Wang, Anmin Cao, Götz Veser. Highly stable, mesoporous mixed lanthanum–cerium oxides with tailored structure and reducibility. Journal of Materials Science 2011, 46 (9) , 2928-2937. https://doi.org/10.1007/s10853-010-5168-y
    52. Manas Kumar Rath, Susant Kumar Acharya, Bok-Hee Kim, Ki Tae Lee, Byung Guk Ahn. Photoluminescence properties of sesquioxide doped ceria synthesized by modified sol–gel route. Materials Letters 2011, 65 (6) , 955-958. https://doi.org/10.1016/j.matlet.2011.01.004
    53. Bo Zhang, Dao Li, Xingyi Wang. Catalytic performance of La–Ce–O mixed oxide for combustion of methane. Catalysis Today 2010, 158 (3-4) , 348-353. https://doi.org/10.1016/j.cattod.2010.04.019
    54. C. Bueno-Ferrer, S. Parres-Esclapez, D. Lozano-Castelló, A. Bueno-López. Relationship between surface area and crystal size of pure and doped cerium oxides. Journal of Rare Earths 2010, 28 (5) , 647-653. https://doi.org/10.1016/S1002-0721(09)60172-1
    55. A. Papavasiliou, A. Tsetsekou, V. Matsouka, M. Konsolakis, I.V. Yentekakis. An investigation of the role of Zr and La dopants into Ce1−−Zr La O enriched γ-Al2O3 TWC washcoats. Applied Catalysis A: General 2010, 382 (1) , 73-84. https://doi.org/10.1016/j.apcata.2010.04.025
    56. Małgorzata A. Małecka, Ulrich Burkhardt, Dariusz Kaczorowski, Marcus P. Schmidt, Daniel Goran, Leszek Kępiński. Structure and phase stability of nanocrystalline Ce1−x Ln x O2−x/2−δ (Ln = Yb, Lu) in oxidizing and reducing atmosphere. Journal of Nanoparticle Research 2009, 11 (8) , 2113-2124. https://doi.org/10.1007/s11051-008-9577-7
    57. Włodzimierz Miśta, Małgorzata A. Małecka, Leszek Kępiński. Redox behavior of nanocrystalline Ce1−xLuxO2−x/2 mixed oxide obtained by microemulsion method. Applied Catalysis A: General 2009, 368 (1-2) , 71-78. https://doi.org/10.1016/j.apcata.2009.08.011
    58. Małgorzata A. Małecka, Leszek Kępiński, Mirosław Mączka. Structure and phase composition of nanocrystalline Ce1−xLuxO2−y. Journal of Solid State Chemistry 2008, 181 (9) , 2306-2312. https://doi.org/10.1016/j.jssc.2008.05.033
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