Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Spectroscopic Characterization of Heterogeneity and Redox Effects in Zirconium−Cerium (1:1) Mixed Oxides Prepared by Microemulsion Methods

View Author Information
Instituto de Catálisis y Petroleoquímica, CSIC, Campus de Cantoblanco, 28049 Madrid, Spain, and Instituto de Ciencia de Materiales de Sevilla (Centro Mixto Universidad de Sevilla-CSIC), Av. Americo Vespucio s/n, Isla de la Cartuja, 41092 Sevilla, Spain
Cite this: J. Phys. Chem. B 2003, 107, 12, 2667–2677
Publication Date (Web):March 1, 2003
https://doi.org/10.1021/jp026563+
Copyright © 2003 American Chemical Society

    Article Views

    463

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options

    Abstract

    Two Zr−Ce (1:1 molar ratio) mixed oxide specimens, made by the same microemulsion method from different cerium precursor salts (samples ZC1 and ZC2), have been studied by a combination of physicochemical techniques. After calcination at 773 K (high surface area materials HS: SBET = 96 ± 1 m2 g-1) both samples present similar characteristics in XRD, Raman and TEM (pseudocubic phase t‘ ‘), and XPS/Ar+-etching experiments. This latter evidence for those materials gives a similar moderate surface enrichment in cerium and a surface anion vacancy concentration (judged from O(1s) peak shifts) lower than in CeO2; the latter effect suggests an easy diffusion of vacancies to bulk or subsurface regions. Only EPR of adsorbed superoxide species detects a difference between both samples, evidencing in ZC2−HS the presence of small, more reducible Ce-rich bidimensional patches over a Zr-richer substrate. According to XPS/Ar+ etching profiles, by calcination at 1173 K (LS materials; SBET < 8 m2 g-1), surface segregation of small (ca. 3 nm) Ce-rich particles, not yet distinguishable by Raman or diffraction data and able to sustain at the surface local anion vacancy concentrations higher than in the other specimens (closer to the behavior of pure CeO2), occurs on the ZC2 material; the ZC1 specimen, in contrast, actually becomes more homogeneous upon calcination at 1173 K. The short-scale heterogeneity indicated by EPR for sample ZC2-HS, and not for ZC1-HS, is presumed to act as a nucleus favoring formation of this new phase upon calcination. The data obtained evidence the ability of EPR and XPS/Ar+-etching methods to reveal in these materials heterogeneity differences, not detectable by the other techniques, leading to higher reducibility of the Ce-rich surface domains in the ZC2 materials. The results are discussed in connection with the oxygen storage and buffering properties of these mixed oxides.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

     Instituto de Catálisis y Petroleoquímica, CSIC.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

     E-mail:  [email protected]

    §

     Instituto de Ciencia de Materiales de Sevilla E-mail:  [email protected]

    Cited By

    This article is cited by 44 publications.

    1. Nicholas D. Petkovich, Stephen G. Rudisill, Luke J. Venstrom, Daniel B. Boman, Jane H. Davidson, and Andreas Stein . Control of Heterogeneity in Nanostructured Ce1–xZrxO2 Binary Oxides for Enhanced Thermal Stability and Water Splitting Activity. The Journal of Physical Chemistry C 2011, 115 (43) , 21022-21033. https://doi.org/10.1021/jp2071315
    2. D. Gamarra,, G. Munuera,, A. B. Hungría,, M. Fernández-García,, J. C. Conesa,, P. A. Midgley,, X. Q. Wang,, J. C. Hanson,, J. A. Rodríguez, and, A. Martínez-Arias. Structure−Activity Relationship in Nanostructured Copper−Ceria-Based Preferential CO Oxidation Catalysts. The Journal of Physical Chemistry C 2007, 111 (29) , 11026-11038. https://doi.org/10.1021/jp072243k
    3. Marcos Fernández-García,, Xianqin Wang,, Carolina Belver,, Ana Iglesias-Juez,, Jonathan C. Hanson, and, José A. Rodriguez. Ca Doping of Nanosize Ce−Zr and Ce−Tb Solid Solutions:  Structural and Electronic Effects. Chemistry of Materials 2005, 17 (16) , 4181-4193. https://doi.org/10.1021/cm050265i
    4. M. Fernández-García,, A. Martínez-Arias,, J. C. Hanson, and, J. A. Rodriguez. Nanostructured Oxides in Chemistry:  Characterization and Properties. Chemical Reviews 2004, 104 (9) , 4063-4104. https://doi.org/10.1021/cr030032f
    5. A. B. Hungría,, A. Martínez-Arias,, M. Fernández-García,, A. Iglesias-Juez,, A. Guerrero-Ruiz,, J. J. Calvino,, J. C. Conesa, and, J. Soria. Structural, Morphological, and Oxygen Handling Properties of Nanosized Cerium−Terbium Mixed Oxides Prepared by Microemulsion. Chemistry of Materials 2003, 15 (22) , 4309-4316. https://doi.org/10.1021/cm031028n
    6. Yiming Ma, Dongjuan Kang, Yanfeng Wen, Yimeng Chen, Yuhan Long, Honghong Yi, Xiaolong Tang, Shunzheng Zhao. Synergistic effects of Pt single atomic site and Cu nanoclusters for catalytic oxidation of methyl mercaptan. Applied Surface Science 2024, 657 , 159718. https://doi.org/10.1016/j.apsusc.2024.159718
    7. Shanshan Li, Jie Deng, Jianli Wang, Yaoqiang Chen, Yun Li. Effects of thermal treatment conditions on redox properties of ceria-zirconia materials. Journal of Rare Earths 2023, 41 (12) , 1969-1975. https://doi.org/10.1016/j.jre.2022.11.009
    8. Seol Hee Oh, Hyun-Kyu Kim, Jason Kim, Yeong-Cheol Kim, Sun-Young Park, Sungeun Yang, Ho-Il Ji, Kyung Joong Yoon, Ji-Won Son, Jong-Ho Lee. Experimental and theoretical study on the complete phase separation of ceria-zirconia solid solution into two end members, ceria and zirconia. Journal of Physics: Energy 2022, 4 (4) , 045004. https://doi.org/10.1088/2515-7655/ac8a76
    9. Mehdi Béjaoui, Abdelhakim Elmhamdi, Laura Pascual, Patricia Pérez-Bailac, Kais Nahdi, Arturo Martínez-Arias. Preferential Oxidation of CO over CoFe2O4 and M/CoFe2O4 (M = Ce, Co, Cu or Zr) Catalysts. Catalysts 2021, 11 (1) , 15. https://doi.org/10.3390/catal11010015
    10. A. López Cámara, V. Cortés Corberán, A. Martínez-Arias, L. Barrio, R. Si, J.C. Hanson, J.A. Rodriguez. Novel manganese-promoted inverse CeO2/CuO catalyst: In situ characterization and activity for the water-gas shift reaction. Catalysis Today 2020, 339 , 24-31. https://doi.org/10.1016/j.cattod.2019.01.014
    11. Shanshan Li, Jie Deng, Lei Xiong, Jianli Wang, Yaoqiang Chen, Yi Jiao, Long Jiang, Yi Dan. Design and construct CeO2-ZrO2-Al2O3 materials with controlled structures via co-precipitation method by using different precipitants. Ceramics International 2018, 44 (17) , 20929-20938. https://doi.org/10.1016/j.ceramint.2018.06.255
    12. Jie Deng, Yi Zhou, Shanshan Li, Lei Xiong, Jianli Wang, Shandong Yuan, Yaoqiang Chen. Designed synthesis and characterization of nanostructured ceria-zirconia based material with enhanced thermal stability and its application in three-way catalysis. Journal of Industrial and Engineering Chemistry 2018, 64 , 219-229. https://doi.org/10.1016/j.jiec.2018.03.018
    13. Yi Zhou, Shanahan Li, Jie Deng, Lei Xiong, Jianli Wang, Yaoqiang Chen. Nanoscale heterogeneity and low-temperature redox property of CeO2-ZrO2-La2O3-Y2O3 quaternary solid solution. Materials Chemistry and Physics 2018, 208 , 123-131. https://doi.org/10.1016/j.matchemphys.2018.01.004
    14. A. Elmhamdi, L. Pascual, K. Nahdi, A. Martínez-Arias. Structure/redox/activity relationships in CeO2/CuMn2O4 CO-PROX catalysts. Applied Catalysis B: Environmental 2017, 217 , 1-11. https://doi.org/10.1016/j.apcatb.2017.05.070
    15. Jie Deng, Yi Zhou, Yajuan Cui, Li Lan, Jianli Wang, Shandong Yuan, Yaoqiang Chen. The influence of H2O2 on the properties of CeO2-ZrO2 mixed oxides. Journal of Materials Science 2017, 52 (9) , 5242-5255. https://doi.org/10.1007/s10853-017-0765-7
    16. Jie Liu, Xinyong Li, Qidong Zhao, Jun Ke, Huining Xiao, Xiaojuan Lv, Shaomin Liu, Moses Tadé, Shaobin Wang. Mechanistic investigation of the enhanced NH3-SCR on cobalt-decorated Ce-Ti mixed oxide: In situ FTIR analysis for structure-activity correlation. Applied Catalysis B: Environmental 2017, 200 , 297-308. https://doi.org/10.1016/j.apcatb.2016.07.020
    17. A. Elmhamdi, R. Castañeda, A. Kubacka, L. Pascual, K. Nahdi, A. Martínez-Arias. Characterization and catalytic properties of CuO/CeO 2 /MgAl 2 O 4 for preferential oxidation of CO in H 2 -rich streams. Applied Catalysis B: Environmental 2016, 188 , 292-304. https://doi.org/10.1016/j.apcatb.2016.02.011
    18. K. Rida, A. López Cámara, M.A. Peña, C.L. Bolívar-Díaz, A. Martínez-Arias. Bimetallic Co–Fe and Co–Cr oxide systems supported on CeO2: Characterization and CO oxidation catalytic behaviour. International Journal of Hydrogen Energy 2015, 40 (34) , 11267-11278. https://doi.org/10.1016/j.ijhydene.2015.03.044
    19. Negahdar Hosseinpour, Yadollah Mortazavi, Abbas Ali Khodadadi. Cumene cracking activity and enhanced regeneration of FCC catalysts comprising HY-zeolite and LaBO 3 (B = Co, Mn, and Fe) perovskites. Applied Catalysis A: General 2014, 487 , 26-35. https://doi.org/10.1016/j.apcata.2014.08.035
    20. Mithlesh Kumar, M. Mohapatra, V. Natarajan. Luminescence characteristics of blue emitting ZnAl2O4: Ce nanophosphors. Journal of Luminescence 2014, 149 , 118-124. https://doi.org/10.1016/j.jlumin.2014.01.015
    21. Arturo Martínez-Arias, Daniel Gamarra, Ana Hungría, Marcos Fernández-García, Guillermo Munuera, Aitor Hornés, Parthasarathi Bera, José Conesa, Antonio Cámara. Characterization of Active Sites/Entities and Redox/Catalytic Correlations in Copper-Ceria-Based Catalysts for Preferential Oxidation of CO in H2-Rich Streams. Catalysts 2013, 3 (2) , 378-400. https://doi.org/10.3390/catal3020378
    22. Chia-Che Chuang, Hsing-I Hsiang, Chih-Cheng Chen, Fu-Su Yen, Masahiro Yoshimura, . Phase Separation Phenomenon and Mechanism of Ce 0.6 Zr 0.4 O 2 Powders Prepared Using Chemical Coprecipitation Method. Journal of the American Ceramic Society 2013, 96 (5) , 1629-1634. https://doi.org/10.1111/jace.12183
    23. Shan Gao, Xiongbo Chen, Haiqiang Wang, Jiansong Mo, Zhongbiao Wu, Yue Liu, Xiaole Weng. Ceria supported on sulfated zirconia as a superacid catalyst for selective catalytic reduction of NO with NH3. Journal of Colloid and Interface Science 2013, 394 , 515-521. https://doi.org/10.1016/j.jcis.2012.12.034
    24. Marcos Fernández-García, José A. Rodriguez. Metal Oxide Nanoparticles. 2011https://doi.org/10.1002/9781119951438.eibc0331
    25. Mithlesh Kumar, T.K. Seshagiri, R.M. Kadam, S.V. Godbole. Photoluminescence, thermally stimulated luminescence and electron paramagnetic resonance investigations of Tb3+ doped SrBPO5. Materials Research Bulletin 2011, 46 (9) , 1359-1365. https://doi.org/10.1016/j.materresbull.2011.05.023
    26. Ricardo Grau-Crespo, Nora H. de Leeuw, Said Hamad, Umesh V. Waghmare. Phase separation and surface segregation in ceria–zirconia solid solutions. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences 2011, 467 (2131) , 1925-1938. https://doi.org/10.1098/rspa.2010.0512
    27. A. Hornés, G. Munuera, A. Fuerte, M.J. Escudero, L. Daza, A. Martínez-Arias. Structural, catalytic/redox and electrical characterization of systems combining Cu–Fe with CeO2 or Ce1−xMxO2−δ (M=Gd or Tb) for direct methane oxidation. Journal of Power Sources 2011, 196 (9) , 4218-4225. https://doi.org/10.1016/j.jpowsour.2010.10.042
    28. B. M. Reddy, L. Katta, G. Thrimurthulu. Reply to Comment on “Novel Nanocrystalline Ce 1− x La x O 2−δ ( x = 0.2) Solid Solutions: Structural Characteristics and Catalytic Performance”. Chemistry of Materials 2010, 22 (15) , 4517-4518. https://doi.org/10.1021/cm101719t
    29. A. Hornés, D. Gamarra, G. Munuera, A. Fuerte, R.X. Valenzuela, M.J. Escudero, L. Daza, J.C. Conesa, P. Bera, A. Martínez-Arias. Structural, catalytic/redox and electrical characterization of systems combining Cu–Ni with CeO2 or Ce1−xMxO2−δ (M=Gd or Tb) for direct methane oxidation. Journal of Power Sources 2009, 192 (1) , 70-77. https://doi.org/10.1016/j.jpowsour.2008.12.015
    30. Marcos Fern��ndez-Garc��a, Jos�� A. Rodriguez. Metal Oxide Nanoparticles. 2009https://doi.org/10.1002/0470862106.ia377
    31. Negahdar Hosseinpour, Abbas Ali Khodadadi, Yadolla Mortazavi, Amin Bazyari. Nano-ceria–zirconia promoter effects on enhanced coke combustion and oxidation of CO formed in regeneration of silica–alumina coked during cracking of triisopropylbenzene. Applied Catalysis A: General 2009, 353 (2) , 271-281. https://doi.org/10.1016/j.apcata.2008.10.051
    32. K. Rida, A. Benabbas, F. Bouremmad, M.A. Peña, E. Sastre, A. Martínez-Arias. Effect of strontium and cerium doping on the structural characteristics and catalytic activity for C3H6 combustion of perovskite LaCrO3 prepared by sol–gel. Applied Catalysis B: Environmental 2008, 84 (3-4) , 457-467. https://doi.org/10.1016/j.apcatb.2008.04.031
    33. R.M. Kadam, T.K. Seshagiri, V. Natarajan, S.V. Godbole. Radiation induced defects in BaBPO5:Ce and their role in thermally stimulated luminescence reactions: EPR and TSL investigations. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 2008, 266 (24) , 5137-5143. https://doi.org/10.1016/j.nimb.2008.10.003
    34. A. Hornés, D. Gamarra, G. Munuera, J.C. Conesa, A. Martínez-Arias. Catalytic properties of monometallic copper and bimetallic copper-nickel systems combined with ceria and Ce-X (X=Gd, Tb) mixed oxides applicable as SOFC anodes for direct oxidation of methane. Journal of Power Sources 2007, 169 (1) , 9-16. https://doi.org/10.1016/j.jpowsour.2007.01.074
    35. I. Alessandri, M. A. Bañares, L. E. Depero, M. Ferroni, P. Fornasiero, F. C. Gennari, N. Hickey, M. V. Martinez-Huerta, T. Montini. Structural investigation of Ce2Zr2O8 after redox treatments which lead to low temperature reduction. Topics in Catalysis 2006, 41 (1-4) , 35-42. https://doi.org/10.1007/s11244-006-0092-8
    36. F. Haaß, H. Fuess. Structural Characterization of Automotive Catalysts. Advanced Engineering Materials 2005, 7 (10) , 899-913. https://doi.org/10.1002/adem.200500120
    37. A. Martínez-Arias, A.B. Hungría, M. Fernández-García, J.C. Conesa, G. Munuera. Preferential oxidation of CO in a H2-rich stream over CuO/CeO2 and CuO/(Ce,M)Ox (M=Zr, Tb) catalysts. Journal of Power Sources 2005, 151 , 32-42. https://doi.org/10.1016/j.jpowsour.2005.02.078
    38. VUK USKOKOVIĆ, MIHA DROFENIK. SYNTHESIS OF MATERIALS WITHIN REVERSE MICELLES. Surface Review and Letters 2005, 12 (02) , 239-277. https://doi.org/10.1142/S0218625X05007001
    39. Roberta Di Monte, Jan Kašpar. Heterogeneous environmental catalysis – a gentle art: CeO2–ZrO2 mixed oxides as a case history. Catalysis Today 2005, 100 (1-2) , 27-35. https://doi.org/10.1016/j.cattod.2004.11.005
    40. Roberta Di Monte, Jan Kašpar. Nanostructured CeO 2 –ZrO 2 mixed oxides. J. Mater. Chem. 2005, 15 (6) , 633-648. https://doi.org/10.1039/B414244F
    41. Akinori Muto, Thallada Bhaskar, Yuki Kaneshiro, Yusaku Sakata, Yoshihiko Kusano, Kazuyuki Murakami. Preparation and characterization of nanocrystalline CeO2–ZrO2 catalysts by dry method: effect of oxidizing conditions. Applied Catalysis A: General 2004, 275 (1-2) , 173-181. https://doi.org/10.1016/j.apcata.2004.07.031
    42. Rui Si, Ya-Wen Zhang, Chao-Xian Xiao, Shi-Jie Li, Bing-Xiong Lin, Yuan Kou, Chun-Hua Yan. Non-template hydrothermal route derived mesoporous Ce 0.2 Zr 0.8 O 2 nanosized powders with blue-shifted UV absorption and high CO conversion activity. Phys. Chem. Chem. Phys. 2004, 6 (5) , 1056-1063. https://doi.org/10.1039/B314885H
    43. Cheikh Diagne, Hicham Idriss, Kenji Pearson, Miguel Angel Gómez-García, Alain Kiennemann. Efficient hydrogen production by ethanol reforming over Rh catalysts. Effect of addition of Zr on CeO2 for the oxidation of CO to CO2. Comptes Rendus. Chimie 2004, 7 (6-7) , 617-622. https://doi.org/10.1016/j.crci.2004.03.004
    44. Akinori Muto, Thallada Bhaskar, Yuki Kaneshiro, Md. Azhar Uddin, Yusaku Sakata, Yoshihiko Kusano, Kazuyuki Murakami. Utilization of waste biomass and replacement of stoichiometric reagents for the synthesis of nanocrystalline CeO 2 , ZrO 2 and CeO 2 –ZrO 2. Green Chem. 2003, 5 (4) , 480-483. https://doi.org/10.1039/B304574A