ACS Publications. Most Trusted. Most Cited. Most Read
Structural Characterization and Redox Catalytic Properties of Cerium(IV) Pyrochlore Oxides

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Chem. Mater. 2011, 23, 24, 5464-5473
    Article

    Structural Characterization and Redox Catalytic Properties of Cerium(IV) Pyrochlore Oxides
    Click to copy article linkArticle link copied!

    View Author Information
    † †Department of Chemistry and ∥Department of Physics, University of Warwick, Coventry, CV4 7AL, U.K.
    ‡ ISIS Facility, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, OX11 0QX, U.K.
    § Sigma-Aldrich Company Ltd, Fancy Road, Poole, Dorset, BH12 4QH, U.K.
    ⊥ Johnson Matthey Technology Centre, Sonning Common, Reading, RG4 9NH, U.K.
    E-mail: [email protected]
    Other Access OptionsSupporting Information (1)

    Chemistry of Materials

    Cite this: Chem. Mater. 2011, 23, 24, 5464–5473
    Click to copy citationCitation copied!
    https://doi.org/10.1021/cm202908s
    Published November 9, 2011
    Copyright © 2011 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Ce(IV) pyrochlore oxides have been prepared by hydrothermal synthesis, and the parent material, a sodium cerium titanate, has been studied using total neutron scattering. While analysis of Bragg diffraction is consistent with an average cubic pyroclore structure, the profile is broadened because of the crystal size of <10 nm. Analysis of the pair distribution function (PDF) produced by Fourier transformation of the total scattering yields a structural model consistent with formulation of the parent material as (Na0.33Ce0.53Ti0.14)2Ti2O7. This contains a proportion of A-site titanium, consistent with the measured bulk density of the material. The PDF also contains evidence that the short-range order of the pyrochlore structure is disordered, with oxide anions displaced from the positions of the ideal Fd3̅m pyrochlore structure to give local symmetry F4̅3m. These observations are supported by static (broadline) solid state 49Ti NMR measurements on a 49Ti isotopically enriched sample, which showed a dominant, narrow resonance at an apparent shift of δ – 912 ppm and a second minor resonance consistent with A-site titanium. Sn(IV) doping of the pyrochlore phase is possible by one-step hydrothermal synthesis: this gives a series of materials with a maximum tin content of Sn:Ti = 0.4:0.6, for which 119Sn solid-state NMR confirms the presence of octahedral, B-site Sn(IV), and powder X-ray diffraction shows an associated expansion of the pyrochlore lattice. Temperature programmed reduction/oxidation studies of the materials reveal that after an activation cycle the parent pyrochlore shows a reversible low temperature reduction at <200 °C, more facile than ceria itself. The Sn-doped analogues also show a low temperature reduction, but on continued heating collapse irreversibly to yield a mixture of products that includes SnO. The parent pyrochlore has been tested as a support for gold in the water gas shift reaction and shows a lower temperature conversion of H2O and CO to H2 and CO2 than a ceria sample of similar surface area.

    Copyright © 2011 American Chemical Society

    Subjects

    what are subjects

    Keywords

    what are keywords

    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. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    Further details about TGA-DSC results (Figure S1.1), neutron scattering results (Figures S2.1–S2.3, Table S2.1), and analysis of pyrochlore after TPR experiments (Figures S3.1 and S3.2). This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 11 publications.

    1. Mikhail V. Talanov, Valeriy M. Talanov. Structural Diversity of Ordered Pyrochlores. Chemistry of Materials 2021, 33 (8) , 2706-2725. https://doi.org/10.1021/acs.chemmater.0c04864
    2. Qiang Deng, Rui Gao, Xiang Li, Jun Wang, Zheling Zeng, Ji-Jun Zou, Shuguang Deng. Hydrogenative Ring-Rearrangement of Biobased Furanic Aldehydes to Cyclopentanone Compounds over Pd/Pyrochlore by Introducing Oxygen Vacancies. ACS Catalysis 2020, 10 (13) , 7355-7366. https://doi.org/10.1021/acscatal.0c01666
    3. Gregory Morrison, Nicholas R. Spagnuolo, Stavros G. Karakalos, Hans-Conrad zur Loye. Cs3REIIIGe3O9 (RE = Pr, Nd, and Sm–Yb) and Cs8TbIII2TbIVGe9O27: A Rare Example of a Mixed-Valent Tb(III)/Tb(IV) Oxide. Inorganic Chemistry 2019, 58 (13) , 8702-8709. https://doi.org/10.1021/acs.inorgchem.9b01033
    4. Luke M. Daniels, Helen Y. Playford, Alex C. Hannon, and Richard I. Walton . Structural Disorder in (Bi, M)2(Fe, Mn, Bi)2O6+x (M = Na or K) Pyrochlores Seen from Reverse Monte Carlo Analysis of Neutron Total Scattering. The Journal of Physical Chemistry C 2017, 121 (33) , 18120-18128. https://doi.org/10.1021/acs.jpcc.7b04972
    5. M. V. Talanov, E. V. Glazunova, V. I. Kozlov, S. P. Kubrin, A. A. Bush, V. M. Talanov, K. E. Kamentsev. Dielectric properties of bismuth-containing pyrochlores: A comparative analysis. Journal of Advanced Dielectrics 2022, 12 (02) https://doi.org/10.1142/S2010135X21600171
    6. Zhikun Tong, Rui Gao, Xiang Li, Lingyun Guo, Jun Wang, Zheling Zeng, Qiang Deng, Shuguang Deng. Highly Controllable Hydrogenative Ring Rearrangement and Complete Hydrogenation Of Biobased Furfurals over Pd/La 2 B 2 O 7 (B=Ti, Zr, Ce). ChemCatChem 2021, 13 (21) , 4549-4556. https://doi.org/10.1002/cctc.202101063
    7. Rui Gao, Xiang Li, Lingyun Guo, Zhikun Tong, Qiang Deng, Jun Wang, Zheling Zeng, Ji-Jun Zou, Shuguang Deng. Pyrochlore/Al2O3 composites supported Pd for the selective synthesis of cyclopentanones from biobased furfurals. Applied Catalysis A: General 2021, 612 , 117985. https://doi.org/10.1016/j.apcata.2020.117985
    8. A. V. Egorysheva, O. G. Ellert, O. M. Gaitko, M. N. Brekhovskikh, I. A. Zhidkova, Yu. V. Maksimov. Fluorination of Bi1.8Fe1.2SbO7 pyrochlore solid solutions. Inorganic Materials 2017, 53 (9) , 962-968. https://doi.org/10.1134/S0020168517090072
    9. T. Yu Kardash, E. M. Slavinskaya, R. V. Gulyaev, A. V. Zaikovskii, S. A. Novopashin, A. I. Boronin. Enhanced Thermal Stability of Pd/Ce–Sn–O Catalysts for CO Oxidation Prepared by Plasma-Arc Synthesis. Topics in Catalysis 2017, 60 (12-14) , 898-913. https://doi.org/10.1007/s11244-017-0755-7
    10. R. Mouta, R. X. Silva, C. W. A. Paschoal. Tolerance factor for pyrochlores and related structures. Acta Crystallographica Section B Structural Science Crystal Engineering and Materials 2013, 69 (5) , 439-445. https://doi.org/10.1107/S2052519213020514
    11. Karena W. Chapman, Peter J. Chupas. Pair Distribution Function Analysis of High‐Energy X‐ray Scattering Data. 2013, 147-168. https://doi.org/10.1002/9781118355923.ch5
    Download PDF
    Go to Chemistry of Materials
    Get e-Alerts
    Get e-Alerts

    Chemistry of Materials

    Cite this: Chem. Mater. 2011, 23, 24, 5464–5473
    Click to copy citationCitation copied!
    https://doi.org/10.1021/cm202908s
    Published November 9, 2011
    Copyright © 2011 American Chemical Society
    Request reuse permissions

    Article Views

    1492

    Altmetric

    -

    Citations

    11
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.