ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Critical Influence of Redox Pretreatments on the CO Oxidation Activity of BaFeO3−δ Perovskites: An in-Depth Atomic-Scale Analysis by Aberration-Corrected and in Situ Diffraction Techniques

View Author Information
Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain
Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Universidad de Cádiz, Campus Río San Pedro, 11510 Puerto Real, Spain
§ Instituto Universitario de Investigación en Microscopía Electrónica y Materiales (IMEYMAT), Facultad de Ciencias, Universidad Complutense, Campus Río San Pedro, 11510 Puerto Real, Spain
Centro Nacional de Microscopia Electrónica, Universidad Complutense, 28040 Madrid, Spain
*J.M.G.-C.: e-mail, [email protected]; tel, +34 91 394 41 88; fax, +34 91 394 43 52.
Cite this: ACS Catal. 2017, 7, 12, 8653–8663
Publication Date (Web):November 7, 2017
Copyright © 2017 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    A BaFeO3−δ (δ ≈ 0.22) perovskite was prepared by a sol–gel method and essayed as a catalyst in the CO oxidation reaction. BaFeO3−δ (0.22 ≤ δ ≤ 0.42) depicts a 6H perovskite hexagonal structural type with Fe in both III and IV oxidation states and oxygen stoichiometry accommodated by a random distribution of anionic vacancies. The perovskite with the highest oxygen content, BaFeO2.78, proved to be more active than its lanthanide-based counterparts, LnFeO3 (Ln = La, Sm, Nd). Removal of the lattice oxygen detected in both temperature-programmed oxidation (TPO) and reduction (TPR) experiments at around 500 K and which leads to the complete reduction of Fe4+ to Fe3+, i.e. to BeFeO2.5, significantly decreases the catalytic activity, especially in the low-temperature range. The analysis of thermogravimetric experiments performed under oxygen and of TPR studies run under CO clearly support the involvement of lattice oxygen in the CO oxidation on these Ba-Fe perovskites, even at the lowest temperatures. Atomically resolved images and chemical maps obtained using different aberration-corrected scanning transmission electron microscopy techniques, as well as some in situ type experiments, have provided a clear picture of the accommodation of oxygen nonstoichiometry in these materials. This atomic-scale view has revealed details of both the cation and anion sublattices of the different perovskites that have allowed us to identify the structural origin of the oxygen species most likely responsible for the low-temperature CO oxidation activity.

    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.


    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.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.7b02595.

    • Experimental details including chemical analysis, microstructural characterization, powder neutron diffraction, thermogravimetric analysis, study of catalyst pretreatment conditions, study of catalyst conditions, XPS analysis, and Rietveld refinement of the XRD under vacuum conditions (PDF)

    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:

    Cited By

    This article is cited by 13 publications.

    1. Kazuyuki Iwase, Masaki Ohtaka, Itaru Honma. Rational Strategy for Tuning Electrocatalytic Oxygen Evolution Activity of Perovskite Oxides via Low-Temperature Fluorination. Chemistry of Materials 2023, 35 (7) , 2773-2781.
    2. Isabel Gómez-Recio, Huiyan Pan, Alberto Azor-Lafarga, María Luisa Ruiz-González, María Hernando, Marina Parras, María Teresa Fernández-Díaz, Juan J. Delgado, Xiaowei Chen, Daniel Goma Jiménez, David Portehault, Clément Sanchez, Mariona Cabero, Arturo Martínez-Arias, José M. González-Calbet, José J. Calvino. Exceptional Low-Temperature CO Oxidation over Noble-Metal-Free Iron-Doped Hollandites: An In-Depth Analysis of the Influence of the Defect Structure on Catalytic Performance. ACS Catalysis 2021, 11 (24) , 15026-15039.
    3. C. V. Ramana, Mallesham Bandi, Aruna N Nair, Felicia S. Manciu, Sreeprasad Sreenivasan, Vaithiyalingam Shutthanandan. Electronic Structure, Chemical Bonding, and Electrocatalytic Activity of Ba(Fe0.7Ta0.3)O3−δ Compounds. ACS Applied Energy Materials 2021, 4 (2) , 1313-1322.
    4. Kazuki Tamai, Saburo Hosokawa, Kenya Onishi, Chikara Watanabe, Kazuo Kato, Hiroyuki Asakura, Kentaro Teramura, Tsunehiro Tanaka. Dynamics of the Lattice Oxygen in a Ruddlesden–Popper-type Sr3Fe2O7−δ Catalyst during NO Oxidation. ACS Catalysis 2020, 10 (4) , 2528-2537.
    5. Ji Yang, Siyu Hu, Yarong Fang, Son Hoang, Li Li, Weiwei Yang, Zhenfeng Liang, Jian Wu, Jinpeng Hu, Wen Xiao, Chuanqi Pan, Zhu Luo, Jun Ding, Lizhi Zhang, Yanbing Guo. Oxygen Vacancy Promoted O2 Activation over Perovskite Oxide for Low-Temperature CO Oxidation. ACS Catalysis 2019, 9 (11) , 9751-9763.
    6. Huayu Gu, Jintong Lan, Haolu Hu, Falong Jia, Zhihui Ai, Lizhi Zhang, Xiao Liu. Surface oxygen vacancy-dependent molecular oxygen activation for propane combustion over α-MnO2. Journal of Hazardous Materials 2023, 460 , 132499.
    7. Pradeep Kumar Yadav, Saroj Kumari, Uppari Naveena, Parag A. Deshpande, Sudhanshu Sharma. Insights into the substitutional chemistry of La1−xSrxCo1−yMyO3 (M = Pd, Ru, Rh, and Pt) probed by in situ DRIFTS and DFT analysis of CO oxidation. Applied Catalysis A: General 2022, 643 , 118768.
    8. David Portehault, Francisco Gonell, Isabel Gómez‐Recio. Addressing Complex Transition Metal Oxides at the Nanoscale: Bottom‐Up Syntheses of Nano‐objects and Properties. 2022, 43-87.
    9. Koichi Suematsu, Yuki Hiroyama, Ken Watanabe, Kengo Shimanoe. Amplifying the receptor function on Ba0.9La0.1FeO3-SnO2 composite particle surface for high sensitivity toward ethanol gas sensing. Sensors and Actuators B: Chemical 2022, 354 , 131256.
    10. Hohan Bae, Bhupendra Singh, Lakshya Mathur, Jong Hoon Joo, Sun-Ju Song. Defect Structure, Transport Properties, and Chemical Expansion in Ba 0.95 La 0.05 FeO 3– δ. Journal of The Electrochemical Society 2021, 168 (3) , 034511.
    11. Hao Zhou, Boyang Qi. Investigation of flame spray synthesized La1-xSrxCoO3 perovskites with promotional catalytic performances on CO oxidation. Journal of the Energy Institute 2020, 93 (6) , 2381-2387.
    12. Chunling Lu, Bingbing Niu, Wendi Yi, Yuan Ji, Baomin Xu. Efficient symmetrical electrodes of PrBaFe2-Co O5+δ (x=0, 0.2,0.4) for solid oxide fuel cells and solid oxide electrolysis cells. Electrochimica Acta 2020, 358 , 136916.
    13. Satomi Shibata, Kosei Sugahara, Keigo Kamata, Michikazu Hara. Liquid-phase oxidation of alkanes with molecular oxygen catalyzed by high valent iron-based perovskite. Chemical Communications 2018, 54 (50) , 6772-6775.

    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.

    Your Mendeley pairing has expired. Please reconnect