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Title: Atomic-Scale Insights into Surface Lattice Oxygen Activation at the Spinel/Perovskite interface of Co3O4/La0.3Sr0.7CoO3

Abstract

Surface lattice oxygen in transition-metal oxides plays a vital role in catalytic processes. Mastering activation of surface lattice oxygen and identifying the activation mechanism are crucial for the development and design of advanced catalysts. A strategy is now developed to create a spinel Co3O4 /perovskite La0.3Sr0.7CoO3 interface by in situ reconstruction of the surface Sr enrichment region in perovskite LSC to activate surface lattice oxygen. XAS and XPS confirm that the regulated chemical interface optimizes the hybridized orbital between Co 3d and O 2p and triggers more electrons in oxygen site of LSC transferred into lattice of Co3O4, leading to more inactive O2- transformed into active O2-x. Furthermore, the activated Co3O4/LSC exhibits the best catalytic activities for CO oxidation, oxygen evolution, and oxygen reduction. This work would provide a fundamental understanding to explain the activation mechanism of surface oxygen sites.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [2];  [2];  [1];  [1]; ORCiD logo [1]
  1. Jilin Univ., Changchun (China)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1546793
Grant/Contract Number:  
AC02-76SF00515; 21427802; 21671076; 21621001; 21831003; 3102018bzc007; 10183201816
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 34; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; electron transfer; electronic structure; perovskite; spinels; surface lattice oxygen

Citation Formats

Wang, Xiyang, Pan, Ziye, Chu, Xuefeng, Huang, Keke, Cong, Yingge, Cao, Rui, Sarangi, Ritimukta, Li, Liping, Li, Guangshe, and Feng, Shouhua. Atomic-Scale Insights into Surface Lattice Oxygen Activation at the Spinel/Perovskite interface of Co3O4/La0.3Sr0.7CoO3. United States: N. p., 2019. Web. doi:10.1002/anie.201905543.
Wang, Xiyang, Pan, Ziye, Chu, Xuefeng, Huang, Keke, Cong, Yingge, Cao, Rui, Sarangi, Ritimukta, Li, Liping, Li, Guangshe, & Feng, Shouhua. Atomic-Scale Insights into Surface Lattice Oxygen Activation at the Spinel/Perovskite interface of Co3O4/La0.3Sr0.7CoO3. United States. doi:10.1002/anie.201905543.
Wang, Xiyang, Pan, Ziye, Chu, Xuefeng, Huang, Keke, Cong, Yingge, Cao, Rui, Sarangi, Ritimukta, Li, Liping, Li, Guangshe, and Feng, Shouhua. Sat . "Atomic-Scale Insights into Surface Lattice Oxygen Activation at the Spinel/Perovskite interface of Co3O4/La0.3Sr0.7CoO3". United States. doi:10.1002/anie.201905543. https://www.osti.gov/servlets/purl/1546793.
@article{osti_1546793,
title = {Atomic-Scale Insights into Surface Lattice Oxygen Activation at the Spinel/Perovskite interface of Co3O4/La0.3Sr0.7CoO3},
author = {Wang, Xiyang and Pan, Ziye and Chu, Xuefeng and Huang, Keke and Cong, Yingge and Cao, Rui and Sarangi, Ritimukta and Li, Liping and Li, Guangshe and Feng, Shouhua},
abstractNote = {Surface lattice oxygen in transition-metal oxides plays a vital role in catalytic processes. Mastering activation of surface lattice oxygen and identifying the activation mechanism are crucial for the development and design of advanced catalysts. A strategy is now developed to create a spinel Co3O4 /perovskite La0.3Sr0.7CoO3 interface by in situ reconstruction of the surface Sr enrichment region in perovskite LSC to activate surface lattice oxygen. XAS and XPS confirm that the regulated chemical interface optimizes the hybridized orbital between Co 3d and O 2p and triggers more electrons in oxygen site of LSC transferred into lattice of Co3O4, leading to more inactive O2- transformed into active O2-x. Furthermore, the activated Co3O4/LSC exhibits the best catalytic activities for CO oxidation, oxygen evolution, and oxygen reduction. This work would provide a fundamental understanding to explain the activation mechanism of surface oxygen sites.},
doi = {10.1002/anie.201905543},
journal = {Angewandte Chemie (International Edition)},
number = 34,
volume = 58,
place = {United States},
year = {2019},
month = {6}
}

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Works referenced in this record:

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New perspective on the synthesis of highly efficient composites: regulating influence distance of interfacial charge transfer
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Real-time impedance monitoring of oxygen reduction during surface modification of thin film cathodes
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Co@Co 3 O 4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode
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    Works referencing / citing this record:

    Superior Bifunctional Electrocatalytic Activity of Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ /Carbon Composite Electrodes: Insight into the Local Electronic Structure
    journal, July 2015

    • Fabbri, Emiliana; Nachtegaal, Maarten; Cheng, Xi
    • Advanced Energy Materials, Vol. 5, Issue 17
    • DOI: 10.1002/aenm.201402033

    Bifunktionale Sauerstoffelektroden durch Einbettung von Co@Co 3 O 4 -Nanopartikeln in CNT-gekoppelte Stickstoff-dotierte Kohlenstoffpolyeder
    journal, February 2016

    • Aijaz, Arshad; Masa, Justus; Rösler, Christoph
    • Angewandte Chemie, Vol. 128, Issue 12
    • DOI: 10.1002/ange.201509382

    Remarkable Oxygen-Evolution Activity of a Perovskite Oxide from the Ca 2− x Sr x Fe 2 O 6− δ Series
    journal, January 2019


    Co@Co 3 O 4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode
    journal, February 2016

    • Aijaz, Arshad; Masa, Justus; Rösler, Christoph
    • Angewandte Chemie International Edition, Vol. 55, Issue 12
    • DOI: 10.1002/anie.201509382

    Remarkable Oxygen-Evolution Activity of a Perovskite Oxide from the Ca 2− x Sr x Fe 2 O 6− δ Series
    journal, January 2019

    • Hona, Ram Krishna; Ramezanipour, Farshid
    • Angewandte Chemie International Edition, Vol. 58, Issue 7
    • DOI: 10.1002/anie.201813000

    Activating p-Blocking Centers in Perovskite for Efficient Water Splitting
    journal, December 2018


    New perspective on the synthesis of highly efficient composites: regulating influence distance of interfacial charge transfer
    journal, February 2018


    Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements
    journal, February 2017


    Enhancing Electrocatalytic Activity of Perovskite Oxides by Tuning Cation Deficiency for Oxygen Reduction and Evolution Reactions
    journal, February 2016


    Activation of Surface Oxygen Sites in a Cobalt-Based Perovskite Model Catalyst for CO Oxidation
    journal, July 2018


    O-K and Co-L XANES Study on Oxygen Intercalation in Perovskite SrCoO3-δ
    journal, January 2010

    • Karvonen, Lassi; Valkeapaa, Markus; Liu, Ru-Shi
    • Chemistry of Materials, Vol. 22, Issue 1, p. 70-76
    • DOI: 10.1021/cm9021563

    Perovskite Oxides: Preparation, Characterizations, and Applications in Heterogeneous Catalysis
    journal, August 2014

    • Zhu, Junjiang; Li, Hailong; Zhong, Linyun
    • ACS Catalysis, Vol. 4, Issue 9
    • DOI: 10.1021/cs500606g

    A Bifunctional Nonprecious Metal Catalyst for Oxygen Reduction and Water Oxidation
    journal, October 2010

    • Gorlin, Yelena; Jaramillo, Thomas F.
    • Journal of the American Chemical Society, Vol. 132, Issue 39, p. 13612-13614
    • DOI: 10.1021/ja104587v

    Contrasting the Role of Ni/Al 2 O 3 Interfaces in Water–Gas Shift and Dry Reforming of Methane
    journal, November 2017

    • Foppa, Lucas; Margossian, Tigran; Kim, Sung Min
    • Journal of the American Chemical Society, Vol. 139, Issue 47
    • DOI: 10.1021/jacs.7b08984

    Catalytically Active Oxygen Species in La 1 - x Sr x CoO 3 - δ Studied by XPS and XAFS Spectroscopy
    journal, August 2000

    • Imamura, M.; Matsubayashi, N.; Shimada, H.
    • The Journal of Physical Chemistry B, Vol. 104, Issue 31
    • DOI: 10.1021/jp994148k

    Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution
    journal, January 2017

    • Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong
    • Nature Chemistry, Vol. 9, Issue 5
    • DOI: 10.1038/nchem.2695

    A high-mobility two-dimensional electron gas at the spinel/perovskite interface of γ-Al2O3/SrTiO3
    journal, January 2013

    • Chen, Y. Z.; Bovet, N.; Trier, F.
    • Nature Communications, Vol. 4, Issue 1
    • DOI: 10.1038/ncomms2394

    Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions
    journal, January 2015

    • Mueller, David N.; Machala, Michael L.; Bluhm, Hendrik
    • Nature Communications, Vol. 6, Issue 1
    • DOI: 10.1038/ncomms7097

    Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction
    journal, December 2016

    • Grimaud, Alexis; Demortière, Arnaud; Saubanère, Matthieu
    • Nature Energy, Vol. 2, Issue 1
    • DOI: 10.1038/nenergy.2016.189

    Titanium dx y ferromagnetism at the LaAlO3/SrTiO3 interface
    journal, June 2013

    • Lee, J. -S.; Xie, Y. W.; Sato, H. K.
    • Nature Materials, Vol. 12, Issue 8
    • DOI: 10.1038/nmat3674

    Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
    journal, July 2013

    • Sathiya, M.; Rousse, G.; Ramesha, K.
    • Nature Materials, Vol. 12, Issue 9
    • DOI: 10.1038/nmat3699

    Anionic redox processes for electrochemical devices
    journal, January 2016

    • Grimaud, A.; Hong, W. T.; Shao-Horn, Y.
    • Nature Materials, Vol. 15, Issue 2
    • DOI: 10.1038/nmat4551

    Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface
    journal, June 2016

    • Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin
    • Nature Materials, Vol. 15, Issue 9
    • DOI: 10.1038/nmat4659

    Real-time impedance monitoring of oxygen reduction during surface modification of thin film cathodes
    journal, March 2017

    • Rupp, Ghislain M.; Opitz, Alexander K.; Nenning, Andreas
    • Nature Materials, Vol. 16, Issue 6
    • DOI: 10.1038/nmat4879

    Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries
    journal, April 2018


    Colossal Ionic Conductivity at Interfaces of Epitaxial ZrO2:Y2O3/SrTiO3 Heterostructures
    journal, August 2008

    • Garcia-Barriocanal, J.; Rivera-Calzada, A.; Varela, M.
    • Science, Vol. 321, Issue 5889
    • DOI: 10.1126/science.1156393

    Thermally stable single-atom platinum-on-ceria catalysts via atom trapping
    journal, July 2016


    Perovskites in catalysis and electrocatalysis
    journal, November 2017