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

Wang, Xiyang; Pan, Ziye; Chu, Xuefeng; Huang, Keke; Cong, Yingge; Cao, Rui; Sarangi, Ritimukta; Li, Liping; Li, Guangshe; Feng, Shouhua

doi:10.1002/anie.201905543

Title: Atomic-Scale Insights into Surface Lattice Oxygen Activation at the Spinel/Perovskite interface of Co₃O₄/La_0.3Sr_0.7CoO₃

Journal Article · 22 June 2019 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201905543 · OSTI ID:1546793

^[1]; Pan, Ziye ^[1]; Chu, Xuefeng ^[1]; Huang, Keke ^[1]; Cong, Yingge ^[1]; Cao, Rui ^[2]; Sarangi, Ritimukta ^[2]; Li, Liping ^[1]; Li, Guangshe ^[1];

^[1]

Jilin Univ., Changchun (China)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

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 La_0.3Sr_0.7CoO₃ 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 O^2- transformed into active O^2-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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: AC02-76SF00515; 21427802; 21671076; 21621001; 21831003; 3102018bzc007; 10183201816

OSTI ID:: 1546793

Journal Information:: Angewandte Chemie (International Edition), Vol. 58, Issue 34; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (28)

Catalytically Active Oxygen Species in La ₁ _- _x Sr _x CoO ₃ _- _δ Studied by XPS and XAFS Spectroscopy Imamura, M.; Matsubayashi, N.; Shimada, H. The Journal of Physical Chemistry B, Vol. 104, Issue 31 https://doi.org/10.1021/jp994148k	journal	August 2000
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes Sathiya, M.; Rousse, G.; Ramesha, K. Nature Materials, Vol. 12, Issue 9 https://doi.org/10.1038/nmat3699	journal	July 2013
Titanium dx y ferromagnetism at the LaAlO3/SrTiO3 interface Lee, J. -S.; Xie, Y. W.; Sato, H. K. Nature Materials, Vol. 12, Issue 8 https://doi.org/10.1038/nmat3674	journal	June 2013
Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements Gao, Wenpei; Hood, Zachary D.; Chi, Miaofang Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00596	journal	February 2017
Activation of Surface Oxygen Sites in a Cobalt-Based Perovskite Model Catalyst for CO Oxidation Wang, Xiyang; Huang, Keke; Yuan, Long The Journal of Physical Chemistry Letters, Vol. 9, Issue 15 https://doi.org/10.1021/acs.jpclett.8b01623	journal	July 2018
A Bifunctional Nonprecious Metal Catalyst for Oxygen Reduction and Water Oxidation Gorlin, Yelena; Jaramillo, Thomas F. Journal of the American Chemical Society, Vol. 132, Issue 39, p. 13612-13614 https://doi.org/10.1021/ja104587v	journal	October 2010
Perovskite Oxides: Preparation, Characterizations, and Applications in Heterogeneous Catalysis Zhu, Junjiang; Li, Hailong; Zhong, Linyun ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500606g	journal	August 2014
Perovskites in catalysis and electrocatalysis Hwang, Jonathan; Rao, Reshma R.; Giordano, Livia Science, Vol. 358, Issue 6364 https://doi.org/10.1126/science.aam7092	journal	November 2017
Bifunktionale Sauerstoffelektroden durch Einbettung von Co@Co ₃ O ₄ -Nanopartikeln in CNT-gekoppelte Stickstoff-dotierte Kohlenstoffpolyeder Aijaz, Arshad; Masa, Justus; Rösler, Christoph Angewandte Chemie, Vol. 128, Issue 12 https://doi.org/10.1002/ange.201509382	journal	February 2016
Remarkable Oxygen-Evolution Activity of a Perovskite Oxide from the Ca _{2− x} Sr _x Fe ₂ O _{6− δ} Series Hona, Ram Krishna; Ramezanipour, Farshid Angewandte Chemie, Vol. 131, Issue 7 https://doi.org/10.1002/ange.201813000	journal	January 2019
Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction Grimaud, Alexis; Demortière, Arnaud; Saubanère, Matthieu Nature Energy, Vol. 2, Issue 1 https://doi.org/10.1038/nenergy.2016.189	journal	December 2016
Anionic redox processes for electrochemical devices Grimaud, A.; Hong, W. T.; Shao-Horn, Y. Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4551	journal	January 2016
New perspective on the synthesis of highly efficient composites: regulating influence distance of interfacial charge transfer Huang, Keke; Geng, Zhibin; Sun, Yu Science Bulletin, Vol. 63, Issue 4 https://doi.org/10.1016/j.scib.2018.01.021	journal	February 2018
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries Assat, Gaurav; Tarascon, Jean-Marie Nature Energy, Vol. 3, Issue 5 https://doi.org/10.1038/s41560-018-0097-0	journal	April 2018
Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions Mueller, David N.; Machala, Michael L.; Bluhm, Hendrik Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7097	journal	January 2015
Real-time impedance monitoring of oxygen reduction during surface modification of thin film cathodes Rupp, Ghislain M.; Opitz, Alexander K.; Nenning, Andreas Nature Materials, Vol. 16, Issue 6 https://doi.org/10.1038/nmat4879	journal	March 2017
Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin Nature Materials, Vol. 15, Issue 9 https://doi.org/10.1038/nmat4659	journal	June 2016
Colossal Ionic Conductivity at Interfaces of Epitaxial ZrO2:Y2O3/SrTiO3 Heterostructures Garcia-Barriocanal, J.; Rivera-Calzada, A.; Varela, M. Science, Vol. 321, Issue 5889 https://doi.org/10.1126/science.1156393	journal	August 2008
Enhancing Electrocatalytic Activity of Perovskite Oxides by Tuning Cation Deficiency for Oxygen Reduction and Evolution Reactions Zhu, Yinlong; Zhou, Wei; Yu, Jie Chemistry of Materials, Vol. 28, Issue 6 https://doi.org/10.1021/acs.chemmater.5b04457	journal	February 2016
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 Fabbri, Emiliana; Nachtegaal, Maarten; Cheng, Xi Advanced Energy Materials, Vol. 5, Issue 17 https://doi.org/10.1002/aenm.201402033	journal	July 2015
Remarkable Oxygen-Evolution Activity of a Perovskite Oxide from the Ca _{2− x} Sr _x Fe ₂ O _{6− δ} Series Hona, Ram Krishna; Ramezanipour, Farshid Angewandte Chemie International Edition, Vol. 58, Issue 7 https://doi.org/10.1002/anie.201813000	journal	January 2019
Co@Co ₃ O ₄ Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode Aijaz, Arshad; Masa, Justus; Rösler, Christoph Angewandte Chemie International Edition, Vol. 55, Issue 12 https://doi.org/10.1002/anie.201509382	journal	February 2016
Contrasting the Role of Ni/Al ₂ O ₃ Interfaces in Water–Gas Shift and Dry Reforming of Methane Foppa, Lucas; Margossian, Tigran; Kim, Sung Min Journal of the American Chemical Society, Vol. 139, Issue 47 https://doi.org/10.1021/jacs.7b08984	journal	November 2017
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping Jones, J.; Xiong, H.; DeLaRiva, A. T. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf8800	journal	July 2016
Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong Nature Chemistry, Vol. 9, Issue 5 https://doi.org/10.1038/nchem.2695	journal	January 2017
O-K and Co-L XANES Study on Oxygen Intercalation in Perovskite SrCoO_3-δ Karvonen, Lassi; Valkeapaa, Markus; Liu, Ru-Shi Chemistry of Materials, Vol. 22, Issue 1, p. 70-76 https://doi.org/10.1021/cm9021563	journal	January 2010
Activating p-Blocking Centers in Perovskite for Efficient Water Splitting Hua, Bin; Li, Meng; Pang, Wanying Chem, Vol. 4, Issue 12 https://doi.org/10.1016/j.chempr.2018.09.012	journal	December 2018
A high-mobility two-dimensional electron gas at the spinel/perovskite interface of γ-Al2O3/SrTiO3 Chen, Y. Z.; Bovet, N.; Trier, F. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2394	journal	January 2013

Cited By (1)

Enhanced catalytic activity of nanostructured, A-site deficient (La _0.7 Sr _0.3 ) _0.95 (Co _0.2 Fe _0.8 )O _3−δ for SOFC cathodes Celikbilek, Ozden; Thieu, Cam-Anh; Agnese, Fabio Journal of Materials Chemistry A, Vol. 7, Issue 43 https://doi.org/10.1039/c9ta07697b	journal	January 2019