Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates

Wang, Le; Stoerzinger, Kelsey A.; Chang, Lei; Zhao, Jiali; Li, Yangyang; Tang, Chi Sin; Yin, Xinmao; Bowden, Mark E.; Yang, Zhenzhong; Guo, Haizhong; You, Lu; Guo, Rui; Wang, Jiaou; Ibrahim, Kurash; Chen, Jingsheng; Rusydi, Andrivo; Wang, Junling; Chambers, Scott A.; Du, Yingge

doi:10.1002/adfm.201803712

Title: Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates

Journal Article · Mon Aug 06 00:00:00 EDT 2018 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.201803712· OSTI ID:1647169

^[1];

^[2]; Chang, Lei ^[3]; Zhao, Jiali ^[4]; Li, Yangyang ^[5]; Tang, Chi Sin ^[5]; Yin, Xinmao ^[5]; Bowden, Mark E. ^[2]; Yang, Zhenzhong ^[2]; Guo, Haizhong ^[6]; You, Lu ^[3]; Guo, Rui ^[5]; Wang, Jiaou ^[4]; Ibrahim, Kurash ^[4]; Chen, Jingsheng ^[5]; Rusydi, Andrivo ^[5]; Wang, Junling ^[3]; Chambers, Scott A. ^[2]; Du, Yingge ^[2]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Nanyang Technological Univ. (Singapore)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Nanyang Technological Univ. (Singapore)
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics
National Univ. of Singapore (Singapore)
Zhengzhou Univ. (China)

Perovskite-structured (ABO₃) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, we investigate a set of epitaxial rare earth nickelates (RNiO₃) thin films with controlled A-site isovalent substitution to correlate their structure and physical properties with ORR/OER activities. The ORR activity is shown to decrease monotonically with decreasing the A-site element ionic radius which lowers the conductivity of the RNiO₃ (R = La, La_0.5Nd_0.5, La_0.2Nd_0.8, Nd, Nd_0.5Sm_0.5, Sm, Gd) films, with LaNiO₃ being the most conductive and active. On the other hand, the OER activity initially increases upon substituting La with Nd and is maximal at La_0.2Nd_0.8NiO₃, in which oxygen vacancies (VOs) start to form. Moreover, the OER activity remains comparable within error through Sm-doped NdNiO₃. Beyond that, we cannot reliably measure activity due to the potential voltage drop across the film. The improved OER activity is ascribed to the partial reduction of Ni³⁺ to Ni²⁺ as a result of VOs, which increases the average occupancy of the e_g antibonding orbital to more than one. Our work highlights the importance of tuning A-site elements as an effective strategy for balancing the ORR and OER activities of bifunctional electrocatalysts.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; 68278

OSTI ID:: 1647169

Alternate ID(s):: OSTI ID: 1463195

Report Number(s):: PNNL-SA-135288

Journal Information:: Advanced Functional Materials, Vol. 28, Issue 39; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 118 works

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References (56)

Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
Design of Efficient Bifunctional Oxygen Reduction/Evolution Electrocatalyst: Recent Advances and Perspectives Huang, Zhen-Feng; Wang, Jiong; Peng, Yuecheng Advanced Energy Materials, Vol. 7, Issue 23 https://doi.org/10.1002/aenm.201700544	journal	July 2017
Energy and fuels from electrochemical interfaces Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4738	journal	December 2016
Free Electrons to Molecular Bonds and Back: Closing the Energetic Oxygen Reduction (ORR)–Oxygen Evolution (OER) Cycle Using Core–Shell Nanoelectrocatalysts Strasser, Peter Accounts of Chemical Research, Vol. 49, Issue 11 https://doi.org/10.1021/acs.accounts.6b00346	journal	October 2016
Oxygen electrocatalysts in metal–air batteries: from aqueous to nonaqueous electrolytes Wang, Zhong-Li; Xu, Dan; Xu, Ji-Jing Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C3CS60248F	journal	January 2014
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Understanding the electrocatalysis of oxygen reduction on platinum and its alloys Stephens, Ifan E. L.; Bondarenko, Alexander S.; Grønbjerg, Ulrik Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee03590a	journal	January 2012
Orientation-Dependent Oxygen Evolution Activities of Rutile IrO ₂ and RuO ₂ Stoerzinger, Kelsey A.; Qiao, Liang; Biegalski, Michael D. The Journal of Physical Chemistry Letters, Vol. 5, Issue 10 https://doi.org/10.1021/jz500610u	journal	April 2014
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C. Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja407115p	journal	October 2013
Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M. Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/ja510442p	journal	March 2015
Toward sustainable fuel cells Stephens, Ifan Erfyl Lester; Rossmeisl, Jan; Chorkendorff, Ib Science, Vol. 354, Issue 6318 https://doi.org/10.1126/science.aal3303	journal	December 2016
Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy Vesborg, Peter C. K.; Jaramillo, Thomas F. RSC Advances, Vol. 2, Issue 21 https://doi.org/10.1039/c2ra20839c	journal	January 2012
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki Nature Chemistry, Vol. 3, Issue 7, p. 546-550 https://doi.org/10.1038/nchem.1069	journal	June 2011
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Oxygen-deficient BaTiO3− perovskite as an efficient bifunctional oxygen electrocatalyst Chen, Ching-Fong; King, Graham; Dickerson, Robert M. Nano Energy, Vol. 13 https://doi.org/10.1016/j.nanoen.2015.03.005	journal	April 2015
Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO ₃ Perovskites Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W. Journal of the American Chemical Society, Vol. 138, Issue 8 https://doi.org/10.1021/jacs.5b11713	journal	February 2016
Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis Hong, Wesley T.; Risch, Marcel; Stoerzinger, Kelsey A. Energy & Environmental Science, Vol. 8, Issue 5 https://doi.org/10.1039/C4EE03869J	journal	January 2015
Oxygen Reduction Reaction Activity of La-Based Perovskite Oxides in Alkaline Medium: A Thin-Film Rotating Ring-Disk Electrode Study Sunarso, Jaka; Torriero, Angel A. J.; Zhou, Wei The Journal of Physical Chemistry C, Vol. 116, Issue 9 https://doi.org/10.1021/jp211946n	journal	February 2012
Oxygen Reduction at Carbon-Supported Lanthanides: The Role of the B-Site Celorrio, Verónica; Dann, Ellie; Calvillo, Laura ChemElectroChem, Vol. 3, Issue 2 https://doi.org/10.1002/celc.201500440	journal	December 2015
Oxygen reduction reaction at La _x Ca _1−x MnO ₃ nanostructures: interplay between A-site segregation and B-site valency Celorrio, Verónica; Calvillo, Laura; Dann, Ellie Catalysis Science & Technology, Vol. 6, Issue 19 https://doi.org/10.1039/C6CY01105E	journal	January 2016
Highly Active Epitaxial La _{(1– x )} Sr _x MnO ₃ Surfaces for the Oxygen Reduction Reaction: Role of Charge Transfer Stoerzinger, Kelsey A.; Lü, Weiming; Li, Changjian The Journal of Physical Chemistry Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acs.jpclett.5b00439	journal	April 2015
Enhancing Perovskite Electrocatalysis through Strain Tuning of the Oxygen Deficiency Petrie, Jonathan R.; Jeen, Hyoungjeen; Barron, Sara C. Journal of the American Chemical Society, Vol. 138, Issue 23 https://doi.org/10.1021/jacs.6b03520	journal	June 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
Ca ₂ Mn ₂ O ₅ as Oxygen-Deficient Perovskite Electrocatalyst for Oxygen Evolution Reaction Kim, Jaemin; Yin, Xi; Tsao, Kai-Chieh Journal of the American Chemical Society, Vol. 136, Issue 42 https://doi.org/10.1021/ja506254g	journal	October 2014
Brownmillerite-type Ca ₂ FeCoO ₅ as a Practicable Oxygen Evolution Reaction Catalyst Tsuji, Etsushi; Motohashi, Teruki; Noda, Hiroyuki ChemSusChem, Vol. 10, Issue 14 https://doi.org/10.1002/cssc.201701192	journal	July 2017
Progress in perovskite nickelate research Catalan, G. Phase Transitions, Vol. 81, Issue 7-8 https://doi.org/10.1080/01411590801992463	journal	July 2008
Orbital Order and Possible Superconductivity in ${LaNiO}_{3} / {LaMO}_{3}$ Superlattices Chaloupka, Jiří; Khaliullin, Giniyat Physical Review Letters, Vol. 100, Issue 1 https://doi.org/10.1103/PhysRevLett.100.016404	journal	January 2008
Colossal resistance switching and band gap modulation in a perovskite nickelate by electron doping Shi, Jian; Zhou, You; Ramanathan, Shriram Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5860	journal	September 2014
Spatially resolved ultrafast magnetic dynamics initiated at a complex oxide heterointerface Först, M.; Caviglia, A. D.; Scherwitzl, R. Nature Materials, Vol. 14, Issue 9 https://doi.org/10.1038/nmat4341	journal	July 2015
Competition between strain and dimensionality effects on the electronic phase transitions in NdNiO3 films Wang, Le; Ju, Sheng; You, Lu Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep18707	journal	December 2015
Polar metals by geometric design Kim, T. H.; Puggioni, D.; Yuan, Y. Nature, Vol. 533, Issue 7601 https://doi.org/10.1038/nature17628	journal	April 2016
Strongly correlated perovskite fuel cells Zhou, You; Guan, Xiaofei; Zhou, Hua Nature, Vol. 534, Issue 7606 https://doi.org/10.1038/nature17653	journal	May 2016
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico ChemCatChem, Vol. 3, Issue 7 https://doi.org/10.1002/cctc.201000397	journal	March 2011
Strain dependent stabilization of metallic paramagnetic state in epitaxial NdNiO ₃ thin films Kumar, Yogesh; Choudhary, R. J.; Sharma, S. K. Applied Physics Letters, Vol. 101, Issue 13 https://doi.org/10.1063/1.4754593	journal	September 2012
Self-powered sensitive and stable UV-visible photodetector based on GdNiO ₃ /Nb-doped SrTiO ₃ heterojunctions Wang, Le; Chang, Lei; Yin, Xinmao Applied Physics Letters, Vol. 110, Issue 4 https://doi.org/10.1063/1.4974144	journal	January 2017
Oxygen Vacancy Induced Room-Temperature Metal–Insulator Transition in Nickelate Films and Its Potential Application in Photovoltaics Wang, Le; Dash, Sibashisa; Chang, Lei ACS Applied Materials & Interfaces, Vol. 8, Issue 15 https://doi.org/10.1021/acsami.6b00650	journal	April 2016
Reversible nano-structuring of SrCrO3-δ through oxidation and reduction at low temperature Zhang, K. H. L.; Sushko, P. V.; Colby, R. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5669	journal	August 2014
Electrochemically Driven Giant Resistive Switching in Perovskite Nickelates Heterostructures Wang, Le; Zhang, Qinghua; Chang, Lei Advanced Electronic Materials, Vol. 3, Issue 10 https://doi.org/10.1002/aelm.201700321	journal	August 2017
Chemical Structures and Performance of Perovskite Oxides Pena, M.; Fierro, J. Chemical Reviews, Vol. 101, Issue 7, p. 1981-2018 https://doi.org/10.1021/cr980129f	journal	July 2001
Oxide enthalpy of formation and band gap energy as accurate descriptors of oxygen vacancy formation energetics Deml, Ann M.; Stevanović, Vladan; Muhich, Christopher L. Energy & Environmental Science, Vol. 7, Issue 6 https://doi.org/10.1039/c3ee43874k	journal	January 2014
Investigation of the metal–insulator transition in NdNiO ₃ films by site-selective X-ray absorption spectroscopy Palina, Natalia; Wang, Le; Dash, Sibashisa Nanoscale, Vol. 9, Issue 18 https://doi.org/10.1039/C7NR00742F	journal	January 2017
Oxygen Diode Formed in Nickelate Heterostructures by Chemical Potential Mismatch Guo, Er-Jia; Liu, Yaohua; Sohn, Changhee Advanced Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adma.201705904	journal	March 2018
Polarity compensation in ultra-thin films of complex oxides: The case of a perovskite nickelate Middey, S.; Rivero, P.; Meyers, D. Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06819	journal	October 2014
Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces Grisolia, M. N.; Varignon, J.; Sanchez-Santolino, G. Nature Physics, Vol. 12, Issue 5 https://doi.org/10.1038/nphys3627	journal	January 2016
Role of Strain and Conductivity in Oxygen Electrocatalysis on LaCoO ₃ Thin Films Stoerzinger, Kelsey A.; Choi, Woo Seok; Jeen, Hyoungjeen The Journal of Physical Chemistry Letters, Vol. 6, Issue 3 https://doi.org/10.1021/jz502692a	journal	January 2015
Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides Hong, Wesley T.; Stoerzinger, Kelsey A.; Lee, Yueh-Lin Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/C7EE02052J	journal	January 2017
Low-cost Oxygen Electrode Material Meadowcroft, D. B. Nature, Vol. 226, Issue 5248 https://doi.org/10.1038/226847a0	journal	May 1970
Influence of the nature of the conduction band of transition metal oxides on catalytic activity for oxygen reduction Matsumoto, Y.; Yoneyama, H.; Tamura, H. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 83, Issue 2 https://doi.org/10.1016/S0022-0728(77)80169-1	journal	October 1977
Strain coupling of oxygen non-stoichiometry in perovskite thin films Herklotz, Andreas; Lee, Dongkyu; Guo, Er-Jia Journal of Physics: Condensed Matter, Vol. 29, Issue 49 https://doi.org/10.1088/1361-648X/aa949b	journal	December 2017
Phase diagram of compressively strained nickelate thin films Disa, A. S.; Kumah, D. P.; Ngai, J. H. APL Materials, Vol. 1, Issue 3 https://doi.org/10.1063/1.4820431	journal	September 2013
SmxNd1−xNiO3 thin-film solid solutions with tunable metal–insulator transition synthesized by alternate-target pulsed-laser deposition Ambrosini, Andrea; Hamet, Jean-François Applied Physics Letters, Vol. 82, Issue 5 https://doi.org/10.1063/1.1541116	journal	February 2003
Metal−Insulator Transitions, Structural and Microstructural Evolution of RNiO ₃ (R = Sm, Eu, Gd, Dy, Ho, Y) Perovskites: Evidence for Room-Temperature Charge Disproportionation in Monoclinic HoNiO ₃ and YNiO ₃ Alonso, José A.; Martínez-Lope, María J.; Casais, María T. Journal of the American Chemical Society, Vol. 121, Issue 20 https://doi.org/10.1021/ja984015x	journal	May 1999
Elastic properties of rhombohedral, cubic, and monoclinic phases of LaNiO 3 by first principles calculations Masys, Š.; Jonauskas, V. Computational Materials Science, Vol. 108 https://doi.org/10.1016/j.commatsci.2015.06.034	journal	October 2015
Brownmillerite-type Ca ₂ FeCoO ₅ as a Practicable Oxygen Evolution Reaction Catalyst Tsuji, Etsushi; Motohashi, Teruki; Noda, Hiroyuki ChemSusChem, Vol. 10, Issue 14 https://doi.org/10.1002/cssc.201700499	journal	June 2017
Spatially resolved ultrafast magnetic dynamics launched at a complex-oxide hetero-interface Först, M.; Caviglia, A. D.; Scherwitzl, R. arXiv https://doi.org/10.48550/arxiv.1505.00601	text	January 2015

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Title: Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates

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