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

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

doi:10.1002/adfm.201803712

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

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

Research output: Contribution to journal › Article › peer-review

151 Scopus citations

Abstract

Perovskite-structured (ABO₃) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, a set of epitaxial rare-earth nickelates (RNiO₃) thin films is investigated with controlled A-site isovalent substitution to correlate their structure and physical properties with ORR/OER activities, examined by using a three-electrode system in O₂-saturated 0.1 m KOH electrolyte. The ORR activity decreases monotonically with decreasing the A-site element ionic radius which lowers the conductivity of RNiO₃ (R = La, La_0.5Nd_0.5, La_0.2Nd_0.8, Nd, Nd_0.5Sm_0.5, Sm, and 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. Moreover, the OER activity remains comparable within error through Sm-doped NdNiO₃. Beyond that, the activity cannot be measured 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 oxygen vacancies, which increases the average occupancy of the e_g antibonding orbital to more than one. The work highlights the importance of tuning A-site elements as an effective strategy for balancing ORR and OER activities of bifunctional electrocatalysts.

Original language	English (US)
Article number	1803712
Journal	Advanced Functional Materials
Volume	28
Issue number	39
DOIs	https://doi.org/10.1002/adfm.201803712
State	Published - Sep 26 2018
Externally published	Yes

Bibliographical note

Funding Information:
The work is support by the U.S. Department of Energy (DOE), Office of Science, Early Career Research Program under Award No. 68278. The XRD reciprocal space maps measurements are supported by U.S. DOE, Office of Basic Energy Sciences, the Division of Materials Sciences and Engineering under Award #10122. J.W. acknowledges financial support from Ministry of Education, Singapore under the Grant No. MOE2014-T2-1-099. H.G. is supported by the National Natural Science Foundation of China (Grant No. 11574365). Electrochemical measurements were supported for K.A.S. by the Linus Pauling Distinguished Post-doctoral Fellowship at Pacific Northwest National Laboratory (PNNL LDRD69319). A portion of the work was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a DOE User Facility sponsored by the Office of Biological and Environmental Research. PNNL is a multiprogram National laboratory operated for DOE by Battelle.

Publisher Copyright:
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

nickelates
oxygen evolution reaction
oxygen reduction reaction
oxygen vacancy
perovskite

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This output contributes to the following UN Sustainable Development Goals (SDGs)

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Wang, L., Stoerzinger, K. A., Chang, L., Zhao, J., Li, Y., Tang, C. S., Yin, X., Bowden, M. E., Yang, Z., Guo, H., You, L., Guo, R., Wang, J., Ibrahim, K., Chen, J., Rusydi, A., Wang, J., Chambers, S. A., & Du, Y. (2018). Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates. Advanced Functional Materials, 28(39), Article 1803712. https://doi.org/10.1002/adfm.201803712

Wang, L, Stoerzinger, KA, Chang, L, Zhao, J, Li, Y, Tang, CS, Yin, X, Bowden, ME, Yang, Z, Guo, H, You, L, Guo, R, Wang, J, Ibrahim, K, Chen, J, Rusydi, A, Wang, J, Chambers, SA & Du, Y 2018, 'Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates', Advanced Functional Materials, vol. 28, no. 39, 1803712. https://doi.org/10.1002/adfm.201803712

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

abstract = "Perovskite-structured (ABO3) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, a set of epitaxial rare-earth nickelates (RNiO3) thin films is investigated with controlled A-site isovalent substitution to correlate their structure and physical properties with ORR/OER activities, examined by using a three-electrode system in O2-saturated 0.1 m KOH electrolyte. The ORR activity decreases monotonically with decreasing the A-site element ionic radius which lowers the conductivity of RNiO3 (R = La, La0.5Nd0.5, La0.2Nd0.8, Nd, Nd0.5Sm0.5, Sm, and 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 La0.2Nd0.8NiO3. Moreover, the OER activity remains comparable within error through Sm-doped NdNiO3. Beyond that, the activity cannot be measured 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 oxygen vacancies, which increases the average occupancy of the eg antibonding orbital to more than one. The work highlights the importance of tuning A-site elements as an effective strategy for balancing ORR and OER activities of bifunctional electrocatalysts.",

keywords = "nickelates, oxygen evolution reaction, oxygen reduction reaction, oxygen vacancy, perovskite",

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

note = "Funding Information: The work is support by the U.S. Department of Energy (DOE), Office of Science, Early Career Research Program under Award No. 68278. The XRD reciprocal space maps measurements are supported by U.S. DOE, Office of Basic Energy Sciences, the Division of Materials Sciences and Engineering under Award #10122. J.W. acknowledges financial support from Ministry of Education, Singapore under the Grant No. MOE2014-T2-1-099. H.G. is supported by the National Natural Science Foundation of China (Grant No. 11574365). Electrochemical measurements were supported for K.A.S. by the Linus Pauling Distinguished Post-doctoral Fellowship at Pacific Northwest National Laboratory (PNNL LDRD69319). A portion of the work was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a DOE User Facility sponsored by the Office of Biological and Environmental Research. PNNL is a multiprogram National laboratory operated for DOE by Battelle. Publisher Copyright: {\textcopyright} 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

month = sep,

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doi = "10.1002/adfm.201803712",

language = "English (US)",

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T1 - Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates

AU - Wang, Le

AU - Stoerzinger, Kelsey A.

AU - Chang, Lei

AU - Zhao, Jiali

AU - Li, Yangyang

AU - Tang, Chi Sin

AU - Yin, Xinmao

AU - Bowden, Mark E.

AU - Yang, Zhenzhong

AU - Guo, Haizhong

AU - You, Lu

AU - Guo, Rui

AU - Wang, Jiaou

AU - Ibrahim, Kurash

AU - Chen, Jingsheng

AU - Rusydi, Andrivo

AU - Wang, Junling

AU - Chambers, Scott A.

AU - Du, Yingge

N1 - Funding Information: The work is support by the U.S. Department of Energy (DOE), Office of Science, Early Career Research Program under Award No. 68278. The XRD reciprocal space maps measurements are supported by U.S. DOE, Office of Basic Energy Sciences, the Division of Materials Sciences and Engineering under Award #10122. J.W. acknowledges financial support from Ministry of Education, Singapore under the Grant No. MOE2014-T2-1-099. H.G. is supported by the National Natural Science Foundation of China (Grant No. 11574365). Electrochemical measurements were supported for K.A.S. by the Linus Pauling Distinguished Post-doctoral Fellowship at Pacific Northwest National Laboratory (PNNL LDRD69319). A portion of the work was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a DOE User Facility sponsored by the Office of Biological and Environmental Research. PNNL is a multiprogram National laboratory operated for DOE by Battelle. Publisher Copyright: © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/9/26

Y1 - 2018/9/26

N2 - Perovskite-structured (ABO3) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, a set of epitaxial rare-earth nickelates (RNiO3) thin films is investigated with controlled A-site isovalent substitution to correlate their structure and physical properties with ORR/OER activities, examined by using a three-electrode system in O2-saturated 0.1 m KOH electrolyte. The ORR activity decreases monotonically with decreasing the A-site element ionic radius which lowers the conductivity of RNiO3 (R = La, La0.5Nd0.5, La0.2Nd0.8, Nd, Nd0.5Sm0.5, Sm, and 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 La0.2Nd0.8NiO3. Moreover, the OER activity remains comparable within error through Sm-doped NdNiO3. Beyond that, the activity cannot be measured 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 oxygen vacancies, which increases the average occupancy of the eg antibonding orbital to more than one. The work highlights the importance of tuning A-site elements as an effective strategy for balancing ORR and OER activities of bifunctional electrocatalysts.

AB - Perovskite-structured (ABO3) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, a set of epitaxial rare-earth nickelates (RNiO3) thin films is investigated with controlled A-site isovalent substitution to correlate their structure and physical properties with ORR/OER activities, examined by using a three-electrode system in O2-saturated 0.1 m KOH electrolyte. The ORR activity decreases monotonically with decreasing the A-site element ionic radius which lowers the conductivity of RNiO3 (R = La, La0.5Nd0.5, La0.2Nd0.8, Nd, Nd0.5Sm0.5, Sm, and 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 La0.2Nd0.8NiO3. Moreover, the OER activity remains comparable within error through Sm-doped NdNiO3. Beyond that, the activity cannot be measured 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 oxygen vacancies, which increases the average occupancy of the eg antibonding orbital to more than one. The work highlights the importance of tuning A-site elements as an effective strategy for balancing ORR and OER activities of bifunctional electrocatalysts.

KW - nickelates

KW - oxygen evolution reaction

KW - oxygen reduction reaction

KW - oxygen vacancy

KW - perovskite

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DO - 10.1002/adfm.201803712

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ER -

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

Abstract

Bibliographical note

Keywords

UN SDGs

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