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

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

187 Citations (Scopus)

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

Original language	English
Article number	1803712
Journal	Advanced Functional Materials
Volume	28
Issue number	39
DOIs	https://doi.org/10.1002/adfm.201803712
Publication status	Published - 26 Sept 2018
Externally published	Yes

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Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

Research Keywords

nickelates
oxygen evolution reaction
oxygen reduction reaction
oxygen vacancy
perovskite

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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

@article{afebdf9f86d542078d1fe587dbf77de1,

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. {\textcopyright} 2018 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim",

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 = "Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].",

year = "2018",

month = sep,

day = "26",

doi = "10.1002/adfm.201803712",

language = "English",

volume = "28",

journal = "Advanced Functional Materials",

issn = "1616-301X",

publisher = "Wiley-VCH Verlag GmbH",

number = "39",

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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

TY - JOUR

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 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

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

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

KW - nickelates

KW - oxygen evolution reaction

KW - oxygen reduction reaction

KW - oxygen vacancy

KW - perovskite

UR - https://www.scopus.com/pages/publications/85052368677

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85052368677&origin=recordpage

U2 - 10.1002/adfm.201803712

DO - 10.1002/adfm.201803712

M3 - RGC 21 - Publication in refereed journal

SN - 1616-301X

VL - 28

JO - Advanced Functional Materials

JF - Advanced Functional Materials

IS - 39

M1 - 1803712

ER -

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

Abstract

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Research Keywords

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