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

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.

View Accepted Manuscript (DOE)

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

OSTI ID:: 1647169

Alternate ID(s):: OSTI ID: 1463195

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

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

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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

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