Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

Jonathan R. Petrie; Valentino R. Cooper; John W. Freeland; Tricia L. Meyer; Zhiyong Zhang; Daniel A. Lutterman; Ho Nyung Lee

doi:10.1021/jacs.5b11713

Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO₃ Perovskites

Jonathan R. Petrie, Valentino R. Cooper, John W. Freeland, Tricia L. Meyer, Zhiyong Zhang, Daniel A. Lutterman, Ho Nyung Lee

Materials Science and Technology Div

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

322 Scopus citations

Abstract

Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. However, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO₃ to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of the e_g orbitals, which can customize orbital asymmetry at the surface. Analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.

Original language	English
Pages (from-to)	2488-2491
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	8
DOIs	https://doi.org/10.1021/jacs.5b11713
State	Published - Mar 2 2016

Funding

We acknowledge S. Okamoto for theoretical insight. This work was supported by the U.S. Department of Energy (DOE), Office of Science (OS), Basic Energy Sciences (BES), Materials Science and Engineering Division (synthesis, physical property characterization, and XAS data analysis) and by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. DOE (electrochemical characterization and theory). Reference electrode preparation was performed as a user project at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, BES, U.S. DOE. Use of electrochemical testing system was supported by the Fluid Interface Reactions, Structures, and Transport (FIRST) Center, an Energy Frontier Research Center funded by the U.S. DOE, OS, BES. Use of the Advanced Photon Source for XAS was supported by the U.S. DOE, OS, under contract no. DE-AC02-06CH11357.

Funders	Funder number
Scientific User Facilities Division
U.S. Department of Energy	DE-AC02-06CH11357
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Division of Materials Sciences and Engineering

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10.1021/jacs.5b11713

Cite this

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abstract = "Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. However, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of the eg orbitals, which can customize orbital asymmetry at the surface. Analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.",

author = "Petrie, {Jonathan R.} and Cooper, {Valentino R.} and Freeland, {John W.} and Meyer, {Tricia L.} and Zhiyong Zhang and Lutterman, {Daniel A.} and Lee, {Ho Nyung}",

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AU - Petrie, Jonathan R.

AU - Cooper, Valentino R.

AU - Freeland, John W.

AU - Meyer, Tricia L.

AU - Zhang, Zhiyong

AU - Lutterman, Daniel A.

AU - Lee, Ho Nyung

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