Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO₃ Perovskites

Abstract

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 (TMO) thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO 3 to systematically determine its influence on both the oxygen reduction (ORR) and oxygen evolution reaction (OER). 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 straininduced splitting of the e g orbitals, which can customize orbital asymmetry at the surface. Analogous to straininduced shifts in the d-band center of noble metals relative to Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides. Advancements in energy storage are essential for driving the development of more sophisticated mobile technologies as well as continuing the trend towards a greener economy. At the forefront of this push are high energy density devices, such as regenerative fuel cells and metal-air batteries. 1 In these and related electrochemical systems, both the oxygen reduction and oxygen evolution reactions (ORR and OER, respectively) are crucial towards successful operation. 2 Traditionally, conductive catalysts incorporating noble metals (e.g., Pt and IrO 2 ) have been used to facilitate these reactions near room temperature. 3 To alleviate costs and poor stabilities during OER in alkaline solutions, significant efforts have focused on transition metal oxides (TMOs) with multivalent Ni, Fe, Co, and Mn, such as NiFeO x .4 Similar to alloying in noble metals, the majority of research into increasing oxygen activities of TMOs involves cationic doping, which often promotes either the ORR or OER but not bifunctionality. 5Here, we explore how another factor, i.e. strain, can influence bifunctionality in TMOs. Contemporary work on high-temperature (>500 C) oxide catalysis in an aprotic environment (e.g. ORR: O 2 + 4e -→ 2O 2-) has emphasized the importance of tensile strain for activating defects to improve catalytic reactions. 6 In an alkaline environment (e. . Among TMOs, the ABO 3 perovskites, in which A is traditionally from Groups I-III and B is a transition metal ion with six-fold octahedral coordination, also have electronic structures that are sensitive to strain. Due to strong hybridization between the O 2p and the transition metal d z 2 and d x 2 -y 2 lobes in the BO 6 octahedra, the σ* states near E F consist of e g orbitals. 10,10b Similar to the Jahn-Teller distortion, strain is known to lift the degeneracy in these symmetry-localized d z 2 and d x 2 -y 2 orbitals, yielding changes in the orbital occupancy, or polarization.7a, 11 By using strain to control the degree of this ...

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“…Recently, Lee et al reported the strained LaNiO 3 for the enhanced bifunctional ORR/OER catalysis using different lattice-mismatched substrates to control strain degree from −2.2% to 2.7% (Figure 7a). [59] They found that when LaAlO 3 (LAO) is used as substrate, the produced small strain of −1.2% in LaNiO 3 can lead to the enhanced bifunctional ORR/OER compared to other strained samples and pristine LaNiO 3 (Figure 7b,c). When ORR and OER activities under the overpotentials of 0.4 V are compared (Figure 7d), the bifunctional activity drastically increases with compressive strain.…”

Perovskite Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

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