Eur. Phys. J. B (2017) 90: 135
https://doi.org/10.1140/epjb/e2017-80041-8

Regular Article

A DFT+U study of the catalytic activity of lanthanum nickelate

Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, 721302 Kharagpur, India

^a e-mail: tkkundu@metal.iitkgp.ernet.in

Received: 16 January 2017
Published online: 17 July 2017

Abstract

A density functional theory + Hubbard U (DFT+U) method is implemented to investigate the catalytic activity of lanthanum nickelate (LaNiO₃) for oxygen reduction reaction. Comparison of the surface energies of different LaNiO₃ surfaces shows that {001} surface has the lowest surface energy and hence maximum stability. Two possible terminations of the {001} surface namely LaO and NiO₂ are considered to carry out all our DFT calculations. Calculation of bond lengths of the atoms near the surface and adsorption energies for the reaction intermediates revealed that LaO terminated {001} surface is unstable for the process of OOH adsorption and hence not preferred for the oxygen reduction reaction. However, NiO₂ terminated {001} surface shows excellent catalytic activity for adsorption of all the reaction intermediates and hence is a favourable surface for reactions to occur. Superiority of the NiO₂ terminated {001} surface as catalyst over the LaO terminated one, is also confirmed from the total and partial density of states of the surfaces in presence of the adsorbates, which also shows that the desorption rate of the reaction intermediates is low in case of LaO terminated {001} surface compared to the NiO₂ terminated one.