Theoretical Optimization of Compositions of High‐Entropy Oxides for the Oxygen Evolution Reaction. Issue 19 (10th March 2022)

• Record Type: Journal Article
• Authors: Svane, Katrine L.; Rossmeisl, Jan
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 19(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-10
• Subjects: Density Functional Calculations -- Electrochemistry -- High-Entropy Oxides -- Oxygen Evolution Reaction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202201146
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: High‐entropy oxides are oxides consisting of five or more metals incorporated in a single lattice, and the large composition space suggests that properties of interest can be readily optimised. For applications within catalysis, the different local atomic environments result in a distribution of binding energies for the catalytic intermediates. Using the oxygen evolution reaction on the rutile (110) surface as example, here we outline a strategy for the theoretical optimization of the composition. Density functional theory calculations performed for a limited number of sites are used to fit a model that predicts the reaction energies for all possible local atomic environments. Two reaction pathways are considered; the conventional pathway on the coordinatively unsaturated sites and an alternative pathway involving transfer of protons to a bridging oxygen. An explicit model of the surface is constructed to describe the interdependency of the two pathways and identify the composition that maximizes catalytic activity. Abstract : High‐entropy oxides are investigated theoretically as catalysts for the oxygen evolution reaction. The energetics of the reaction is calculated on individual active sites following two different pathways, and it is shown that the overpotential and preferred pathway depend on the local atomic environment. A surface model is constructed in order to identify the composition that maximises the catalytic activity.