Regensburg 2019 – wissenschaftliches Programm
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O: Fachverband Oberflächenphysik
O 13: Solid-Liquid Interfaces I: Electrocatalysis and Photoelectrochemistry
O 13.5: Vortrag
Montag, 1. April 2019, 16:00–16:15, H16
A Kinetics-Based Computational Catalyst Design Strategy for the Oxygen Evolution Reaction on Transition Metal Oxide Surfaces — •Simeon D. Beinlich1, Craig P. Plaisance2, and Karsten Reuter1 — 1Technische Universität München, Germany — 2Louisiana State University, USA
Aiming to extend over prevalent thermodynamical models, we present a catalyst design strategy for the oxygen evolution reaction (OER) at transition metal oxide (TMO) surfaces that explicitly considers aspects of the reaction kinetics. This strategy is based on extensive DFT+U calculations for a large number of doped active sites on three different surface terminations of cobalt(II,II) oxide.
On this basis, we adapt existing Brønstead-Evans-Polanyi relationships to achieve an accurate description of the two-step nature of the rate-limiting water addition step in the OER. This reveals that the electrochemical and nonelectrochemical pathways of water addition are kinetically equivalent under certain conditions. It also yields a simplified kinetic model to derive a generalized expression for the catalytic activity. We use this model to formulate design criteria for optimal catalytic performance, which pose structure-sensitive and electrode-potential-dependent restrictions for the oxidation potentials of the metal centers involved in the reaction.
The kinetics-based design strategy as well as these design criteria are expected to be transferable to other TMOs and similar electrocatalytic systems dominated by kinetic barriers.