TY - JOUR

T1 - A Flexible Theory for Catalysis

T2 - Learning Alkaline Oxygen Reduction on Complex Solid Solutions within the Ag−Pd−Pt−Ru Composition Space**

AU - Clausen, Christian M.

AU - Krysiak, Olga A.

AU - Banko, Lars

AU - Pedersen, Jack K.

AU - Schuhmann, Wolfgang

AU - Ludwig, Alfred

AU - Rossmeisl, Jan

N1 - Publisher Copyright: © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2023

Y1 - 2023

N2 - Compositionally complex materials such as high-entropy alloys and oxides have the potential to be efficient platforms for catalyst discovery because of the vast chemical space spanned by these novel materials. Identifying the composition of the most active catalyst materials, however, requires unraveling the descriptor-activity relationship, as experimentally screening the multitude of possible element ratios quickly becomes a daunting task. In this work, we show that inferred adsorption energy distributions of *OH and *O on complex solid solution surfaces within the space spanned by the system Ag−Pd−Pt−Ru are coupled to the experimentally observed electrocatalytic performance for the oxygen reduction reaction. In total, the catalytic activity of 1582 alloy compositions is predicted with a cross-validated mean absolute error of 0.042 mA/cm2 by applying a theory-derived model with only two adjustable parameters. Trends in the discrepancies between predicted electrochemical performance values of the model and the measured values on thin film surfaces subsequently provide insight into the alloys’ surface compositions during reaction conditions. Bridging this gap between computationally modeled and experimentally observed catalytic activities, not only reveals insight into the underlying theory of catalysis but also takes a step closer to realizing exploration and exploitation of high-entropy materials.

AB - Compositionally complex materials such as high-entropy alloys and oxides have the potential to be efficient platforms for catalyst discovery because of the vast chemical space spanned by these novel materials. Identifying the composition of the most active catalyst materials, however, requires unraveling the descriptor-activity relationship, as experimentally screening the multitude of possible element ratios quickly becomes a daunting task. In this work, we show that inferred adsorption energy distributions of *OH and *O on complex solid solution surfaces within the space spanned by the system Ag−Pd−Pt−Ru are coupled to the experimentally observed electrocatalytic performance for the oxygen reduction reaction. In total, the catalytic activity of 1582 alloy compositions is predicted with a cross-validated mean absolute error of 0.042 mA/cm2 by applying a theory-derived model with only two adjustable parameters. Trends in the discrepancies between predicted electrochemical performance values of the model and the measured values on thin film surfaces subsequently provide insight into the alloys’ surface compositions during reaction conditions. Bridging this gap between computationally modeled and experimentally observed catalytic activities, not only reveals insight into the underlying theory of catalysis but also takes a step closer to realizing exploration and exploitation of high-entropy materials.

KW - Catalyst Discovery

KW - Combinatorial Co-Sputtering

KW - Density Functional Theory

KW - High-Entropy Alloys

KW - Scanning Droplet Cell

U2 - 10.1002/anie.202307187

DO - 10.1002/anie.202307187

M3 - Journal article

C2 - 37534574

AN - SCOPUS:85168329221

VL - 62

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 39

M1 - e202307187

ER -