Cluster Expansion Method for Simulating Realistic Size of Nanoparticle Catalysts with an Application in CO2 Electroreduction

Abstract

For the last several decades, there has been a rapid development of nanoscience and nanotechnology. In particular, nanoparticles (NPs) are applied in various catalyst problems, where their enormously large surface-to-volume ratio not only is advantageous for high catalytic performance but also allows the quantum size effect to play a key role in modifying their chemical properties. However, when understanding the size effect of NPs on the catalytic properties by employing density functional theory (DFT) calculations, there has been an obvious experiment–theory gap in simulating nanocatalysts with realistic sizes. In this study, we developed a new simulation method based on the cluster expansion model, namely, CE-np, which enables efficient and accurate calculations of the intermediate binding energies for various sizes of NPs. We then applied CE-np to investigate the electrochemical CO2 reduction reaction (CO2RR) of gold NPs (AuNPs). CE-np reproduces not only DFT-level accuracies in predicting the interme...