Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Subnanometer catalysts offer high noble metal utilization and superior performance for several reactions. However, understanding their structures and properties on an atomic scale under working conditions is challenging due to the large configurational space. Here, we introduce an efficient multiscale framework to predict their stability exposed to an adsorbate. The framework integrates a comprehensive toolset including density functional theory (DFT) calculations, cluster expansion, machine learning, and structure optimization. The end-to-end machine-learning workflow guides DFT data generation and enables significant computational acceleration. We demonstrate the approach for CO-adsorbed Pd-n (n = 1-55) clusters on CeO2(111). Simulation results reveal that CO can facilitate restructuring by stabilizing smaller planar structures and bilayer structures of specific intermediate sizes, consistent with experimental reports. Metal-support interactions, preferential CO adsorption, and metal nuclearity and structure control catalyst stability. The framework allows automatic discovery of stable catalyst structures and a systematic strategy to exploit properties in the subnanometer scale.

Automated summary

Subnanometer catalysts provide high noble metal utilization and superior performance for various reactions. However, understanding their atomic-scale structures and properties under working conditions is challenging due to the large configurational space. In this study, an efficient multiscale framework integrating density functional theory (DFT) calculations, cluster expansion, machine learning, and structure optimization is introduced to predict the stability of catalysts exposed to adsorbates. The framework enables automatic discovery of stable catalyst structures and a systematic strategy to exploit properties at the subnanometer scale. Simulation results for CO-adsorbed Pd-n (n = 1-55) clusters on CeO2(111) reveal that CO can facilitate restructuring by stabilizing smaller planar structures and bilayer structures of specific intermediate sizes.