Machine Learning-Enabled Exploration of the Electrochemical Stability of Real-Scale Metallic Nanoparticles

Abstract Surface Pourbaix diagrams are critical to understanding the stability of nanomaterials in electrochemical environments. Their construction based on density functional theory (DFT) is, however, prohibitively expensive for real-scale systems, such as several nanometer-size nanoparticles (NPs) involving at least thousands of noble metal atoms, and this limitation calls for machine learning (ML)-driven approaches. Herein, with the aim of accelerating the accurate prediction of adsorption energies for a wide range of surface coverages on large-size NPs, we developed a bond-type embedded crystal graph convolutional neural network (BE-CGCNN) model in which four bonding types were treated differently. Owing to the much enhanced accuracy of the bond-type embedding approach compared to the original CGCNN, we demonstrate the construction of reliable Pourbaix diagrams for very large-size NPs involving up to 6,525 atoms (approximately 4.8 nm in diameter), which enables the exploration of electrochemical stability over various NP sizes and shapes. We reveal that ML-based Pourbaix diagrams well reproduce the experimental observations with increasing NP size, such as the increasing O- to OH-covered phase ratio and the decreasing Pt dissolution phase in the diagrams. This work suggests a new method for accelerated Pourbaix diagram construction for real-scale and arbitrarily shaped NPs, which would significantly open up an avenue for electrochemical stability studies.