Machine-Learning-Assisted Screening of Nanocluster Electrocatalysts: Mapping and Reshaping the Activity Volcano for the Oxygen Reduction Reaction

In computational heterogeneous catalysis, Sabatier's principle-based activity volcano plots provide an intuitive guide to catalyst design but impose a fundamental constraint on the maximum achievable catalytic performance. Recently, subnano clusters have emerged as an exciting platform, offering high noble metal utilization and superior performance for various reactions compared to extended surfaces, reflecting a complex structure-activity relationship in the non-scalable regime. However, understanding their non-monotonic catalytic activity, attributed to the large configurational space and their fluxional identity, poses a formidable challenge. Here, we present a machine learning (ML) framework that captures the non-monotonic trends in oxygen reduction reaction (ORR) activity at the subnanometer scale, attributed to their dynamic fluxional characteristics. We demonstrate a size-dependent shifting and reshaping of the ORR activity volcano, with Au replacing Pt at the peak. Leveraging only upon the non-<i>ab initio</i> geometric and electronic properties, our trained ML model accurately captures the site-specific adsorption energies of intermediates at the subnanometer regime. To account for the inconsistent trend in activity, we analyzed the correlation between electronic and geometric properties. Our findings reveal that the d-filling and coupling matrix of the neighboring metal atom significantly influences the intermediate adsorption on the local chemical environment compared to the d-band center. Following this analysis, we utilized ML to map the catalyst distribution in the activity volcano and identified the five best sub-nano electrocatalysts, demonstrating overpotential values lower than or comparable to the Pt(111) surface for the ORR. This study provides intuitive guidelines for the rational designing of highly efficient electrocatalysts for fuel cell applications while modifying the activity volcano plots for electrocatalysts at the subnanometer regime.