High-throughput screening of bifunctional catalysts for oxygen evolution/reduction reaction at the subnanometer...

The development of low-cost, stable, and highly efficient electrocatalysts for the bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is crucial for advancing future renewable technologies. In this study, we systematically investigated the OER and ORR performance of subnano clusters across the 3d, 4d, and 5d transition metal (TM) series of varying sizes using first-principles calculations. The fluxional identity of these clusters in the subnanometer regime is reflected in their non-monotonic catalytic activity. We established a size-dependent scaling relationship between OER/ORR intermediates, leading to a reshaping of the activity volcano plot at the subnanometer scale. Our detailed mechanistic investigation revealed a shift in the apex of the activity volcano from the Pt(111) and IrO₂ surfaces to the Au₁₁ clusters for both OER and ORR. Late transition metal subnano clusters, specifically Au₁₁, emerged as the best bifunctional electrocatalyst, demonstrating significantly lower overpotential values. Furthermore, we categorized our catalysts into three clusters and employed the Random Forest Regression method to evaluate the impact of non-ab initio electronic features on OER and ORR activities. Interestingly, d-band filling emerged as the primary contributor to the bifunctional activity of the subnano clusters. This work not only provides a comprehensive view of OER and ORR activities but also presents a new pathway for designing and discovering highly efficient bifunctional catalysts.