A Unified Framework for Co-optimizing Activity, Selectivity, and Stability in Single-Atom Alloy Catalysts for CO ₂ Electroreduction

Balancing stability, activity, and selectivity in single-atom alloy (SAA) catalysts for CO 2 electroreduction remains a fundamental challenge, constrained by the vast host-dopant-surface design space and the prohibitive cost of exhaustive first-principles exploration. Here, we establish a unified computational framework for co-optimizing activity, selectivity, and stability in SAA catalysts. By integrating literature-informed design-space construction with physically constrained, data-efficient exploration, the framework rapidly identifies high-performance regions under a tightly controlled number of first-principles evaluations. Pt 1 /Cu(100) is identified as an optimal catalyst that simultaneously delivers high activity toward HCOOH formation, effective suppression of CO production, and intrinsic thermodynamic stability of the single-atom configuration. Mechanistic analysis reveals that dopant-host electronic coupling selectively stabilizes OCHO* intermediates while destabilizing the competing COOH* pathway, thereby governing product selectivity at the atomic scale. This work establishes a unified framework for stability-activity-selectivity co-optimization in SAA catalysts and provides transferable design principles for selective CO 2 electroreduction.