Theory-Guided Synthesis of Stable Low-Nuclearity Cluster Catalysts via Atom-Stabilizer Locking

Low-nuclearity clusters (LNCs), offering maximum atom utilization and distinct electronic structures, have attracted widespread interest across numerous fields. However, their inherent thermodynamic instability due to high surface free energy severely impedes their practical applications, especially in heterogeneous catalysis. Here, we report a theory-guided, general synthesis strategy to overcome this challenge. By integrating computational modeling of 14 single-atom and 20 homo/heteronuclear dimer configurations on nitrogen-doped carbon with experimental verification via atom-by-atom fabrication, we demonstrate that high adsorption energies alone are insufficient to prevent LNC aggregation under hydrogen at elevated temperatures, limiting their applications in hydrogen-involved catalytic reactions. Instead, incorporating an atom stabilizer (e.g., Co or Cu atoms), capable of forming robust bonds with the support in hydrogen, into LNCs is essential. This strategy has proved universal; six dimeric and three trimeric LNC catalysts with exceptionally high stability in hydrogen above 400 °C were successfully synthesized, paving a practical way for the rational design of ultrastable LNC catalysts.