Real-Time Kinetic Control in the Electrosynthesis of Au₁₀Ag₄ Nanoclusters Via Electrical Signal Modulation

Conventional coinage metal nanocluster (NC) synthesis usually requires premixing reagents in bulk solution until thermodynamic equilibrium, inherently precluding on-demand kinetic manipulation. This study reports the first electrosynthesis of a bimetallic NC with atomic precision, demonstrating real-time kinetic control via electrical signal modulations. Key findings reveal that (1) pulsed potential suppresses cathodic deposition more effectively than constant potential; (2) reaction kinetics exhibit a volcano-shaped dependence on pulse duration, with optimal performance at ∼ 10 s; (3) reactions can be instantaneously switched on or off by applying or removing the potential; and (4) reaction rates are precisely tunable via pulse off-time adjustment. This work establishes an electrical signal-modulated strategy for real-time reaction control, presenting a viable strategy for the programmable and controllable synthesis of metal NCs.