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.