Piece by Piece—Electrochemical Synthesis of Individual Nanoparticles and their Performance in ORR Electrocatalysis

The impact of individual HAuCl₄ nanoreactors is measured electrochemically, which provides operando insights and precise control over the modification of electrodes with functional nanoparticles of well‐defined size. Uniformly sized micelles are loaded with a dissolved metal salt. These solution‐phase precursor entities are then reduced electrochemically—one by one—to form nanoparticles (NPs). The charge transferred during the reduction of each micelle is measured individually and allows operando sizing of each of the formed nanoparticles. Thus, particles of known number and sizes can be deposited homogenously even on nonplanar electrodes. This is demonstrated for the decoration of cylindrical carbon fibre electrodes with 25±7 nm sized Au particles from HAuCl₄‐filled micelles. These Au NP‐decorated electrodes show great catalyst performance for ORR (oxygen reduction reaction) already at low catalyst loadings. Hence, collisions of individual precursor‐filled nanocontainers are presented as a new route to nanoparticle‐modified electrodes with high catalyst utilization.