Investigation on the Nucleation Stage of Palladium Nanoparticles Using a Microfluidic Droplet Generator Integrated with In Situ Sol‐Gel Quencher

Abstract The nanoparticle (NP) synthesis undergoes stepwise processes starting from the input metal ions: nucleation, coalescence, ripening, and growth. Considering the whole process is completed in a very short time, the conventional flask‐scale method, which requires at least minutes, is not adequate to trace the mechanism of NP nucleation. In this study, a microfluidic droplet generator is developed, which is capable of in situ sol–gel polymerization for synthetic reaction quenching. As a model, palladium (Pd) NPs are synthesized within microdroplets, and the reaction time is controlled by tuning the length of the microchannel. In the microfluidic design, the outmost microchannel is incorporated, in which tetraethyl orthosilicate (TEOS) dissolved in ethanol is injected. The generated droplets are merged to the outmost flow under the variety of time interval (50 to 5,000 ms), so that the tens of milliseconds observation on NP nucleation is conducted via flash‐like sol–gel quenching. Based on the result analysis, the seeds of Pd NPs have undergone slight size fluctuation and then a thermodynamically stable aggregation/coalescence step within 5 s before moving into the growth stage. This microfluidic platform permits the study of the fundamental and initial stage of the NP synthesis, which cannot be approached by the conventional methodology.