Sub-millisecond microfluidic mixers coupled to time-resolved in situ photonics to study ultra-fast reaction kinetics: the case of ultra-small gold nanoparticle synthesis

We report a continuous microreactor platform achieving sub-millisecond homogeneous reagent mixing (similar to 300 mu s) for a time-resolved study on the synthesis of ultra-small gold nanoparticles (NPs). The microreactor (coupled with small angle X-ray scattering, UV-vis, and X-ray absorption spectroscopy for in situ and in operando characterizations), operates within mixing time frames below system characteristic times, providing a unique opportunity to deepen the comprehension of reaction and phase transition pathways with unprecedented details. The microreactor channel length can be approximated to a given reaction time when operated in continuous mode and steady state. As a result, the system can be statically investigated, eliminating technique-dependent probing time constraints and local inhomogeneities caused by mixing issues. We have studied Au(0) NP formation kinetics from Au(iii) precursors complexed with oleylamine in organic media, using triisopropylsilane as a reducing agent. The existence of Au(iii)/Au(i) prenucleation clusters and the formation of a transient Au(i) lamellar phase under certain conditions, before the onset of Au(0) formation, have been observed. Taking advantage of the high frequency time-resolved information, we propose and model two different reaction pathways associated with the presence or absence of the Au(i) lamellar phase. In both cases, non-classical pathways leading to the formation of NPs are discussed.