Controlling nanoparticle formation from the onset of nucleation through a multi-step continuous flow approach

Abstract

Hypothesis: Metallic nanoparticles of various shapes and sizes can be synthesised through a diversity of bottom-up pathways, such as precipitation induced by chemical reduction. Varying composition, by adjusting concentrations or adding/replacing species, is the predominant strategy to tune nanoparticles structures. However, controlling time down to the onset of precipitation, nucleation, should also provide a powerful means to control nanostructuration.

Experiments: We perform sequential reagent additions with a time resolution down to the millisecond. We use a millifluidic continuous flow setup consisting of tangential mixers in series, which allows flow rates up to dozens of litres per hour. We systematically vary both addition order and delay for each reagent involved in the synthesis of silver nanoplates. The resulting dispersions are compared using UV-visible spectroscopy, transmission electron microscopy and small-angle X-ray scattering.

Findings: We show that synthesis pathways differing only in the order of sub-second additions lead to drastically different synthetic outcomes. Silver nanoparticles of different shapes and sizes, displaying an array of plasmonic colours, are synthesised at the same final composition by tuning the composition pathways along time. Our results unlock a previously inaccessible portion of the space of parameters, which will lead to an enhanced structural diversity, control and understanding of nanoparticles syntheses.

Keywords: Anisotropy; Continuous flow; Millifluidic; Nanoparticle; Nanoplates; Rapid mixer; Sequential addition; Silver; Synthesis; Time.