Direct <i>in Situ</i> Observation of Nanoparticle Synthesis in a Liquid Crystal Surfactant Template

Abstract

Controlled and reproducible synthesis of tailored materials is essential in many fields of nanoscience. In order to control synthesis, there must be a fundamental understanding of nanostructure evolution on the length scale of its features. Growth mechanisms are usually inferred from methods such as (scanning) transmission electron microscopy ((S)TEM), where nanostructures are characterized after growth is complete. Such <i>post mortem</i> analysis techniques cannot provide the information essential to optimize the synthesis process, because they cannot measure nanostructure development as it proceeds in real time. This is especially true in the complex rheological fluids used in preparation of nanoporous materials. Here we show direct <i>in situ</i> observations of synthesis in a highly viscous lyotropic liquid crystal template on the nanoscale using a fluid stage in the STEM. The nanoparticles nucleate and grow to ∼5 nm particles, at which point growth continues through the formation of connections with other nanoparticles around the micelles to form clusters. Upon reaching a critical size (>10–15 nm), the clusters become highly mobile in the template, displacing and trapping micelles within the growing structure to form spherical, porous nanoparticles. The final products match those synthesized in the lab <i>ex situ</i>. This ability to directly observe synthesis on the nanoscale in rheological fluids, such as concentrated aqueous surfactants, provides an unprecedented understanding of the fundamental steps of nanomaterial synthesis. This in turn allows for the synthesis of next-generation materials that can strongly impact important technologies such as organic photovoltaics, energy storage devices, catalysis, and biomedical devices