Unraveling chemical processes during nanoparticle synthesis with liquid phase electron microscopy and correlative techniques.

Liquid phase transmission electron microscopy (LPTEM) has enabled unprecedented direct real time imaging of physicochemical processes during solution phase synthesis of metallic nanoparticles. LPTEM primarily provides images of nanometer scale, and sometimes atomic scale, metal nanoparticle crystallization processes, but provides little chemical information about organic surface ligands, metal-ligand complexes and reaction intermediates, and redox reactions. Likewise, complex electron beam-solvent interactions during LPTEM make it challenging to pinpoint the chemical processes, some involving exotic highly reactive radicals, impacting nanoparticle formation. Pairing LPTEM with correlative solution synthesis, chemical analysis, and theoretical modeling represents a powerful approach to gain a holistic understanding of the chemical processes involved in nanoparticle synthesis. In this feature article, we review recent work by our lab and others that has focused on elucidating chemical processes during nanoparticle synthesis using LPTEM and correlative chemical characterization and modeling, including mass and optical spectrometry, fluorescence microscopy, solution chemistry, and reaction kinetic modeling. In particular, we show how these approaches enable investigating redox chemistry during LPTEM, polymeric and organic capping ligands, metal deposition mechanisms on plasmonic nanoparticles, metal clusters and complexes, and multimetallic nanoparticle formation. Future avenues of research are discussed, including moving beyond electron beam induced nanoparticle formation by using light and thermal stimuli during LPTEM. We discuss prospects for real time LPTEM imaging and online chemical analysis of reaction intermediates using microfluidic flow reactors.