On the Use of Laser Fragmentation for the Synthesis of Ligand-Free Ultra-Small Iron Nanoparticles in Various Liquid Environments.

Traditionally, the synthesis of nanomaterials in the ultra-small size regime (1-3 nm diameter) has been linked with the employment of excessive amounts of hazardous chemicals, inevitably leading to significant environmentally detrimental effects. In the current work, we demonstrate the potential of laser fragmentation in liquids (LFL) to produce highly pure and stable iron ultra-small nanoparticles. This is carried out by reducing the size of carbonyl iron microparticles dispersed in various polar solvents (water, ethanol, ethylene glycol, polyethylene glycol 400) and liquid nitrogen. The explored method enables the fabrication of ligand-free iron oxide ultra-small nanoparticles with diameter in the 1-3 nm range, a tight size distribution, and excellent hydrodynamic stability (zeta potential > 50 mV). The generated particles can be found in different forms, including separated ultra-small NPs, ultra-small NPs forming agglomerates, and ultra-small NPs together with zero-valent iron, iron carbide, or iron oxide NPs embedded in matrices, depending on the employed solvent and their dipolar moment. The LFL technique, aside from avoiding chemical waste generation, does not require any additional chemical agent, other than the precursor microparticles immersed in the corresponding solvent. In contrast to their widely exploited chemically synthesized counterparts, the lack of additives and chemical residuals may be of fundamental interest in sectors requiring colloidal stability and the largest possible number of chemically active sites, making the presented pathway a promising alternative for the clean design of new-generation nanomaterials.