Quantitative Analysis of Different Formation Modes of Platinum Nanocrystals Controlled by Ligand Chemistry

Well-defined metal nanocrystals play important roles in various fields, such as catalysis, medicine, and nanotechnology. They are often synthesized through kinetically controlled process in colloidal systems that contain metal precursors and surfactant molecules. The chemical functionality of surfactants as coordinating ligands to metal ions however remains a largely unsolved problem in this process. Understanding the metal-ligand complexation and its effect on formation kinetics at the molecular level is challenging but essential to the synthesis design of colloidal nanocrystals. Herein we report that spontaneous ligand replacement and anion exchange control the form of coordinated Pt-ligand intermediates in the system of platinum acetylacetonate [Pt(acac)₂], primary aliphatic amine, and carboxylic acid ligands. The formed intermediates govern the formation mode of Pt nanocrystals, leading to either a pseudo two-step or a one-step mechanism by switching on or off an autocatalytic surface growth. This finding shows the importance of metal-ligand complexation at the prenucleation stage and represents a critical step forward for the designed synthesis of nanocrystal-based materials.