A Mechanistic Study of the Multiple Roles of Oleic Acid in the Oil‐Phase Synthesis of Pt Nanocrystals

Abstract Oleic acid (OAc) is commonly used as a surfactant and/or solvent for the oil‐phase synthesis of metal nanocrystals but its explicit roles are yet to be resolved. Here, we report a systematic study of this problem by focusing on a synthesis that simply involves heating of Pt(acac) 2 in OAc for the generation of Pt nanocrystals. When heated at 80 °C, the ligand exchange between Pt(acac) 2 and OAc leads to the formation of a Pt II –oleate complex that serves as the actual precursor to Pt atoms. Upon increasing the temperature to 120 °C, the decarbonylation of OAc produces CO, which can act as a reducing agent for the generation of Pt atoms and thus formation of nuclei. Afterwards, several catalytic reactions can take place on the surface of the Pt nuclei to produce more CO, which also serves as a capping agent for the formation of Pt nanocrystals enclosed by {100} facets. The emergence of Pt nanocrystals further promotes the autocatalytic surface reduction of Pt II precursor to enable the continuation of growth. This work not only elucidates the critical roles of OAc at different stages in a synthesis of Pt nanocrystals, but also represents a pivotal step forward toward the rational synthesis of metal nanocrystals.