XPS analysis of oleylamine/oleic acid capped Fe3O4 nanoparticles as a function of temperature

Fe3O4 nanoparticles were synthesized solvothermally using oleylamine and oleic acid as surfactants, and the surface composition was determined by X-ray photoelectron spectroscopy (XPS) as a function of temperature, from the as-synthesized nanoparticles to those annealed under vacuum at 883K. XPS of the as-synthesized nanoparticles was consistent with a surface composition of stoichiometric Fe3O4 capped with a mixture of monodentate carboxylate and chemisorbed amine, although the surface was enriched in carboxylate over that present in the synthesis reaction concentration. The method of synthesis and capping surfactants effectively protect the nanoparticle surface from detectable hydroxylation. The capped nanoparticle is stable for 24 h at 373K, and the capping agents persist to 523K, at which point the oleylamine decomposes to desorb nitrogen and deposit aliphatic carbon from the capping tail. The carboxylate decomposes over a wider range and at 883K some carboxylate remains on the surface. The iron oxide nanoparticle undergoes substantial reduction as the aliphatic capping tail decomposes. While the as-introduced nanoparticle is essentially Fe3O4, reduction to FeO, Fe and Fe3C occurs sequentially as the nanoparticle is heated to higher temperatures.