Environmental STEM Study of the Oxidation Mechanism for Iron and Iron Carbide Nanoparticles

The oxidation of solution-synthesized iron (Fe) and iron carbide (Fe₂C) nanoparticles was studied in an environmental scanning transmission electron microscope (ESTEM) at elevated temperatures under oxygen gas. The nanoparticles studied had a native oxide shell present, that formed after synthesis, an ~3 nm iron oxide (Fe_xO_y) shell for the Fe nanoparticles and ~2 nm for the Fe₂C nanoparticles, with small void areas seen in several places between the core and shell for the Fe and an ~0.8 nm space between the core and shell for the Fe₂C. The iron nanoparticles oxidized asymmetrically, with voids on the borders between the Fe core and Fe_xO_y shell increasing in size until the void coalesced, and finally the Fe core disappeared. In comparison, the oxidation of the Fe₂C progressed symmetrically, with the core shrinking in the center and the outer oxide shell growing until the iron carbide had fully disappeared. Small bridges of iron oxide formed during oxidation, indicating that the Fe transitioned to the oxide shell surface across the channels, while leaving the carbon behind in the hollow core. The carbon in the carbide is hypothesized to suppress the formation of larger crystallites of iron oxide during oxidation, and alter the diffusion rates of the Fe and O during the reaction, which explains the lower sensitivity to oxidation of the Fe₂C nanoparticles.