Reaction Atmosphere-Controlled Thermal Conversion of Ferrocene to Hematite and Cementite Nanomaterials─Structural and Spectroscopic Investigations

Abstract

Recently, we have reported the influence of various reaction atmospheres on the solid-state reaction kinetics of ferrocene, where oxalic acid dihydrate was used as a coprecursor. In this light, present study discusses on the nature of decomposed materials of the solid-state reactions of ferrocene in O 2 , air, and N 2 atmospheres. The ambient and oxidative atmospheres caused the decomposition to yield pure hematite nanomaterials, whereas cementite nanomaterials along with α-Fe were obtained in N 2 atmosphere. The obtained materials were mostly agglomerated. Elemental composition of each material was estimated. Using the absorbance data, the energy band gap values were estimated and the related electronic transitions from the observed absorption spectra were explored. Urbach energy was calculated for hematite, which described the role of defects in the decomposed materials. The nanostructures exhibited photoluminescence due to selftrapped states linked to their optical characteristics. Raman spectroscopy of hematite detected seven Raman modes, confirming the rhombohedral structure, whereas the D and G bands were visible in the Raman spectra for cementite. Thus, the reaction atmosphere significantly influenced the thermal decomposition of ferrocene and controls the type of nanomaterials obtained. Plausible reactions of the undergoing solid-state decomposition have been proposed.