Prospects for the incorporation of cobalt into α-Fe₂O₃ nanorods during hydrothermal synthesis

Abstract

A feasibility study on the incorporation of cobalt into α-Fe₂O₃ nanorods (NRs) during hydrothermal synthesis (HS) is presented as a function of FeCl₃ and CoCl₂ concentration, phosphate surfactant concentration and pH value, with samples assessed using X-ray diffractometry, transmission electron microscopy, selected area electron diffraction and energy dispersive X-ray analysis. No evidence was found for the incorporation of cobalt into α-Fe₂O₃ NRs at low pH, whilst synthesis at intermediate and high pH values favoured the formation of CoFe₂O₄ NPs. The critical role of pH value over the precipitation, size and phase purity of the nanostructured reaction products is emphasised. At pH ~2, large, well crystalline α-Fe₂O₃ nanoparticles (NPs) and NRs were grown from FeCl₃ solution in the absence and presence of phosphate, respectively, whilst no evidence was found for Co precipitation or incorporation in α-Fe₂O₃ following HS in the presence of CoCl₂. At pH ~8, smaller α-Fe₂O₃ NPs, as well as Co₃O₄ and CoFe₂O₄ NPs were synthesised from FeCl₃, CoCl₂, or a mixture thereof. HS at pH ~12 produced a mixture of larger CoFe₂O₄ NPs and α-Fe₂O₃ NPs depending on the Fe:Co molar ratio. The formation of intermediate metastable (oxy)hydroxide phases is considered pH dependent, providing for a variety of different reaction pathways. Further, inclusion of preformed Co₃O₄ and CoFe₂O₄ NPs to the FeCl₃ solution at pH ~2 in the presence of phosphate surfactant resulted in the synthesis of α-Fe₂O₃ NRs with residual Co₃O₄ and CoFe₂O₄ NPs attached to their surfaces. The CoFe₂O₄ NPs encouraged local dissolution leading to the formation of α-Fe₂O₃ NR surface corrugations.