Formation of Iron Phosphide Nanobundles from an Iron Oxyhydroxide Precursor

Iron phosphide (FeP) nanoparticles have excellent properties such as fast charge transfer kinetics, high electrical conductivity, and high stability, making them a promising catalyst for hydrogen evolution reaction (HER). A challenge to the wide use of iron phosphide nanomaterials for this application is the available synthesis protocols that limit control over the resulting crystalline phase of the product. In this study, we report a method for synthesizing FeP through a solution-based process. Here, we use iron oxyhydroxide (β-FeOOH) as a cost-effective, environmentally friendly, and air-stable source of iron, along with tri-n-octylphosphine (TOP) as the phosphorus source and solvent. FeP is formed in a nanobundle morphology in the solution phase reaction at a temperature of 320 °C. The materials were characterized by pXRD and transmission electron microscopy (TEM). The optimization parameters evaluated to produce the phosphorus-rich FeP phase included the reaction rate, time, amount of TOP, and reaction temperature. Mixtures of Fe₂P and FeP phases were obtained at shorter reaction times and slow heating rates (4.5 °C /min), while longer reaction times and faster heating rates (18.8 °C/min) favored the formation of phosphorus-rich FeP. Overall, the reaction lever that consistently yielded FeP as the predominant crystalline phase was a fast heat rate.