Homogeneous Nanoparticles of Multimetallic Phosphides via Precursor Tuning: Ternary and Quaternary M2P Phases (M = Fe, Co, Ni).

Transition metal phosphides (TMPs) are a highly investigated class of nanomaterials due to their unique magnetic and catalytic properties. Although robust and reproducible synthetic routes to narrow polydispersity monometallic phosphide nanoparticles (M2P; M = Fe, Co, Ni) have been established, the preparation of multimetallic nanoparticle phases (M2-x M' x P; M, M' = Fe, Co, Ni) remains a significant challenge. Colloidal syntheses employ zero-valent metal carbonyl or multivalent acetylacetonate salt precursors in combination with trioctylphosphine as the source of phosphorus, oleylamine as the reducing agent, and additional solvents such as octadecene or octyl ether as "noncoordinating" cosolvents. Understanding how these different metal precursors behave in identical reaction environments is critical to assessing the role the relative reactivity of the metal precursor plays in synthesizing complex, homogeneous multimetallic TMP phases. In this study, phosphorus incorporation as a function of temperature and time was evaluated to probe how the relative rate of phosphidation of organometallic carbonyl and acetylacetonate salt precursors influences the homogeneous formation of bimetallic phosphide phases (M2-x M' x P; M, M' = Fe, Co, Ni). From the relative rate of phosphidation studies, we found that where reactivity with TOP for the various metal precursors differs significantly, prealloying steps are necessary to isolate the desired bimetallic phosphide phase. These insights were then translated to establish streamlined synthetic protocols for the formation of new trimetallic Fe2-x-y Ni x Co y P phases.