Controlled Design of Phase- and Size-Tunable Monodisperse Ni₂P Nanoparticles in a Phosphonium-Based Ionic Liquid through Response Surface Methodology

Nanoparticles of nickel phosphide are finding wide ranging utility as catalysts for hydrodesulfurization, hydrogen evolution reaction, and hydrodeoxygenation of bio-oils. Herein, we present a methodology to tailor monodisperse nickel phosphide nanoparticles in terms of size and phase through the use of a statistical response surface methodology. Colloidal nickel phosphide nanoparticles were synthesized by replacing octadecene (ODE), a commonly used organic solvent, by a more sustainable phosphonium-based ionic liquid (IL). The replacement of ODE with the phosphonium-based IL resulted in faster crystallization at lower temperatures to yield phase-pure, monodisperse Ni2P nanoparticles. Using a first-order design, the PPh3/Ni precursor ratio was identified as the most critical factor influencing the resulting size and phase of the nanoparticles. Optimization using a Doehlert matrix for second-order design yielded a second-degree polynomial equation used to predict the mean diameter of the nanoparticles (over a range of 4–12 nm) as a function of the PPh3/Ni precursor ratio and the temperature used during synthesis. The resulting model was validated by performing reactions using randomly chosen sets of conditions; the experimentally determined nanoparticle sizes were in excellent agreement with the theoretical sizes predicted by our model. This demonstrates the utility of a multivariate experimental design as a powerful tool in the development of synthetic strategies toward the preparation of colloidal nanoparticles with highly controlled size, size distribution, and phase