A General and Flexible Synthesis of Transition-Metal Polyphosphides via PCl₃ Elimination

Abstract

We report a straight-forward, solvent-free moderate temperature synthetic method for the production of several phosphorus-rich transition-metal phosphides (orthorhombic FeP2, cubic CoP3, cubic NiP2, monoclinic CuP2, and monoclinic PdP2). Notably, this synthetic approach provides facile access to the high-temperature/high-pressure cubic phase of NiP2. The general synthetic strategy involves the direct reaction of anhydrous metal dichloride pressed pellets with molecular P4 vapor or solid−solid reactions between the metal dichloride and red phosphorus that are intimately mixed into pellets. Both of these reaction strategies involve the evolution of a volatile PCl3 byproduct and produce crystalline MP x (x ≥ 2) at moderate temperatures of 500−700 °C. The pellets remain intact throughout the synthesis, and the macrostructure of the MP x products resembles that of the reactant pellets. By varying the phosphorus source, the percentage of the pellet precursor mass that is retained in the final metal phosphide pellet products changes, which influences the morphology and microstructure of the final phosphide pellet.

Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals

“…38−48 Nanocrystalline nickel phosphides are also of interest as electrodes for lithium ion batteries. 49 Several methods exist for the synthesis of nickel phosphide nanocrystals (mostly Ni 2 P and Ni 12 P 5 ), including chemical vapor deposition, 50 solution phase (colloidal) synthesis, 16,51−70 solvothermal synthesis, 71−77 electrosynthesis, 78 hydrothermal synthesis, 79 solid-state synthesis, 80 microwave synthesis, 81 and temperature-programmed phosphate reduction. 82 These methods yield nickel phosphide nanocrystals with various morphologies.…”

One-pot synthesis of carbon-coated Ni5P4 nanoparticles and CoP nanorods for high-rate and high-stability lithium-ion batteries

“…The rare report of nanostructured mono-phosphorus TMPs is mainly resulted from their high nucleation energy and the lack 75 of suitable synthetic routes. 25,26 Hence, to obtain carbon coated nanostructured mono-phosphorus TMPs is highly potential to further improve their rate capability.…”

Stability and electronic structure of the Co–P compounds from first-principle calculations

“…Due to excellent properties of Co-P compounds, the synthesis technologies have been extensively investigated [16][17][18] and the structural analysis has also been conducted in order to understand the intrinsic mechanism [19][20][21][22][23]. By the linear muffin-tin orbital method in the atomic sphere approximation (LMTO-ASA), it has been found that Co 2 P with hexagonal structure exhibits ferromagnetism while Co 2 P with orthorhombic structure reveals non-magnetic character [19].…”