Phosphorus Rich d¹⁰ Ion Polyphosphides and Selected Materials

Abstract

Polyphosphides composed by late transition metal ions with closed d10 shells are subject of this review. Recent progress has been made during the past years in this field and many new compounds have been discovered. The spectrum of compounds extends from classical binary and ternary compounds, adduct phases of metal halides and molecular species to composites of intermetalloid clusters and molecular anion substructures. Phosphorus is highly reactive to late transition metals forming d10 ions and they entirely react to a plenthora of materials. Only a handful of elements do not form binary compounds with phosphorus and the number is decreasing. This review is focussed on synthetic procedures and the structure property relations of d10 ion polyphosphides. A brief overview is also given to the progress in phosphorus allotrope chemistry and their perspectives and applications. Especially black phosphorus as active material for batteries and its de‐laminated form “phosphorene” is added.

Computational Investigation of Copper Phosphides as Conversion Anodes for Lithium-Ion Batteries

“…While Cu 3 P 11 is unlikely to be used as a Li-ion battery anode, given its high P content, and therefore susceptibility to volume expansion, it could be a novel phase to consider within the Cu–P phase diagram. CuP 10 was identified experimentally by preparing Cu 2 P 7 in excess P; 70 given the structural similarity between Cm –Cu 3 P 11 and C 2/ m –Cu 2 P 7 shown in Figure 2 , it is possible that Cm –Cu 3 P 11 is also formed in excess P. Using the PXRD patterns presented in Figure 3 , it may be possible to distinguish the Cm –Cu 3 P 11 phase from C 2/ m –Cu 2 P 7 experimentally, from the change in the peak intensity at 16° and peak differences at 2θ values < 20°; however, further experimental analysis is likely required given the low intensity of this peak.…”

Vapor growth of binary and ternary phosphorus-based semiconductors into TiO2 nanotube arrays and application in visible light driven water splitting

“…[8][9][10][11][12][13] Polyphosphides are an intriguing class of low band gap semiconductors for this purpose. 14,15 We selected three polyphosphides, namely NaP 7 , SnIP (ranging from 1.71-1.86 eV) [16][17][18] and (CuI) 3 P 12 (2.84 eV, own measurement see below) because of their different band gaps and their ability to be synthesized in a mineralizer-assisted transport reaction. 19,20 NaP 7 , a 2 eVsemiconductor material, plays a crucial role in the sodication and desodication processes in sodium ion batteries.…”

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

“…Most polyphosphides prepared by solid‐state methods are insoluble in common organic solvents and exhibit very high chemical stability . In contrast, the solution methods furnish soluble and reactive polyphosphide fragments, many of which were not detected in the solid‐state reactions.…”