Preparation and Characterization of a Material of Composition BiP (Bismuth Phosphide) and Other Intergroup 15 Element Phases

Abstract

The reaction between equimolar quantities of BiCl3 and the silylphosphine P(SiMe3)3 in toluene or THF (tetrahydrofuran) solution affords a black precipitate with the composition of bismuth phosphide, BiP, which has been examined by EDXA, SEM, XPS, powder XRD, solid-state 31P NMR spectroscopy, and elemental analysis. Alternative possible routes to BiP involving the reactions between Na3P and BiCl3 and between Bi(NMe2)3 and P(SiMe3)3 have also been investigated, both of which afford black powders of composition close to BiP, although in the latter case there is some contamination with bismuth metal. Analogous reactions with either SbCl3 or AsCl3 and P(SiMe3)3 afford black and dark brown precipitates, respectively, which are formulated as the materials antimony phosphide, SbP, and arsenic phosphide, AsP, on the basis of similar analyses. Preliminary experiments have also shown that the related arsenides, BiAs and SbAs, can be prepared from reactions between either BiCl3 or SbCl3 and the silylarsine As(SiMe3)3, and that a ternary phase with the composition BiSbP2 is formed in the reaction between BiCl3, SbCl3, and P(SiMe3)3 in a 1:1:2 mole ratio. A material of composition close to elemental phosphorus is obtained from the reaction between PCl3 and P(SiMe3)3.

The chemical bond as an emergent phenomenon

“…The compounds were chosen to cover a broad range of electronegativity variation; note that AsP, BiAs and SbAs solids have been reported experimentally. 79 Since the phase diagram is constructed with two arsenics in mind, we must readjust our results to account for the difference in the atomic size and mass of the diatomic compounds from elemental arsenic. In view of our results for mixed-pnictogen trimers from the preceding Section, we used the ionic radii as the rescaling factor for the length.…”

Nanoscale Metal Phosphide Phase Segregation to Bi/P Core/Shell Structure. Reactivity as a Source of Elemental Phosphorus

“…[34][35][36] Thus, we envisaged to prepare Bi/P NPs under smoother conditions in order to control the nanosized Bi/P materials, avoiding the formation of bulk materials. 20 For this purpose, we selected the reaction applied by Allen and coworkers, 21 relying on R 3 Si-X elimination as a driving force and using stabilizers to control the growth of nanoparticles in order to prevent precipitation of bulk material (Scheme 1). We have previously proved that ligands such as CD or PPP allow nanoparticles stabilization by coordination at the metal surface, [37][38][39][40][41] while polymers such as PVP provide steric stabilization 5 for nanoparticles of different transition metals.…”

“…Following this strategy, Allen et al reported the formation of an insoluble black material at room temperature from the reaction of BiCl 3 with P(SiMe 3 ) 3 . 21 A range of analyses were carried out to characterize this material, including SEM, EDX, XRD, XPS, thermogravimetric analyses (TGA and DSC) as well as conductivity measurements. These analyses prompted the authors to propose the formation of amorphous hybrid "BiP" materials.…”

“…In other words, is "nanoalloy-BiP" stable or can phase segregation (hitherto unprecedented) at nanosized scale be observed to form core-shell and/or independent Bi and P nanostructures? Furthermore, if "nanoalloy-BiP" is stable enough, the semiconductor nature of bulk BiP shown by Allen and coworkers 21 should lead to desirable size dependent properties.…”

I. Magnesium Promoted Coupling of Carbodiimides and Terminal Acetylenes, II. Bismuth Compounds Supported by Di(amido) Chelating Ligands

“…Bismuth phosphide, BiP, is of interest in materials science as an isoelectronic analogue of PbS, a common semiconducting material. 64 Despite this, few examples of structurally characterised bismuth phosphide compounds have been reported in the literature (Figure 1.3), and the majority contain silyl-substituted phosphides. The…”