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

Abstract

We report for the first time the synthesis of well-defined bismuth/phosphorus nanoparticles (Bi/P NPs) based on silyl-halide elimination, by reaction of BiX 3 (X= I, Cl) and P(SiMe 3 ) 3 in the presence of different types of stabilizing ligands, such as cinchonidine, 4-(3phenylpropyl)pyridine and polyvinylpyrrolidone. This synthetic approach led to spherical, small and monodisperse nanoparticles (mean diameter ca. 2.0-2.5 nm determined by TEM). Wideranging characterization of these nanoparticles including TEM, PXRD and SAXS, and several spectroscopic techniques, like X-ray fluorescence, IR and solid state NMR, proved the formation of a core-shell structure constituted by a crystalline Bi(0) core and amorphous P-containing shells, representing a unique case of phase segregation for metal/phosphorus materials reported in the literature. The assessed reactivity of the as-prepared Bi/P NPs evidenced their potential application in the synthesis of phosphine PH 3 in a safer way than the conventional approach using P 4 (white phosphorus) and in a sharp contrast with the reported reactivity of amorphous red phosphorus.

Boosting Potassium Storage Kinetics, Stability, and Volumetric Performance of Honeycomb‐Like Porous Red Phosphorus via In Situ Embedding Self‐Growing Conductive Nano‐Metal Networks

“…As for the un‐etched HPRP@Bi (Figure 2I; Figure S3, Supporting Information), the Bi 3+ peaks showed strong peaks of Bi 4f 5/2 (164.95 eV) and Bi 4f 7/2 (159.65 eV), while the metal Bi 0 peaks showed weak peaks of Bi 4f 5/2 (163.00 eV) and Bi 4f 7/2 (157.60 eV). [ 36 ] This results demonstrate the formation of Bi nanoparticles on HPRP. For the etched depth with 2 nm (Figure 2I), the Bi 3+ peaks in Bi 4f also showed the strong peaks of Bi 4f 5/2 (164.95 eV) and Bi 4f 7/2 (159.65 eV), and the metal Bi 0 peaks also displayed the strong peaks of Bi 4f 5/2 (162.70 eV) and Bi 4f 7/2 (157.35 eV).…”

Bi Works as a Li Reservoir for Promoting the Fast‐Charging Performance of Phosphorus Anode for Li‐Ion Batteries

“…The P 2p XPS spectra can be deconvoluted into 2p 1/2 , 2p 3/2 peaks of P‐P, P‐C, and P‐Bi, respectively, as well as P‐O‐C, and P‐O‐Bi bonds. [ 20–24 ] The P‐Bi and P‐C bonds can be also observed in Bi 4f and C 1s XPS spectra of Bi‐P/C, respectively, which are conducive to improve the structural stability and electrochemical performance of Bi‐P/C composite.…”

High-Quality Circularly Polarized Organic Afterglow from Nonconjugated Amorphous Chiral Copolymers

“…Diastereomeric pairs of cinchonidine ( CD )/cinchonine ( CN ) and quinidine ( QD )/quinine ( QN ) collectively termed as “cinchona alkaloids” are a class of natural chiral molecules derived from cinchona bark and have shown a wide range of applications in the catalysis and treatment of malaria. − However, the chiral properties of cinchona alkaloids in luminescence have been seldom studied, mainly due to their weak emissions. , The molecules of cinchona alkaloids contain four parts: quinuclidine base, quinoline ring, hydroxy-substituted stereogenic linkage with polychiral carbons, and vinyl group (Figure a). The N atom of the quinuclidine moiety can interact with other molecules through hydrogen bonding, and the conjugated quinoline unit with π-electron and N-lone pair electron may promote the photoactivities and intermolecular interactions. , The stereogenic configurations of these chiral C atoms could define the sense of enantioselectivity in emission, while the vinyl group will react with other vinyl monomers in forming copolymers.…”