Unveiling the Degradation Chemistry of Fibrous Red Phosphorus under Ambient Conditions

Abstract

The practical applications of fibrous red phosphorus (FRP), an emerging quasi-one-dimensional material, might be hindered by its environmental instability. Although other phosphorus allotropes such as white phosphorus, violet phosphorus, and black phosphorus are reported unstable under ambient conditions, the chemical stability of FRP remains unexplored. Herein, we investigate the degradation chemistry of FRP by combining experimental study and density functional theory calculations. The results reveal that both oxygen and water can react with FRP, while light illumination may accelerate these reactions. Furthermore, the degradation behavior of FRP shows a pseudo-first-order reaction in oxygenated water, while it follows a pseudo-zero-order reaction in deoxygenated water. Such different reaction kinetics originates from the preferable dissociative adsorption behaviors of O 2 molecular and H 2 O molecular on a FRP surface or at a FRP edge. A covalent modification approach using an aryl diazonium salt was adopted to passivate the surface of FRP flakes and significantly enhance their stability in air.

RETRACTED: Two-Dimensional Violet Phosphorus P11: A Large Band Gap Phosphorus Allotrope

“…The allotropes of phosphorus remain exciting for decades due to the continual discovery of new 2D materials. − Experiments and theory calculations continue to discover and predict more 2D materials. − In this work, a new phosphorus allotrope violet-P 11 was grown as large crystals by a novel method that combines high-temperature salt flux and bismuth metal. The newly discovered layered violet phosphorus P 11 has a band gap of 2.0(1) eV for bulk crystals, coupled with good bulk stability and high predicted electron mobility (1307.32 cm 2 V –1 s –1 ).…”

Solution phase synthesis of the less-known Form II crystalline red phosphorus

“…27 The nanorod II was occasionally abbreviated as n2, 5 but sometimes referred to as Type II as well. 15,16,75,76 This may erroneously lead to confusion between nanorod II and crystalline Form II. 15,16,75 Thus, it is necessary to clarify that the three nanorods and Form I to III are two sets of completely different red phosphorus allotropes, in which case there is no solid evidence showing that Form I to III with limited structural information could match any of the three nanorods whose lattice parameters and atomic coordinates are well defined.…”

Chemical Vapor Transport Synthesis of Fibrous Red Phosphorus Crystal as Anodes for Lithium-Ion Batteries

“…In addition, the 2p 1/2 and 2p 3/2 peaks at 130.0 eV and 131.4 eV, respectively, correspond to the P-P bond [ 18 ]. The peak at 134.7 eV corresponds to the P-O bond ( Figure 2 d), which indicates that FP undergoes oxidation in air, which is identical to the oxidative nature of BP [ 26 , 27 ].…”