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 O2 molecular and H2O 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.