2016/10/24 by Andrey A. Kistanov, Andrey A Kistanov, Yongqing Cai +5 · 2 citations
Chemistry · Energy · Materials Science · Physics and Astronomy · #2D Materials and Applications #Advanced Photocatalysis Techniques #Antibonding molecular orbital #Atomic orbital #Chemical physics #Chemistry #Computational chemistry #Crystallography #Electron #Graphene #Lone pair #MXene and MAX Phase Materials #Materials science #Molecule #Nanotechnology #Phosphorene #Physics #Vacancy defect #cond-mat.mtrl-sci
paper · pdf · doi:10.1088/2053-1583/4/1/015010
published as 2D Mater. 4 (2017) 015010
arxiv created 2016/10/24 · openalex publication_date 2016/11/03 · openalex created_date 2016/11/04 · arxiv updated 2016/11/08 · openalex updated_date 2026/08/05
Abstract The poor structural stability of phosphorene in air was commonly ascribed to humidity and oxygen molecules. Recent exfoliation of phosphorene in deoxygenated water promotes the need to re-examine the role of H 2 O and O 2 molecules. Considering the presence of high population of vacancies in phosphorene, we investigate the interaction of H 2 O and O 2 molecules with vacancy-contained phosphorene using first-principles calculations. In contrast to the common notion that physisorbed molecules tend to have a stronger adsorption at vacancy sites, we show that H 2 O has nearly the same adsorption energy at the vacancy site as that at the perfect one. Charge transfer analysis shows that O 2 is a strong electron scavenger, which transfers the lone-pair electrons of the phosphorus atoms to the 2 π * antibonding orbital of O 2 . As a result, the barrier for the O–O bond splitting to form O–P bonds is reduced from 0.81 eV at the perfect site to 0.59 eV at the defect site, leading to an about 5000 faster oxidizing rate at the defect site than at the perfect site at room temperature. Hence, our work reveals that the vacancy in phosphorene shows a stronger oxygen affinity than the perfect phosphorene lattice site. Structural degradation of phosphorene due to oxidization may occur rapidly at edges and grain boundaries where vacancies tend to agglomerate.