Energetics, Charge Transfer and Magnetism of Small Molecules Physisorbed on Phosphorene

TL;DR

This study uses first-principles calculations to analyze how small molecules interact with phosphorene, revealing charge transfer behaviors and potential applications in gas sensing and hydrogen storage.

Contribution

It provides detailed insights into the energetics, charge transfer, and magnetic properties of various molecules physisorbed on phosphorene, highlighting their potential for sensing and storage.

Findings

O2 and NO2 act as strong acceptors

H2 binds with 0.13 eV, suitable for hydrogen storage

Charge transfer modulates phosphorene's properties

Abstract

First-principles calculations are performed to investigate the interaction of physisorbed small molecules, including CO, H2, H2O, NH3, NO, NO2, and O2, with phosphorene, and their energetics, charge transfer, and magnetic moment are evaluated on the basis of dispersion corrected density functional theory. Our calculations reveal that CO, H2, H2O and NH3 molecules act as a weak donor, whereas O2 and NO2 act as a strong acceptor. While NO molecule donates electrons to graphene, it receives electrons from phosphorene. Among all the investigated molecules, NO2 has the strongest interaction through hybridizing its frontier orbitals with the 3p orbital of phosphorene. The nontrivial and distinct charge transfer occurring between phosphorene and these physisorbed molecules not only renders phosphorene promising for application as a gas sensor, but also provides an effective route to modulating the polarity and density of carriers in phosphorene. In addition, the binding energy of H2 on phosphorene is found to be 0.13 eV/H2, indicating that phosphorene is suitable for both stable room-temperature hydrogen storage and its subsequent facile release.