The Effects of Halogen (Cl, Br) Decorating on the Gas Adsorption Behaviors of the Pristine Black Phosphorene: A First-Principles Study

Abstract

As a novel two-dimensional (2D) material, black phosphorene (BP) finds wide applications in gas adsorption and detection devices due to its distinctive optical, thermoelectric, and surface properties. However, numerous studies have demonstrated that BP exhibits strong selectivity towards gas adsorption and displays significant affinity towards gas molecules containing the element N, thereby greatly impeding its utilization in gas detection. To partially compensate for this deficiency, this study investigates the impact of halogen atom decoration on the adsorption behavior of BP towards CO2, H2O, and O2 molecules. Furthermore, a comparison is made between the variations in gas adsorption energy with and without decorated halogen atoms. The results showed that the adsorbates of CO2, H2O, and O2 molecules and halogen atoms (Cl, Br) adsorbed at the top (T) site of BP was much stronger than those at the bridge (B) and the hollow (H) sites of the P-P bond of BP, owing to their low adsorption energies. After the t position of BP is modified by the halogen (Cl, Br) atom, the optimal adsorption of CO2 changes from −0.85 eV to −1.70 eV (Cl) and −1.64 eV (Br), and the optimal adsorption of H2O changes from −0.72 eV to −1.48 eV (Cl) and −1.23 eV (Br), respectively. The adsorption properties were significantly enhanced. That is to say, the gas adsorption properties of BP have been largely improved by halogen Cl (Br) atoms decorating.