Defects engineering promotes the electrochemical hydrogen evolution reaction property of phosphorene surface

Abstract

Compared with Pt and MoS2, the pristine phosphorene surface is limited in the development of electrocatalysts for hydrogen evolution reaction (HER) due to the much lower HER activity. Herein, the HER properties of defective phosphorene are studied based on the first-principle calculations. Defect engineering can break the inertia of phosphorene surface, enhance the interactions between H∗ and adsorption sites, and promote the HER activity of phosphorene surface obviously, as a result of that the defective phosphorene structures SV-(55|66), DV-(5|8|5)-1, DV-(12|12), DV-(9|4|9), DV-(55|66)-1 and DV-(55|66)-2 present the better or equivalent HER activity compared to Pt (111). In particular, the monoatomic defect SV-(55|66) shows the far better HER activity than Pt (111), and its energy barrier for Tafel reaction in the H2 desorption process decreases by 47.2% and 17.1% by comparison with those of pristine phosphorene for Tafel and Heyrovsky reaction, respectively. This study can provide a novel way to promote the HER activity of phosphorene surface via defect engineering at atomic level and a theoretical basis for designing metal-free phosphorene based electrocatalysts with high catalytic activity and stability.