Tuning the Electrocatalytic Properties of Black and Gray Arsenene by Introducing Heteroatoms

[Image: see text] On the basis of density functional theory calculations, we explored the catalytic properties of various heteroatom-doped black and gray arsenene toward the oxygen reduction reaction (ORR), the oxygen evolution reaction (OER), and the hydrogen evolution reaction (HER). The calculation results show that pristine black (b-As) and gray arsenene (g-As) exhibit poor catalytic performance because of too weak intermediate adsorption. Heteroatom doping plays a key role in optimizing catalytic performance. Among the candidate dopants O, C, P, S, and Sb, O is the most promising one used in arsenene to improve the ORR and OER catalytic performance. Embedding O atoms could widely tune the binding strength of reactive intermediates and improve the catalytic activity. Single O-doped g-As(O)(1) can achieve efficient bifunctional activity for both the OER and the ORR with optimal potential gap. b-As(O)(1) and b-As(O)(2) exhibit the optimal OER and ORR catalytic performance, respectively. For the HER, double C-doped g-As(C)(2) could tune the adsorption of hydrogen to an optimal value and significantly enhance the catalytic performance. These findings indicate that arsenene could provide a new platform to explore high-efficiency electrocatalysts.