Tuning Electrocatalytic Properties of Bismuthene by Heteroatom Decoration Toward Overall Water Splitting

Abstract Developing of effective electrocatalysts for overall water splitting is of importance for the achievement of hydrogen energy cycling. In this work, hydrogen evolution and oxygen evolution of the defective bismuthene with decoration of a transition metal atom have been fully investigated via density functional theory calculations. The results indicate that the fixation of transition metal dopant into defective bismuthene is achieved via the interaction between the Bi sp band and TM sd band. Wherein, Sc@Bi, Ti@Bi, Zn@Bi, Y@Bi, Rh@Bi, Pd@Bi, Ag@Bi, Pt@Bi, and Au@Bi are thermodynamically stable according to the data of the formation energy. Furthermore, Sc@Bi, Ti@Bi, Y@Bi, Rh@Bi, Pd@Bi, and Pt@Bi have good performances toward hydrogen evolution, and the overpotentials η HER are 0.11, 0.22, 0.30, 0.13, 0.27, and 0.01 V, respectively. Furthermore, the optimal candidates toward oxygen evolution are Rh@Bi and Pt@Bi, endowed with the overpotentials η OER of 0.66 and 0.36 V, respectively. Therefore, Pt@Bi and Rh@Bi are bifunctional‐active toward overall water splitting. These findings indicate that bismuthene could provide a new platform to explore high‐efficiency electrocatalysts in overall water splitting.