Enhance Hydrogen Evolution Reaction Performance via Double-Stacked Edges of Black Phosphorene

Based on the density functional theory (DFT) calculations, we explored the structures and HER catalytic properties of reconstructed and double-stacked black phosphorene (BP) edges. Ten bilayer BP edges were constructed by the double stacking of three typical monolayer edges, i.e., zigzag (ZZ) edge, armchair (AC) edge, skewed diagonal (SD) edge, and their reconstructed derivatives with their layer's configurations, edge deformations and thermodynamic stabilities were discussed. Based on these edges, five chemical sites on four bilayer BP edges were selected to be promising candidates for a HER catalyst, which present higher HER activities than that of Pt(111). Besides, among these four edges, two edges have even lower energetic barriers for the Tafel reaction. Compared with the monolayer edges, these selected bilayer BP edges confirm the remarkable enhancement of the HER catalytic properties, which can be attributed to their unique edge structures and the enhanced electronic densities after the hydrogen adsorptions. Finally, the thermostability of these edges at room temperature has also been proved by the DFT-MD simulations. This theoretic study deepens our fundamental understanding of the double-stacked edge structures of the BP and provides a new way for the rational design of highly efficient and noble-metal-free HER catalysts.