Strain Modulation of Black Phosphorene for the Hydrogen Evolution Reaction Activity

Abstract

The first‐principles calculation within the density functional theory (DFT) is used to study the hydrogen evolution reaction (HER) activity and related electronic properties of monolayer black phosphorus under the uniaxial strains. Herein, it is found that different compressive and tensile strains would modulate the Gibbs free energy (ΔGH*), partial charge density of the lowest unoccupied state (εLUS), and band structure of black phosphorene. Specifically, as the ΔGH* decreases, the HER activity of phosphorene system with uniaxial strain is improved except for the +3% strain case. Importantly, the HER catalytic performance of phosphorene can be reduced by 0.4 eV and the bandgap decreased to 0.23 eV by applying the −10% strain. Comparing with strained‐free case, the larger partial charge density of εLUS on the surface of black phosphorene shows more H adsorption sites for electrocatalysis. Moreover, the HER activity is related to the partial charge density of εLUS rather than the value of εLUS site. These results reveal that strain could effectively modulate the HER performance for electrocatalysis. And it is expected to provide further understanding in practical applications.