Study on the Properties of the Ferroelectric Photocatalytic Hydrogen Evolution Reaction for Chemically Functionalized Phosphorene Nanosheets

Investigating efficient photocatalysts for the hydrogenevolutionreaction (HER) is of paramount importance for advancing renewableenergy technologies. Herein, based on the density functional theorycalculations, we constructed halogen atom X-intercalated (X = F, Cl,and Br) bilayer phosphorene (BP-X) to achieve efficient HERproperties. The results demonstrate that X intercalation can breakthe inversion of symmetry and generate vertical polarization, whichcan promote HER properties. In particular, the intercalation of Clatoms broadens the light absorption peak, reduces the work function,enhances the transition dipole moment, and makes & epsilon;(P-center) move to the Fermi level, thus enhancing the photocatalytic HER properties.Additionally, we have provided a comprehensive explanation of thepolarization properties and the underlying reasons for how polarizationreversal enhances the HER properties upon Cl intercalation. This studyrepresents a significant advancement in the development of a novelphosphorene-based ferroelectric photocatalyst, which not only enhancesthe efficiency of HER properties but also sets the stage for the designof 2D ferroelectric photocatalysts.