Optimizing Ferroelectricity in 2D Materials: Intralayer and Interlayer Engineering for Enhanced Photocatalysis

Abstract

Ferroelectric materials exhibit inherent polarization characteristics that render them viable options for improving photocatalytic performance via efficient charge carrier separation. Nonetheless, the majority of two dimensional (2D) materials exhibit an absence of ferroelectric properties owing to their elevated symmetry, which presents obstacles for their utilization in photocatalysis. This study presents two novel strategies for inducing ferroelectricity in 2D materials: intralayer polarization, accomplished by substituting phosphorus atoms in black phosphorus (BP) with elements like nitrogen (N), arsenic (As), or antimony (Sb); and interlayer polarization, realized through a controlled heterostructure design. Density functional theory (DFT) simulations indicate that these tailored materials demonstrate markedly diminished overpotentials for the oxygen evolution reaction (OER) and carbon dioxide reduction reaction (CO₂RR), with values as low as 1.04 and 1.12 eV, respectively. The materials exhibit competitive Gibbs free energy profiles for the hydrogen evolution process (HER), highlighting their adaptability. The findings provide a framework for utilizing intralayer and interlayer engineering to improve the ferroelectric characteristics of 2D materials, facilitating advanced applications in photocatalysis and renewable energy conversion.