Pentagonal PdTe2 monolayer for sustainable solar-driven hydrogen production

This investigation demonstrates that the pentagonal PdTe2 (penta-PdTe2) monolayer is a highly tunable twodimensional (2D) photocatalyst, characterized by the bandgap of 1.87 eV and high hole mobility. Using density functional theory calculations with the HSE06 functional, we show that tensile strain engineering (particularly at +2% and +3%) is essential for enabling spontaneous water splitting. At these strain values, the valenceband maximum and conduction-band maximum straddle the water redox potentials (H+/H2 and O2/H2O) under both acidic (pH = 0) and neutral (pH = 7) conditions. The monolayer’s low hole effective mass facilitates rapid charge extraction, mitigating recombination and driving the oxygen evolution reaction (OER) more effectively than many hexagonal and pentagonal counterparts. The Gibbs free energy (ΔG) pathways indicate that overpotentials for the hydrogen evolution reaction (HER) and OER are highly sensitive to mechanical deformation, specifically biaxial strain, through which +3% tensile strain, yielding an optimized balance of overpotentials of ηHER = 0.70 V at pH = 0 and ηOER = 0.72 V at pH = 7. Finally, integrating optical absorption with thermodynamic driving forces results in a Solar-to-Hydrogen (STH) efficiency of 20.40% at pH = 7. This exceeds the performance of several previously reported 2D catalysts, positioning penta-PdTe2 as a superior candidate for sustainable, solar-driven hydrogen production.