Design and First-Principles Calculation of Pt-Doped Phenalene Basket for Enhanced Photocatalytic Hydrogen Evolution: Structural, Optical, and Electronic Insights

Charge recombination represents a significant challenge to progress in the field of photocatalytic hydrogen evolution reaction. In this study, we present our findings on the design and first-principle calculation of a proposed efficient photocatalytic basket material with the potential to significantly enhance photocatalytic hydrogen evolution. The modeling of the design was executed using Chemdraw, while the optimization, optical and electronic property calculation, and adsorption property calculation were conducted utilizing DMOL3 and Adsorption Locator. Confirmation of the structure's platinum content was obtained through the reassignment of bond characteristics previously observed between C4-C5, C5-C6, and C5-C10. These bonds were redefined to reflect interactions involving platinum, specifically Pt4-C5, Pt4-C7, and Pt4-C3. The bond angles Pt4-C3-C2 (120.625°) and Pt4-C5-C10 (120.624°) were not present in the original phenalene structure. The absorption peak of 0.0223 nm and 0.005 nm for Pt-doped phenalene provide critical insights into its optical properties, underscoring its potential for advanced photonic applications. The HOMO-LUMO energy difference for platinum-doped phenalene ranges from -0.409 eV to -0.285 eV. The Mulliken electrophilic indices reveal that platinum in the Pt-doped phenalene carries a partial positive charge of 0.101eV, whereas the bonding carbons (C3, C5, and C7) have much smaller partial charges of 0.017eV. The observed Gibbs free energy values for H2 (-0.24157 eV) and H+ (-0.11589 eV) are further confirmed. This study's findings highlight the Pt-doped phenalenes' excellent performance and stability as catalysts. Its optical and electronic properties make it a contender in photocatalytic energy conversion and environmental remediation, propelling sustainable hydrogen production.