Abstract
Addressing the pressing needs for alternatives to fossil fuel-based energy sources, this research explores the intricate interplay between Rhodium (Rh(3)) clusters and titanium dioxide (TiO(2)) to improve photocatalytic water splitting for the generation of eco-friendly hydrogen. This research applies the density functional theory (DFT) coupled with the Hartree-Fock theory to meticulously examine the structural and electronic structures of Rh(3) clusters on TiO(2) (110) interfaces. Considering the photocatalytic capabilities of TiO(2) and its inherent limitations in harnessing visible light, the potential for metals such as Rh(3) clusters to act as co-catalysts is assessed. The results show that triangular Rh(3) clusters demonstrate remarkable stability and efficacy in charge transfer when integrated into rutile TiO(2) (110), undergoing oxidation in optimal adsorption conditions and altering the electronic structures of TiO(2). The subsequent analysis of TiO(2) surfaces exhibiting defects indicates that Rh(3) clusters elevate the energy necessary for the formation of an oxygen vacancy, thereby enhancing the stability of the metal oxide. Additionally, the combination of Rh(3)-cluster adsorption and oxygen-vacancy formation generates polaronic and localized states, crucial for enhancing the photocatalytic activity of metal oxide in the visible light range. Through the DFT analysis, this study elucidates the importance of Rh(3) clusters as co-catalysts in TiO(2)-based photocatalytic frameworks, paving the way for empirical testing and the fabrication of effective photocatalysts for hydrogen production. The elucidated impact on oxygen vacancy formation and electronic structures highlights the complex interplay between Rh(3) clusters and TiO(2) surfaces, providing insightful guidance for subsequent studies aimed at achieving clean and sustainable energy solutions.