Publication date: 15th December 2025
Recent progress in photocatalysis highlights the critical role of self-assembled monolayers (SAMs) in enhancing the performance of single-atom catalysts (SACs) on semiconductor surfaces. This study investigates the effect of a phosphonic acid-based SAM on the photocatalytic hydrogen evolution of iridium-decorated titanium dioxide nanotube (TiO₂ NT) surfaces. TiO₂ NTs were synthesized by anodization followed by thermal annealing. Iridium atoms were anchored using an ultrasonication-assisted deposition method under inert conditions. Subsequently, the phosphonic SAM was embedded in the solution under dark conditions via immersion. Co-presence of Ir and the SAM was confirmed by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Under UV irradiation, SAM-functionalized samples exhibited significantly higher hydrogen evolution rates compared to untreated controls. This enhancement is attributed to improved charge separation and the prevention of Ir atom aggregation. The formation of the anatase phase was verified by X-ray diffraction (XRD), while surface chemistry and functionalization were validated using X-ray photoelectron spectroscopy (XPS) and ToF-SIMS. Hydrogen evolution rates were quantified via gas chromatography (GC).These results demonstrate a synergistic effect between SAM modification and single-atom catalysis, offering a promising strategy to boost photocatalytic efficiency in solar-to-fuel conversion applications.
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