The Contradicting Influences of Silica and Titania Supports on the Properties of Au0 Nanoparticles as Catalysts for Reductions by Borohydride

Abstract

This study investigates the significant impact of metal–support interactions on catalytic reaction mechanisms at the interface of oxide-supported metal nanoparticles. The distinct and contrasting effects of SiO2 and TiO2 supports on reaction dynamics using NaBD4 were studied and focused on the relative yields of [HD]/[H2] and [D2]/[H2]. The findings show a consistent increase in HD yields with rising [BD4−] concentrations. Notably, the sequence of HD yield enhancement follows the order of TiO2-Au0-NPs < Au0-NPs < SiO2-Au0-NPs. Conversely, the rate of H2 evolution during BH4- hydrolysis exhibits an inverse trend, with TiO2-Au0-NPs outperforming the others, followed by Au0-NPs and SiO2-Au0-NPs, demonstrating the opposing effects exerted by the TiO2 and SiO2 supports on the catalytic processes. Further, the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) confirms the catalytic mechanism, with TiO2-Au0-NPs demonstrating superior activity. The catalytic activity observed aligns with the order of TiO2-Au0-NPs > Au0-NPs > SiO2-Au0-NPs, suggesting that SiO2 donates electrons to Au0-NPs, while TiO2 withdraws them. It is of interest to note that two very different processes, that clearly proceed via different mechanisms, are affected similarly by the supports. This study reveals that the choice of support material influences catalytic activity, impacting overall yield and efficiency. These findings underscore the importance of selecting appropriate support materials for tailored catalytic outcomes.