Single-Molecule Spectroscopy Reveals the Plasmon-Assisted Nanozyme Catalysis on AuNR@TiO₂

Gold nanoparticles are frequently employed as nanozyme materials due to their capacity to catalyze various enzymatic reactions. Given their plasmonic nature, gold nanoparticles have also found extensive utility in chemical and photochemical catalysis owing to their ability to generate excitons upon exposure to light. However, their potential for plasmon-assisted catalytic enhancement as nanozymes has remained largely unexplored due to the inherent challenge of rapid charge recombination. In this study, we have developed a strategy involving the encapsulation of gold nanorods (AuNRs) within a titanium dioxide (TiO₂) shell to facilitate the efficient separation of hot electron/hole pairs, thereby enhancing nanozyme reactivity. Our investigations have revealed a remarkable 10-fold enhancement in reactivity when subjected to 530 nm light excitation following the introduction of a TiO₂ shell. Leveraging single-molecule kinetic analyses, we discovered that the presence of the TiO₂ shell not only amplifies catalytic reactivity by prolonging charge relaxation times but also engenders additional reactive sites within the nanozyme's intricate structure. We anticipate that further enhancements in nanozyme performance can be achieved by optimizing interfacial interactions between plasmonic metals and semiconductors.