Tetrametallic Au@Ag-Pd-Pt Nanozyme with Surface-Exposed Active Sites for Enhanced Catalytic Activity

Metal nanoparticles (NPs) with enzyme-mimicking activities, known as nanozymes, are being actively explored for biomedical and analytical applications. Enhancing their catalytic activity and metal utilization efficiency is crucial for advancing these technologies. Here, we report an aqueous-phase, room-temperature synthesis of tetra-metallic Au@Ag-Pd-Pt NPs that exhibit superior peroxidase-like activity compared to their mono-, bi-, and trimetallic counterparts. The synthesis involves a sequential, seed-mediated approach comprising the formation of Au NP seeds, the overgrowth of a Ag shell, and the galvanic replacement of Ag with Pd and Pt ions. We systematically investigated the effects of the Au core diameter (15, 40, 55 nm), Ag precursor concentration (50-400 µM), and the Pd-to-Pt ratio on the optical and catalytic properties. By changing the particle composition, we were able to tune the absorbance maximum from 520 nm to 650 nm while maintaining high extinction coefficients (10⁹-10¹⁰ M^-1cm^-1) comparable to that of the initial Au nanoparticles. Mapping of chemical element distributions in the nanoscale range confirmed a core-shell-shell architecture with surface-enriched Pd and Pt. This structure ensures the surface-exposed localization of catalytically active atoms, yielding a more than 10-fold improvement in specific peroxidase-like activity while utilizing up to two orders of magnitude less Pt and Pd than bimetallic particles. The synthesized NPs thus combine high catalytic activity with tunable optical properties, making them promising multifunctional labels for biosensing.