Engineering a hierarchically micro-/nanostructured Si@Au-based artificial enzyme with improved accessibility of...

The active site accessibility and high loading of gold nanoparticles (AuNPs) are key factors affecting the catalytic activity of supported AuNP-based catalysts. However, the preparation of supported AuNP-based catalysts with highly accessible active sites still remains a challenge. Herein, sphere-on-sphere (SoS) silica microspheres with a hierarchical structure, good dispersion and high surface density of thiol groups (10 SH nm^-2) are prepared and used as a platform for the growth of high-density AuNPs. The obtained hierarchical Si@Au micro-/nanostructure consisting of 0.55 μm SoS silica microspheres and 7.3 nm AuNPs (SoS-0.55@Au-7.3) is found to show excellent peroxidase-mimicking activity (K_m = 0.033 mM and V_max = 34.6 × 10^-8 M s^-1) with merits of high stability and good reusability. Furthermore, the as-obtained SoS-0.55@Au-7.3-based system can sensitively detect hydrogen peroxide (H₂O₂) with a low detection limit of 1.6 μM and a wide linear range from 2.5 μM to 1.0 mM. The high catalytic activity, excellent stability and good reusability of SoS-0.55@Au-7.3 imply its great prospects in biosensing and biomedical analysis.