Glutathione-stabilized palladium nanozyme for colorimetric assay of silver(i) ions

Abstract

Glutathione-capped Pd nanoparticles with a size of 1.4–3.5 nm are facilely synthesized for peroxidase nanomimetics. The molar ratio of [Na₂PdCl₄]/[GSH] greatly affects the physicochemical properties including particle sizes, surface charge states and enzymatic activities. The most efficient Pd-based nanozyme, consisting of approximately 57% metallic Pd⁰ species with an average diameter of 2.6 nm, exhibits the K_m value of 0.068 mM toward 3,3′,5,5′-tetramethylbenzidine and 156 mM toward hydrogen peroxide. Ag⁺ selectively binds to Pd⁰ species through metallophilic interactions and induces an apparent aggregation of Pd nanoparticles. This is the first report that Ag⁺ significantly inhibits the peroxidase mimicking activity of Pd nanoparticles. A Pd-based nanozyme is employed to explore colorimetric detection of Ag⁺ with the limit of detection of 1.2 nM. This developed sensing system is potentially applicable for quantitative detection of Ag⁺ in drinking water as well as Ag nanoparticles in aqueous solution.