In Situ Exsolution of Noble-Metal Nanoparticles on Perovskites as Enhanced Peroxidase Mimics for Bioanalysis.

Abstract

Various transition-metal oxide (TMO)-based nanomaterials have been explored as peroxidase mimics. However, the moderate peroxidase-like activity of TMOs limited their widespread use. Decorating highly active noble-metal nanozymes on the surface of TMOs can not only enhance the peroxidase-like activity of TMOs but also prevent the small-sized metal nanoparticles (NPs) from aggregation. Herein, in situ exsolution of noble-metal NPs (i.e., Ir and Ru) from A-site-deficient perovskite oxides (i.e., chemical formula La0.9B0.9B'0.1O3-δ, B = Mn/Fe, B' = Ir/Ru) under a reducing atmosphere was achieved for preparing noble-metal NPs/perovskite composites. The exsolved NPs were socketed on the surface of parent perovskite oxides, which significantly enhanced the stability of metal NPs. In addition, the peroxidase-like activity of perovskite oxides increased remarkably after NPs egress. We then used the optimized Ir/LMIO with high stability and excellent peroxidase-like activity to develop a colorimetric assay for the determination of alkaline phosphatase (ALP). Benefiting from the remarkable peroxidase-like activity of Ir/LMIO, the sensing platform exhibited a wide linear range. The practical application of the colorimetric sensing method was demonstrated by detecting the ALP in serum samples. This work not only provides new insights into the synthesis of highly active peroxidase-like nanozymes but expands their applications for constructing a high-performance biosensing platform.