Oxygen Activation Biocatalytic Precipitation Strategy Based on a Bimetallic Single-Atom Catalyst for Photoelectrochemical Biosensing

The traditional biocatalytic precipitation (BCP) strategy often required the participation of H2O2, but H2O2 had the problem of self-decomposition, which prevented its application in quantitative analysis. This work first found that a bimetallic single-atom catalyst (Co/Zn-N-C SAC) could effectively activate dissolved O2 to produce reactive oxygen species (ROS) due to its superior oxidase (OXD)-like activity. Experimental investigations demonstrated that Co/Zn-N-C SAC preferred to produce highly active hydroxyl radicals (center dot OH), which oxidized 3-amino-9-ethyl carbazole (AEC) to produce reddish-brown insoluble precipitates. Based on this property, a unique oxygen-activated photoelectrochemical (PEC) biosensor was developed for chloramphenicol (CAP) detection. Cesium platinum bromide nanocrystals (Cs2PtBr6 NCs) were a new type of halide perovskite with lead-free, narrow band gaps, and water-oxygen resistance. Cs2PtBr6 NCs showed excellent cathodal PEC performance without an exogenous coreactant and were first used for PEC detection. As a "proof-of-concept application", Co/Zn-N-C SAC was introduced onto the surface of Cs2PtBr6 NCs by using the CAP dual-aptamer sandwich strategy. Co/Zn-N-C SAC activated dissolved O2 to produce ROS, which oxidized AEC to produce precipitates, quenching the cathodal PEC signal of Cs2PtBr6 NCs for CAP detection. In summary, this work first used SAC to overcome the restriction of the traditional enzymatic BCP strategy requiring H2O2, improved the stability and accuracy of quantitative analysis, and also broadened the application range of coreactant-free perovskite-type PEC biosensors.