Photocathodic Activation of Peroxymonosulfate in a Photofuel Cell: A Synergetic Signal Amplification Strategy for a Self-Powered Photoelectrochemical Sensor

A self-powered photoelectrochemical (PEC) sensor has attracted widespread attention in the field of analysis, but it is still a challenge to enhance its response signals with rational strategies. In this work, a novel self-powered PEC sensing platform was developed for the quantitative detection of gatifloxacin (GAT) based on a photofuel cell consisting of two types of ZIF-derived ZnO/Co₃O₄ heterojunctions as photoactive materials. Peroxymonosulfate (PMS) was first used as an electron acceptor coupled with a photofuel cell to develop a synergetic signal amplification strategy. In a dual-photoelectrode system, the PMS activation on the ZnO@Co₃O₄ photocathode not only accelerated electron transfer from the Co₃O₄@ZnO photoanode to achieve strong signal intensity but also improved the sensing sensitivity by the oxidation reaction of generated highly active radicals to GAT. Compared with the absence of electron acceptors, the introduction of PMS produced a 2-fold enhancement in the signal output performance and a more than 72-fold improvement in the signal sensitivity. For the construction of the sensing interface, a molecularly imprinted polymer was assembled on the photocathode to specifically recognize GAT. The proposed sensor exhibited a detection range of 10^-1 to 10⁵ pM with a detection limit of 0.065 pM. The proposed sensing method has the advantages of sensitivity, simplicity, reliable stability, and anti-interference ability, which opens the door to the design of high-performance self-powered PEC sensors.