Dissociable photoelectrode materials boost ultrasensitive photoelectrochemical detection of organophosphorus pesticides

Generally, the photoactive materials are always tightly fixed on the photoelectrode of photoelectrochemical (PEC) sensors to produce excellent photocurrent response, while obvious and constant background currents will appear as well and then hamper the ultrasensitive sensing of target molecules. In this work, ultrasensitive detection of organophosphorus pesticides (OPs) is successfully fulfilled by using dissociable photoelectrode based on CdS nanocrystal-functionalized MnO2 nanosheets. With the assistance of acetylcholinesterase (AChE), acetylthiocholine (ATCh) is hydrolyzed into thiocholine (TCh) which can effectively etch the ultrathin MnO2 nanosheets, resulting in the dissociation of MnO2–CdS from the photoelectrode. Benefiting from the dissociation of photoactive materials, the background photocurrent induced by semiconductor itself dramatically decreases. OPs, as a specific inhibitor for AChE activity, can prevent the generation of TCh and the dissociation of MnO2 nanosheets, building a relationship between OPs concentration and photocurrent. Under the optimized test conditions, the PEC sensor for the detection of paraoxon displays a wide linear range from 0.05 to 10 ng/mL with a detection limit of 0.017 ng/mL. Furthermore, the PEC sensor shows good sensitivity, stability, and promising application in practical samples.