Enzyme-Free Molecularly Imprinted and Graphene-Functionalized Photoelectrochemical Sensor Platform for Pollutants

In this work, a label-free nonenzymatic photoelectrochemical (PEC) sensor is successfully developed for the detection of a typical pollutant, microcystin-LR (MC-LR), based on a visible-light-responsive alloy oxide, with highly ordered and vertically aligned Ti–Fe–O nanotubes (NTs) as substrates. Ti–Fe–O NTs consisting mainly of TiO₂ and atomically doped Fe₂O₃ are in situ prepared on a Ti–Fe alloy by electrochemical anodic oxidation. Using a simple electrochemical deposition technique, reduced graphene oxide (RGO) could be grown onto Ti–Fe–O NTs, exhibiting significant bifunctions. It not only provides an ideal microenvironment for functionalization of molecularly imprinted polymers (MIPs) on the surface but also serves as the PEC signal amplification element because of its outstanding conductivity for photons and electrons. The designed MIP/RGO/Ti–Fe–O NT PEC sensor exhibits high sensitivity toward MC-LR with a limit of detection as low as 10 pM. High selectivity toward MC-LR is also proven for the sensor. A promising detection platform not only for MC-LR but also for other pollutants has therefore been provided.