Universal Hydrogen-Treated TiO Nanorod Array/TiCO MXene PEC Aptamer Sensor Modulated by the Transport Characteristic of Photogenerated Holes.

A semiconductor photoelectrochemical (PEC) aptamer sensor has been widely researched in recent years because of its broad application prospects. However, a universal PEC sensor has not been achieved, and its sensing mechanism based on a photogenerated carrier transfer process has yet to be elucidated. Herein, a novel hydrogen-treated TiO nanorod array one-dimensional (1D)/TiCO MXene two-dimensional (2D) (H-TiO/TiCO) PEC aptamer sensor is presented, which achieved a record detection range of 10-10 μg/L and a limit of detection (LOD) of 1 fg/L for microcystic toxins-LR detection. Besides, the PEC sensor can also test serotonin (5-HT), aflatoxin-B1, and prostate-specific antigen (PSA) with high performance by changing the aptamers, exhibiting favorable application universality. Furthermore, a new phenomenon of a switchable enhanced/suppressed photocurrent detection signal was discovered from H-TiO/TiCO PEC aptamer sensors through the variation of the length of the TiO nanorod. Meanwhile, it reveals that the steric hindrance effect determines the photogenerated hole transfer and depolarization processes, which is proposed for the first time as the predominant mechanism of the switchable enhanced/suppressed photocurrent signal for PEC sensors, giving possibilities to develop PEC sensors with higher efficiency.