In order to achieve rapid and sensitive detection of CYFRA 21-1, a signal-off photoelectrochemical (PEC) immunosensor was devised with NiCo2O4/CdIn2S4/In2S3 heterojunction photoactive materials as sensing platform and ReS2@Au NPs as the secondary antibody labels amplifying signal based on the energy band-matching cascade structure and double suppression effect. NiCo2O4 possessed a faster charge transfer rate due to the abundance of redox electron pairs (Co3+/Co2+ and Ni3+/Ni2+). To further improve the PEC properties of NiCo2O4 under visible light, CdIn2S4 with matching bandgap energy was selected to form heterojunction with NiCo2O4 and sensitized with In2S3. The proposed heterojunctions with well-matched band structure promoted the transfer of photo-generated carriers and were exploited as signal transducers for immobilization of antibodies and recognition of CYFRA 21-1. Furthermore, a novel urchin-like p-type ReS2 semiconductor nanostructure functionalized by Au NPs was firstly used as a nanolabel to quench the signal. On the one hand, the Schottky heterojunction generated by ReS2 and Au NPs could compete with the transducer substrate for both light and electron donors. On the other hand, the large space steric hindrance of ReS2 prevented contact between the matrix and AA. Subsequently, the sensor was sensitive in a wide range of concentrations for CYFRA 21-1 (0.0001–50 ng/mL), and the detection limit was 0.05 pg/mL.
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