CuS QDs/Co₃O₄ Polyhedra-Driven Multiple Signal Amplifications Activated h-BN Photoeletrochemical Biosensing Platform

Abstract

Herein, we developed an unmodified hexagonal boron nitride (h-BN) photoelectrochemical (PEC) biosensing platform with a low background signal and high sensitivity based on CuS quantum dots (QDs)/Co3O4 polyhedra-driven multiple signal amplifications. The prepared porous h-BN nanosheets with large specific surface areas, as the photoelectric substrate material, can provide extensive active reaction sites. Meanwhile, the CuS QDs/Co3O4 polyhedra were synthesized by the zeolitic imidazolate framework (ZIF-67) and utilized as a multiple signal amplifier, which can not only drive the p-n semiconductor quenching effect to compete with the h-BN photoelectrode for the consumption of electron donors and exciting light but also trigger a mimetic enzymatic catalytic precipitation effect to inhibit electron transfer. The quenching ability and peroxidase-like activity of CuS QDs/Co3O4 polyhedra were evaluated to prove its superiority, and the possible mechanisms of electron transfer and enzymatic catalytic were further analyzed in detail. The developed PEC biosensing platform for the chlorpyrifos assay presented outstanding performance with a wide linear range from 1 × 10–1 to 1 × 107 ng mL–1 and a low detection limit of 0.34 pg mL–1 and exhibited excellent selectivity, reproducibility, and stability. In addition, the CuS QDs/Co3O4 polyhedra-activated h-BN PEC biosensing platform may exhibit universality for various analytes via replacing the corresponding target aptamer sequence. This work provides a remarkable inspiration and valuable reference for the development of the PEC biosensor, and the signal amplifier-enabled unmodified PEC biosensing platform strategy has a bright application in early safety warning, bioanalysis and clinical diagnosis.

Research progress on photoelectrochemical sensors for contamination analysis in agricultural fields

“…To enhance the sensitivity of the detection of chlorpyrifos, PEC sensors based on different detection mechanisms have been developed. 44,[130][131][132][133][134][135][136][137][138] Tan et al used h-BN as a PEC aptasensing platform and CuS QDs/Co3O4 polyhedra as multiple signal amplifications for the turn on sensing of chlorpyrifos. 130 The sensing platform drives the p-n semiconductor quenching effect to compete with the h-BN photoelectrode for the consumption of electron donors and the excitation of light, and it trigger a mimetic enzymatic catalytic precipitation effect to inhibit electron transfer (Fig.…”

“…Copyright©2020, American Chemical Society. 130 (B) Schematic diagrams of the PEC sensor for selective detection of chlorpyrifos. Copyright©2018, American Chemical Society.…”

Photoelectrochemical Assay Based on SnO2/BiOBr p–n Heterojunction for Ultrasensitive DNA Detection

“…9 Unfortunately, single photoelectric materials usually have the disadvantage of low photoelectric conversion efficiency, which limits their practical applications. 10,11 In recent years, the construction of heterojunctions is considered to be a feasible and effective way to facilitate the electron−hole separation and restrain the recombination of electron−hole of optoelectronic materials. 12−15 For instance, Xiong's group synthesized a ZnO/ CeO 2 Z-scheme heterojunction for photodegradating rhodamine B.…”

Ultrasensitive Photoelectrochemical Biosensor Based on Novel Z-Scheme Heterojunctions of Zn-Defective CdS/ZnS for MicroRNA Assay

“…6,7 Nevertheless, the conversion efficiency of these semiconductor nanomaterials is primarily limited due to a high electron−hole pair recombination rate and poor light absorption capacity in actual analysis. 8,9 In recent years, the homojunction strategies using single semiconductor components and heterojunctions by utilizing multiple semiconductor components have been proven to promote the separation of electron−hole pairs and inhibit the recombination of electron−hole pairs. 10,11 Compared to homojunctions, heterojunctions could not only overcome the deficiencies of weak light absorption capacity but also exhibit remarkable physicochemical properties.…”

“…Photoelectrochemical (PEC) bioanalysis has been extensively explored and developed over the past decade with a higher sensitivity, lower background noise, and faster response compared with traditional electrochemical methods, along with simpler and easier operation in terms of apparatus than the optical methods. − Notably, photoactive materials play important roles in the proposed PEC biosensor as their superior photocurrent intensity and detection sensitivity properties directly determine the efficiency of PEC biosensors . Up to now, numerous inorganic semiconductor materials such as metal oxides, carbon materials, and sulfides have been widely used in PEC assay with excellent photoelectric performance. , Nevertheless, the conversion efficiency of these semiconductor nanomaterials is primarily limited due to a high electron–hole pair recombination rate and poor light absorption capacity in actual analysis. , In recent years, the homojunction strategies using single semiconductor components and heterojunctions by utilizing multiple semiconductor components have been proven to promote the separation of electron–hole pairs and inhibit the recombination of electron–hole pairs. , Compared to homojunctions, heterojunctions could not only overcome the deficiencies of weak light absorption capacity but also exhibit remarkable physicochemical properties . Therefore, it is essential to develop unique heterojunction-based nanomaterials for PEC bioanalysis.…”