Black phosphorene quantum dots (BPQDs) were prepared by ultrasonic-assisted liquid-phase exfoliation and centrifugation with morphologies proved by TEM results. Furthermore, an electrochemical enzyme sensor was prepared by co-modification of BPQDs with horseradish peroxidase (HRP) on the surface of a carbon ionic liquid electrode (CILE) for the first time. The direct electrochemical behavior of HRP was studied with a pair of well-shaped voltammetric peaks that appeared, indicating that the existence of BPQDs was beneficial to accelerate the electron transfer rate between HRP and the electrode surface. This was due to the excellent properties of BPQDs, such as small particle size, high interfacial reaction activity, fast conductivity, and good biocompatibility. The presence of BPQDs on the electrode surface provided a fast channel for direct electron transfer of HRP. Therefore, the constructed electrochemical HRP biosensor was firstly used to investigate the electrocatalytic behavior of trichloroacetic acid (TCA) and potassium bromate (KBrO3), and the wide linear detection ranges of TCA and KBrO3 were 4.0–600.0 mmol/L and 2.0–57.0 mmol/L, respectively. The modified electrode was applied to the actual samples detection with satisfactory results.
In this work, a novel and sensitive electrochemical biosensor was constructed based on a black phosphorene (BP) and nanosized zinc oxide (ZnO@BP) nanocomposite as a modifier, which was used for the immobilization of horseradish peroxidase (HRP) on a carbon ionic liquid electrode (CILE). The ZnO@BP nanocomposite was synthesized by a simple in situ hydrothermal method with stripped black phosphorus nanoplates and ZnO. The ZnO@BP and HRP-modified electrode was developed by a casting method. ZnO@BP with highly conductivity, large surface area and good biocompatibility could maintain the bioactivity of HRP and accelerate the electron transfer rate. Cyclic voltammetry was used to study the direct electrochemistry of HRP on the Nafion/HRP/ZnO@BP/CILE with the appearance of a pair of distinct redox peaks. The constructed electrochemical HRP biosensor exhibited excellent electrocatalytic effects on the reduction of trichloroacetic acid and sodium nitrite. Real samples were detected with satisfactory results, which demonstrated the potential applications of this electrochemical HRP biosensor.
To design a new electrochemical horseradish peroxidase (HRP) biosensor with excellent analytical performance, black phosphorene (BP) nanosheets and single-walled carbon nanotubes (SWCNTs) nanocomposites were used as the modifier, with a carbon ionic liquid electrode (CILE) as the substrate electrode. The SWCNTs-BP nanocomposite was synthesized by a simple in situ mixing procedure and modified on the CILE surface by the direct casting method. Then HRP was immobilized on the modified electrode with Nafion film. The electrocatalysis of this electrochemical HRP biosensor to various targets was further explored. Experimental results indicated that the direct electrochemistry of HRP was realized with a pair of symmetric and quasi-reversible redox peaks appeared, which was due to the presence of SWCNTs-BP on the surface of CILE, exhibiting synergistic effects with high electrical conductivity and good biocompatibility. Excellent electrocatalytic activity to trichloroacetic acid (TCA), sodium nitrite (NaNO2), and hydrogen peroxide (H2O2) were realized, with a wide linear range and a low detection limit. Different real samples, such as a medical facial peel solution, the soak water of pickled vegetables, and a 3% H2O2 disinfectant, were further analyzed, with satisfactory results, further proving the potential practical applications for the electrochemical biosensor.
In this work, a novel portable and wireless intelligent electrochemical nanosensor was developed for the detection of 6,7-dihydroxycoumarin (6,7-DHC) using a modified screen-printed electrode (SPE). Black phosphorene (BP) nanosheets were prepared via exfoliation of black phosphorus nanoplates. The BP nanosheets were then mixed with nano-diamond (ND) to prepare ND@BP nanocomposites using the self-assembly method, achieving high environmental stability. The nanocomposite was characterized by SEM, TEM, Raman, XPS and XRD. The nanocomposite was used for the modification of SPE to improve its electrochemical performances. The nanosensor displayed a wide linear range of 0.01–450.0 μmol/L with a low detection limit of 0.003 μmol/L for 6,7-DHC analysis. The portable and wireless intelligent electrochemical nanosensor was applied to detect 6,7-DHC in real drug samples by the standard addition method with satisfactory recoveries, which extends the application of BP-based nanocomposite for electroanalysis.