Conventional enzyme-based glucose sensors have good selectivity and sensing performance, but the disadvantages of the enzyme itself (enzyme activity is susceptible to pH and temperature) lead to a limited number of uses and result in high costs. Therefore, photoelectrochemical enzyme-free glucose sensors have attracted research interest in recent years. In this work, the TiO2/CuO heterojunction was constructed and photoelectrochemical enzyme-free glucose sensing was realized. The sensing sensitivity of the TiO2/CuO heterojunction photoelectrode prepared by magnetron sputtering and thermal annealing process was 864 μAμM-1 cm-2 in the range of 1–9 mM with a detection limit of 58.6 μM at 0.2 V, exhibiting satisfactory stability as well as interference resistance. This better sensing performance mainly comes from: 1) the absorption of photogenerated carriers generated from sunlight by TiO2 films, which participate in glucose redox; 2) the conversion of the metal valence state (Cu2+/Cu3+) of the P-type semiconductor CuO under alkaline conditions can promote glucose redox; 3) the heterojunction formed by CuO and TiO2 reducing the compounding of photogenerated carriers thus improving the photoelectric conversion efficiency. The heterojunction formed by CuO and TiO2 greatly facilitates the surface carrier transfer of glucose oxidation reaction. This work provides a new way for enzyme-free glucose sensing and promotes the development of glucose detection technology.
Constructing novel hybrid nanostructure has become an effective strategy to enhance the performance of photoelectrochemical (PEC) biosensors. However, most of the H2O2-sensing photoelectrodes require enzyme modification, which limits the working environment and sensing performance. Herein, the burr-like CuO nanostructures are modified on the entire surfaces of the ordered Si nanowires (SiNWs) by using a combination of magnetron sputtering and hydrothermal growth. The optimized CuO@SiNWs heterojunction with a core-shell structure enables enzyme-free PEC detection of H2O2, achieving a sensitivity of 227.76 μAmM-1cm-2 in the concentration range of 0–588 mM and a detection limit of 7.14 μM (Signal/Noise=3). The excellent sensing performance of the CuO@SiNWs is attributed to the large specific surface area provided by SiNWs and the CuO possess desired H2O2-catalytic activity while providing a great number of active sites. In addition, the CuO@SiNWs demonstrates satisfactory optical absorption. This work demonstrates that enzyme-free and highly sensitive H2O2 detection can be achieved by hybrid nanostructure, providing an alternative route to H2O2 sensing.
Recently, bio/chemical sensors are widely used in the fields of medical diagnostics, environmental monitoring, and food safety. Among them, reflection interference spectroscopy sensor has significant advantages in real-time, label-free and non-destructive detection. However, reflective interferometer sensors are mainly based on porous materials with a small variation range of the aperture size, and flow of the measured molecules is not smooth in the semi-closed nanopores, leading to the limited detection range, long response time and poor anti-interference ability. In this work, we experimentally demonstrate a real-time reflective interferometric optical sensing system based on the ordered nanowires/disordered porous Si hybrid structure. Combined with an optical fiber spectrometer and a microfluidic unit, our constructed sensor can realize the selective detection of glucose molecules. The peak shift of fast Fourier transform (FFT) spectrum can be up to 308.6 nm as the glucose concentration changes at 1 mol/L. The response time is about 80 s, and the linear range is from 2 mmol/L to 3 mol/L. The proposed hybrid structure is much superior in sensitivity and response time as compared to the sensors based on the double-layer porous Si, and can simultaneously realize the selective detection of both large and small molecules under reasonable design, while the sensors based on single layer of order Si nanowires or porous Si cannot. This work opens a pathway for label-free and selective sensing in the circumstances of mixed large and small molecules, which expands the functions and applications of reflective interference optical sensors.
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