BiVO4-Liquid Junction Photovoltaic Cell with 0.2% Solar Energy Conversion Efficiency.

BiVO4 is an important photoanode material for water oxidation, but its photoelectrochemistry regarding the triiodide/iodide redox couple is not well understood. Here, we use a combination of open circuit potential measurements, photoelectrochemical scans, and liquid surface photovoltage spectroscopy (SPS) to confirm that BiVO4/triiodide/iodide electrolyte contacts produce up to 0.55 V photovoltage under 23 mW/cm-2 illumination from a 470 nm LED. Inspired by these results, we construct FTO/BiVO4/KI(I2)aq/Pt sandwich photoelectrochemical cells from electrochemically grown 0.5 × 0.5 cm2 BiVO4 and Mo-doped BiVO4 films. Under AM 1.5 illumination, the devices have up to 0.22% energy conversion efficiency, 0.32 V photovoltage, and 1.8 mA cm-2 photocurrent. Based on SPS, hole transfer to iodide is sufficiently fast to prevent the competing water oxidation reaction. Mo doping increases the incident photon-to-current efficiency to up to 55% (at 425 nm under front illumination) by improving the BiVO4 conductivity, but this comes at the expense of a lower photovoltage resulting from recombination at the Mo defects and a detrimental Schottky junction at the interface with FTO. Additional photovoltage losses are caused by the offset between the BiVO4 valence band edge and the triiodide/iodide electrochemical potential and by electron back transfer to iodide at the FTO back contact (shunting). Overall, this work provides the first example of a BiVO4-liquid photovoltaic cell and an analysis of its limitations. Even though the larger band gaps of metal oxides constrain their solar energy conversion efficiency, their transparency to visible light and deep valence bands makes them suitable for tandem photovoltaic devices.

Mesoporous CuFe2 O4 Photoanodes for Solar Water Oxidation: Impact of Surface Morphology on the Photoelectrochemical Properties.

Metal oxide-based photoelectrodes for solar water splitting often utilize nanostructures to increase the solid-liquid interface area. This reduces charge transport distances and increases the photocurrent for materials with short minority charge carrier diffusion lengths. While the merits of nanostructuring are well established, the effect of surface order on the photocurrent and carrier recombination has not yet received much attention in the literature. To evaluate the impact of pore ordering on the photoelectrochemical properties, mesoporous CuFe2 O4 (CFO) thin film photoanodes were prepared by dip-coating and soft-templating. Here, the pore order and geometry can be controlled by addition of copolymer surfactants poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic® F-127), polyisobutylene-block-poly(ethylene oxide) (PIB-PEO) and poly(ethylene-co-butylene)-block-poly(ethylene oxide) (Kraton liquid™-PEO, KLE). The non-ordered CFO showed the highest photocurrent density of 0.2 mA/cm2 at 1.3 V vs. RHE for sulfite oxidation, but the least photocurrent density for water oxidation. Conversely, the ordered CFO presented the best photoelectrochemical water oxidation performance. These differences can be understood on the basis of the high surface area, which promotes hole transfer to sulfite (a fast hole acceptor), but retards oxidation of water (a slow hole acceptor) due to electron-hole recombination at the defective surface. This interpretation is confirmed by intensity-modulated photocurrent (IMPS) and vibrating Kelvin probe surface photovoltage spectroscopy (VKP-SPS). The lowest surface recombination rate was observed for the ordered KLE-based mesoporous CFO, which retains spherical pore shapes at the surface resulting in fewer surface defects. Overall, this work shows that the photoelectrochemical energy conversion efficiency of copper ferrite thin films is not just controlled by the surface area, but also by surface order.

Two-Dimensional Nanomaterials beyond Graphene for Biomedical Applications.

Two-dimensional (2D) nanomaterials (e.g., graphene) have shown to have a high potential in future biomedical applications due to their unique physicochemical properties such as unusual electrical conductivity, high biocompatibility, large surface area, and extraordinary thermal and mechanical properties. Although the potential of graphene as the most common 2D nanomaterials in biomedical applications has been extensively investigated, the practical use of other nanoengineered 2D materials beyond graphene such as transition metal dichalcogenides (TMDs), topological insulators (TIs), phosphorene, antimonene, bismuthene, metal-organic frameworks (MOFs) and MXenes for biomedical applications have not been appreciated so far. This review highlights not only the unique opportunities of 2D nanomaterials beyond graphene in various biomedical research areas such as bioelectronics, imaging, drug delivery, tissue engineering, and regenerative medicine but also addresses the risk factors and challenges ahead from the medical perspective and clinical translation of nanoengineered 2D materials. In conclusion, the perspectives and future roadmap of nanoengineered 2D materials beyond graphene are outlined for biomedical applications.

Electrospun CuO-ZnO nanohybrid: Tuning the nanostructure for improved amperometric detection of hydrogen peroxide as a non-enzymatic sensor.

Hydrogen peroxide (H2O2) is a by-product of some biochemical processes which is catalyzed by enzymes such as glucose oxidase (GOx), cholesterol oxidase (ChoOx), etc and its overproduction in living cells can trigger cancer growth and various diseases. Therefore, H2O2 sensing is of great importance in the determination of diseases as well as industries and environmental health plans. We produced ZnO-CuO nanofibers by electrospinning method for non-enzymatic electrochemical H2O2 sensing. The sensing properties of the carbon paste electrode (CPE) modified with ZnO (0.3 wt%)/CuO (0.7 wt%) nanofibers (named as ZnO3-CuO7) for detection of H2O2 were explored in phosphate-buffered saline (PBS) at pH ∼ 7.4 solution. The ZnO3-CuO7 nanofiber exhibited the lowest charge transfer resistance and the highest electrocatalytic performance among other modified electrodes for detection of H2O2 and considered as an optimized sample. The effect of scan rate and H2O2 concentration in the reduction process were also investigated by cyclic voltammetry (CV) and the mechanism for the electrochemical reaction of H2O2 at the surface of the optimized electrode was studied. The diffusion coefficient of H2O2 and the catalytic rate constant were evaluated by chronoamperometry as 1.65 × 10-5 cm2 s-1 and 6 × 103 cm3 mol-1 s-1, respectively. Furthermore, amperometric detection of H2O2 with a low detection limit of 2.4 µM and a wide linear range of 3 to 530 µM were obtained. Meanwhile, the optimized electrode displayed no recognizable response towards some biomolecules such as ascorbic acid, uric acid, dopamine and glucose. The obtained results confirmed that the modified electrode shows high sensitivity and selectivity as a H2O2 biosensor with improved reproducibility and stability.

Gold nanocages decorated biocompatible amine functionalized graphene as an efficient dopamine sensor platform.

Nanocomposite of gold nanocages and chemically modified graphene oxide (GNCs/CMG) was synthesized in N,N-dimethylformamide (DMF) for sensitive detection of dopamine (DA). DA is widely spread in central nervous system which can regulates essential body functions like movement and emotional behaviour. In this regard sensitive and fast detection of DA level in human body is still challenging considering its interference with other biomolecules in biological samples. CMG was synthesized through amine modification of graphene oxide (GO) with DMF at relatively high temperature followed by attachment of GNCs, fabricated using a galvanic replacement between silver nanocubes and HAuCl4 solution in the DMF. X-ray diffraction (XRD) pattern of GNCs/CMG nanocomposite revealed high crystallization of GNCs attached to the graphene nanosheets and microscopic images revealed relatively uniform decoration of GNCs on the surface of CMG. Nanocomposite modified glassy carbon electrode (GNCs/CMG/GCE) was used to investigate the electrochemical behaviour of DA with cyclic voltammetry and amperometry techniques. The linear range for dopamine was between 0.1 and 80µM with a low detection limit of 0.02µM. Furthermore, GNCs/CMG/GCE exhibited satisfying reproducibility, long-term stability and high selectivity for DA detection in large amount of ascorbic acid with good results for determination in human serum samples.