Low-cost synthesis of pure ZnO nanowalls showing three-fold symmetry.

ZnO nanowalls (NWLs) represent a non-toxic, Earth abundant, high surface-to-volume ratio, semiconducting nanostructure which has already showed potential applications in biosensing, environmental monitoring and energy. Low-cost synthesis of these nanostructures is extremely appealing for large scale upgrading of laboratory results, and its implementation has to be tested at the nanoscale, at least in terms of chemical purity and crystallographic orientation. Here, we have produced pure and texturized ZnO NWLs by using chemical bath deposition (CBD) synthesis followed by a thermal treatment at 300 °C. We examined the NWL formation process and the new obtained structure at the nanoscale, by means of scanning and transmission electron microscopy in combination with x-ray diffraction and Rutherford backscattering spectrometry. We have shown that only after annealing at 300 °C in nitrogen does the as-grown material, composed of a mixture of Zn compounds NWLs, show its peculiar crystal arrangement. The resulting ZnO sheets are in fact made by ZnO wurtzite domains (4-5 nm) that show a particular kind of texturization; indeed, they are aligned with their own c-axis always perpendicular to the sheets forming the wall and rotated (around the c-axis) by multiples of 20° from each other. The presented data show that low-cost CBD, followed by an annealing process, gives pure ZnO with a peculiarly ordered nanostructure that shows three-fold symmetry. Such evidence at the nanoscale will have significant implications for realizing sensing or catalyst devices based on ZnO NWLs.

Pain-Free Alpha-Synuclein Detection by Low-Cost Hierarchical Nanowire Based Electrode.

Analytical methods for the early detection of the neurodegenerative biomarker for Parkinson's disease (PD), α-synuclein, are time-consuming and invasive, and require skilled personnel and sophisticated and expensive equipment. Thus, a pain-free, prompt and simple α-synuclein biosensor for detection in plasma is highly demanded. In this paper, an α-synuclein electrochemical biosensor based on hierarchical polyglutamic acid/ZnO nanowires decorated by gold nanoparticles, assembled as nanostars (NSs), for the determination of α-synuclein in human plasma is proposed. ZnO NSs were prepared by chemical bath deposition (CBD) and decorated with electrodeposited Au nanoparticles (Au NPs). Then, electro-polymerized glutamic acid was grown and functionalized with anti-α-synuclein. A synergistic enhancement of electrode sensitivity was observed when Au NPs were embedded into ZnO NSs. The analytical performance of the biosensor was evaluated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), using the Fe(II)(CN)64-/Fe(III)(CN)63- probe. The charge transfer resistance after α-synuclein recognition was found to be linear, with a concentration in the range of 0.5 pg·mL-1 to 10 pg·mL-1, a limit of detection of 0.08 pg·mL-1, and good reproducibility (5% variation) and stability (90%). The biosensor was also shown to reliably discriminate between healthy plasma and PD plasma. These results suggest that the proposed biosensor provides a rapid, quantitative and high-sensitivity result of the α-synuclein content in plasma, and represents a feasible tool capable of accelerating the early and non-invasive identification of Parkinson's disease.

Low-Cost, High-Yield Zinc Oxide-Based Nanostars for Alkaline Overall Water Splitting.

The investigation of high-efficiency and sustainable electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media is critical for renewable energy technologies. Here, we report a low-cost and high-yield method to obtain ZnOHF-ZnO-based 2D nanostars (NSs) by means of chemical bath deposition (CBD). The obtained NSs, cast onto graphene paper substrates, were used as active materials for the development of a full water splitting cell. For the HER, NSs were decorated with an ultralow amount of Pt nanoparticles (11.2 µg cm-2), demonstrating an overpotential of 181 mV at a current density of 10 mA cm-2. The intrinsic activity of Pt was optimized, thanks to the ZnO supporting nanostructures, as outlined by the mass activity of Pt (0.9 mA mgPt-1) and its turnover frequency (0.27 s-1 for a Pt loading of 11.2 µg cm-2). For the OER, bare NSs showed a remarkable result of 355 mV at 10 mA cm-2 in alkaline media. Pt-decorated and bare NSs were used as the cathode and anode, respectively, for alkaline electrochemical water splitting, assessing a stable overpotential of 1.7 V at a current density of 10 mA cm-2. The reported data pave the way toward large-scale production of low-cost electrocatalysts for green hydrogen production.

Low-Cost, High-Yield ZnO Nanostars Synthesis for Pseudocapacitor Applications.

Energy storage devices based on earth-abundant materials are key steps towards portable and sustainable technologies used in daily life. Pseudocapacitive devices, combining high power and high energy density features, are widely required, and transition metal oxides represent promising building materials owing to their excellent stability, abundance, and ease of synthesis. Here, we report an original ZnO-based nanostructure, named nanostars (NSs), obtained at high yields by chemical bath deposition (CBD) and applied as pseudocapacitors. The ZnO NSs appeared as bundles of crystalline ZnO nanostrips (30 nm thin and up to 12 µm long) with a six-point star shape, self-assembled onto a plane. X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence spectroscopy (PL) were used to confirm the crystal structure, shape, and defect-mediated radiation. The ZnO NSs, dispersed onto graphene paper, were tested for energy storage by cyclic voltammetry (CV) and galvanostatic charge−discharge (GCD) analyses, showing a clear pseudocapacitor behavior. The energy storage mechanism was analyzed and related to oxygen vacancy defects at the surface. A proper evaluation of the charge stored on the ZnO NSs and the substrate allowed us to investigate the storage efficiency, measuring a maximum specific capacitance of 94 F g−1 due to ZnO nanostars alone, with a marked diffusion-limited behavior. The obtained results demonstrate the promising efficacy of ZnO-based NSs as sustainable materials for pseudocapacitors.

Localized Energy Band Bending in ZnO Nanorods Decorated with Au Nanoparticles.

Surface decoration by means of metal nanostructures is an effective way to locally modify the electronic properties of materials. The decoration of ZnO nanorods by means of Au nanoparticles was experimentally investigated and modelled in terms of energy band bending. ZnO nanorods were synthesized by chemical bath deposition. Decoration with Au nanoparticles was achieved by immersion in a colloidal solution obtained through the modified Turkevich method. The surface of ZnO nanorods was quantitatively investigated by Scanning Electron Microscopy, Transmission Electron Microscopy and Rutherford Backscattering Spectrometry. The Photoluminescence and Cathodoluminescence of bare and decorated ZnO nanorods were investigated, as well as the band bending through Mott-Schottky electrochemical analyses. Decoration with Au nanoparticles induced a 10 times reduction in free electrons below the surface of ZnO, together with a decrease in UV luminescence and an increase in visible-UV intensity ratio. The effect of decoration was modelled with a nano-Schottky junction at ZnO surface below the Au nanoparticle with a Multiphysics approach. An extensive electric field with a specific halo effect formed beneath the metal-semiconductor interface. ZnO nanorod decoration with Au nanoparticles was shown to be a versatile method to tailor the electronic properties at the semiconductor surface.

Performance of natural-dye-sensitized solar cells by ZnO nanorod and nanowall enhanced photoelectrodes.

In this work, two natural dyes extracted from henna and mallow plants with a maximum absorbance at 665 nm were studied and used as sensitizers in the fabrication of dye-sensitized solar cells (DSSCs). Fourier transform infrared (FTIR) spectra of the extract revealed the presence of anchoring groups and coloring constituents. Two different structures were prepared by chemical bath deposition (CBD) using zinc oxide (ZnO) layers to obtain ZnO nanowall (NW) or nanorod (NR) layers employed as a thin film at the photoanode side of the DSSC. The ZnO layers were annealed at different temperatures under various gas sources. Indeed, the forming gas (FG) (N2/H2 95:5) was found to enhance the conductivity by a factor of 103 compared to nitrogen (N2) or oxygen (O2) annealing gas. The NR width varied between 40 and 100 nm and the length from 500 to 1000 nm, depending on the growth time. The obtained NWs had a length of 850 nm. The properties of the developed ZnO NW and NR layers with different thicknesses and their effect on the photovoltaic parameters were studied. An internal coverage of the ZnO NWs was also applied by the deposition of a thin TiO2 layer by reactive sputtering to improve the cell performance. The application of this layer increased the overall short circuit current Jsc by seven times from 2.45 × 10-3 mA/cm2 to 1.70 × 10-2 mA /cm2.