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.

Advances in WO3-Based Supercapacitors: State-of-the-Art Research and Future Perspectives.

Electrochemical energy storage devices are one of the main protagonists in the ongoing technological advances in the energy field, whereby the development of efficient, sustainable, and durable storage systems aroused a great interest in the scientific community. Batteries, electrical double layer capacitors (EDLC), and pseudocapacitors are characterized in depth in the literature as the most powerful energy storage devices for practical applications. Pseudocapacitors bridge the gap between batteries and EDLCs, thus supplying both high energy and power densities, and transition metal oxide (TMO)-based nanostructures are used for their realization. Among them, WO3 nanostructures inspired the scientific community, thanks to WO3's excellent electrochemical stability, low cost, and abundance in nature. This review analyzes the morphological and electrochemical properties of WO3 nanostructures and their most used synthesis techniques. Moreover, a brief description of the electrochemical characterization methods of electrodes for energy storage, such as Cyclic Voltammetry (CV), Galvanostatic Charge-Discharge (GCD), and Electrochemical Impedance Spectroscopy (EIS) are reported, to better understand the recent advances in WO3-based nanostructures, such as pore WO3 nanostructures, WO3/carbon nanocomposites, and metal-doped WO3 nanostructure-based electrodes for pseudocapacitor applications. This analysis is reported in terms of specific capacitance calculated as a function of current density and scan rate. Then we move to the recent progress made for the design and fabrication of WO3-based symmetric and asymmetric supercapacitors (SSCs and ASCs), thus studying a comparative Ragone plot of the state-of-the-art research.

WO3 Nanorods Decorated with Very Small Amount of Pt for Effective Hydrogen Evolution Reaction.

The electrochemical hydrogen evolution reaction (HER) is one of the most promising green methods for the efficient production of renewable and sustainable H2, for which platinum possesses the highest catalytic activity. Cost-effective alternatives can be obtained by reducing the Pt amount and still preserving its activity. The Pt nanoparticle decoration of suitable current collectors can be effectively realized by using transition metal oxide (TMO) nanostructures. Among them, WO3 nanorods are the most eligible option, thanks to their high stability in acidic environments, and large availability. Herein, a simple and affordable hydrothermal route is used for the synthesis of hexagonal WO3 nanorods (average length and diameter of 400 and 50 nm, respectively), whose crystal structure is modified after annealing at 400 °C for 60 min, to obtain a mixed hexagonal/monoclinic crystal structure. These nanostructures were investigated as support for the ultra-low-Pt nanoparticles (0.2-1.13 µg/cm2): decoration occurs by drop casting some drops of a Pt nanoparticle aqueous solution and the electrodes were tested for the HER in acidic environment. Pt-decorated WO3 nanorods were characterized by performing scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Rutherford backscattering spectrometry (RBS), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and chronopotentiometry. HER catalytic activity is studied as a function of the total Pt nanoparticle loading, thus obtaining an outstanding overpotential of 32 mV at 10 mA/cm2, a Tafel slope of 31 mV/dec, a turn-over frequency of 5 Hz at -15 mV, and a mass activity of 9 A/mg at 10 mA/cm2 for the sample decorated with the highest Pt amount (1.13 µg/cm2). These data show that WO3 nanorods act as excellent supports for the development of an ultra-low-Pt-amount-based cathode for efficient and low-cost electrochemical HER.

Engineering of Nanostructured WO3 Powders for Asymmetric Supercapacitors.

Transition metal oxide nanostructures are promising materials for energy storage devices, exploiting electrochemical reactions at nanometer solid-liquid interface. Herein, WO3 nanorods and hierarchical urchin-like nanostructures were obtained by hydrothermal method and calcination processes. The morphology and crystal phase of WO3 nanostructures were investigated by scanning and transmission electron microscopy (SEM and TEM) and X-ray diffraction (XRD), while energy storage performances of WO3 nanostructures-based electrodes were evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) tests. Promising values of specific capacitance (632 F/g at 5 mV/s and 466 F/g at 0.5 A/g) are obtained when pure hexagonal crystal phase WO3 hierarchical urchin-like nanostructures are used. A detailed modeling is given of surface and diffusion-controlled mechanisms in the energy storage process. An asymmetric supercapacitor has also been realized by using WO3 urchin-like nanostructures and a graphene paper electrode, revealing the highest energy density (90 W × h/kg) at a power density of 90 W × kg-1 and the highest power density (9000 W/kg) at an energy density of 18 W × h/kg. The presented correlation among physical features and electrochemical performances of WO3 nanostructures provides a solid base for further developing energy storage devices based on transition metal oxides.

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.