Photoluminescence and cathodoluminescence ͑CL͒ spectra of stoichiometric and oxygen-deficient ZnO films grown on sapphire were examined. It was found that the intensities of the green and yellow emissions depend on the width of the free-carrier depletion region at the particle surface; the thinner the width, the larger the intensity. Experimental results and spectral analyses suggest that the mechanism responsible for the green ͑yellow͒ emission is the recombination of a delocalized electron close to the conduction band with a deeply trapped hole in the single ionized oxygen vacancy V o ϩ ͑the single negatively charged interstitial oxygen ion O i Ϫ) center in the particle.

Long-term instability of Li-S batteries is one of their major disadvantages compare to other secondary batteries. The reasons for the instability include dissolution of polysulfide intermediates and mechanical instability of the electrode film caused by volume changes during charging/discharging cycles. In this paper, we report a novel graphene-sulfur-carbon nanofibers (G-S-CNFs) multilayer and coaxial nanocomposite for the cathode of Li-S batteries with increased capacity and significantly improved long-cycle stability. Electrodes made with such nanocomposites were able to deliver a reversible capacity of 694 mA h g(-1) at 0.1C and 313 mA h g(-1) at 2C, which are both substantially higher than electrodes assembled without graphene wrapping. More importantly, the long-cycle stability was significantly improved by graphene wrapping. The cathode made with G-S-CNFs with a initial capacity of 745 mA h g(-1) was able to maintain ~273 mA h g(-1) even after 1500 charge-discharge cycles at a high rate of 1C, representing an extremely low decay rate (0.043% per cycle after 1500 cycles). In contrast, the capacity of an electrode assembled without graphene wrapping decayed dramatically with a 10 times high rate (~0.40% per cycle after 200 cycles). These results demonstrate that the coaxial nanocomposites are of great potential as the cathode for high-rate rechargeable Li-S batteries. Such improved rate capability and cycle stability could be attributed to the unique coaxial architecture of the nanocomposite, in which the contributions from graphene and CNFs enable electrodes with improved electrical conductivity, better ability to trap soluble the polysulfides intermediate and accommodate volume expansion/shrinkage of sulfur during repeated charge/discharge cycles.

Ultra-long rutile tin dioxide nanowires and nanobelts are synthesized by thermal oxidation of tin powder using gold film as the catalyst. Nanowire or nanobelts can be selectively produced by tuning the reaction temperature. The vapour-liquid-solid growth mechanism is proposed. The band gaps of the nanowires and nanobelts are 3.74 and 3.81 eV respectively, determined from UV/visible absorption spectral results. The SnO2 nanowires show stable photoluminescence with two emission peaks centred at around 470 and 560 nm. Their wavelengths stay almost fixed while their intensities depend sensitively on the temperatures within the examination ranges from 10 to 300 K. The SnO2 nanobelts show similar photoluminescence behaviours and the origin of the luminescence is discussed.

Raman spectra acquired from spherical SnO 2 nanocrystals prepared by pulsed laser ablation and hydrothermal synthesis exhibit three oxygen-vacancy-related Raman modes at 234, 573, and 618 cm À1 . The peak location and intensity vary with annealing temperature under O 2 finally approaching those of bulk materials. Density functional calculation discloses that the three Raman modes stem from subbridging, in-plane, and bridging oxygen vacancies, respectively. Raman spectra can thus be used to discern different types of oxygen vacancies in SnO 2 nanocrystals.

The introduction of Prussian blue (PB), an inexpensive pigment material, elegantly breaks the solubility limit of the [Fe(CN) 6 ] 4À/3À electrolyte, and substantially boosts the capacity via an off-electrode chemical reaction. In the reversible redoxtargeting reaction cycles, PB acts as the energy reservoir, while [Fe(CN) 6 ] 4À/3À plays a role in mediating the reactions between the electrode and storage tank. The volumetric capacity surpasses other reported [Fe(CN) 6 ] 4À/3À -based and most other organic aqueous redox flow batteries.

Figure 1. TEM images of GO (a) and GQDs (b). The inset of (b) shows the size distribution of GQDs with a probable size of 8.3 nm. wileyonlinelibrary.com

Hydrogen generated by water splitting provides a renewable energy source, but development of materials with efficient electrocatalytic water splitting capability is challenging. Thin-film electrocatalytic material (H 2 −NiCat) with robust water reduction properties, which can be readily prepared by a reduction-induced electrodeposition method from nickel salts in a borate-buffered electrolyte (pH 9.2), is reported. The material consists of nanoparticles with nickel oxide or hydroxide species located at the surface and metallic nickel in the bulk. The catalyst mediates H 2 evolution in a near-neutral aqueous buffer at low overpotential. The catalyst requires a subsequent oxidative pretreatment in order to attain a well-defined hydrogen evolution reaction (HER) activity, and the 1.5 h anodized catalyst film exhibits a HER current density of about 1.50 mA cm −2 at 0.452 V overpotential over a period of 24 h with no observable corrosion. In addition, it can be converted by anodic equilibration into an amorphous Ni-based oxide film (O 2 −NiCat) to catalyze O 2 evolution, and the switch between the two catalytic forms is fully reversible. The robust, bifunctional, switchable, and noble-metal-free catalytic material has immense potential in artificial solar water-splitting devices.

Although zinc oxide (ZnO), a low-cost and naturally abundant material, has a high theoretical specific capacity of 987 mA h g for hosting lithium ions, its application as an anode material has been hindered by its rapid capacity fading, mainly due to a large volume change (around 228%) upon repeated charge-discharge cycles. Herein, using carbon black (CB) powder as a support, ZnO-carbon black (denoted as ZnO-CB) nanocomposites were successfully fabricated using the atomic layer deposition (ALD) method. This method was able to produce strong interfacial molecular bindings between ZnO nanoclusters and the carbon surface that provide stable and robust electrical contact during lithiation and delithiation processes, as well as ZnO nanoclusters rich in oxygen vacancies (OVs) for faster Li-ion transport. Overall, the nanocomposites were able to deliver a high discharge specific capacity of 2096 mA h g at 100 mA g and stable cyclic stability with a specific capacity of 1026 mA h g maintained after 500 cycles. The composites also have excellent rate capability, and a reversible capacity at a high 1080 mA h g at 2000 mA g. The facile but unique synthesis method demonstrated in this work for producing nanostructures rich in OVs and nanocomposites with strong coupling via interfacial molecular bindings could be extended to the synthesis of other oxide based anode materials and therefore could have general significance for developing high energy density lithium ion batteries.