Structural Evolution of Air-Exposed Layered Oxide Cathodes for Sodium-Ion Batteries: An Example of Ni-doped NaxMnO2.

Sodium-ion batteries have recently aroused the interest of industries as possible replacements for lithium-ion batteries in some areas. With their high theoretical capacities and competitive prices, P2-type layered oxides (NaxTMO2) are among the obvious choices in terms of cathode materials. On the other hand, many of these materials are unstable in air due to their reactivity toward water and carbon dioxide. Here, Na0.67Mn0.9Ni0.1O2 (NMNO), one of such materials, has been synthesized by a classic sol-gel method and then exposed to air for several weeks as a way to allow a simple and reproducible transition toward a Na-rich birnessite phase. The transition between the anhydrous P2 to the hydrated birnessite structure has been followed via periodic XRD analyses, as well as neutron diffraction ones. Extensive electrochemical characterizations of both pristine NMNO and the air-exposed one vs sodium in organic medium showed comparable performances, with capacities fading from 140 to 60 mAh g-1 in around 100 cycles. Structural evolution of the air-exposed NMNO has been investigated both with ex situ synchrotron XRD and Raman. Finally, DFT analyses showed similar charge compensation mechanisms between P2 and birnessite phases, providing a reason for the similarities between the electrochemical properties of both materials.

Charge Storage Mechanism in Electrospun Spinel-Structured High-Entropy (Mn0.2 Fe0.2 Co0.2 Ni0.2 Zn0.2 )3 O4 Oxide Nanofibers as Anode Material for Li-Ion Batteries.

High-entropy oxides (HEOs) have emerged as promising anode materials for next-generation lithium-ion batteries (LIBs). Among them, spinel HEOs with vacant lattice sites allowing for lithium insertion and diffusion seem particularly attractive. In this work, electrospun oxygen-deficient (Mn,Fe,Co,Ni,Zn) HEO nanofibers are produced under environmentally friendly calcination conditions and evaluated as anode active material in LIBs. A thorough investigation of the material properties and Li+ storage mechanism is carried out by several analytical techniques, including ex situ synchrotron X-ray absorption spectroscopy. The lithiation process is elucidated in terms of lithium insertion, cation migration, and metal-forming conversion reaction. The process is not fully reversible and the reduction of cations to the metallic form is not complete. In particular, iron, cobalt, and nickel, initially present mainly as Fe3+ , Co3+ /Co2+ , and Ni2+ , undergo reduction to Fe0 , Co0 , and Ni0 to different extent (Fe < Co < Ni). Manganese undergoes partial reduction to Mn3+ /Mn2+ and, upon re-oxidation, does not revert to the pristine oxidation state (+4). Zn2+ cations do not electrochemically participate in the conversion reaction, but migrating from tetrahedral to octahedral positions, they facilitate Li-ion transport within lattice channels opened by their migration. Partially reversible crystal phase transitions are observed.

Structure and magnetism of electrospun porous high-entropy (Cr1/5Mn1/5Fe1/5Co1/5Ni1/5)3O4, (Cr1/5Mn1/5Fe1/5Co1/5Zn1/5)3O4 and (Cr1/5Mn1/5Fe1/5Ni1/5Zn1/5)3O4 spinel oxide nanofibers.

High-entropy oxide nanofibers, based on equimolar (Cr,Mn,Fe,Co,Ni), (Cr,Mn,Fe,Co,Zn) and (Cr,Mn,Fe,Ni,Zn) combinations, were prepared by electrospinning followed by calcination. The obtained hollow nanofibers exhibited a porous structure consisting of interconnected nearly strain-free (Cr1/5Mn1/5Fe1/5Co1/5Ni1/5)3O4, (Cr1/5Mn1/5Fe1/5Co1/5Zn1/5)3O4 and (Cr1/5Mn1/5Fe1/5Ni1/5Zn1/5)3O4 single crystals with a pure Fd3̄m spinel structure. Oxidation state of the cations at the nanofiber surface was assessed by X-ray photoelectron spectroscopy and cation distributions were proposed satisfying electroneutrality and optimizing octahedral stabilization. The magnetic data are consistent with a distribution of cations that satisfies the energetic preferences for octahedral vs. tetrahedral sites and is random only within the octahedral and tetrahedral sublattices. The nanofibers are ferrimagnets with relatively low critical temperature more similar to cubic chromites and manganites than to ferrites. Replacing the magnetic cations Co or Ni with non-magnetic Zn lowers the critical temperature from 374 K (Cr,Mn,Fe,Co,Ni) to 233 and 105 K for (Cr,Mn,Fe,Ni,Zn) and (Cr,Mn,Fe,Co,Zn), respectively. The latter nanofibers additionally have a low temperature transition to a reentrant spin-glass-like state.

Light Emission Properties of Thermally Evaporated CH3NH3PbBr3 Perovskite from Nano- to Macro-Scale: Role of Free and Localized Excitons.

Over the past decade, interest about metal halide perovskites has rapidly increased, as they can find wide application in optoelectronic devices. Nevertheless, although thermal evaporation is crucial for the development and engineering of such devices based on multilayer structures, the optical properties of thermally deposited perovskite layers (spontaneous and amplified spontaneous emission) have been poorly investigated. This paper is a study from a nano- to micro- and macro-scale about the role of light-emitting species (namely free carriers and excitons) and trap states in the spontaneous emission of thermally evaporated thin layers of CH3NH3PbBr3 perovskite after wet air UV light trap passivation. The map of light emission from grains, carried out by SNOM at the nanoscale and by micro-PL techniques, clearly indicates that free and localized excitons (EXs) are the dominant light-emitting species, the localized excitons being the dominant ones in the presence of crystallites. These species also have a key role in the amplified spontaneous emission (ASE) process: for higher excitation densities, the relative contribution of localized EXs basically remains constant, while a clear competition between ASE and free EXs spontaneous emission is present, which suggests that ASE is due to stimulated emission from the free EXs.

Evaluation of Electrospun Self-Supporting Paper-Like Fibrous Membranes as Oil Sorbents.

Presently, adsorption/absorption is one of the most efficient and cost-effective methods to clean oil spill up. In this work, self-supporting paper-like fibrous membranes were prepared via electrospinning and carbonisation at different temperatures (500, 650 or 800 °C) by using polyacrylonitrile/polymethylmethacrylate blends with a different mass ratio of the two polymers (1:0, 6:1 or 2:1). After morphological and microstructural characterisation, the as-produced membranes were evaluated as sorbents by immersion in vegetable (sunflower seed or olive) and mineral (motor) oil or in 1:4 (v:v) oil/water mixture. Nitrogen-rich membrane carbonised at the lowest temperature behaves differently from the others, whose sorption capacity by immersion in oil, despite the great number of sorbent and oil properties involved, is mainly controlled by the fraction of micropores. The encapsulation of water nanodroplets by the oil occurring during the immersion in oil/water mixture causes the oil-from-water separation ability to show an opposite behaviour compared to the sorption capacity. Overall, among the investigated membranes, the support produced with 2:1 mass ratio of the polymers and carbonisation at 650 °C exhibits the best performance both in terms of sorption capacity (73.5, 54.8 and 12.5 g g-1 for olive, sunflower seed and motor oil, respectively) and oil-from-water separation ability (74, 69 and 16 for olive, sunflower seed and motor oil, respectively).

Effect of Hematite Doping with Aliovalent Impurities on the Electrochemical Performance of α-Fe2O3@rGO-Based Anodes in Sodium-Ion Batteries.

The effect of the type of dopant (titanium and manganese) and of the reduced graphene oxide content (rGO, 30 or 50 wt %) of the α-Fe2O3@rGO nanocomposites on their microstructural properties and electrochemical performance was investigated. Nanostructured composites were synthesized by a simple one-step solvothermal method and evaluated as anode materials for sodium ion batteries. The doping does not influence the crystalline phase and morphology of the iron oxide nanoparticles, but remarkably increases stability and Coulombic efficiency with respect to the anode based on the composite α-Fe2O3@rGO. For fixed rGO content, Ti-doping improves the rate capability at lower rates, whereas Mn-doping enhances the electrode stability at higher rates, retaining a specific capacity of 56 mAhg-1 at a rate of 2C. Nanocomposites with higher rGO content exhibit better electrochemical performance.

Structure, Defects, and Magnetism of Electrospun Hematite Nanofibers Silica-Coated by Atomic Layer Deposition.

In the last years, hematite has been utilized in a plethora of applications. High aspect-ratio nanohematite and hematite/silica core-shell nanostructures are arousing growing interest for applications exploiting their magnetic properties. Atomic layer deposition (ALD) is utilized here to produce SiO2-coated α-Fe2O3 nanofibers (NFs) through two synthetic routes, viz. electrospinning/calcination/ALD or electrospinning/ALD/calcination. The number of ALD cycles (10-100) modulates the coating thickness, while the chosen route controls the final nanostructure. Porous and partially hollow NFs are produced. Their hierarchical structure and the nature and density of the lattice defects and strain are characterized by combining electron microscopy, diffraction, and spectroscopy techniques. The uncoated hematite NFs mostly have surface-related strain, which is attributed to oxygen vacancies/Fe2+ sites. ALD coating causes microstrain release and decrease of surface states. NFs calcined after ALD have extensive bulk strain, which is ascribed to the presence of dislocations throughout the volume of the NF grains. Bulk strain determines the remanent magnetization, whereas both surface and bulk strain influence the coercive field and the thermal behavior across the Morin temperature, including the magnetic memory effect. To the best of the authors' knowledge, the correlation between lattice defects/strain and magnetic properties of SiO2-coated α-Fe2O3 NFs has never been reported before.

Role of the carbon defects in the catalytic oxygen reduction by graphite nanoparticles: a spectromagnetic, electrochemical and computational integrated approach.

The chemical groups present at the surface of graphite have been thought for a long time to be mainly responsible for its catalytic activity in the oxygen reduction reaction. Recently, it was proposed that the surface defects of graphite also significantly contribute to promote this reaction. Although the behaviour of surface defects has been reported, only few comments have been dedicated to their involvement in the mechanism and the possible intermediate species in the oxygen reduction reaction. Herein, we aim to present a more detailed explanation of the catalytic activity of graphite particles based on the structure of their defects and their size. Structural, spectroscopic and magnetic investigation (X-ray diffraction, Raman and electron spin resonance) and electrochemical measurements were performed to describe the nature of the defects and their aptitude to transfer electrons. Computational description supplied precise details of the energy of the different defects and their ability to promote the reduction, also suggesting the structure of the intermediate adduct in the oxygen reduction. The results indicated that molecular oxygen preferentially interacts with graphite defects, which involve the π-electron system and accumulation of the spin density on the edges of the grains, in particular, on the zig-zag edges present on ball-milled graphite. This promotes the reactivity of this nanomaterial. Furthermore, the activation increases by decreasing the particle size.

Synergistic Effects of Active Sites' Nature and Hydrophilicity on the Oxygen Reduction Reaction Activity of Pt-Free Catalysts.

This work highlights the importance of the hydrophilicity of a catalyst's active sites on an oxygen reduction reaction (ORR) through an electrochemical and physico-chemical study on catalysts based on nitrogen-modified carbon doped with different metals (Fe, Cu, and a mixture of them). BET, X-ray Powder Diffraction (XRPD), micro-Raman, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), and hydrophilicity measurements were performed. All synthesized catalysts are characterized not only by a porous structure, with the porosity distribution centered in the mesoporosity range, but also by the presence of carbon nanostructures. In iron-doped materials, these nanostructures are bamboo-like structures typical of nitrogen carbon nanotubes, which are better organized, in a larger amount, and longer than those in the copper-doped material. Electrochemical ORR results highlight that the presence of iron and nitrogen carbon nanotubes is beneficial to the electroactivity of these materials, but also that the hydrophilicity of the active site is an important parameter affecting electrocatalytic properties. The most active material contains a mixture of Fe and Cu.

CO2 sensing properties of electro-spun Ca-doped ZnO fibres.

The availability of low-cost, high-performing sensors for carbon dioxide detection in the environment may play a crucial role for reducing CO2 emissions and limiting global warming. In this study, calcium-doped zinc oxide nanofibres with different Ca to Zn loading ratios (1:40 or 1:20) are synthesised via electro-spinning, thoroughly characterised and, for the first time, tested as an active material for the detection of carbon dioxide. The results of their characterisation show that the highly porous fibres consist of interconnected grains of oxide with the hexagonal wurtzite structure of zincite. Depending on the Ca:Zn loading ratio, calcium fully or partly segregates to form calcite on the fibre surface. The high response of the sensor based on the fibres with the highest Ca-doping level can be attributed to the synergy between the fibre morphology and the basicity of Ca-ion sites, which favour the diffusion of the gas molecules within the sensing layer and the CO2 adsorption, respectively.

Stabilization of Titanium Dioxide Nanoparticles at the Surface of Carbon Nanomaterials Promoted by Microwave Heating.

TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO2 @C, and that microwave irradiation can be advantageous for the synthesis of carbon-based materials. Composites of TiO2 with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO2 nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO2 is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance.

Chemical Modification of Graphene Oxide through Diazonium Chemistry and Its Influence on the Structure-Property Relationships of Graphene Oxide-Iron Oxide Nanocomposites.

4-Carboxyphenyl groups are covalently grafted onto graphene oxide via diazonium chemistry for studying their role on the adsorption of iron oxide nanoparticles. The nanoparticles are deposited via a novel phase-transfer approach involving specific interactions at the interface between two immiscible solvents. The increased density and the homogeneous distribution of surface carboxyl moieties enable the preparation of a nanocomposite with improved iron oxide distribution and loading. Structure-properties relationships are investigated by analysing the electrochemical properties of the nanocomposites, which are regarded as promising active materials for application in supercapacitors. It is demonstrated that the nature of the interactions between the components similarly affects the overall electrochemical performances of the nanocomposites and the structure of the materials.

Effect of nature and location of defects on bandgap narrowing in black TiO2 nanoparticles.

The increasing need for new materials capable of solar fuel generation is central in the development of a green energy economy. In this contribution, we demonstrate that black TiO(2) nanoparticles obtained through a one-step reduction/crystallization process exhibit a bandgap of only 1.85 eV, which matches well with visible light absorption. The electronic structure of black TiO(2) nanoparticles is determined by the unique crystalline and defective core/disordered shell morphology. We introduce new insights that will be useful for the design of nanostructured photocatalysts for energy applications.

Crystalline quality evaluation of carbon nanotubes by kinetic analysis in quasi-isothermal conditions.

We demonstrate that the crystalline quality of multi-walled carbon nanotubes (MWCNTs) is better estimated by the apparent activation energy of the oxidation reaction, obtained by kinetic analysis in quasi-isothermal conditions, than by the peak-temperature position in the derivative mass loss curves. This is proven by the existence of a good correlation, reported for the first time herein, between apparent activation energy and G'-band to D-band intensity ratio derived from micro-Raman spectroscopy, which is largely accepted as an indicator of the overall MWCNT crystalline quality. In contrast, no clear reliance is found between G'/D intensity ratio and the peak-temperature position in the derivative mass loss curves. These conclusions were drawn after investigation of a large number of commercially available and laboratory prepared MWCNTs.