Dissolution Mechanism of Eutectic and Hypereutectic Mg-Sn Alloy Anodes for Magnesium Rechargeable Batteries.

Magnesium rechargeable batteries (MRBs) are presently attracting much attention due to their low cost, high safety, and high theoretical volumetric capacity. Traditionally, pure magnesium metal has been used as an anode for MRBs, but its poor cycle performance, modest compatibility with conventional electrolytes, and sluggish kinetics limit the further development of MRBs. In this work, eutectic and hypereutectic Mg-Sn alloys were designed and studied as anodes for MRBs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results confirmed that these alloys contained unique microstructures consisting of α-Mg, Mg2Sn, and eutectic phases. The dissolution processes of the Mg-Sn alloys were studied in an all-phenyl-complex (APC) electrolyte. A multiple-step electrochemical dissolution process and a special adsorption interface layer were established for the Mg-Sn alloy anodes with an eutectic phase. Hypereutectic alloys with mixed phases showed better battery performance than the eutectic alloy owing to their superior mechanical properties. In addition, the morphology and Mg dissolution mechanism of the Mg-Sn alloys during the 1st dissolution process were characterized and discussed.

Fast Room-Temperature Mg2+ Conductivity in Mg(BH4)2·1.6NH3-Al2O3 Nanocomposites.

Design of new functional materials with fast Mg-ion mobility is crucial for the development of competitive solid-state magnesium batteries. Herein, we present new nanocomposites, Mg(BH4)2·1.6NH3-Al2O3, reaching a high magnesium conductivity of σ(Mg2+) = 2.5 × 10-5 S cm-1 at 22 °C assigned to favorable interfaces between amorphous state Mg(BH4)2·1.6NH3; inert and insulating Al2O3 nanoparticles; and a minor fraction of crystalline material, mainly Mg(BH4)2·2NH3. Furthermore, quasi-elastic neutron scattering reveals that the Mg2+-ion mobility in the solid state appears to be correlated to relatively slow motion of NH3 molecules rather than the fast dynamics of BH4- complexes. The nanocomposite is compatible with a metallic Mg anode and shows stable Mg2+ stripping/plating in a symmetric cell and an electrochemical stability of ∼1.2 V. The nanocomposite has high mechanical stability and ductility and is a promising Mg2+ electrolyte for future solid-state magnesium batteries.

Size Effect of MgO on the Ionic Conduction Properties of a LiBH4·1/2NH3-MgO Nanocomposite.

A solid-state electrolyte (SSE) is the core component for fabricating solid-state batteries competitive with the currently commercial Li-ion batteries. In the present study, a LiBH4·1/2NH3-MgO nanocomposite has been developed as a fast Li-ion conductor. The conductive properties depend strongly on the size of MgO nanopowders. By adding MgO nanoparticles, the first-order transition at 55 °C observed in the crystalline LiBH4·1/2NH3 is suppressed due to the conversion of LiBH4·1/2NH3 into the amorphous state. When the size of MgO decreases from 163.6 to 13.9 nm, the MgO amount required for the phase-transition suppression of LiBH4·1/2NH3 decreases linearly from 92 to 75 wt %, accompanied by a significant enhancement of ionic conductivity. The optimized nanocomposite with 75 wt % MgO of size 13.9 nm exhibits a pronouncedly high conductivity of 4.0 × 10-3 S cm-1 at room temperature, which is 20 times higher than that of the crystalline LiBH4·1/2NH3. Furthermore, a smaller size MgO contributes to a higher electrochemical stability window (ESW) owing to the stronger interfacial interaction via B-O bonds, i.e., an ESW of 4.0 V is achieved with the addition of 75 wt % MgO of size 13.9 nm.

Enhanced room temperature ionic conductivity of the LiBH4·1/2NH3-Al2O3 composite.

A novel LiBH4·1/2NH3-Al2O3 composite was demonstrated, in which amorphous LiBH4·1/2NH3 was in situ formed on the surface of Al2O3 owing to the strong interfacial interaction via B-O bonds. The ionic conductivity of LiBH4·1/2NH3 is improved by one order of magnitude to 10-3 S cm-1 and the electrochemical window up to 3.6 V.

Evolution of Zn(II) single atom catalyst sites during the pyrolysis-induced transformation of ZIF-8 to N-doped carbons.

The pyrolysis of zeolitic imidazolate frameworks (ZIFs) is becoming a popular approach for the synthesis of catalysts comprising porphyrin-like metal single atom catalysts (SACs) on N-doped carbons (M-N-C). Understanding the structural evolution of M-N-C as a function of ZIF pyrolysis temperature is important for realizing high performance catalysts. Herein, we report a detailed investigation of the evolution of Zn single atom catalyst sites during the pyrolysis of ZIF-8 at temperatures ranging from 500 to 900 °C. Results from Zn L-edge and Zn K-edge X-ray absorption spectroscopy studies reveal that tetrahedral ZnN4 centers in ZIF-8 transform to porphyrin-like ZnN4 centers supported on N-doped carbon at temperatures as low as 600 °C. As the pyrolysis temperature increased in the range 600-900 °C, the Zn atoms moved closer to the N4 coordination plane. This subtle geometry change in the ZnN4 sites alters the electron density on the Zn atoms (formally Zn2+), strongly impacting the catalytic performance for the peroxidase-like decomposition of H2O2. The catalyst obtained at 800 °C (Zn-N-C-800) offered the best performance for H2O2 decomposition. This work provides valuable new insights about the evolution of porphyrin-like single metal sites on N-doped carbons from ZIF precursors and the factors influencing SAC activity.

Enhancing photocatalytic activities of titanium dioxide via well-dispersed copper nanoparticles.

The modification of titanium dioxide (TiO2) using noble metal nanoparticles is considered as a promising technique to make electrode with outstanding photocatalytic performance. In this paper, self-organized anodic TiO2 nanotube arrays were decorated with well-distributed small Cu nanoparticles through a novel technique that combines magnetron sputtering and thermal dewetting. The obtained nanocomposite catalyst exhibited 4-fold increase in the photodegradation rate of methylene blue aqueous solution under solar light irradiation than anatase TiO2 prepared with same anodization conditions. The enhanced photocatalytic activity was attributed to the synergistic effect of Schottky barrier and Surface plasmon resonance. The influence of post annealing process, sputtering time and thermal dewetting temperature on photocatalytic performance was studied and the optimal preparation conditions were proposed. The results of this study may provide a new strategy to improve photocatalytic efficiency of TiO2 without using high-cost noble metals.

Protein nanorings organized by poly(styrene-block-ethylene oxide) self-assembled thin films.

This study explores the use of block copolymer self-assembly to organize Lsmα, a protein which forms stable doughnut-shaped heptameric structures. Here, we have explored the idea that 2-D crystalline arrays of protein filaments can be prepared by stacking doughnut shaped Lsmα protein into the poly(ethylene oxide) blocks of a hexagonal microphase-separated polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer. We were able to demonstrate the coordinated assembly of such a complex hierarchical nanostructure. The key to success was the choice of solvent systems and protein functionalization that achieved sufficient compatibility whilst still promoting assembly. Unambiguous characterisation of these structures is difficult; however AFM and TEM measurements confirmed that the protein was sequestered into the PEO blocks. The use of a protein that assembles into stackable doughnuts offers the possibility of assembling nanoscale optical, magnetic and electronic structures.

Ag/ZnO heterostructures and their photocatalytic activity under visible light: effect of reducing medium.

Decoration of ZnO by Ag is a promising method to improve its photocatalytic activity and extend the photoreactivity to the visible light. In this paper, Ag/ZnO heterostructures have been synthesised by photoreduction in various reducing mediums. When the Ag/ZnO nanocomposite arrays were obtained in the air, only a small amount of Ag was reduced. Ag nanosheets and nanoparticles were formed in the water and attached on the top and side surfaces of ZnO nanorods, forming Ag/ZnO heterostructures with a nano(sheet-rod-particle) multi-level structure. In the mixture of water and ethanol, a large amount of Ag nanoclusters was produced and embedded in the ZnO nanorod arrays. The influence of reducing mediums on the microstructure, morphology, quantity and dispersion of Ag nanostructures was investigated; and the effect of Ag component on the optical properties and visible light driven photocatalytic behaviour of the Ag/ZnO heterostructures was discussed.

Defective black TiOTiO2 synthesized via anodization for visible-light photocatalysis.

Defective TiO(2-x) was synthesized via a facile anodization technique. Electron paramagnetic resonance spectra confirmed the presence of oxygen vacancy, which extended the photon-absorbance deeply into the visible-light region. By stripping off the nanotubes on top, a hexagonally dimpled layer of black TiO(2-x) was exposed and exhibited remarkable photocatalytic activity.