A Mixed Ionic and Electronic Conducting Dual‐Phase Membrane with High Oxygen Permeability

To combine good chemical stability and high oxygen permeability, a mixed ionic‐electronic conducting (MIEC) 75 wt % Ce_0.85Gd_0.1Cu_0.05O_2?δ‐25 wt % La_0.6Ca_0.4FeO_3?δ (CGCO‐LCF) dual‐phase membrane based on a MIEC–MIEC composite has been developed. Copper doping into Ce_0.9Gd_0.1O_2?δ (CGO) oxide enhances both ionic and electronic conductivity, which then leads to a change from ionic conduction to mixed conduction at elevated temperatures. For the first time we demonstrate that an intergranular film with 2–10 nm thickness containing Ce, Ca, Gd, La, and Fe has been formed between the CGCO grains in the CGCO‐LCF one‐pot dual‐phase membrane. A high oxygen permeation flux of 0.70 mL min^?1 cm^?2 is obtained by the CGCO‐LCF one‐pot dual‐phase membrane with 0.5 mm thickness at 950 °C using pure CO₂ as the sweep gas, and the membrane shows excellent stability in the presence of CO₂ even at lower temperatures (800 °C) during long‐term operation.     

Cooperative Bond Activation and Catalytic Reduction of Carbon Dioxide at a Group 13 Metal Center

A single‐component ambiphilic system capable of the cooperative activation of protic, hydridic and apolar H? X bonds across a Group 13 metal/activated β‐diketiminato (Nacnac) ligand framework is reported. The hydride complex derived from the activation of H₂ is shown to be a competent catalyst for the highly selective reduction of CO₂ to a methanol derivative. To our knowledge, this process represents the first example of a reduction process of this type catalyzed by a molecular gallium complex.     

Crystalline Hetero‐Stereocomplexed Polycarbonates Produced from Amorphous Opposite Enantiomers Having Different Chemical Structures

Stereocomplexation is the stereoselective interaction between two opposite enantiomeric polymers through an interlocked orderly assembly. Most studies focus on the stereocomplex formation from the crystalline opposite enantiomers having the identical structure; nevertheless, rare examples were reported regarding the crystalline stereocomplexes from enantiomeric polymers having different chemical structures. Herein we show a strategy for polymer orderly assembly through the formation of crystalline hetero‐stereocomplexed polymeric materials by the cocrystallization of amorphous isotactic polycarbonates with different chemical structures and opposite configurations. The behaviors in the crystalline state are significantly different from that of the component enantiomeric polymers or their homo‐stereocomplexes. This study is expected to open up a new way to prepare various semicrystalline materials having a wide variety of physical properties and degradability.     

Carbon Dioxide Fixation and Sulfate Sequestration by a Supramolecular Trigonal Bipyramid

The subcomponent self‐assembly of a bent dialdehyde ligand and different cationic and anionic templates led to the formation of two new metallosupramolecular architectures: a Fe^II₄L₆ molecular rectangle was isolated following reaction of the ligand with iron(II) tetrafluoroborate, and a M₅L₆ trigonal bipyramidal structure was constructed from either zinc(II) tetrafluoroborate or cadmium(II) trifluoromethanesulfonate. The spatially constrained arrangement of the three equatorial metal ions in the M₅L₆ structures was found to induce small‐molecule transformations. Atmospheric carbon dioxide was fixed as carbonate and bound to the equatorial metal centers in both the Zn₅L₆ and Cd₅L₆ assemblies, and sulfur dioxide was hydrated and bound as the sulfite dianion in the Zn₅L₆ structure. Subsequent in situ oxidation of the sulfite dianion resulted in a sulfate dianion bound within the supramolecular pocket.     

Remarkable Effect of Chalcogen Substitution on an Enzyme Mimetic for Deiodination of Thyroid Hormones

Iodothyronine deiodinases are selenoenzymes which regulate the thyroid hormone homeostasis by catalyzing the regioselective deiodination of thyroxine (T4). Synthetic deiodinase mimetics are important not only to understand the mechanism of enzyme catalysis, but also to develop therapeutic agents as abnormal thyroid hormone levels have implications in different diseases, such as hypoxia, myocardial infarction, critical illness, neuronal ischemia, tissue injury, and cancer. Described herein is that the replacement of sulfur/selenium atoms in a series of deiodinase mimetics by tellurium remarkably alters the reactivity as well as regioselectivity toward T4. The tellurium compounds reported in this paper represent the first examples of deiodinase mimetics which mediate sequential deiodination of T4 to produce all the hormone derivatives including T0 under physiologically relevant conditions.     

Hollow Carbon Nanofibers Filled with MnO2 Nanosheets as Efficient Sulfur Hosts for Lithium–Sulfur Batteries

Lithium–sulfur batteries have been investigated as promising electrochemical‐energy storage systems owing to their high theoretical energy density. Sulfur‐based cathodes must not only be highly conductive to enhance the utilization of sulfur, but also effectively confine polysulfides to mitigate their dissolution. A new physical and chemical entrapment strategy is based on a highly efficient sulfur host, namely hollow carbon nanofibers (HCFs) filled with MnO₂ nanosheets. Benefiting from both the HCFs and birnessite‐type MnO₂ nanosheets, the MnO₂@HCF hybrid host not only facilitates electron and ion transfer during the redox reactions, but also efficiently prevents polysulfide dissolution. With a high sulfur content of 71 wt % in the composite and an areal sulfur mass loading of 3.5 mg cm^?2 in the electrode, the MnO₂@HCF/S electrode delivered a specific capacity of 1161 mAh g^?1 (4.1 mAh cm^?2) at 0.05 C and maintained a stable cycling performance at 0.5 C over 300 cycles.     

天然盐渍土冻融循环时水盐迁移规律及强度变化试验研究

通过对新疆喀什地区12处天然盐渍土室内基本性质试验分析,选取典型天然盐渍土,在开放系统中进行反复冻融循环条件下的试验研究。研究了天然盐渍土在多次冻融循环时的水分和盐分迁移规律及强度变化特征。试验结果表明:经多次冻融循环,低液限粘土试样水分重分布与盐分重分布有很大的一致性,水分和盐分自下而上迁移;试样粘聚力自下而上线形减小,内摩擦角呈s形分布。含砂低液限粘土试样冻融循环过程中,易溶盐均随水分向冷端面迁移,离子剖面呈现中间大两端小的趋势;试样粘聚力呈反s形分布,内摩擦角均呈s形分布。     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals [Phys. Status Solidi RRL 5, No. 3, R107–R109 (2011)]

In our article, we reported the observation of monoclinic M2 to M1 structural phase transition in VO₂ single crystal near the temperature of ～49 °C. However, the re‐examination of Laue patterns reveals that previously defined monoclinic M1 and M2 phases can be interpreted as monoclinic M2 and triclinic T phases instead. Careful experimental geometry calibration and further refinement of the lattice parameter ratios and angles show that monoclinic M2 and triclinic T phases fit better with the experimental data. On the other hand, our previous misidentification of the insulating phases does NOT affect the conclusions of our article. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Enhanced photocatalytic performance of TiO2 particles via effect of anatase–rutile ratio

In the present work anatase–rutile transformation temperature and its effect on physical/chemical properties as well as photocatalytic activity of TiO₂ particles were investigated. The characterisation of the synthesised and annealed TiO₂ particles were determined by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS) and Brunauer–Emmett–Teller surface area analysis (BET). The refraction in the ultraviolet–visible (UV–vis) range was assessed using a dual-beam spectrophotometer. The photocatalytic performance of the particles was tested on methylene blue solution. The XRD data indicated that the percentage of rutile increased with the annealing temperature and almost 100% of anatase transformed to rutile at 1000 °C. In addition, the phase transformation was a linear function of annealing temperature so phase composition of TiO₂ can be controlled by changing the annealing temperature. The SEM and BET results presented the increase of agglomerate size and the decrease of specific surface area with the increasing annealing temperature. This proved that anatase has smaller particle size and higher surface area than rutile. The photocatalytic activity of the annealed TiO₂ powders reduced with the increase of annealing temperature. The samples annealed at 900 °C and 925 °C with anatase: rutile ratio of 92:8 and 77:23, respectively, showed the best activity. These results suggested that the photocatalytic activity of TiO₂ particles is a function of phase composition. Thus it can be enhanced by changing its phase composition which can be controlled by annealing temperature.