Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

Graphite Oxide and Aromatic Amines: Size Matters

Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molecules prefer to covalently connect to the graphene oxide matrix via chemical grafting, while napthalene amine molecules bind with the graphene oxide surface through π–π interactions. The presence of intercalated aromatic molecules between the graphene oxide layers is demonstrated by X‐ray diffraction, while the type of interaction between graphene oxide and polycyclic organic molecules is elucidated by X‐ray photoelectron spectroscopy. Combined quantum mechanical and molecular mechanical calculations describe the intercalation mechanism and the aniline grafting, rationalizing the experimental data. The present work opens new perspectives for the interaction of various aromatic molecules with graphite oxide and the so‐called “intercalation chemistry”.     

Efficacy of alpha-cypermethrin and thiamethoxam against Trogoderma granarium Everts (Coleoptera: Dermestidae) and Tenebrio molitor L. (Coleoptera: Tenebrionidae) on concrete

Laboratory bioassays were conducted to evaluate alpha-cypermethrin and thiamethoxam for the control of adults, small larvae and large larvae of the khapra beetle Trogoderma granarium, and the yellow mealworm beetle Tenebrio molitor, on concrete. Factors such as dose (0.025 and 0.1 mg alpha-cypermethrin or thiamethoxam/cm²), exposure interval (1, 3 and 7 d), and formulation (alpha-cypermethrin SC and thiamethoxam WG) were evaluated. Apart from immediate assessment at end of exposure, an assessment of delayed mortality was performed with the survivors of the 7-d exposure by removing them from the treated substrate and keeping them on untreated surfaces for 7 more days. After the 7-d exposure, more T. granarium adults were dead on dishes treated with alpha-cypermethrin than with thiamethoxam. Small larvae were generally less susceptible than adults. After 7 d, small larval mortality reached 64.4% for alpha-cypermethrin, while for thiamethoxam it was <6%. Large T. granarium larvae were more tolerant than the small ones. Delayed mortality of T. granarium adults was generally high for both insecticides and doses, and ranged between 43.3 and 63.3% of those that were still alive immediately after the 7-d treatment. For both larval categories, delayed mortality was higher for larvae that had been previously exposed to alpha-cypermethrin, than with thiamethoxam. For T. molitor, after the 7-d exposure, significantly more adults were dead on dishes treated with alpha-cypermethrin than with thiamethoxam. For small larvae mortality was 38.9% at the lowest thiamethoxam dose, but in the other cases ranged between 88.9 and 95.6%. In the case of large larvae, the overall mortality was low in all tested combinations. Regarding delayed mortality of this species, it remained at low levels, for both adults and small larvae. Our results indicate that T. molitor was more susceptible than T. granarium in both insecticides tested, but alpha-cypermethrin was more effective than thiamethoxam.     

Adaptive backstepping repetitive learning control design for nonlinear discrete‐time systems with periodic uncertainties

This paper addresses a tracking problem for uncertain nonlinear discrete‐time systems in which the uncertainties, including parametric uncertainty and external disturbance, are periodic with known periodicity. Repetitive learning control (RLC) is an effective tool to deal with periodic unknown components. By using the backstepping procedures, an adaptive RLC law with periodic parameter estimation is designed. The overparameterization problem is overcome by postponing the parameter estimation to the last backstepping step, which could not be easily solved in robust adaptive control. It is shown that the proposed adaptive RLC law without overparameterization can guarantee the perfect tracking and boundedness of the states of the whole closed‐loop systems in presence of periodic uncertainties. In addition, the effectiveness of the developed controller is demonstrated by an implementation example on a single‐link flexible‐joint robot. Copyright © 2014 John Wiley & Sons, Ltd.     

Lipase‐catalyzed synthesis of aliphatic poly(β‐thioether ester) with various methylene group contents: thermal properties,crystallization and degradation

A series of novel aliphatic poly(β‐thioether ester)s with various methylene group contents were prepared by direct lipase‐catalyzed polycondensation of the monomer with an acid‐labile β‐thiopropionate group. The polycondensation reaction using immobilized lipase B from Candida antarctica was carried out in diphenyl ether at 90 °C. Poly(β‐thioether ester)s with high molecular weights of 20 500–57 000 Da and narrow polydispersities in the range 1.40–1.48 were obtained. Thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction were used to investigate the thermal properties and crystal structures of these polyesters. All the poly(β‐thioether ester)s were semicrystalline polymers and thermally stable up to at least 200 °C. In vitro degradation studies showed that they can rapidly degrade under acidic conditions by the hydrolysis of the β‐thiopropionate groups, suggesting their potential as acid‐degradable polymeric materials. © 2019 Society of Chemical Industry     

Strain‐rate‐dependent mechanical properties of polypropylene separator for lithium‐ion batteries

The mechanical integrity of battery separators is critical for battery safety and durability. A comprehensive study of strain‐rate‐dependent tensile and puncture properties of a polypropylene lithium‐ion battery separator is presented here with a new model. Due to anisotropy of the polymeric membrane, tensile testing was conducted for different directions. Results showed that tensile strength and elastic modulus were increased 1000% and 500%, respectively, for different directions. It was also demonstrated that tensile strength changed 10 to 25% with strain rate (1.67 × 10^?4 to 1.67 × 10^?1 s^?1) for different directions. An equation was obtained for the first time for flow stress versus strain rate at varied tensile directions with respect to machine direction. Moreover, puncture testing was performed and it was shown that puncture strength was increased 140% with increasing strain rate from 0.25 to 250 mm min^?1. Two failure modes were also observed in puncture samples. Finally, Eyring's model was used to calculate activation enthalpy of the porous polypropylene separator. © 2020 Society of Chemical Industry     

Seawater-softening process through formation of calcite ooids

Conventional water-softening processes usually involve the exchange of Na⁺ ions for Ca²⁺ and Mg²⁺ using commercial or synthesized ion exchangers. The differences in chemical compositions of the ooids can be attributed to the formation in different environments. In this paper, ooid grains form inside assembled semi-pilot softening unit through a continuous chemical process involving reaction between bicarbonate ions and added lime using natural seawater. Our sample of Mediterranean seawater has low Mg²⁺/Ca²⁺ ratio (1.98%) within the range chemically favorable for precipitation of low-Mg calcite ooids. Precipitation of calcite occurs around pure quartz sand grains which act as nucleation points (the bed required for sand vessel is 1.65 l). The shape of the sand grains controls the overall external morphology of the resulting ooids; they vary in size from 0.5 to 3.0 mm and have a high degree of polish due to surface abrasion caused by continuous agitation inside the softening system. Calcite ooid grains (1.53 kg) formed within the seawater-softening unit every 18 days have many of the ooid features formed in marine environments. Ooids grow to a significant size, at a rate of about 0.17 mm of one layer thickness per day inside the softening unit. The average weight percent of calcite precipitate is 35.48% after 18 days, at 10 °C, 60 l/min and pH 9.0. The pellets comprise mainly CaCO₃ and SiO₂ and some metal ions which may substitute for calcium ions in calcite are present only in trace amounts of the total composition.     

Improvement of adhesion and paint ability of EVA copolymers with different vinyl acetate contents by treatment with UV-ozone

The surface modifications produced by UV-ozone treatment of two ethylene-vinyl acetate (EVA) copolymers containing 12 and 20 wt% vinyl acetate (EVA12 and EVA20 respectively) were studied. The treatment with UV-ozone improved the wettability of both EVAs due to the creation of new carbon–oxygen moieties. The extent of these modifications increased with increasing length of the treatment and the modifications produced in EVA20 were produced for shorter lengths of treatment. The UV-ozone treatment also created roughness and heterogeneities on the EVA surfaces. Whereas roughness formation prevailed on the UV-ozone treated EVA12, important ablation was dominant on the treated EVA20. T-peel strength values in joints made with polychloroprene adhesive increased when the EVAs were treated with UV-ozone. Short length of UV-ozone treatment (1 min) produced higher T-peel strength in joints made with EVA20 whereas higher T-peel strength values in joints made with EVA12 were obtained after treatment for 5–7.5 min in which a cohesive failure into a weak boundary layer on the treated EVA surface was found. Furthermore, the adhesion of UV-ozone treated EVA20 to acrylic paint increased. Finally, the ageing resistance of the treated EVA/polychloroprene adhesive joints was good and the surface modifications on the UV-ozone treated EVAs lasted for 24 h after treatment at least.     

Isolation of antimicrobial agent from the marine algae Cystoseira hakodatensis

Cystoseira hakodatensis is an unutilised brown algae belonging to family Sargassaceae. A crude methanol extract from the algae showed inhibitory effects on the growths of Bacillus cereus and Bacillus licheniformis. To isolate the major antimicrobial agent, a sequential active‐guided isolation procedure was applied: liquid–liquid extraction, column chromatography and bio‐autography. A marked antimicrobial agent (active α) was isolated in hydrophobic fraction and was determined to phenolics without carbohydrates and proteins by phytochemical test. Regarding the antimicrobial potential, the isolated active α showed better inhibitory effects against B. cereus and B. licheniformis at 2 and 4 times of lower concentrations (62.5 and 31.3 μg mL^?1) in comparison with epigallocatechin gallate. These results showed that C. hakodatensis is a potential source of antimicrobial agent capable of preventing the growth of the two bacteria.     

尿素装置液位仪表失真分析及处理

介绍了尿素装置中3起液位仪表失真案例,分析了故障现象和设备工况,确定失真原因,采取了相应的处理措施,解决了仪表故障。