Mesoporous Carbon Nanofibers Embedded with MoS2 Nanocrystals for Extraordinary Li‐Ion Storage

MoS₂ nanocrystals embedded in mesoporous carbon nanofibers are synthesized through an electrospinning process followed by calcination. The resultant nanofibers are 100–150 nm in diameter and constructed from MoS₂ nanocrystals with a lateral diameter of around 7 nm with specific surface areas of 135.9 m² g^?1. The MoS₂@C nanofibers are treated at 450 °C in H₂ and comparison samples annealed at 800 °C in N₂. The heat treatments are designed to achieve good crystallinity and desired mesoporous microstructure, resulting in enhanced electrochemical performance. The small amount of oxygen in the nanofibers annealed in H₂ contributes to obtaining a lower internal resistance, and thus, improving the conductivity. The results show that the nanofibers obtained at 450 °C in H₂ deliver an extraordinary capacity of 1022 mA h g^?1 and improved cyclic stability, with only 2.3 % capacity loss after 165 cycles at a current density of 100 mA g^?1, as well as an outstanding rate capability. The greatly improved kinetics and cycling stability of the mesoporous MoS₂@C nanofibers can be attributed to the crosslinked conductive carbon nanofibers, the large specific surface area, the good crystallinity of MoS₂, and the robust mesoporous microstructure. The resulting nanofiber electrodes, with short mass‐ and charge‐transport pathways, improved electrical conductivity, and large contact area exposed to electrolyte, permitting fast diffusional flux of Li ions, explains the improved kinetics of the interfacial charge‐transfer reaction and the diffusivity of the MoS₂@C mesoporous nanofibers. It is believed that the integration of MoS₂ nanocrystals and mesoporous carbon nanofibers may have a synergistic effect, giving a promising anode, and widening the applicability range into high performance and mass production in the Li‐ion battery market.     

A {Nb6P2W12}‐Based Hexameric Manganese Cluster with Single‐Molecule Magnet Properties

By deliberately using a metastable polyanion [(NbO₂)₆P₂W₁₂O₅₆]^12? ( 1 ), which was formed in situ, we have discovered the unprecedented hexameric cluster {Mn₁₅(Nb₆P₂W₁₂O₆₂)₆} ( 2 ), in which the six polyanions [Nb₆P₂W₁₂O₆₁]^10? are alternately connected by four intriguing trinuclear {Mn^III₃} moieties and four {Mn^II} linkers. This discovery is the first in which the phosphoniobotungstate has been made accessible by using transition‐metal ions; furthermore, polyanion 2 represents the largest niobotungstate cluster reported to date. Analysis by means of electrospray ionization mass spectrometry (ESI‐MS ) provides insight into the self‐assembly process, and the peaks observed relate to the different charge states of the parent cluster, thus confirming the stability of 2 . In addition, magnetic‐susceptibility measurements reveal that each {Mn^III₃} subunit is a separate single‐molecule magnet (SMM). This discovery results from the exploration of the reverse effect of metastable polyanion 1 possessing high reactivity, thereby turning a disadvantage into an advantage. This finding could define a new synthetic strategy for the design and synthesis of magnetic polyoxometalate (POM) clusters.     

纳米SiO_2表面基团在MMA原位本体聚合中的阻缓聚作用

分别以3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)和辛基三甲氧基硅烷(OTMS)为活性和惰性硅烷的代表,对SiO2进行不同锚固密度的表面修饰,并以改性SiO2的甲基丙烯酸甲酯(MMA)单体分散液为原料,通过原位本体聚合制得一系列SiO2含量不同的高分散性SiO2/PMMA复合材料.考察SiO2表面基团活性程度和SiO2含量对聚合反应动力学、基体聚合物分子量以及复合材料硬度的影响,探究修饰状态不同SiO2在本体自由基聚合中的作用机制.发现SiO2表面硅羟基及其锚固MPS的活性双键会对聚合反应起阻缓聚作用,进而会显著降低基体聚合物的分子量及复合材料的硬度.而惰性硅烷OTMS对SiO2表面的锚固则会消耗SiO2表面硅羟基、并屏蔽其影响,因而随着OTMS锚固密度的提高,基体分子量和复合材料硬度均会随之提高,特别是当表面修饰达到饱和状态时,SiO2的阻缓聚作用已可忽略.     

SAXS and WAXD study of periodical structure for polyacrylonitrile fiber during coagulation

Small angle X‐ray scattering (SAXS) and wide angle X‐ray diffraction (WAXD) were adopted to investigate the formation and development of high order structure within polyacrylonitrile (PAN) precursor during coagulation. The scattering signal came from the microvoids and long period structure was separated reasonably by the analog computation method of decomposition of the one‐dimensional profile. Based on the established methodology, the statistic parameters of long period structure, such as length of the long period structure, crystalline region and amorphous region, were obtained by the analysis of correlation function. The results indicated that during the coagulation, the length of long period of the nascent coagulated fiber was 56.1 nm (meridional direction) and 35.6 nm (equatorial direction), respectively. The evolution of the long period during the coagulation was also discussed by combining WAXD data. With the processing of coagulation, the long period was decreased since the crystallinity increased. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of β‐nucleating agent and crystallization conditions on the crystallization behavior and polymorphic composition of isotactic polypropylene/multi‐walled carbon nanotubes composites

In this study, the effects of crystallization conditions (cooling rate and end temperature of cooling) on crystallization behavior and polymorphic composition of isotactic polypropylene/multi‐walled carbon nanotubes (iPP/MWCNTs) composites nucleated with different concentrations of β‐nucleating agent (tradename TMB‐5) were investigated by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and scanning electronic microscopy (SEM). The results of DSC, WAXD and SEM revealed that the addition of MWCNTs and TMB‐5 evidently elevates crystallization temperatures and significantly decreases the crystal sizes of iPP. Because of the competition between α‐nucleation (provided by MWCNTs) and β‐nucleation (induced by TMB‐5), the β‐phase crystallization takes place only when 0.15 wt% and higher concentration of TMB‐5 is added. Non‐isothermal crystallization kinetics study showed that the crystallization activation energy ΔE of β‐nucleated iPP/MWCNTs composites is obviously higher than that of pure iPP, which slightly increases with the increase of TMB‐5 concentration, accompanying with the transition of its polymorphic crystallization behavior. The results of non‐isothermal crystallization and melting behavior suggested that the cooling rate and end temperature of cooling (T_end) are important factors in determining the proportion and thermal stability of β‐phase: Lower cooling rate favors the formation of less amount of β‐phase with higher thermal stability, while higher cooling rate encourages the formation of higher proportion of β‐phase with lower thermal stability. The T_end = 100°C can eliminate the β–α recrystallization during the subsequent heating and therefore enhance the thermal stability of the β‐phase. By properly selecting TMB‐5 concentration, cooling rate and T_end, high β‐phase proportion of 88.9% of the sample was obtained. Copyright © 2014 John Wiley & Sons, Ltd.     

Target‐Based Whole‐Cell Screening by 1H NMR Spectroscopy

An NMR‐based approach marries the two traditional screening technologies (phenotypic and target‐based screening) to find compounds inhibiting a specific enzymatic reaction in bacterial cells. Building on a previous study in which it was demonstrated that hydrolytic decomposition of meropenem in living Escherichia coli cells carrying New Delhi metallo‐β‐lactamase subclass 1 (NDM‐1) can be monitored in real time by NMR spectroscopy, we designed a cell‐based NMR screening platform. A strong NDM‐1 inhibitor was identified with cellular IC₅₀ of 0.51 μM , which is over 300‐fold more potent than captopril, a known NDM‐1 inhibitor. This new screening approach has great potential to be applied to targets in other cell types, such as mammalian cells, and to targets that are only stable or functionally competent in the cellular environment.     

Direct Insight into the Three‐Dimensional Internal Morphology of Solid–Liquid–Vapor Interfaces at Microscale

Solid–liquid–vapor interfaces dominated by the three‐phase contact line, usually performing as the active center in reactions, are important in biological and industrial processes. In this contribution, we provide direct three‐dimensional (3D) experimental evidence for the inside morphology of interfaces with either Cassie or Wenzel states at micron level using X‐ray micro‐computed tomography, which allows us to accurately “see inside” the morphological structures and quantitatively visualize their internal 3D fine structures and phases in intact samples. Furthermore, the in‐depth measurements revealed that the liquid randomly and partly located on the top of protrusions on the natural and artificial superhydrophobic surfaces in Cassie regime, resulting from thermodynamically optimal minimization of the surface energy. These new findings are useful for the optimization of classical wetting theories and models, which should promote the surface scientific and technological developments.     

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.