Cu3V2O8 Nanoparticles as Intercalation‐Type Anode Material for Lithium‐Ion Batteries

Cu₃V₂O₈ nanoparticles with particle sizes of 40–50 nm have been prepared by the co‐precipitation method. The Cu₃V₂O₈ electrode delivers a discharge capacity of 462 mA h g^?1 for the first 10 cycles and then the specific capacity, surprisingly, increases to 773 mA h g^?1 after 50 cycles, possibly as a result of extra lithium interfacial storage through the reversible formation/decomposition of a solid electrolyte interface (SEI) film. In addition, the electrode shows good rate capability with discharge capacities of 218 mA h g^?1 under current densities of 1000 mA g^?1. Moreover, the lithium storage mechanism for Cu₃V₂O₈ nanoparticles is explained on the basis of ex situ X‐ray diffraction data and high‐resolution transmission electron microscopy analyses at different charge/discharge depths. It was evidenced that Cu₃V₂O₈ decomposes into copper metal and Li₃VO₄ on being initially discharged to 0.01 V, and the Li₃VO₄ is then likely to act as the host for lithium ions in subsequent cycles by means of the intercalation mechanism. Such an “in situ” compositing phenomenon during the electrochemical processes is novel and provides a very useful insight into the design of new anode materials for application in lithium‐ion batteries.     

从头计算方法比较研究B_2Au_4,Al_2Au_4和BAlAu_4的几何和电子结构(英文)

Au/H相似性的研究是现代化学中的一个热门话题.我们从理论上报道Au/H相似的新成员:共价化合物B2Au4,离子化合物Al2Au4和BAl Au4.采用密度泛函和波函数理论方法对比研究了缺电子体系B2Au4、Al2Au4和BAl Au4的几何和电子结构.详细讨论了它们基态结构的轨道、适应性自然密度划分(Ad NDP)和电子局域函数(ELF)分析.计算结果表明稍微扭曲变形的C2B2Au4是基态结构,在这个共价化合物中含有两个B―Au―B三中心二电子(3c-2e)键.然而C3vAl+(Al Au4)-和C3vAl+(BAu4)-被研究证明是含有三个X―Au―Al三中心二电子键的类盐化合物(在Al2Au4中X=Al,BAl Au4中X=B).Al2Au4和BAl Au4是至今为止首例报道的在离子缺电子体系中含有金桥键的化合物.同时计算了B2Au4-、Al2Au4-和BAl Au4-阴离子基态结构的绝热剥离能和垂直剥离能,为实验表征提供依据.文中报道的金桥键为共价键和离子键相结合的缺电子体系提供了一个有趣的键合模式,有助于设计含有高度分散金原子的新材料和催化剂.     

表面增强拉曼光谱研究自组装单分子层在化学接触和纳米隔绝下的分子振动活性变化(英文)

为确定表面增强拉曼光谱中某些有争议的弱振动模式是来自高阶的影响还是分子基团对称性变化的影响,本文以1,4-苯二硫醇作为探针分子提供了一种实验验证的框架方法.光谱实验显示,观测到的有争议的弱振动模式并不是来自高阶的影响,而是分子基团对称性变化所致.我们的实验框架方法很容易拓展开来,如用于研究其它波长激光激发的类似体系或有机分子搭接的分子结.     

A novel method for making ultra-fine metal fibers and particles

A novel method based on plastic processing and equipment for preparing ultra-fine metal fibers and particles is reported. With this new method, metal fibers and particles can both be produced on the same equipment and the surfaces of the fibers and particles can be protected from oxidation by the polymers or solvents during the preparation process. Metal-alloy powders with lower melt point were filled into polymer by an extruder, followed by a die-drawing process at a temperature lower than the melt temperature of the metal alloy. Metal fibers or particles were obtained after the polymer matrix was washed away. Metal alloy fibers can be obtained when a polymer that strongly interacts with metal alloy, such as a special polyvinyl alcohol with a low alcoholysis degree, is used as the polymer matrix. Metal-alloy particles can be obtained when a polymer with weak interaction with metal alloy, such as polyethylene (PE), is used as the polymer matrix. Based on the principle of this new method, it is possible to produce finer or even nano-sized metal fibers and particles with higher melting points.     

Controlled Synthesis of N‐Doped Carbon Nanospheres with Tailored Mesopores through Self‐Assembly of Colloidal Silica

Limited strategies have been established to prepare monodisperse mesoporous carbon nanospheres (MCNs) with tailored pore sizes. In this work, a method is reported to synthesize MCNs by combining polymerization of aniline with co‐assembly of colloidal silica nanoparticles. The controlled self‐assembly behavior of colloidal silica enables the formation of uniform composite nanospheres and convenient modulation over mesopores. After carbonization and removal of sacrificial templates, the resultant MCNs possess tunable mesopores (7–42 nm) and spherical diameters (90–300 nm), as well as high surface area (785–1117 m² g^?1), large pore volume (1.46–2.01 cm³ g^?1) and abundant nitrogen moieties (5.54–8.73 at %). When serving as metal‐free electrocatalysts for the oxygen reduction reaction (ORR), MCNs with an optimum pore size of 22 nm, compared to those with 7 and 42 nm, exhibit the best ORR performance in alkaline medium.     

Ferrocenylethynyl‐Terminated Azobenzenes: Synthesis,Electrochemical, and Photoisomerization Studies

Ferrocenylethynyl‐terminated derivatives 8 – 12 have been synthesized and characterized by electrochemistry and UV/Vis spectroscopy. The electrochemical and photophysical studies indicate that the electronic communication in ferrocenylethynyl‐substituted derivatives is strongly influenced by the substituted position of the ferrocenylethynyl moiety. In situ electrochemical oxidation or chemical oxidation caused a characteristically weak ligand‐to‐metal charge‐transfer (LMCT) band to appear at 700–1000 nm. Subsequent electrochemical reduction or chemical reduction recovered the most of the original curve and the color of the solution as well. Among the derivatives, compound 8 exhibits the highest cis/trans molar ratio (64:36) in the photostationary state (PSS) upon light irradiation at 365 nm. Compound 8 exhibits excellent fatigue resistance and reversibility under several repeated reversible isomerization cycles.     

Preparation and Electrochemical Properties of Tin–Iron–Carbon Nanocomposite as the Anode of Lithium‐Ion Batteries

Tin–iron–carbon nanocomposite is successfully prepared by a sol–gel method followed by a chemical vapor deposition (CVD) process with acetylene gas as the carbon source. The structural properties, morphology, and electrochemical performances of the nanocomposite are comprehensively studied in comparison with those properties of tin–carbon and iron–carbon nanocomposites. Sheet‐like carbon architecture and different carbon contents are induced thanks to the catalytic effect of iron during CVD. Among three nanocomposites, tin–iron–carbon demonstrates the highest reversible capacity of 800 mA h g^?1 with 96.9 % capacity retention after 50 cycles. It also exhibits the best rate capability with a discharge capacity of 420 mA h g^?1 at a current density of 1000 mA g^?1. This enhanced performance is strongly related to the carbon morphology and content, which can not only accommodate the large volume change, but also improve the electronic conductivity of the nanocomposite. Hence, the tin–iron–carbon nanocomposite is expected to be a promising anode for lithium‐ion batteries.     

Insights into the structure–photoreactivity relationships in well-defined perovskite ferroelectric KNbO3 nanowires

Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this study, the geometric and electronic structure of perovskite ferroelectric KNbO₃ nanowires with respective orthorhombic and monoclinic polymorphs have been systematically addressed. By virtue of aberration-corrected scanning transmission electron microscopy, we directly visualize surface photocatalytic active sites, measure local atomic displacements at an accuracy of several picometers, and quantify ferroelectric polarization combined with first-principles calculations. The photoreactivity of the as-prepared KNbO₃ nanowires is assessed toward aqueous rhodamine B degradation under UV light. A synergy between the ferroelectric polarization and electronic structure in photoreactivity enhancement is uncovered, which accounts for the prominent reactivity order: orthorhombic > monoclinic. Additionally, by identifying new photocatalytic products, rhodamine B degradation pathways involving N-deethylation and conjugated structure cleavage are proposed. Our findings not only provide new insights into the structure–photoreactivity relationships in perovskite ferroelectric photocatalysts, but also have broad implications in perovskite-based water splitting and photovoltaics, among others.     

Capping nanoparticles with graphene quantum dots for enhanced thermoelectric performance

Graphene quantum dots (GQDs) are shown to serve as phase transfer agents to transfer various types of nanoparticles (NPs) from non-polar to polar solvents. Thorough characterization of the NPs proves complete native ligand exchange. Pellets of this GQD–NP composite show that the GQDs limit the crystal size during spark plasma sintering, yielding enhanced thermoelectric performance compared with NPs exchanged with inorganic ions. A photoluminescence study of the GQD–NP composite also suggests energy transfer from GQDs to NPs.