Surface-assembled highly flexible Na_3(VOPO_4)_2F nanocube cathode for high-rate binder-free Na-ion batteries

Flexible Na-ion storage cathodes are still very few due to the challenge in achieving both reliable mechanical flexibility and excellent electrochemical performances.Herein,a new type of flexible Na_3(VOPO_4)_2F cathode with nanocubes tightly assembled on carbon cloth is fabricated by a facile solvothe rmal method for the first time.The cathode is able to exhibit superior rate capability and stable cycling performa nce up to 1000 cycles,due to the surface-assembling of crystalline nanocubes on carbon fibers.In addition,it shows good mechanical flexibility,nearly no capacity decay is observed after continuous bending of 500 times.With this novel cathode and a directly-grown Na_2Ti_2O_5 anode,a fully binde r-free Na-ion battery is assembled.It can deliver a high wo rking voltage and increased gravimetric energy/power densities(maximum values:220.2 Wh/kg;5674,7 W/kg),and can power a LED indicator at bending angles fro m 0° to 180°.     

Determination of Trace Elements in Marine Cetaceans by ICP-MS and Health Risk AssessmentSCIEI北大核心CSCD

The liver, kidney and muscle samples from seven cetaceans were digested by microwave digestion, and trace elements amounts of V, Cd, Cu, Zn, As, Cr, Ni, Mn, Se, Hg and Pb were determined by inductively coupled plasma mass spectrometry (ICP-MS), and the health risk assessment for Zn, Cu, Cd, Hg, Se in the liver was conducted. The results of international lobster hepatopancreas standard (TORT-2) showed acceptable agreement with the certified values, and the relative standard deviation (RSD) of eleven kinds of trace elements were less than 3.54%, showing that the method is suitable for the determination of trace elements in cetaceans. The experimental results indicated that different tissues and organs of the dolphins had different trace elements, presenting the tissue specificity. There is a certain inter-species difference among different dolphins about the bioaccumulation ability of the trace elements. The distribution of trace elements in whales presented a certain regularity: the contents of most elements in liver, kidney were much higher than the contents of muscle tissues, Cu, Mn, Hg, Se, and Zn exhibit the higher concentrations in liver, while Cd was mainly accumulated in kidney. And according to the health risk assessment in liver, the exceeding standardrate of selenium and copper in seven kinds of whales was 100%, suggesting that these whales were suffering the contamination of trace elements. The experimental results is instructive to the study of trace elements in cetaceans, while this is the first report for the concentrations in organs of Striped dolphin, Bottlenose dolphin, Fraser's Dolphin and Risso's dolphin in China, it may provide us valuable data for the conservation of cetaceans.     

煤矿顶板离层回归分析与稳定性评价

以光纤Bragg光栅位移传感器对淮北朱仙庄煤矿顶板离层监测为实际数据依据,选择最佳的典型函数模型对顶板离层进行非线性回归分析,得出能够反映位移发展趋势的回归曲线。监测结果与回归拟合数据表明:非线性回归分析预测方法不仅可以反映煤矿顶板离层实时变化过程,还能根据其变化趋势进行巷道稳定性判断。     

基于碳纳米管分子封装的一维电子波函数扫描

利用第一性原理,设计并研究了一类基于单臂碳纳米管的分子封装的分子体系．计算表明,半环葫芦脲类化合物可有效封装碳纳米管,引入微弱的分子间相互作用,对碳纳米管的电子态能级结构分布 仅带来微弱影响．半环葫芦脲分子与碳纳米管在管径方向的一维电子态波函数充分耦合,进而有效改变了一些前沿分子轨道的波函数在管径两头的分布以及相应的电子布居浓度．基于电子输运的模拟,发现半环葫芦脲分子在碳纳米管一维方向滑动时的某个电压下的电导变化可准确反映电子态波函数在相应分子导电通道上的一维分布信息．     

Microwave-Assisted Synthesis,Structure and Properties of a Nano-Double-Bowl-Like Heptanuclear Nickel(II) Cluster

A nano-double-bowl-like heptanuclear nickel cluster [Ni₇(mmp)₆(OH)₆]₂·(ClO₄)₂·12H₂O (1, Hmmp is 2-methoxy-6-methyliminomethyl-phenol) has been synthesized through the microwave-assisted reaction of Ni(ClO₄)₂·6H₂O with 2-hydroxy-3-methoxy-benzaldehyde (Hhmb) and methylamine in distilled water only 29 min. The core of the complex 1 can be described as a double-bowl-like, while the dodecanuclear water cluster stands on the bowl. The magnetic investigation shows that 1 displays very weak ferromagnetic coupling between Ni^II ions.     

Influence of anodizing voltage mode on the nanostructure of TiO2 nanotubes

The nanostructure of self-ordered porous anodic TiO₂ nanotubes (PATNTs) has extraordinary influence on their physical and chemical properties. For this reason, extensive attention has been paid on pulse anodization to regulate the nanostructure of PATNT. However, the relationships between the nanostructures and current curves still remain unclear. Based on the traditional potentiostatic and pulse anodizations, five different modes (i.e., potentiostatic, pulse, triangle wave, decrease, and increase step by step) of applied voltage and their influences on the nanostructures of PATNT have been investigated in detail. The growing rates of the nanotubes anodized under five different modes were compared for the first time. The results show that the growing rate of pulse voltage anodization is the fastest, reaching 116.4 nm min^?1. The slowest is triangle wave voltage anodization, only 59.3 nm min^?1. When the applied voltage decreases step-by-step, branched nanotubes can be formed in the bottom of PATNT. Yet, when the applied voltage increases step-by-step, triple-layer nanotubes with different diameters are formed, and the forming mechanism of this special nanostructure is discussed. The present results may be helpful to understand the mechanism of PATNT and facilitate the assembling diverse nanostructures for extensive applications in photocatalysis, dye-sensitized solar cells, and biomedical devices.     

Synthesis of Chiral Exocyclic Amines by Asymmetric Hydrogenation of Aromatic Quinolin‐3‐amines

Asymmetric hydrogenation of aromatic quinolin‐3‐amines was successfully developed with up to 94 % enantiomeric excess (ee). Introduction of the phthaloyl moiety to the amino group is crucial to eliminate the inhibition effect caused by the substrate and product, to activate the aromatic ring, and to improve the diastereoselectivity. This new methodology provides direct and facile access to chiral exocyclic amines. Notably, this report is the first on the highly enantioselective hydrogenation of aromatic amines.     

Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation

The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O^?.) is an important species in C?H activation. The mechanistic details of C?H activation by O^?. radicals can be well understood by studying the reactions between O^?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc₂O₃)_NO^? (N=1–18) clusters was observed. The reactivity of (Sc₂O₃)_NO^? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc₈O₁₃^?) and 12 (Sc₂₄O₃₇^?). Larger (Sc₂O₃)_NO^? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc₂O₃)_NO^? (N=1–5) clusters, which were found to contain the O^?. radicals as the active sites. The local charge environment around the O^?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O^?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation.     

Methane Activation by Diatomic Molybdenum Carbide Cations

Metal carbide species have been proposed as a new type of chemical entity to activate methane in both gas‐phase and condensed‐phase studies. Herein, methane activation by the diatomic cation MoC⁺ is presented. MoC⁺ ions have been prepared and mass‐selected by a quadrupole mass filter and then allowed to interact with methane in a hexapole reaction cell. The reactant and product ions have been detected by a reflectron time‐of‐flight mass spectrometer. Bare metal Mo⁺ and MoC₂H₂⁺ ions have been observed as products, suggesting the occurrence of ethylene elimination and dehydrogenation reactions. The branching ratio of the C₂H₄ elimination channel is much larger than that of the dehydrogenation channel. Density functional theory calculations have been performed to explore in detail the mechanism of the reaction of MoC⁺ with CH₄. The computed results indicate that the ethylene elimination process involves the occurrence of spin conversions in the C?C coupling (doublet→quartet) and hydrogen atom transfer (quartet→sextet) steps. The carbon atom in MoC⁺ plays a key role in methane activation because it becomes sp³ hybridized in the initial stages of the ethylene elimination reaction, which leads to much lower energy barriers and more stable intermediates. This study provides insights into the C?H bond activation and C?C coupling involved in methane transformation over molybdenum carbide‐based catalysts.     

Infrared spectroscopy of N-methylacetamide in water from high-level QM/MM calculations简

The infrared(IR) spectra of the N-methylacetamide molecule in water are calculated by using the MD simulation with high-level QM/MM corrections. The B3LYP and MP2 levels with 6-311++G** basis set are used for the QM region, respectively. Our results show all IR spectra at the B3LYP level are well consistent with the corresponding MP2 results. A dynamical charge fluctuation is observed for each atom along the simulation trajectories due to the electrostatic polarization(EP) effects from surrounding solvent environment. We find that the QM/MM corrected IR spectra satisfactorily reproduce the experimental vibrational features of amide I–III modes.