Baeyer–Villiger oxidation of cyclohexanone by molecular oxygen with Fe–Sn–O mixed oxides as catalysts

Fe–Sn–O mixed oxides were synthesized and used as catalysts for Baeyer–Villiger oxidation of cyclohexanone, which showed both high catalytic activity and selectivity. X‐ray powder diffraction and scanning electron microscopy suggested that the Fe–Sn–O catalysts had a tetragonal structure with a grain size of 29.3 nm. An ε‐caprolactone yield as high as 98.8% was obtained in a small‐scale experiment (5 mmol of cyclohexanone). In a scale‐up test (20 mmol of cyclohexanone), the cyclohexanone conversion and ε‐caprolactone yield were 96.7 and 96.5%, respectively. In addition, the catalysts can be reused five times without any major decline in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Theory and model implementation for analyzing line structures subject to dynamic motions of large deformation and elongation using the absolute nodal coordinate formulation (ANCF) approach

This paper presents the theory development and numerical implementation of a new gradient-deficient-based ANCF (Absolute Nodal Coordinate Formulation) model applied to perform the nonlinear dynamic analysis of elastic line structures subject to large stretching and deformation. The derivations of model equations, introduced numerical approaches, and result validations are the focuses of this study. Different from the traditional rod theory for small stretching consideration, the present model implements the line structures’ large elongation concepts into both the control mechanisms of constitutive formulations and equations of motion. The effect of external hydrodynamic forces on structures is also included in the model formulations. Based on the conservation of energy, the line model developed in this study covers the variation in strain and takes a full account of the bending effect with large stretching. A finite-element-based implicit scheme according to a modified Newmark-beta method is employed to solve the assembled system equations with unknown variables of nodal position vectors, their tangential derivatives, and strains. Selected cases with dynamic motions, such as nonlinear oscillation of a compound pendulum, free falling of a horizontal elastic beam in air with two different settings of gravity, free falling of a submerged horizontal tether with and without an attached concentrated mass, and a submerged vertical tether with a prescribed translational motion, are simulated to verify the developed model by comparing the results with analytical solutions and published experimental data and numerical results. It is found the present ANCF model, as noticed with good matched results with analytical solutions, measurements and other published solutions, is demonstrated to be able to provide converged and reasonably accurate predictions on the responses of line structures subject to large dynamic motions.

     

Synthesis of Cyclohexene Carbonate Catalyzed by Polymer-Supported Catalysts

A series of polystyrene-divinylbenzene cross-linked resin (PS)–supported zinc chloride catalysts were prepared in this study. They can efficiently catalyze the solventless cycloaddition of cyclohexene oxide with carbon dioxide in the presence of tetrabutylammonium bromide (TBAB) as cocatalyst under relatively mild reaction conditions. The catalyst is composed of carrier, connecting arm, ligand, and active ingredient. The connecting arms of different lengths can significantly affect the catalytic activity. Among these catalysts, the one using diethylene glycol as connecting arm and 2-aminopyridine as ligand, named PS-DEG-2ap-ZnCl₂, showed the optimal catalytic performance. The yield of cyclohexene carbonate was 95.18% calculated by gas chromatographic analysis under the optimal conditions (393 K, 5 MPa, 6 h). Moreover, the catalyst showed good stability and reusability. From the viewpoint of industrial application, the catalyst is attractive because of its excellent catalytic efficiency on the synthesis of cyclohexene carbonate.     

锂离子电池铜锡锑合金负极材料研究

以化学还原法制备了锂离子电池纳米铜锡锑三元合金负极材料Cu6Sn5Sb5,通过XRD、TEM和电化学测试对材料进行了表征,用非原位XRD测试方法研究了材料的贮锂机理.所制备的材料颗粒粒径大小分布在15～30nm之间.在充放电电压为1.5～OV范围内,初始可逆充电容量为595mAh/g,经过30次循环后,充电容量保持79...     

微波作用下卤素交换氟化制备氟代苯甲醛及二苯甲酮类化合物

在微波作用下,采用高效催化剂体系,于中等极性非质子溶剂中经卤素交换氟化高效制备了系列含氟芳香醛(酮)类化合物,产品收率53·3%~92·6%,反应时间较常规加热最多可缩短80%以上。采用中等极性反应溶剂,还可突出表现出微波对反应促进的“非热效应”,从而大大拓宽了氟化反应溶剂的选择范围。     

Adsorption isotherms and kinetics of methylene blue on a low-cost adsorbent recovered from a spent catalyst of vinyl acetate synthesis

A regenerated activated carbon used as catalyst support in the synthesis of vinyl acetate has been tested as a low-cost adsorbent for the removal of dyes. After a thorough textural characterization of the regenerated activated carbon, its adsorption isotherms and kinetics were determined using methylene blue as model compound at different initial concentrations. Both Langmuir and Freundlich isotherm models were developed and then compared. It was found that the equilibrium data were best represented by the Langmuir isotherm model. The kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models, and it was found that the best fitting corresponded to the pseudo-second-order kinetic model. The results showed that this novel adsorbent had a high adsorption capacity, making it suitable for use in the treatment of methylene blue enriched wastewater.     

Transition-Metal Carbides as Hydrogen Evolution Reduction Electrocatalysts: Synthetic Methods and Optimization Strategies

With the strengths of zero carbon emission and high gravimetric energy density, hydrogen energy is recognized as a primary choice for future energy supply. Electrochemical water splitting provides a promising strategy for effective and sustainable hydrogen production through renewable electricity, and one of the immediate challenges toward its large-scale application is the availability of low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER). Given the enormous efforts in the exploration of potential transition-metal carbide (TMC) electrocatalysts, this review aims to summarize the recent advances in synthetic methods and optimization strategies of TMC electrocatalysts. Additionally, the perspectives for the development of novel efficient TMC-based catalysts are also proposed.     

Surface‐Electron Coupling for Efficient Hydrogen Evolution

Maximizing the activity of materials towards the alkaline hydrogen evolution reaction while maintaining their structural stability under realistic working conditions remains an area of active research. Herein, we report the first controllable surface modification of graphene(G)/V₈C₇ heterostructures by nitrogen. Because the introduced N atoms couple electronically with V atoms, the V sites can reduce the energy barrier for water adsorption and dissociation. Investigation of the multi‐regional synergistic catalysis on N‐modified G/V₈C₇ by experimental observations and density‐functional‐theory calculations reveals that the increase of electron density on the epitaxial graphene enable it to become favorable for H* adsorption and the subsequent reaction with another H₂O molecule. This work extends the range of surface‐engineering approaches to optimize the intrinsic properties of materials and could be generalized to the surface modification of other transition‐metal carbides.     

一种环金属铱、铂双核配合物的合成及光电性能

设计合成了一种双核环金属铱,铂配合物二[N,N-2-(2,4-二氟苯基吡啶)C3,N1](吡啶甲酸)合铱(Ⅲ)-C₆-[苯基吡啶-C3,N1](吡啶甲酸)合铂(Ⅱ)(FIrPPyPt)。 通过核磁共振仪、元素分析仪、紫外-可见吸收光谱仪和光致发光光谱仪对其结构和性能进行了表征。 结果表明,配合物FIrPPyPt的紫外-可见吸收位于250~450 nm之间,荧光发射峰位于465和493 nm。 将配合物FIrPPyPt以质量分数1%~8%掺杂到主体材料聚乙烯基咔唑(PVK)+2-(联苯-4-芳基)-5-(4-叔丁基苯)-1,3,4-噁二唑(PBD)(30%)中制作了电致发光器件,在不同电压下电致发光光谱中,显现出铱配合物和铂配合物的特征峰,波峰位于400、500和530 nm蓝绿光区发射区。 该双核配合物用于单掺杂有机白光电致发光器件具有制作简单、色稳定性和重复性好等特点,为单掺杂白光发光器件提供了一种好的思路。