Electrocatalytic Synthesis of Nylon-6 Precursor at Almost 100 % Yield

Synthesis of cyclohexanone oxime via the cyclohexanone-hydroxylamine process is widespread in the caprolactam industry, which is an upstream industry for nylon-6 production. However, there are two shortcomings in this process, harsh reaction conditions and the potential danger posed by explosive hydroxylamine. In this study, we presented a direct electrosynthesis of cyclohexanone oxime using nitrogen oxides and cyclohexanone, which eliminated the usage of hydroxylamine and demonstrated a green production of caprolactam. With the Fe electrocatalysts, a production rate of 55.9 g h⁻¹ g_cat⁻¹ can be achieved in a flow cell with almost 100 % yield of cyclohexanone oxime. The high efficiency was attributed to their ability of accumulating adsorbed hydroxylamine and cyclohexanone. This study provides a theoretical basis for electrocatalyst design for C−N coupling reactions and illuminates the tantalizing possibility to upgrade the caprolactam industry towards safety and sustainability.     

CO_2捕集炭膜的前驱体结构设计及性能

从分子结构设计出发,合成了一系列新型刚性、高自由体积的聚酰亚胺炭膜前驱体,并制备了炭膜.采用热重分析(TGA)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和高分辨透射电子显微镜(HRTEM)研究了不同聚酰亚胺前驱体的热分解特性及在热解炭化过程中化学结构、微结构的变化规律;测试了所制备炭膜的气体分离性能.结果表明,前驱体的自由体积分数显著影响炭膜的气体分离性能;聚合物结构越具刚性,自由体积越大,所得炭膜结构越疏松,极微孔道尺寸越大,越有利于气体分子在炭膜极微孔道中的渗透、扩散与传输.其中,刚性大体积基团芴基、酚酞cardo基团和六氟异丙基的引入能有效破坏分子链间的堆积,提高聚合物的自由体积,所形成炭膜的结构较疏松,均表现出优异的气体渗透性和分离选择性,超越了Robeson上限,解决了传统炭膜气体渗透性能低的问题.特别是采用羟基官能化聚酰亚胺前驱体制备的炭膜在保持较高气体分离选择性的同时,CO_2气体的渗透性高达24770 Barrer(1 Barrer≈7.5×10-18m2·s-1·Pa-1),可实现对CO_2的有效分离和捕集,展现出良好的商业化应用前景.     

纺丝法制备木质素基碳纤维的研究进展

目前全球制备碳纤维主要以聚丙烯腈(PAN)或沥青为原丝,但是这类碳纤维制备成本高,限制了其自动化工业领域的大规模应用。木质素由于具有较高的含碳量和碳化收率高,其可以作为前驱体来制备碳纤维。作为一种新型材料,木质素基碳纤维因其具有价格低廉、环保、原料丰富、可实现废弃资源再生利用等优点而备受关注。本文详细介绍了木质素的分类及结构特征,阐述了不同纺丝方法制备的碳纤维的力学性能,并对其未来发展进行展望。     

苯并咪唑基铜配位聚合物定向合成子代配合物：小分子配体取代反应及配合物晶体结构

由配合物作前驱体(简称:前驱体配合物)来制备子代配合物是配合物定向合成的有效方法之一。与一般的有机配体相比,前驱体配合物拥有特定的、相对稳定的结构骨架,并且在一定的反应条件下能够与有机配体之间进行定向自组装,形成具有预期结构的配合物,同时还能把自己的结构特征"遗传"给子代配合物。本论文选择一个一维长链铜配合物{[Cu(bbbm)(CH_3COO)_2]·(CH_3OH)_2}n(Q)[bbbm=1,1’-(1,4-丁基)-二-(1-H-苯并咪唑)]作为前驱体配合物,通过小分子配体的取代、加成反应获得了一个新的子代配合物[Cu(bbbm)(N_3)_2(Py)]n(1)。单晶衍射分析结果显示子代配合物(1)"遗传"了前驱体配合物(Q)的一维长链结构。我们还进一步研究了反应前后配合物的配位方式、bbbm配体构象变化及其催化性能变化。     

Weak Interactions under Pressure: hp‐CuBi and Its Analogues

The metastable binary compound hp‐CuBi was obtained from the direct chemical reaction between copper and bismuth at a pressure of 5 GPa and a temperature of 720 K. The atomic arrangement comprises slabs of puckered Cu layers sandwiched between Bi planes. The QTAIM charges calculated for compounds of bismuth with transition metals reveal negligible charge transfer for hp‐CuBi. Analysis of the chemical bonding with position‐space techniques discloses multicenter interactions within the Bi‐Cu‐Bi slabs and lone‐pair interactions of the van der Waals type between these entities. hp‐CuBi exhibits metal‐type electrical conductivity with superconductivity below T_c=1.3 K.     

Magnetic bottles for the Neumann problem: The case of dimension 3

The main object of this paper is to analyze the recent results obtained on the Neumann realization of the Schrödinger operator in the case of dimension 3 by Lu and Pan. After presenting a short treatment of their spectral analysis of keymodels, we show briefly how to implement the techniques of Helffer-Morame in order to give some localization of the ground state. This leaves open the question of the localization by curvature effect which was solved in the case of dimension 2 in our previous work and will be analysed in the case of dimension 3 in a future paper.     

Effect of Mg and C contents in MgCNi3, and structure and superconductivity of MgCNi3- x -Co x

The effect of Mg and C contents on T_C in MgCN₃, and structure and superconductivity of MgCNi_3-x Co _x were studied. It is found that the excess of Mg and C in initial material mixture is favorable to improvement inT _c and helps to obtain single-phase samples. For preparing MgCNi₃ superconductor, the optimum composition of starting materials is MgC_1.45Ni₃ with excess of Mg (20 wt.%) of the stoichiometric composition. In gCNi_3-x Co _x system, a continuous solid solution is formed, lattice parameter decreases slightly andT _c decreases obviously with increasingx. A suppression of superconductivity is observed due to the substitution of Co (Mn) for Ni. The suppression effect is smaller for the substitution of Co than that of Mn     

Global existence of strong solutions to a time‐dependent 3D Ginzburg‐Landau model for superconductivity with partial viscous terms

We study an initial boundary value problem for a time‐dependent 3D Ginzburg‐Landau model of superconductivity with partial viscous terms. We prove the global existence of strong solutions.     

Approximations of a Ginzburg-Landau model for superconducting hollow spheres based on spherical centroidal Voronoi tessellations

In this paper the numerical approximations of the Ginzburg- Landau model for a superconducting hollow spheres are constructed using a gauge invariant discretization on spherical centroidal Voronoi tessellations. A reduced model equation is used on the surface of the sphere which is valid in the thin spherical shell limit. We present the numerical algorithms and their theoretical convergence as well as interesting numerical results on the vortex configurations. Properties of the spherical centroidal Voronoi tessellations are also utilized to provide a high resolution scheme for computing the supercurrent and the induced magnetic field.

     

Experimental observation of lattice distortions due to a flux line lattice in niobium

A polarized neutron scattering investigation of the flux line lattice in the type-II superconductor niobium is reported. A modulation of the nuclear lattice has been detected, and the magnitude of the first Fourier component of the lattice distortion established relative to the magnitude of the magnetic scattering. This constitutes the first experimental observation of lattice distortions due to the presence of magnetic flux lines within the bulk of a type-II superconductor. Using a simple microscopic model the lattice distortion in niobium is estimated. A new mechanism is suggested for the coupling of the flux line lattice to the crystallographic lattice. The experimental technique opens up the possibility of investigating the microscopic mechanism of flux line - nuclear lattice interactions, in particular the pinning of flux lines within the bulk of a type-II superconductor. Received: 8 August 1997 / Accepted: 16 October 1997