1,3,2—氧氮磷杂环戊烷衍生物晶体结构研究

用X射线衍射方法测定了两个1,3,2-氧氮磷杂环戊烷衍生物的晶体结构:2-二乙氨基-3-(4′-甲基苯甲酰基)-2-硫代-1,3,2-氧氮磷杂环戊烷,C_(14)H_(21)N_2O_2PS(1),空间群为P_(bco),α=0.9057(5)nm,b=1.3974(6)nm,c=2.5130(7)nm,Z=8,R=0.051;2-二乙氨基-3-(2′,4′-二氯苯甲酰基)-2-硫代-1,3,2-氧氮磷杂环戊烷,C_(13)H_(17)N_2O_2PSCl_2(2),空间群P2_1/c,α=0.7375(1)nm,b=1.4370(3)nm,c=1.6015(7)nm,β=93.70(2)°,Z=4,R=0.054。结构均由直接法解出。两个化合物中氧氮磷杂五元环均为半椅式构象。其中P—N键长环内分别为0.1712(2)nm和0.1723(0)nn;环外为0.1620(3)nm和0.1620(0)nm,由于成环作用所致环内P—N键长大于环外的。     

乙醇在杂多酸上的氧化、脱水和程序升温脱附研究

合成了两个系列具有Keggin结构的12-钒钼磷酸和钨钼磷酸,研究了它们对乙醇氧化、脱水的催化反应。借助程序升温脱附技术研究了反应物及产物乙醇、乙烯、乙醚等在样品上的程脱作用。讨论了钨、钒取代部分钼原于后对杂多酸酸性及氧化性能的影响。     

硅胶担载四核羰基钴催化剂的EXAFS和IR研究

本文以透射法EXAFS和IR等手段研究了四核羰基钴金属簇Co_4(CO)_(10)(PPh)_2担载在SiO_2上以后及用于烯烃醛化反应前后的变化,确定了相应的结构参数并探讨了催化活性与结构的关系。     

锂离子电池正极材料LiMn2O4的合成与晶体结构（英）

Spinel LiMn₂O₄ powders were prepared using two-step synthesis method consisting of solid-state reaction method and citrate modified sol-gel method. The effects of the calcination temperature and the Li/Mn ratio of raw materials were studied on the physicochemical and electrochemical properties of the spinel LiMn₂O₄ powders, such as crystallinity, lattice constant and density. The title compound was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polycrystalline LiMn₂O₄ powers calcined at 750 ℃ were found to be composed of very uniformly-sized microcrystal with an average particle size of 300 nm. The improvement in electrochemical properties was mainly attributed to the process of re-grinding by absolute alcohol.     

一维链状锰配位聚合物[Mn(4-CPOA)(2,2-bipy)(H_2O)]_n的合成与晶体结构(英文)

0IntroductionThe solid-state chemistry of manganese!car-boxylate coordination polymers has received growingattention over the past few years,owing to their fasci-nating network topologies and potential application inthe field of molecular magnetism and bi…     

The surface and materials science of tin oxide

The study of tin oxide is motivated by its applications as a solid state gas sensor material, oxidation catalyst, and transparent conductor. This review describes the physical and chemical properties that make tin oxide a suitable material for these purposes. The emphasis is on surface science studies of single crystal surfaces, but selected studies on powder and polycrystalline films are also incorporated in order to provide connecting points between surface science studies with the broader field of materials science of tin oxide. The key for understanding many aspects of SnO₂ surface properties is the dual valency of Sn. The dual valency facilitates a reversible transformation of the surface composition from stoichiometric surfaces with Sn⁴⁺ surface cations into a reduced surface with Sn²⁺ surface cations depending on the oxygen chemical potential of the system. Reduction of the surface modifies the surface electronic structure by formation of Sn 5s derived surface states that lie deep within the band gap and also cause a lowering of the work function. The gas sensing mechanism appears, however, only to be indirectly influenced by the surface composition of SnO₂. Critical for triggering a gas response are not the lattice oxygen concentration but chemisorbed (or ionosorbed) oxygen and other molecules with a net electric charge. Band bending induced by charged molecules cause the increase or decrease in surface conductivity responsible for the gas response signal. In most applications tin oxide is modified by additives to either increase the charge carrier concentration by donor atoms, or to increase the gas sensitivity or the catalytic activity by metal additives. Some of the basic concepts by which additives modify the gas sensing and catalytic properties of SnO₂ are discussed and the few surface science studies of doped SnO₂ are reviewed. Epitaxial SnO₂ films may facilitate the surface science studies of doped films in the future. To this end film growth on titania, alumina, and Pt(1 1 1) is reviewed. Thin films on alumina also make promising test systems for probing gas sensing behavior. Molecular adsorption and reaction studies on SnO₂ surfaces have been hampered by the challenges of preparing well-characterized surfaces. Nevertheless some experimental and theoretical studies have been performed and are reviewed. Of particular interest in these studies was the influence of the surface composition on its chemical properties. Finally, the variety of recently synthesized tin oxide nanoscopic materials is summarized.     

A Novel Polyoxovanadium Cluster Shell: β‐As8V14O42

The hydrothermal reaction of VOSO₄, As₂O₅, piperazine and H₂O produces [H₂N(CH₂)₄NH₂]₄[β‐As₈V₁₄O₄₂(SO₄)]·2HSO₄ ( 1 ), which is the first arsenic‐vanadium cluster containing a spherical β‐As₈V₁₄O₄₂ shell. The structure of this compound was characterized by single crystal X‐ray diffraction, elemental analysis, TG, and IR spectrum. Crystal data for 1 : Orthorhombic, Cmcm, a = 15.369(1) Å, b = 16.404(1) Å, c = 25.772(1) Å, V = 6497.4(9) ų, Z = 4.     

Mathematical Modeling of Multicomponent Nonisothermal Adsorption in Sorbent Particles Under Pressure Swing Conditions

A detailed model for nonisothermal sorption of multicomponent mixtures in a single sorbent particle (monodisperse or bidisperse with negligible intracrystalline mass transport limitations) under pressure swing conditions is developed in this study. The dusty-gas model is used to describe the coupling of the molar fluxes, the temperature, the partial pressures and the partial pressure gradients of the components in the pore space of the particle. The variations of the temperature are described by an energy equation in which both convective and conductive modes of heat transport are accounted for. No limitations are imposed on the number of the components in the mixture and on the type of the adsorption isotherm. The model is applied in the investigation of the industrially important air-zeolite 5A system. Two cases with respect to the surrounding gas phase are examined: infinite environment, which is representative for single particle experiments, and finite environment, which is representative for the situation in packed bed adsorbers. It is found that in an infinite environment the external and internal temperature gradients are equally important while in a finite environment the external heat transport limitations are negligible. It is concluded that in modeling the nonisothermal operation of adsorption processes occurring in packed beds it is not necessary to allow for the temperature differences between the gas phase and the surface of the adsorbing particles. Furthermore, if the temperature gradients within the particles can be neglected, only a single temperature equation is needed to describe the energy transport in the bed.     

配位聚合物{[Co(μ-4,4′-bpy)(4,4′-bpy)2·(H2O)2]·(4,4′-bipy)·(H2O)4·(OH)3·(Me)4N}n的晶体结构及性质

配位聚合物通常是通过某种有机配体与金属的配位几何选择以及无限网络的拓扑结构控制而形成的具有无限结构的化合物 [1] ,其结构新颖并具有不寻常的光电效应、非线性光学性能、磁性、超导及催化等诸多具有诱人应用前景的独特性能 .因此 ,近年来倍受化学家和材料学家的重视 [2～ 5] .以 Co为配位中心的配位聚合物若具有八面体构型 ,在一定条件下具有自旋转换能力 ,而且往往可与光电转换能力相关联 ,是一种潜在的新型信息存储材料 [6 ] .对于配位聚合物的形成 ,配体的选择最重要 . 4,4′-联吡啶及其衍生物是一种较好的刚性配体 ,相关的配位聚…     

Synthesis of Hexadentate Hexahydro-1,3,5-triazine-Based Ligands and their Copper(I) Complexes

Summary.  Hexadentate ligands were formed by the reaction of primary dimethylaminoethyl- or methoxyethylamines with formaldehyde. The resulting N, N′, N″-functionalized hexahydro-1,3,5-triazines contain pending amino or ether functionalities which are able to coordinate to metals in addition to the ring nitrogen atoms. Both ligands were reacted with CuBr, and novel tricopper clusters were isolated and characterized by X-ray structure analysis. In these compounds a ring nitrogen atom, the pending amino or ether functionality, and two bridging bromine atoms coordinate each of the copper atoms. Received January 22, 2002; accepted (revised) March 22, 2002