己二酸柱撑水滑石的制备及表征

水滑石（Layered Double Hydroxidex,简称LDHs）是一类具有层状结构的阴离子型粘土^[1]。水滑石的一个重要性质是层间阴离子具有可交换性,引入不同的阴离子,能够得到不同结构和功能和柱撑水石滑,因而阴离子插层是水滑石研究的一个重要方向。各类阴离子如有机和无机阴离子、同多和杂多阴离子以及金属配合物阴离子的柱撑水滑石在文献中都有报道^[2-5]。其中有机阴离子由于在结构上的多样性,使有机阴离子柱撑水滑石具有巨大的应用开发潜力,已经引起了人们的广泛关注^[6-12]。     

新型层柱催化剂Zn2Al－XW11Z的催化氧化活性及热稳定性

新型层柱催化剂Ｚｎ２Ａｌ┐ＸＷ１１Ｚ的催化氧化活性及热稳定性＊贺庆林胡长文＊＊张云峰王恩波（东北师范大学化学系，长春１３００２４）关键词层柱催化剂，杂多阴离子，氧化活性，热稳定性，苯甲醛，氧化同多和杂多阴离子柱撑水滑石是近年来新开发的层柱状催化材料，...     

杂多阴离子柱撑水滑石层柱相互作用的XPS研究(II)

水滑石（LayeredDoubleHydroxides，简称LDHs）作为一类重要的柱层材料已引起人们的重视[1，2]．人们利用水滑石间柱阴离子的可交换性的特点[3].将各种阴离子如无机和有机阴离子[4]、同多和杂多阴离子（Polyoxometalates；简称POMs）[5]相继被引入水滑石层间．因此得到了具有高     

Zn_2Al－PW_（12－n）V_nO_（40）（n＝1～4）的合成与表征

Ｚｎ_２Ａｌ－ＰＷ_（１２－ｎ）Ｖ_ｎＯ_（４０）（ｎ＝１～４）的合成与表征郭军，孙铁，沈剑平，蒋大振闵恩泽（吉林大学化学系，长春，１３００２３）（石油化工科学研究院）关键词Ｐ－Ｗ－Ｖ杂多阴离子，柱撑水滑石，合成同多和杂多阴离子柱撑水滑石（简称ＰＯＭｓ－...     

柱撑阴离子粘土的合成、表征及催化性能研究(II)

层柱状阴离子粘土可用化学通式口艺Ms”（OH）：［A”叫。／n·YH。0表示，M’”、u’十分别为二、三价金属离子，l。一为层间阴离子．由于其具有独特的微初结构，对某些有机反应具有极高的活性和选择性，引起了人们的关注［‘，2］．近年来，Pinnavaia等人［‘刘成功地合成了体积较大的同多及杂多含氧酸根柱撑的阴离子粘土，并发现ZnAI－VI。028对异丙醇光氧化成丙酮的反应具有极高的选择性．最近，笔者将过渡元素取代型三元杂多含氧酸根嵌入到ZnAINO。层间，并发现这些阴离子粘土对乙酸与正丁醉酯化反应具有较高活性和酯化选择性…     

柱撑阴离子粘土的合成、表征及催化性能研究(Ⅴ)

近年来，同多酸和杂多酸型层往化合物作为新型微孔催化剂，在固体无机合成化学和多酸催化化学等领域引起人们的关注[1-3]．Pinnavaia[3]等人首先将同多阴离子发通过与Zn2AlNO3进行离子交换反应，制备了通道高度为0．72urn的新型无机层柱化合物Zn2Al－V10O28．并发现它在液·固相体系中，对异丙醇光氧化成丙酮的反应具有较高活性与选择性．最近，我们采用类似的方法制备了单取代和三取代型Keggin结构杂多阴离子XW11ZO39（H2O）n-[4]和XW9Z3O37（H2O）[5]（分别缩写成XW11Z和XW9Z3）柱撑的ZnAl层柱双羟基化合物Zn2Al－HPOMs（H…     

杂多阴离子柱撑水滑石层柱相互作用(Ⅰ)

杂多阴离子柱撑水滑石层柱相互作用（Ⅰ）李兴林＊佘益民郭军蒋大振（中国科学院长春应用化学研究所长春１３００２２）（吉林大学化学系长春）关键词杂多阴离子，柱撑水滑石，ＸＰＳ，ＩＲ，ＸＲＤ１９９６－０６－１８收稿，１９９６－１０－１２修回国家自然科学基金资...     

类水滑石及其杂多阴离子柱撑物的合成与表面酸性研究

合成了一些类水滑石和过渡金属取代型杂多酸盐，并由此制备了相应杂多阴离子柱撑水滑石层柱材料。用ＸＲＤ，ＩＲ和元素分析等手段对合成产物进行组成和结构表征，用ＮＨ３－ＴＰＤ，Ｐｙ－ＩＲ研究了合成产物的表面酸性和酸类型，并在异丙醇反应中考察了合成物的酸碱催化行为，结果表明，水滑石和柱撑水滑石均同时存在酸碱中心，且酸碱相对强度与柱阴离子类型密切相关。杂多阴离子进入水滑石层，同时改变了水滑石和杂多酸盐的酸强度     

P-Cu-Mo杂多阴离子柱撑水滑石的制备

杂多阴离子柱撑水滑石作为一类新型的催化材料,近年来日益受到人们的关注。但由于杂多化合物对碱不稳定及水滑石在酸性条件下层结构易被破环,故文献中仅有制得钨硅系杂多阴离子柱水滑石的报道。作者将过渡金属引入钼磷酸的Keggin结构骨架中,提高了其溶液稳定性,并在微波场中快速地制得了P-Cu-Mo杂多阴离子柱撑水滑石。     

柱撑化合物Zn2Al-PW11Z的结构模型及酯化活性

杂多化合物是性能优异的酸型和氧化型或双功能催化剂[1－4]，而通式为的阴离子粘土通常具有减催化或还原催化性能[5，6]．因此，从在分子及原子水平上设计催化剂，调控催化性能观点出发，人们期望将体积较大的杂多阴离子嵌入阴离子粘土层间，合成大层间距的新型柱撑微孔材料．1988年Pinnavaia等人[7]首次报导了Zn2Al－V10O28是具有2．0nm孔径分布的中微孔材料．最近，笔者将单取代型Keggin结构杂多阴离子GeW11O39Z（H2O）6－（其中Z＝Ni2 和Cu2 ）和缺位Keggin结构的GeW11O嵌入Zn2Al－NO3层间，合成了通道高度为0．9nm的新型柱撑…     

POROUS MEMBRANE TEMPLATED SYNTHESIS OF POLYMER PILLARED LAYER

The anodic porous alumina membranes with a definite pore diameter and aspect ratio were used as templates tosynthesize polymer pillared layer structures. The pillared polymer was produced in the template membrane pores, and thelayer on the template surfaces. Rigid cured epoxy resin, polystyrene and soft hydrogel were chosen to confirm themethodology. The pillars were in the form of either tubes or fibers, which were controlled by the alumina membrane pore surface wettability. The structural features were confirmed by scanning electron microscopy results.     

Layered cobalt hydroxysulfates with both rigid and flexible organic pillars: synthesis, structure, porosity, and cooperative magnetism.

The synthesis and characterization of two members of a family of porous magnetic materials is described. The structures of Co4(SO4)(OH)6(C2N2H8)0.5*3H2O and Co4(SO4)(OH)6(C6N2H12)0.5*H2O and their thermal stability can be tailored via the choice of organic pillar. The interactions between the pillaring agent and the compositionally complex inorganic layer are discussed. The influences of two pillaring agents i.e., the flexible ethylenediamine and the relatively rigid 1,4-diazabicyclo[2,2,2]octane, on thermal stability, rigidity upon guest loss, and magnetic behavior of the pillared solids are compared. The magnetism of the pillared layered cobalt hydroxides is complex due to the influences of multiple metal sites, inter- and intralayer exchange, spin-orbit coupling, and geometrical frustration. The wide variety of potential pillars, oxyanions, and possible metal substitutions at the octahedral and tetrahedral sites offers the possibility of tailoring the magnetic and porous properties of these materials.     

Influence of MgO template on carbon dioxide adsorption of cation exchange resin-based nanoporous carbon

In this work, porous carbons with well-developed pore structures were directly prepared from a weak acid cation exchange resin (CER) by the carbonization of a mixture with Mg acetate in different ratios. The effect of the Mg acetate-to-CER ratio on the pore structure and CO(2) adsorption capacities of the obtained porous carbons was studied. The textural properties and morphologies of the porous carbons were analyzed via N(2)/77K adsorption/desorption isotherms, SEM, and TEM, respectively. The CO(2) adsorption capacities of the prepared porous carbons were measured at 298 K and 1 bar and 30 bar. By dissolving the MgO template, the porous carbons exhibited high specific surface areas (326-1276 m(2)/g) and high pore volumes (0.258-0.687 cm(3)/g). The CO(2) adsorption capacities of the porous carbons were enhanced to 164.4 mg/g at 1 bar and 1045 mg/g at 30 bar by increasing the Mg acetate-to-CER ratio. This result indicates that CER was one of the carbon precursors to producing the porous structure, as well as for improving the CO(2) adsorption capacities of the carbon species.     

两个三维柱层式Ce混合羧酸多孔金属-有机骨架配合物的合成、结构与磁性

采用水热法合成了两个新的混合羧酸铈多孔金属-有机骨架配合物[Ce2(fum)3 (H2O)4?(bdc)?(H2O)2]n（1）和[Ce2(suc)2(ox)(H2O)4?(H2O)4]n（2）,利用元素分析、红外光谱、热重分析和单晶X射线衍射对其组成和结构进行了表征,并通过磁性测量研究了其磁学性能. 单晶X射线衍射结果表明,配合物1和2均为三维柱层式多孔金属-有机骨架结构. 配合物1由Ce离子和富马酸（fumarate, fum）形成层,层与层之间再通过富马酸作为柱状配体支撑形成三维结构,并在层间的两个方向上形成相互交错的通道,未配位的中性对苯二甲酸分子（p-benzenedicarboxylate, bdc）和晶格水分子填充于孔道中. 与配合物1类似,配合物2由Ce离子和丁二酸（succinate, suc）形成层,层间通过草酸（oxalate, ox）作为柱状配体支撑形成三维结构,在层间的三个方向上具有相互交错的通道,晶格水分子填充于孔道中.     

一步聚合法制备壳核型、可控阶层结构的羰基铁/聚苯乙烯复合微球

采用改进的悬浮聚合法合成了一系列粒径和结构可调的羰基铁粉/聚苯乙烯磁性高分子微球.利用傅立叶变换红外光谱仪、热重分析仪、X射线衍射仪、扫描电镜等分析了微球的结构、化学成分及形貌.结果表明,通过改变苯乙烯单体和聚乙烯醇(PVA)的加入量,可以制备三类不同形貌和结构的复合微球,即多孔复合微球,无孔复合微球和含"带状"突起的...     

A bridge between pillared-layer and helical structures: a series of three-dimensional pillared coordination polymers with multiform helical chains

Rational self-assembly of a long V-shaped 3,3',4,4'-benzophenonetetracarboxylate (bptc) ligand and metal salts in the presence of linear bidentate ligand yield a series of novel pillared helical-layer complexes, namely, [Cu2(bptc)(bpy)2] (1), [M3(Hbptc)2(bpy)3(H2O)4].2 H2O (M = Fe(2) and Ni(3)), [Co2(bptc)(bpy)(H2O)].0.5 bpy (4), [Cd2(bptc)(bpy)(H2O)2].H2O (5), [Mn2(bptc)(bpy)1.5(H2O)3] (6) and [M2(bptc)(bpy)0.5(H2O)5].0.5 bpy (M = Mn(7), Mg(8) and Co(9), bpy=4,4'-bipyridine). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. The structure of 1 consists of two types of chiral layers, one left-handed and the other right-handed, which are connected by bpy pillars to generate a novel 3D open framework featuring four distinct helical chains. Compounds 2 and 3 are isostructural and feature 3D structures formed from the interconnection of arm-shaped helical layers with bpy pillars. Compound 4 is a pillared helical double-layer complex containing four different types of helices, among which the nine-fold interwoven helices constructed from triple-stranded helical motifs are unprecedented. Compound 5 exhibits a novel 3D covalent framework which features nanosized tubular channels. These channels are built from helical layers pillared by bptc ligands. The structure of 6 is constructed from {Mn(bptc)(H2O)}n2n- layers, which consist of left- and right-handed helical chains, pillared by [Mn2(bpy)3(H2O)4]4+ complexes into a 3D framework. To the best of our knowledge, compounds 1-6 are the first examples of pillared helical-layer coordination polymers. Compounds 7-9 are isostructural and exhibit interesting 2D helical double-layer structures, which are constructed from {M(bptc)(H2O)2}n2n- ribbons cross-linked by [M2(bpy)(H2O)6]4+ complexes. Furthermore, the 3D supramolecular structures of 7-9 are similar to the 3D structure of 6, and the 2D structure of 7 can be transformed into the 3D structure of 6 at higher reaction temperature. By inspection of the structures of 1-9, it is believed that the V-shaped bptc ligand and V-shaped phthalic group of the bptc ligand are important for the formation of the helical structures. The magnetic behavior of compounds 1, 2, 4, 6, and 9 was studied and indicated the existence of antiferromagnetic interactions. Moreover, compound 5 shows intense photoluminescence at room temperature.     

介孔硅层柱蒙脱石材料合成的新方法与表征

利用十六烷基三甲基溴化铵(CTAB)将天然钠基蒙脱石改性成有机蒙脱石,以十二烷胺为模板剂,正硅酸乙酯为层柱前驱体,在室温下合成了新型介孔硅层柱蒙脱石材料.用XRD,TG,FTIR以及N₂等温吸附-脱附等技术对产物进行了表征.结果表明,合成材料具有大通道(净层间距为2.75nm)、介孔孔径且孔分布窄(平均孔径为2.17nm)、比表面积高(SBET=821.6m²/g)、热稳定性高(大于800℃)等特征.同时,通过改变中性胺的链长,研究了孔结构的调变规律,分析了材料的成孔机理和热稳定性提高的原因.     

One-, two- and three-periodic metal-organic rotaxane frameworks (MORFs): linking cationic transition-metal nodes with an anionic rotaxane ligand

A new singly charged pyridinium axle was prepared and combined with disulfonated dibenzo[24]crown-8 ether to form a [2]pseudorotaxane. The reaction of this new, anionic ligand with Zn(II) ions, under various crystallization conditions, resulted in the formation of three metal-organic rotaxane framework (MORF) solids; a one-periodic ML coordination polymer and two, two-periodic ML(2) square grid frameworks. The layers of square grids can be pillared to create full three-periodic MORF structures, which have completely neutral frameworks and are porous. These three-periodic materials represent the first examples of neutral porous MOFs in which one (or more) of the linkers is a mechanically interlocked molecule (MIM).     

Preparation of Porous Polylactide Microspheres and Their Application in Tissue Engineering

In this study,porous polylactide (PLA) microspheres with different structures were prepared through the multiple emulsion solvent evaporation method.By changing organic solvents (ethyl acetate and chloroform) and adding effervescent salt NH4HCO3 in the inner water phase,microspheres with porous capsular,matrix,microcapsular and multivesicular structures were prepared.The protein encapsulation and release,and the cell growth behavior of porous microspheres were further explored.Under the same inner water phase,microspheres prepared with chloroform had higher protein encapsulation efficiency and less protein release rate as compared with those prepared with ethyl acetate.Cell experiments showed that the relatively rough surface of microspheres prepared with chloroform was more favorable for the cell growth in comparison with the smooth surface of microspheres prepared with ethyl acetate.This study shows a simple and effective method to control the protein release and cell growth behaviors of polymer microspheres by tuning their porous structure.     

Impact of metal-ion dependence on the porous and electronic properties of TCNQ-dianion-based porous coordination polymers

A series of TCNQ-dianion-based porous coordination polymers [M(TCNQ)bpy] (M = Fe, Zn, Mn, Co, Cd) have been synthesized and characterized. The synthesis reactions of these compounds are promoted by the addition of ascorbic acid, which is the key to obtaining a high yield. They form almost identical three-dimensional pillared layer structures with the M-TCNQ two-dimensional layers linked by bpy pillar ligands. The electronic properties of these compounds vary depending on the constitutional metal ions and guest molecules. We found that the electronic interaction between metal ions and TCNQ moieties in the frameworks strongly impacted the electronic properties of the compounds.