2-羟基-4-甲氧基二苯甲酮-5-磺酸插层水滑石的制备及性能

以层状镁铝双金属氢氧化物（MgAl Layered Double Hydroxides,Mg-Al LDHs）为主体,以有机紫外光稳定剂2-羟基-4-甲氧基二苯甲酮-5-磺酸（BP）为客体,结合焙烧复原法和阴离子交换法合成了具有超分子结构有机-无机插层复合物（MgAl-BP-LDHs）,研究了层间阴离子、反应介质、pH值、反应时间等因素对于插层材料超分子结构的影响。用FTIR、XRD、TG-DTA、UV-Vis和粒度分析对其不同尺度的结构、热稳定性和紫外光稳定性等进行表征。结果表明,采用阴离子交换法难以进行插层反应;通过焙烧复原法可显著降低MgAl-LDHs层间CO₂^-离子,从而有利于BP阴离子交换进入MgAl-LDHs层间,在去离子水中,水温100℃,pH=7,反应时间为48 h,BP过饱和的条件下合成得到最高插层率的MgAl-BP-LDHs;主体水滑石层板与客体以静电力和氢键相互作用,得到的超分子结构材料具有良好的热稳定及兼具优异的紫外屏蔽、吸收性能,是一种新型的有机-无机复合光热稳定剂。     

酸性橙插层锌铝水滑石的组装及其结构与性能

采用共沉淀法合成酸性橙阴离子插层锌铝水滑石(Zn/Al-AO7 LDHs),研究不同pH值及原料金属离子配比对产物结构的影响,利用X射线粉末衍射(XRD),热分析(TG-DTA),傅里叶变换红外(FT-IR)等表征手段,对插层产物的结构进行表征,确定了制备酸性橙插层锌铝水滑石的最适宜条件.用量子化学的B3PW91/6-31G(d,p)方法对Zn/Al-AO7 LDHs模型分子的空间几何构型进行了优化,通过结构组合得到的层间距为2.33 nm,接近XRD测试得到的层间距,从而说明了酸性橙离子在水滑石层板间的排列方式.进一步以甲酰胺为溶剂对水滑石层板进行剥离,得到澄清溶液,根据剥离产物的XRD谱可以确定剥离实验成功.     

超分子结构草甘膦插层水滑石的组装及结构研究

提出了一种新的绿色农药缓释剂模型——超分子结构草甘膦缓释剂.依据插层组装理论,以阴离子层状材料镁铝水滑石(MgAl-LDH)为插层主体,以除草剂草甘膦为插层客体,由共沉淀法一步组装得到超分子结构草甘膦插层镁铝水滑石(MgAl-LDH-gly).通过对MgAl-LDH-gly的结构、主客体相互作用及化学组成确认,建立了MgAl-LDH-gly的近似超分子结构模型,并对其缓慢释放草甘膦的可行性进行了分析.     

超分子结构姜黄素插层镁铝水滑石的组装、结构及缓释性能

以镁铝水滑石为主体, 以中药提取物姜黄素为客体, 由共沉淀法、离子交换法和焙烧复原法三种不同方法组装得到超分子结构复合材料——姜黄素插层镁铝水滑石. 并用XRD, IR, HPLC等手段对该材料进行了表征. 结果表明, 共沉淀法和离子交换法成功组装得到两种不同结构的姜黄素插层产物, 使材料的层间距扩大为0.82～1.36 nm, 层间客体姜黄素阴离子是以平行或者单层垂直的定位方向排列于层间的. 考察了该材料在不同pH值的磷酸盐缓冲溶液中的缓释性能, 其缓释历程为客体阴离子与介质中 的离子交换过程. 该研究指出了阴离子层状材料——水滑石在中药释释剂领域的应用潜力.     

高荧光性含锌类水滑石研究

本研究将适量锌离子(II)取代镁铝水滑石中的镁离子(II), 以及将一定量的8-羟基喹啉(8-hydroxyquinoline)分散于镁铝水滑石层间的亲油性阴离子中, 使与其板层表面上的锌离子配位, 经共沉淀法, 合成、组装得到一类迄今未见报道的具高荧光性的类水滑石(Zn-HTLC)荧光材料. 采用荧光光谱、红外光谱、紫外光谱、X射线衍射和热分析等对其进行了表征. 研究表明, 这种类水滑石在紫外光下可发出强烈的蓝绿色荧光(501 nm), 荧光强度高达4.5×10⁵ a.u., 说明锌离子(II)分散于类水滑石的氢氧化镁板层中, 可有效防止发光结构单元的荧光猝灭, 而且溶于层间阴离子中的配体与板层上的锌离子(II)配位所形成的特殊组装结构, 增强了发光中心的不对称性, 也是其具有高荧光性的可能原因. 热分析结果显示, 这种类水滑石耐热性强, 有望应用于各种功能性荧光材料.     

表面预处理对镁铝水滑石结构性质和缓释性能影响

以Mg-Al-NO₃水滑石（LDHs）为载体,将5-氟尿嘧啶（5-FU）通过离子交换法插入其层间,得5-FU/LDHs缓释材料。并对水滑石表面进行弱酸预处理改性,利用XRD、FTIR、TG-DSC、SEM和零电荷点（pHPZC）等表征手段,考察酸预处理对水滑石表面化学性质及微观结构的影响。结果表明,5-FU/LDHs的层间距从0.858nm扩大到1.064nm,层间5-FU₂阴离子与主体层板通过氢键与静电作用,以呈一定角度单层交替排列于层间。酸预处理的水滑石粒径变小,层板正电荷密度增大。5-FU的释放机理是物理扩散、离子交换和药物溶解等协同作用,酸预处理可提高水滑石的缓释性能和稳定性。     

层状复合金属氢氧化物：主客体结构研究进展

近年来, 基于层状复合金属氢氧化物（layered double hydroxides, 简称LDHs）的主客体插层化学在功能材料的构筑和应用方面得到了学术界和产业界的广泛关注. 本文从LDHs材料的层板主体及层间客体的结构、层间客体种类、层板堆积模式等角度总结了LDHs层状结构及主-客体、客-客体相互作用的最新研究进展.     

硼酸根插层水滑石层间组成及取向结构的控制

以Mg0 .67Al0 .3 3 (OH) 2 (CO3 ) 0 .165·0 .62H2 OLDHs为前体 ,以水为分散介质 ,由离子交换法组装了硼酸根插层LDHs ,并用XRD ,FT IR ,TG DTA ,ICP ,11BMASNMR等手段对样品进行了分析和表征 .结果表明 ,通过控制离子交换时的pH ,可使硼酸根取代Mg Al CO3 LDHs前体层间的CO2 -3 ,且可控制离子交换程度及客体的取向 ,从而控制插层结构 .对硼酸根插层LDHs的结构进行研究发现 ,控制pH =4.5 ,层间阴离子主要是一硼酸根和离子平面与LDHs层板平行的三硼酸根 ,出于结构稳定的需要 ,CO2 -3 不能完全被置换 ;控制pH =3 .5 ,层间阴离子是一硼酸根和离子平面与LDHs层板垂直的三硼酸根     

[Eu（Bipy）2]Cl3和[Tb（Bipy）2]Cl3在有机功能化剥层水滑石表面上的组装及光致发光性质

以乙酰基丙氨基三乙氧基硅烷对剥层镁铝水滑石进行了表面硅烷化修饰,得到了表面硅烷化修饰的剥层水滑石复合材料.然后在该复合材料表面进行了[Eu(Bipy)2]3+和[Tb(Bipy)2]3+分子组装,得到了剥层水滑石复合稀土发光体.组装体的紫外激发发射光谱表明,稀土配合物被组装到经硅烷化试剂修饰的剥层水滑石表面后,其电偶极跃迁较原配合物有很大提高,热稳定性也有提高.从主客体材料相互作用角度对稀土配合物电偶极跃迁的提高进行了解释.     

类水滑石主体层板与客体CO2-3、H2O间的超分子作用

通过构建类水滑石双层计算模型, 采用混合密度泛函B3LYP/6-31G(d)//B3LYP/3-21G方法计算类水滑石(LDHs-CO3-yH2O)的结构与能量, 探讨LDHs限域空间中客体阴离子及水分子的分布形态以及主客体超分子作用. 计算结果表明, 客体阴离子与水分子以平行层板的方式存在于水滑石层间. 主客体发生作用时, CO2-3的HOMO轨道向层板的LUMO轨道转移电子. 所形成的LDHs-CO3主客体作用要强于LDHs-F以及LDHs-Cl, 与其离子交换性能相一致. 水滑石去水结构(LDHs-CO3)水合过程, 氢键作用较静电作用更占优势, 并且layer-water型氢键要强于anion-water 型氢键. 此外, 水合能计算表明LDHs水合具有一定的饱和量.     

超分子结构甲基橙插层水滑石的组装及其光热稳定性研究

甲基橙是一种酸性染料,但因为它的光和热稳定性较差,使其应用范围和使用效果受到了一定限制.以Mg_0.67Al_0.33(OH)₂(CO₃)_0.165·0.58H₂OLDHs为前体,采用离子交换法,将甲基橙插入到LDHs层间,借助XRD,FTIR,UV-Vis和TG-DTA等手段对样品进行表征.结果表明,甲基橙阴离子可以完全取代前体层间的CO₃^2-离子,组装得到晶体结构良好的甲基橙插层LDHs.对其结构进行研究发现,LDHs主体层板与客体甲基橙阴离子之间存在静电吸引、氢键和其它弱化学键相互作用,具有超分子结构特征.该超分子结构材料不仅保持了甲基橙本身的颜色,而且与甲基橙相比,其耐光性和耐热性均有大幅度的提高.     

Molecular assembly in synthesised hydrotalcites of formula Cu(x)Zn(6 - x)Al2(OH)16(CO3) x 4H2O--a vibrational spectroscopic study

Infrared and Raman spectroscopy have been used to characterise synthetic hydrotalcites of formula Cu(x)Zn(6 - x)Al2(OH)16(CO3) x 4H2O. The spectra have been used to assess the molecular assembly of the cations in the hydrotalcite structure. The spectra may be conveniently subdivided into spectral features based (a) upon the carbonate anion (b) the hydroxyl units (c) water units. The Raman spectra of the hydroxyl-stretching region enable bands to be assigned to the CuOH, ZnOH and AlOH units. It is proposed that in the hydrotalcites with minimal cationic replacement that the cations are arranged in a regular array. For the Cu(x)Zn(6 - x)Al2(OH)16(CO3) x 4H2O hydrotalcites, spectroscopic evidence suggests that 'islands' of cations are formed in the structure. In a similar fashion, the bands assigned to the interlayer water suggest that the water molecules are also in a regular well-structured arrangement. Bands are assigned to the hydroxyl stretching vibrations of water. Three types of water are identified (a) water hydrogen bonded to the interlayer carbonate ion (b) water hydrogen bonded to the hydrotalcite hydroxyl surface and (c) interlamellar water. It is proposed that the water is highly structured in the hydrotalcite as it is hydrogen bonded to both the carbonate anion and the hydroxyl surface.     

并流淤浆混合法制备铜基甲醇合成催化剂及助剂Al2O3的作用研究

采用并流淤浆混合法制备了一系列具有不同铜锌铝比的铜基甲醇合成催化剂CuO/ZnO/Al2O3，测试了其催化性能(甲醇收率和CO转化率)及物相结构，并对该制备方法进行评价。Cu∶Zn∶Al摩尔比为4∶5∶1 的铜基催化剂显示了最好的催化活性。通过对催化剂前驱物煅烧过程进行DTA分析及对前驱物进行XRD分析表明， 催化剂前驱物的物相与Al2O3的量有关。当Al2O3的量较低时，前驱物的物相以(Cu0.3 Zn0.7)5(CO3)2(OH)6为主；当Al2O3的量较高时，前驱物中物相(Cu0.3Zn0.7)5(CO3)2(OH)6的量下降，而物相Cu2CO3(OH)2的量增加。物相(Cu0.3 Zn0.7)5(CO3)2(OH)6对终态催化剂的活性是十分有利的 。     

不同锌铝比水滑石的合成及其吸附脱除水中邻苯二甲酸性能

采用共沉淀法合成一系列具有不同锌铝比的水滑石,并利用X射线衍射(XRD)、扫描电镜(SEM)、热重(TG)、氮气吸脱附及电感耦合等离子体质谱(ICP-MS)等表征手段对其结构与组成进行了测试。将上述水滑石材料用于吸附脱除水中邻苯二甲酸污染物,考察了不同锌铝比水滑石吸附邻苯二甲酸性能的差异。结果表明,在较低锌铝比时,随着水滑石锌铝比的增加,其对邻苯二甲酸的吸附量逐渐增大;当锌铝比较大时(6),随着锌铝比的增加,水滑石的吸附量基本保持不变。进一步选取锌铝比为6的水滑石,分别对其吸附邻苯二甲酸的动力学和热力学进行了研究,发现其吸附等温线和吸附动力学数据分别符合Freundlich等温吸附模型和准二级动力学模型,且循环吸附性能较好。     

不同锌铝比水滑石的合成及吸附脱除水中邻苯二甲酸性能的研究

采用共沉淀法合成一系列具有不同锌铝比的水滑石,并利用X射线衍射（XRD）、扫描电镜（SEM）、热重（TG）、氮气吸脱附及电感耦合等离子体质谱（ICP-MS）等表征手段对其结构与组成进行了测试。将上述水滑石材料用于吸附脱除水中邻苯二甲酸污染物,考察了不同锌铝比水滑石吸附邻苯二甲酸性能的差异。结果表明,在较低锌铝比时,随着水滑石锌铝比的增加,其对邻苯二甲酸的吸附量逐渐增大;当锌铝比较大时（>6）,随着锌铝比的增加,水滑石的吸附量基本保持不变。进一步选取锌铝比为6的水滑石,分别对其吸附邻苯二甲酸的动力学和热力学进行了研究,发现其吸附等温线和吸附动力学数据分别符合Freundlich等温吸附模型和准二级动力学模型,且循环吸附性能较好。     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

Preparation of supported metal catalysts starting from hydrotalcites as the precursors and their improvements by adopting “memory effect”

Hydrotalcite-like compounds (HTlcs) can be used as the catalysts as it is since they contain various transition metal cations as the catalytically active species well dispersed on the basic support materials. Moreover, increasing numbers of the applications of HTlcs after the heat treatment have been found since the oxides with very small crystal size, stable to thermal treatments, are obtained after the calcination. The oxides possess interesting properties such as high surface area, basic properties and further form small and thermally stable metal crystallites by reduction. Moreover, the calcined oxides show a unique property, i.e., “memory effect,” which allows the reconstitution of the original hydrotalcite structure. We have developed the catalytic applications of hydrotalcites as it is and moreover the mixed oxides derived from hydrotalcites for various catalytic reactions, i.e., oxidation, dehydrogenation and reforming of hydrocarbons, and even for the reforming of methanol and the CO shift reaction. Aerobic oxidation of alcohols, Baeyer−Villiger oxidation of ketones and O₃ oxidation of oxalic acid have been successfully carried out with the Mg−Al hydrotalcites containing Ni, Fe and Cu, respectively, as the catalysts in liquid phase. In the O₃ oxidation of oxalic acid, the catalytic activity was enhanced by the “memory effect,” i.e., Mg(Cu)–Al hydrotaclite was reconstituted on the surface of Mg(Cu,Al)O periclase particles and oxalic acid was incorporated as anions in the hydrotalcite layer, resulting in an enhanced oxidation of oxalic acid. As the catalysts in the vapor phase reactions, Mg/Fe/Al mixed oxides prepared from Mg–Al(Fe) hydrotalcites and effectively catalyzed the dehydrogenation of ethylbenzene. Supported Ni metal catalysts have been prepared from Mg(Ni)–Al hydrotalcites and successfully used in the steam reforming and the oxidative reforming of methane and propane. Moreover, the Ni catalysts have been improved by combining a trace amount of noble metals by adopting the “memory effect” and used in the production of hydrogen for the PEFC under the daily startup and shutdown operation. Also starting from aurichalcite or hydrotalcite precursor as the precursor, Cu/Zn/Al catalysts with high Cu metal surface area have been prepared and successfully applied in the steam reforming of methanol and dimethyl ether, and moreover in the CO shift reaction.     

Tossing and turning: guests in the flexible frameworks of metal(III) dicarboxylates

Single crystals of Ga(OH)(C(8)H(4)O(4)).0.74C(8)H(6)O(4) (2) and Ga(OH,F)(C(8)H(4)O(4)).0.74C(8)H(6)O(4) (3) were obtained under hydrothermal conditions. The structures of 2 and 3 have the same topological framework as the previously reported aluminum 1,4-benzenedicarboxylate (BDC), Al(OH)(C(8)H(4)O(4)).0.7C(8)H(6)O(4) (1). The frameworks are built by interconnecting M-OH-M chains (M = Al, Ga) with BDC anions to form large diamond-shaped one-dimensional channels filled with additional H(2)BDC guest molecules occupying disordered positions in the channels. Upon removal of H(2)BDC, other guest molecules such as H(2)O and pyridine can be inserted. In this work, we present a study of the intercalation of aromatic guests (BDC and pyridine) into frameworks of 1-3 by liquid and vapor diffusion into the empty channels of 1 and by single-crystal-to-single-crystal solvothermal guest exchange for 2 and 3. In the case of Al(OH)BDC and Ga(OH,F)BDC, two interconvertible, guest-concentration-dependent phases with different orientations of the pyridine guests have been observed, while only one pyridine orientation is found in Ga(OH)BDC.     

前驱体物相转变对浆态床合成甲醇催化剂活性的影响

采用并流共沉淀法, 通过考察老化温度, 研究CuO/ZnO/Al₂O₃催化剂前驱体晶相及组成的变化对浆态床催化合成甲醇的反应活性的影响. 结果表明, 前驱体的物相转变对浆态床合成甲醇活性影响显著, 单斜晶系锌孔雀石(Cu,Zn)₂CO₃(OH)2和斜方晶系绿铜锌矿(Cu,Zn)₅(CO₃)₂(OH)₆晶体是产生高活性催化剂的主要物相. 随着Cu²⁺/Zn²⁺进入Zn₅(CO₃)₂(OH)₆/Cu₂CO₃(OH)₂晶格, 离子同晶取代量增加, 催化剂前驱体中形成了固定铜锌比的锌孔雀石和绿铜锌矿物相. 焙烧后催化剂比表面积增大, CuO-ZnO固溶体协同作用加强, 浆态床催化合成甲醇的活性提高.     

New insights into the intercalation chemistry of Al(OH)3

This paper reports a number of recent developments in the intercalation chemistry of Al(OH)(3). From Rietveld refinement and solid-state NMR, it has been possible to develop a structural model for the recently reported [M(II)Al(4)(OH)(12)](NO(3))(2)·yH(2)O family of layered double hydroxides (LDHs). The M(2+) cations occupy half of the octahedral holes in the Al(OH)(3) layers, and it is thought that there is complete ordering of the metal ions while the interlayer nitrate anions are highly disordered. Filling the remainder of the octahedral holes in the layers proved impossible. While the intercalation of Li salts into Al(OH)(3) is facile, it was found that the intercalation of M(II) salts is much more capricious. Only with Co, Ni, Cu, and Zn nitrates and Zn sulfate were phase-pure LDHs produced. In other cases, there is either no reaction or a phase believed to be an LDH forms concomitantly with impurity phases. Reacting Al(OH)(3) with mixtures of M(II) salts can lead to the production of three-metal M(II)-M(II)'-Al LDHs, but it is necessary to control precisely the starting ratios of the two M(II) salts in the reaction gel because Al(OH)(3) displays selective intercalation of M nitrate (Li > Ni > Co ≈ Zn). The three-metal M(II)-M(II)'-Al LDHs exhibit facile ion exchange intercalation, which has been investigated in the first energy dispersive X-ray diffraction study of a chemical reaction system performed on Beamline I12 of the Diamond Light Source.