镁铝水滑石层板与层间阴离子相互作用的理论研究

本文采用以ASED-MO(含原子对排斥的EHMO法)为基础的结构自动优化的EHTOPT程序,对镁铝水滑石(LDHs)层板与层间阴离子相互作用进行了理论研究.以Mg6Al2(OH)16X@H2O为分子结构单元,计算并分析了与不同层间阴离子形成稳定结构的能量变化、成键状况及电荷转移情况,揭示了层间作用力的本质.结果表明,LDHs层板与层间阴离子间存在静电吸引、氢键等非共价键弱相互作用,且氢键作用为主,其强弱与阴离子电荷分布、空间排布方式密切相关;层间阴离子电荷分布同时还影响着层板酸碱性的变化.     

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.     

镁铝水滑石的有机改性实验研究

采用共沉淀法合成了对甲基苯磺酸有机插层改性的镁铝水滑石,用XRD、FTIR、TG-DSC等技术表征产物特征.研究表明,合成的对甲基苯磺酸插层LDH物相纯净、结晶度高,层间无硝酸根,而且2:1型有更好的晶形;2:1型对甲基苯磺酸插层LDH在450-500℃层状结构逐渐被破坏,而3:1型在400-460℃0层状结构被破坏....     

杂多阴离子柱撑锰铝水滑石的合成、表征及催化性能

杂多阴离子柱撑锰铝水滑石的合成、表征及催化性能刘继广，孙铁，蒋大振（吉林大学化学系，长春１３００２３）关键词杂多阴离子，柱撑，锰铝水滑石，异丁烷，烷基化类水滑石化合物属于阴离子型粘土‘’‘，其中心金属离子Ｍ２＋或Ｍ３＋及平衡阴离子可根据需要进行改变．...     

钴铝和锌铝水滑石的合成

采用低过饱和共沉淀法合成了一系列锌铝和钴铝水滑石,其结构经IR和XRD表征。研究结果表明,两类水滑石晶体结构相似;钴铝水滑石的稳定性高于锌铝水滑石。     

铜镁铝三元水滑石的姜-泰勒效应

采用密度泛函理论(DFT),用CASTEP程序模块,对类水滑石(CuxMg3-xAl-LDHs,x=0-3)周期性模型进行几何全优化,通过分析各体系的结构参数、电子排布、氢键、Mulliken电荷布居、结合能,总结出体系中的姜-泰勒效应和结构稳定性规律.结果表明,姜-泰勒效应不仅存在于d轨道未排满的Cu2+中,在p轨道未排满的Mg2+中也可能存在,且未饱和的d、p轨道共同影响着金属离子姜-泰勒畸变的大小.在CuxMg3-xAl-LDHs(x=0-3)中,铝八面体和镁八面体分别以稳定的拉长的八面体形式存在.而随着Cu2+的增加,铜八面体逐渐从压扁的八面体向稳定的拉长的八面体形式转变,体系获得了逐渐增多的姜-泰勒稳定化能.总体上,随着Cu2+的增加,体系中姜-泰勒效应导致的畸变使主客体间的氢键和静电作用力均有减弱趋势,且体系的结合能绝对值逐渐减小,故体系稳定性下降.这有助于从理论上进一步认识含铜水滑石的姜-泰勒效应.     

铜锌镁铝四元水滑石的微观结构及其姜-泰勒畸变

采用密度泛函理论(DFT),选取CASTEP程序模块,对铜锌镁铝四元水滑石[(M)-IV-LDHs(M=Cu,Zn,Mg,Al)]周期性模型进行几何全优化,从各体系的结构参数、电子排布、Mulliken电荷布居、结合能、氢键等方面,研究了体系中的姜-泰勒效应、氯离子位置对层板畸变及体系稳定性的影响.优化结果表明,姜-泰勒效应不仅存在于d轨道未排满的Cu2+中,也存在于理论上d轨道排满的Zn2+与p轨道未排满的Mg2+中.氯离子排在金属上方的体系,其金属畸变程度大于氯离子排在非金属上方的体系.同时,对于本文选取的8个CuAl-IV-LDHs体系,结合能绝对值按照1-8号逐渐降低,体系的稳定性下降,最终转变为不稳定的压扁的八面体构型.这有助于从理论上对含铜四元水滑石的姜-泰勒效应进一步认识.     

层状化合物镍铝水滑石的制备和表征

采用变化pH值法和恒定pH值法 ,以硝酸镍、硝酸铝为原料 ,NaOH为沉淀剂水热合成了层状化合物镍铝水滑石。分别测定了Ni/Al摩尔比为0 5、1 0、2 0、6 0和10 0混合金属盐溶液的NaOH滴定曲线 ,并利用XRD对滴定过程中不同pH值阶段的合成物进行物相鉴定。实验结果表明 ,在Ni/Al=1 0～6 0范围内 ,不论起始混合盐溶液中Ni/Al摩尔比如何 ,在pH=5.0～6 .0范围内 ,均能合成结构单一的镍铝水滑石 ,随Ni/Al比的增加 ,合成的HTLc(水滑石)中镍含量随之增加 ;合成体系在较低pH(3 3～4 .8)范围为Al(OH) 3 生成阶段 ,较高pH(6.0～7 .5)范围为Ni(OH) 2 和HTLc 的共生阶段。该研究同时考察了其它因素在合成过程中的影响 ,筛选出镍铝水滑石合成的最佳条件。     

反相气相色谱法探究铜镁铝水滑石的表面性质

采用共沉淀法合成了Cu_xMg_3-xAl-LDHs (x＝0～3), 利用FTIR 及IGC 法(反相气相色谱法)对合成的样品进行测试和表征, 并结合计算机模拟的结果来探讨铜镁铝水滑石的表面性质. 结果表明, 随 Cu²⁺含量的增加, 铜镁铝水滑石表面吸附自由能及表面能色散组分增加, 稳定性下降, 这可能由于Cu²⁺本身具有的Jahn-Teller 畸变会很大程度地影响层板的稳定性, 导致含铜水滑石体系的稳定性降低; 随着Cu²⁺含量的增加, 水滑石表面碱性先减小后增大.     

First principles study of microscopic structures and layer-anion interactions in layered double hydroxides intercalated various univalent anions

Density functional theory has been used to investigate microscopic structures and electronic properties of LDHs containing F⁻, Cl⁻, Br⁻, I⁻, OH⁻, , , . Both electrovalent bonds and covalent bonds were found in the layer. For halogen anions, the strength of interaction was accorded with electronegative intensity. And the LUMOs dispersed throughout the interlayer region. While for complicated anions, the strength was accorded with the discrepancy of electronegative intensity between center atom and bonding atoms, the LUMOs almost localized in interlayer anions. p Orbital of metal cations and s orbital of anions provided major contributions to electrovalent parts of system, while s orbital of metal cations and p orbital of anions provided major contributions to covalent parts. This has the further significance in Forcefield design for LDHs simulation. Multiple hydrogen bonds were existed in LDHs-X system. The more the number of multiple hydrogen bonds formed, the weaker the strength of single multi-hydrogen bonds was. Multiple hydrogen bonds will bring stronger interaction between interlayer guest anion and host LDHs-layer than single hydrogen bond.     

均匀沉淀法直接合成有机阴离子柱撑水滑石

以尿素为沉淀剂用均匀沉淀法直接合成有机阴离子柱撑水滑石(Layered Double Hydroxides，LDH)及CoAl水滑石等，并用XRD，FT—IR，TGA，TEM等分析手段对所合成的水滑石进行了表征．结果表明，尿素均匀沉淀法可以直接合成有机阴离子柱撑水滑石及CoAl水滑石等，并且可以方便地消除原料中阴离子的干扰，是合成有机阴离子柱撑水滑石及CoAl水滑石等的一个简便快速的新方法。     

Preparation and thermal decomposition study of pyridinedicarboxylate intercalated layered double hydroxides

Supramolecular 2,3- and 2,5-pyridinedicarboxylate (PDC) intercalated ZnAl-layered double hydroxides (2,3- and 2,5-PDC–ZnAl–LDHs) have been prepared by ion exchange method. The structure and composition of the intercalated materials have been studied by X-ray diffraction (XRD) and inductively coupled plasma emission spectroscopy (ICP). The study indicates that the 2,3-PDC and 2,5-PDC anions are accommodated as interdigitated bilayer and monolayer arrangement respectively between the sheets of LDHs. Furthermore, their thermal decomposition processes were studied by the use of in situ high temperature X-ray diffraction (HT-XRD), and the combined technique of thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS) under N2 atmosphere. Based on the comparison study on the temperatures of both decarboxylation and complete decomposition of interlayer PDC, it can be concluded that 2,5-PDC–ZnAl–LDHs has higher thermal stability than that of 2,3-PDC–ZnAl–LDHs.     

Variation of benzyl anions in MgAl-layered double hydroxides: Fire and thermal properties in PMMA

Magnesium aluminum layered double hydroxides (MgAl-LDHs) intercalated with a range of benzyl anions were prepared using the coprecipitation method. The benzyl anions differ in functionality (i.e. carboxylate, sulfonate, and phosphonate) and presence or absence of an amino substituent. Various methods for preparing LDHs (i.e. ion exchange, coprecipitation and rehydration of the calcined LDH methods) have been compared with the MgAl-benzene phosphonate and their effect on fire and thermal properties was studied. After characterization, the MgAl-LDHs were melt-blended with poly(methyl methacrylate) (PMMA) at loadings of 3 and 10% by weight to prepare composites. Characterization of the LDHs and the PMMA composites was performed using FTIR, XRD, TGA, transmission electron microscopy (TEM) and cone calorimetry. FTIR and XRD analyses confirmed the presence of the charge balancing benzyl anions in the galleries of the MgAl-LDHs. Improvements in fire and thermal properties of the PMMA composites were observed. The cone calorimeter revealed that the addition of 10% MgAl-LDHs reduces the peak heat release rate by more than 30%.     

LDHs主体层板与卤素阴离子超分子作用的理论研究

构建了LDHs主客体作用模型, 采用混合密度泛函B3LYP方法, 在6-31G(d)水平上进行结构优化和频率分析, 然后分别用6-31G(d)和6-311++G(d, p)基组计算主客体相互作用能, 从几何参数、电荷布居、前线轨道、能量以及热力学参数等角度探讨LDHs主体层板与卤素阴离子(F?, Cl?)间的超分子作用. 计算结果表明, LDHs主体层板复合卤素阴离子是一个自发过程. LDHs主客体间存在着较强的超分子作用, 主要包括静电和氢键作用, 相互作用能分别为?592.45和?444.01 kJ·mol?1. LDHs主体层板与卤素阴离子的前线轨道发生作用, 电子容易从卤素阴离子的HOMO向层板的LUMO转移, 形成的组装产物Mg6Al(OH)14+?F?比Mg6Al(OH)14+?Cl?稳定.     

Synthesis and characterization of layered double hydroxides (LDH) intercalated with non-steroidal anti-inflammatory drugs (NSAID)

Layered double hydroxides (LDHs) with the hydrotalcite type structure and a Mg:Al ratio of two have been prepared, with salicylate or naproxen in the interlayer. Two synthetic routes have been used: reconstruction from a mildly calcined hydrotalcite-CO₃ precursor, and a coprecipitation method with chlorides of the metals. The solids have been characterized using several physicochemical techniques, i.e., powder X-ray diffraction, FTIR and ¹³C CP/MAS NMR spectroscopies and thermal analysis (thermogravimetric and differential thermal analyses). The gallery height determined is in all cases larger than the size of the drug, 11.5 Å for salicylate and 15.8 and 16.6 Å for naproxen, depending on the specific synthesis route followed. Experimental data suggest the anion molecules form a tilted bilayer, with the carboxylate groups pointing towards the brucite-like layers. The solids are stable up to 230 °C and their evolution from 350 °C upwards is very similar to that observed for a carbonate-containing hydrotalcite, forming mostly amorphous solids with a large specific surface area.     

Synthesis, sustained release properties of magnetically functionalized organic–inorganic materials: Amoxicillin anions intercalated magnetic layered double hydroxides via calcined precursors at room temperature

Zinc–aluminum–carbonate–layered double hydroxides (ZnAl–CO₃–LDHs), loaded with magnetic substrates (Fe₃O₄), were prepared for sustained drug-targeting delivery. From the X-ray diffraction results, it was found that the magnetic substrates were successfully incorporated with LDHs and highly dispersed in the hydrotalcite structure. After intercalation with an antibiotic drug (amoxicillin) by using a calcinations–reconstruction method, the basal spacing of layered double hydroxides increased from 7.51 Å to 12.35 Å, indicating that amoxicillin was successfully intercalated into the interlay space of LDHs as a monolayer. Furthermore, in vitro drug release experiments in pH 7.4 phosphate buffer solution (PBS) showed sustained release profiles with amoxicillin as a model drug. Magnetic measurements revealed that the composite possessed paramagnetic properties at room temperature.     

Synthesis and intracrystalline oxidation of nitrite-intercalated layered double hydroxides

Nitrite-intercalated LDHs could be prepared by a two-stage process that involves coprecipitation in the presence of nitrite ions followed by stirring the product with excess of nitrite ions. The nitrite ion lies flat in these LDHs with its c₂-axis lying approximately perpendicular to the crystallographic c-axis. The interlayer nitrite ions in these LDHs could be quantitatively oxidized to nitrate ions using H₂O₂ solution. In the LDHs thus obtained the nitrate ion lies flat with its c₃-axis parallel to the crystallographic c-axis (D_3h symmetry) in the interlayer region resulting in lower basal spacing.     

Synthesis and selective IR absorption properties of iminodiacetic-acid intercalated MgAl-layered double hydroxide

An MgAl-NO₃-layered double hydroxide (LDH) precursor has been prepared by a method involving separate nucleation and aging steps (SNAS). Reaction with iminodiacetic acid (IDA) under weakly acidic conditions led to the replacement of the interlayer nitrate anions by iminodiacetic acid anions. The product was characterized by XRD, FT-IR, TG-DTA, ICP, elemental analysis and SEM. The results show that the original interlayer nitrate anions of LDHs precursor were replaced by iminodiacetic acid anions and that the resulting intercalation product MgAl-IDA-LDH has an ordered crystalline structure. MgAl-IDA-LDH was mixed with low density polyethylene (LDPE) using a masterbatch method. LDPE films filled with MgAl-IDA-LDH showed a higher mid to far infrared absorption than films filled with MgAl-CO₃-LDH in the 7-25 μm range, particularly in the key 9-11 μm range required for application in agricultural plastic films.     

A magnetic organic-inorganic composite: Synthesis and characterization of magnetic 5-aminosalicylic acid intercalated layered double hydroxides

A core-shell structured magnetic layered organic-inorganic material involving 5-aminosalicylic acid (5-ASA) intercalated Zn-Al layered double hydroxides (LDHs) and magnesium ferrite (MgFe₂O₄) is assembled by a coprecipitation method. The powder X-ray diffraction results show the coexistence of the clear but weak diffractions of MgFe₂O₄ and ordered relatively stronger reflections of 5-ASA intercalated LDHs. The TEM image of magnetic 5-ASA intercalated LDHs reveals that the LDHs layer covers the MgFe₂O₄ particles or their aggregates with particle size of 50-80 nm. The vibration sample magnetization (VSM) measurements exhibit the increase in saturation magnetization of magnetic 5-ASA intercalated LDHs samples with increasing amount of magnetic core. The XPS analyses account for a majority of Zn, Al and O atoms on the surface of magnetic particles. It is suggested that the magnetic core MgFe₂O₄ was coated with LDHs layer probably through Zn-O-Mg and Al-O-Mg linkages, and a core-shell structured model is tentatively proposed.