聚苯胺/H2W2O7层状复合材料的制备研究

以层状钨基氧化物(H2W2O7)为无机主体, 用正庚胺改性后的正庚胺/H2W2O7复合物(HTT)为中间体, 通过离子交换、层间O2引发聚合等步骤成功制备了聚苯胺/H2W2O7层状复合材料(PANI/H2W2O7). X射线衍射、扫描电子显微镜、红外光谱及差热分析结果表明: 聚苯胺分子已成功地嵌入H2W2O7层间, 层状结构没被破坏, 层间距变至1.19 nm; 聚苯胺的嵌入还大大提高了材料的热稳定性. 讨论了无机主体与有机客体之间的相互作用、聚苯胺在层间的排布形式及苯胺和聚苯胺插入层间的反应机理.     

超分子结构二氟尼柳插层镁铝水滑石的合成与表征

采用离子交换和共沉淀两种不同方法将二氟尼柳插入镁铝水滑石层间，得到一种新型的有机-无机层状复合材料。通过X射线粉末衍射、红外光谱、元素分析和热重-差热等手段对材料进行了表征。结果表明，离子交换法和共沉淀法成功地将二氟尼柳插入水滑石，得到的材料层状结构完整、晶相单一，且层间距均大于二氟尼柳分子尺寸，扩大为1.81～2.14 nm；二氟尼柳插入后，复合水滑石材料的热稳定性大幅度提高。客体二氟尼柳与主体层板之间存在超分子作用力，二氟尼柳分子的羧基与水滑石层板之间相互作用，以双层倾斜交替地排列于层板之间。此外，根据其超分子作用力建立了二氟尼柳插层镁铝水滑石的超分子结构模型。     

正丁胺对晶态层状苯乙烯基膦酸-磷酸氢锆的插层研究

合成了晶态层状有机-无机多功能材料苯乙烯基膦酸-磷酸氢锆(α-ZPPVPA),并研究了正丁胺(BA)对α-ZPPVPA的插层性能。用元素分析、XRD、IR、TG、SEM和TEM等分析方法对α-ZPPVPA及其插层化合物α-ZPPVPA-BA进行了结构表征和形貌分析。结果表明,正丁胺成功地插入了α-ZPPVPA层板之间,层间距为2.41 nm,正丁胺的插入使α-ZPPVPA的层间距(1.66 nm)增大了0.75 nm,插入的正丁胺在α-ZPPVPA中呈双分子层排列,且苯乙烯基侧链不饱和双键的存在不影响α-ZPPVPA与正丁胺的插层反应。     

高分子-无机夹层化合物的合成、结构和性能

由高分子和插入无机层状固体层间形成的夹层化合物是近年发展起来的一类具有诱人前景的新型功能材料,在许多领域具有广的前景。本文对这夹层化合的合成、结构、性能及应用前景等方面的研究进展进行了评述。     

多酸插层水滑石复合材料的新进展

层状双金属氢氧化物是一类重要的阴离子层状材料,通过调变层间阴离子的种类和数量,可以得到性能丰富的复合材料.多金属氧酸盐(简称多酸)是一类结构明确、种类多样、性能丰富的阴离子材料.将多酸插入阴离子层状材料中,可以实现电荷平衡以及尺寸匹配,并且主体和客体之间的多重相互作用有助于多酸的分散和稳定.这类多酸插层水滑石复合材料在环境、能源、催化等领域具有重要的应用.本文综述了近年来多酸插层水滑石材料的制备方法及其在不同应用领域的最新进展.     

精氨酸插层氧化锰纳米结构材料的制备和表征

应用氧化法水热合成了Na型层状氧化锰[BirMO(Na)], 通过离子交换反应在0.1 mol/L HCl溶液中Na型层状氧化锰转化成H型层状氧化锰[BirMO(H)]. BirMO(H)在四甲基氢氧化铵[(CH3)4NOH]溶液中搅拌处理7 d后, 剥离生成了MnO2纳米层胶体分散液. 剥离的MnO2纳米层胶体分散液在pH＝4.0～11.0的精氨酸溶液中搅拌2 d, 得到了层间距为1.49 nm的精氨酸插层氧化锰纳米结构材料. 通过XRD, DSC-TGA, SEM, IR及元素分析对合成试样进行了分析表征. 结果表明精氨酸在氧化锰层间的插入量及插入形式与重组溶液的pH值密切相关, 其最大插入量为1.80 mmol/g.     

层状(脯氨酸-N-甲基膦酸-磷酸氢)锆的合成及插层性能研究

以高结晶度制备了层状(脯氨酸-N-甲基膦酸-磷酸氢)锆(α-ZPMPP)晶体(层间距为1.52nm),并研究了其常温下对正丁胺的插层性能,用元素分析、IR、XRD和TG-DSC热分析对α-ZPMPP及其插层复合物进行了表征.结果表明,层状α-ZPMPP具有形成超分子主-客体化合物的插层性能,正丁胺客体分子在主体底物中形成单分子层,并插入α-ZPMPP中,使层间距增大0.45nm,插入的正丁胺可在150～250℃被脱除.     

剥离型硅橡胶/黏土纳米复合材料研究

利用层状硅酸盐制备有机 无机纳米复合材料是当前人们研究的热点[1,2 ] ,这类材料具有较常规聚合物 无机填料复合材料无法比拟的优点 ,可以明显改善高分子材料的物理机械性能、热稳定性、气体阻隔性、阻燃性、导电性、光学性等 .一般来说 ,聚合物 层状硅酸盐 (Ｐｏｌｙｍｅｒｌａｙｅｒｅｄｓｉｌｉｃａｔｅ ,ＰＬＳ)纳米复合材料可分为插层型和剥离型两种类型 .插层型纳米复合材料即聚合物插入到硅酸盐层中 ,硅酸盐在近程仍保持原有的有序晶体结构 ,在远程则是无序的 .对弹性体而言 ,硅酸盐含量在插层型杂化材料中的含量比较高 ,力学性能…     

以1,6-己二胺为模板剂的层状磷酸锆晶体的合成与表征

 采用水热法合成了以1,6-己二胺(HDA)为模板剂的层状磷酸锆晶体0.5·1.5H2O,并用单晶及粉末XRD,IR和TG-DTA等对其结构和性质进行了表征. 该晶体是由磷酸锆无机层、有机胺以及水分子三部分构成的层状结构,层间距约为1.77 nm,无机层结构为γ-型. 位于有机胺两端的氮与无机层表面部分羟基的氧以氢键连接,水分子占据磷酸锆层间的两种位置. 单晶结构模拟得到的XRD谱与从粉末样品采集的XRD谱基本吻合. 此晶体在180 ℃下脱去水分子,在220 ℃下加热3 h其结构未发生明显变化; 有机胺模板剂在250 ℃下开始分解.     

10-羟基喜树碱-癸二酸-LDH杂化物的制备及性能

采用二次插层法成功制备了10-羟基喜树碱(HCPT)-癸二酸(SC)插层的层状双金属氢氧化物(LDH). 先采用共沉淀法制备SC柱撑LDH杂化物(SC-LDH), 再在乙醇介质中将HCPT插入LDH层间形成HCPT-SC-LDH纳米杂化物. 依据SC和HCPT的分子尺寸和纳米杂化物的通道高度, 推测SC分子在层间可能为双层排列, SC分子两端的羧基同时键合在同一个LDH层片表面上; HCPT分子插入(或溶入)SC分子碳氢链形成的疏水区中. 所制备的纳米杂化物既可稳定HCPT的内酯环, 又可明显提高HCPT的溶解度, 还具有明显的药物缓释效果, 其释放动力学过程符合准二级动力学方程.     

熔融法制备聚氧化乙烯/蒙脱土杂化材料及其结晶行为

聚氧化乙烯;熔融插入;纳米杂化;熔融法制备聚氧化乙烯/蒙脱土杂化材料及其结晶行为     

Polymerization of aniline in the interlayer space of molybdenum trioxide and its electrochemical properties

Molybdenum trioxide/polyaniline (MoO₃/PANI) composite was prepared first by ion-exchange reaction between aniline (ANI) and dodecylamine (DDA) which was intercalated precursor, and then was formed under the polymerization of ANI within the interlayer space of MoO₃ at 120 °C for 3 d in air. According to powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy and electrochemical testing, MoO₃/PANI composite has layered structure, and its interlayer spacing is 1.127 nm. Moreover, it has high thermal stability with the compound and completes its weight loss at 751.9 °C. Electrochemical investigation shows that MoO₃ is the major active substance in the MoO₃/PANI electrode, and MoO₃/PANI electrode demonstrates better conductivity and electrochemical activity than pure MoO₃ electrode, attributed to the promotion of Li⁺ and/or electron transport. In addition, the alternating current impedance proves that if the resistance of MoO₃/PANI electrode reduces apparently, the electrochemical activity will increase correspondingly, the same as the relationship between the ohmic resistance and the electrical conductivity.     

Intercalation of magnesium into a graphite-like layered material of composition BC2N

Magnesium was intercalated into a graphite-like layered material with an approximate composition of BC(2)N. The obtained material was a second-stage compound with a d-spacing of 0.367 nm for the intercalated layers. This is the first example of magnesium intercalation into a graphite-network-based material.     

Redoxable nanosheet crystallites of MnO2 derived via delamination of a layered manganese oxide

This paper reports on the swelling and exfoliation behavior of a layered protonic manganese oxide, H(0.13)MnO(2).0.7H(2)O, in a solution of tetrabutylammonium (TBA) hydroxide and the formation and characterizations of unilamellar two-dimensional crystallites of MnO(2). At low doses of TBA ions, layered manganese oxide was observed to undergo normal intercalation, yielding a TBA intercalated phase with a gallery height of 1.25 nm. With a large excess of TBA ions, osmotic swelling occurred, giving rise to a very large intersheet separation of 3.5-7 nm. In an intermediate TBA concentration range, the sample exhibited a broad X-ray diffraction profile with superimposed diffraction features due to intercalation and osmotic swelling. The component responsible for the broad profile was isolated by centrifuging the mixture twice at different speeds, and the recovered colloid was identified as a pile of MnO(2) nanosheets, corresponding to the individual host layer of the precursor layered manganese oxide. Observations by transmission electron microscopy and atomic force microscopy revealed high two-dimensional anisotropy with a lateral dimension of submicrometers and a thickness of approximately 0.8 nm. The nanosheet exhibited broad optical absorption with a peak at 374 nm (epsilon = 1.13 x 10(4) mol(-1) dm(3) cm(-1)). The restacking process of the colloidal MnO(2) nanosheets was followed by aging the colloid at a relative humidity of 95%. The broad diffraction pattern due to the exfoliated sheets weakened with time and eventually resolved into two sharp distinct profiles attributable to a TBA intercalation compound with an intersheet spacing of 1.72 nm and an osmotically swollen hydrate with >10 nm at a very early stage. As drying progressed, the former phase became more abundant without a change in interlayer distance, while the degree of swelling of the latter phase gradually decreased to 2.7 nm that remained unchanged on further aging. Subsequent drying at a lower humidity collapsed the 2.7 nm phase. The resulting single 1.72 nm phase was dehydrated by heating at 150 degrees C to produce a phase with a contracted interlayer spacing of 1.3 nm.     

The dynamic process in the formation of Tyr/LDH nanohybrids

The dynamic intercalation process of tyrosine (Tyr) into layered double hydroxide (LDHs) by co-precipitation method was investigated by powder X-ray diffractometry, Fourier transform infrared spectroscopy, specific surface area measurements, pore size distributions as well as thermal analysis. The nanohybrids were found to have an expanded layered structure indicating that amino acid anions were intercalated into the gallery space. Two kinds of arrangements such as mono- or bilayers of the tyrosinate anions could be deduced from the XRD patterns. The arrangement changed from monolayer to bilayer, then again to monolayer with increasing aging time of the synthesis solution. The diffraction intensity increased then decreased with aging time, because of the variation in the orientation and ordering of the particles. TG analysis and the varying M²⁺/M³⁺ results revealed that the amount of tyrosinate anions in the gallery first decreased then increased with the increase of aging time. In addition, the morphology results showed that the degree of ordering also increased then decreased with aging time. On all accounts, the intercalation of the tyrosinate anions was a typical dynamic process. At the beginning numerous biomolecules entered the gallery space, giving rise to increased basal spacings and BET surface areas. Later the increase of aging time led to the escape of amino acid anions from the gallery space, hence to the decrease of basal spacing and surface areas.     

新型超分子复合发光材料四足配体铕配合物-蒙脱土的插层组装及发光性质

通过离子交换反应将四足配体铕配合物[EuL(NO3)]2+[L=1,1,1’,1’-四(吡啶-2-羧酸酯基)联三甲基丙烷]插层组装到蒙脱土(MT)层板间, 制备出一种新型的超分子复合发光材料[EuL(NO3)]2+-MT. 用元素分析、XRD、FTIR、UV-Vis和热分析对材料进行了表征, 并对其荧光性质进行了研究. 结果表明, 复合材料保持了蒙脱土良好的层柱结构特征, 其层间距d(001)值与插层配离子的直径吻合得较好, 配离子以单层形式分布于蒙脱土层板间. 在紫外光激发下, 复合材料发出较强的Eu3+特征荧光, 其相对荧光强度、荧光单色性和荧光寿命大大优于相应配合物的乙醇溶液. 复合材料中配合物的发光性能、光稳定性和热稳定性较纯配合物有明显提高.     

新型层柱微孔材料──Ga-W9-Co3三取代柱撑ZnAl型阴离子粘土的合成、表征及催化研究

新型层柱微孔材料──Ｇａ－Ｗ_９－Ｃｏ_３三取代柱撑ＺｎＡｌ型阴离子粘土的合成、表征及催化研究张继余,余新武,张淑云,胡长文,梁兆君,王恩波（东北师范大学化学系,长春,１３００２４）关键词过渡金属,三取代,杂多阴离子,嵌入,阴离子粘土杂多化合物是具有优...     

Influence of pH on the Formation of Tyr/LDH Nanohybrids

In this article, the intercalation of amphoteric amino acid tyrosine (Tyr) into LDH by the co‐precipitation method is systematically examined. The influence of pH values has been examined. Powder X‐ray diffraction, Fourier transform infrared spectroscopy, specific surface areas and pore size distributions, and thermal analysis have been employed for the characterization of the nanocomposites. The nanohybrids were found to have expanded layered structure, indicating that the biomolecules were intercalated into the gallery as anions. The intercalation of amino acids resulted in the increase of surface areas and pore volumes, and these values increased with increasing of biomolecules intercalated. TEM analysis revealed that with the decrease of pH values, the nanohybrids changed from hexagonal particles to spherical ones. Moreover, the configuration of Tyr anions varied under different pH values, the configuration changing from monolayer to bilayers with more biomolecules in the gallery.     

Sugar-anionic clay composite materials: intercalation of pentoses in layered double hydroxide

The intercalation of non-ionized guest pentoses (ribose and 2-deoxyribose) into the Mg-Al and Zn-Al layered double hydroxides (LDHs) was carried out at 298 K by the calcination-rehydration reaction using the Mg-Al and Zn-Al oxide precursors calcined at 773 K. The resulting solid products reconstructed the LDH structure with incorporating pentoses, and the maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 20 times that by the Zn-Al oxide precursor. The ribose/Mg-Al LDH was observed to have the expanded LDH structure with a broad (003) spacing of 0.85 nm. As the thickness of the LDH hydroxide basal layer is 0.48 nm, the interlayer distance of the ribose/Mg-Al LDH is 0.37 nm. This value corresponds to molecular size of ribose in thickness (0.36 nm), supporting that ribose is horizontally oriented in the interlayer space of LDH. The maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 5 times that of 2-deoxyribose. Ribose is substituted only by the hydroxyl group at C-2 position for 2-deoxyribose. Therefore, the number of hydroxyl group of sugar is essentially important for the intercalation of sugar molecule into the LDH, suggesting that the intercalation behavior of sugar for the LDH was greatly influenced by hydrogen bond between hydroxyl group of the intercalated pentose and the LDH hydroxide basal layers.