Intercalation of Azo Compounds into Layered Aluminium Dihydrogentriphosphate and a Layered Double Hydroxide

The inner surfaces of inorganic layered compounds such as aluminium dihydrogen-triphosphate (ADHP) and layered double hydroxide (LDH) were modified by azo compounds. Upon intercalation of 4-phenylazoaniline and 4,4-azodianiline into ADHP, the interlayer spacing increased from 6.4 to 21.5 Å and 20.6 Å, respectively. The intensity of IR peaks due to P-–OH of ADHP and amino groups of guests decreased by the thermal treatment of the intercalates. The interlayer spacings also decreased to 16.9 Å and 16.7 Å, respectively, indicating a dehydration reaction between P–-OH and amino groups. The LDH inner surface was modified by the reaction with trans-p-phenylazobenzoylchloride (PAB-Cl). Upon surface modification, the interlayer spacing increased from 7.6 Å to about 27 Å. The absorption of this surface-modified LDH near 410 nm increased upon irradiation with UV light and decreased upon irradation with visible light, indicating the occurrence of trans–cis isomerization of PAB-Cl between the layers.     

Biopolymer-layered polysilicate micro/nanocomposite based on chitosan intercalated in magadiite

On the basis of their high adsorption and cation exchange capacity, swelling potential and low toxicity, layered sodium silicate magadiite (Na–magadiite) is an attractive solid for intercalation of polymers. This study envisages the intercalation of cationic biopolymer chitosan (Chit) in Na–magadiite to prepare a Chit/magadiite micro/nanocomposite. Characterisation of starting-magadiite, pure chitosan and Chit/magadiite were investigated using powder X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy and thermal analysis. XRD confirmed that the chitosan had been intercalated into the interlayer space of magadiite by increasing the basal spacing, d₀₀₁ from 15.6 Å to 21.45 Å. The presence of characteristic bands of biopolymer and layered silicate in Chit/magadiite were confirmed by FTIR analysis. The thermal stability of micro/nanocomposite was evaluated by thermogravimetry analysis. The results suggested the formation of electrostatic interactions by protonated amine groups with the negatively charged magadiite surface as well as intercalation in the form of a predominant monolayer arrangement of chitosan chains in layered silicate magadiite.     

The functional layered organosilica materials prepared with anion surfactant templates

A novel strategy for the synthesis of layered organosilica is demonstrated. The ionic interaction between the anionic group of a surfactant (sodium dodecyl sulfate) and the cationic organic group of an organosilane (3-aminopropyltrimethoxysilane, ATMS) under acidic conditions was utilized to create a layered organosilica at room temperature. The inorganic part of the organosilica layer was an Si-O hexagonal sheet, and organofunctional groups were alternately arranged on both sides of the sheet. The layered structure of the ATMS organosilica was retained after the removal of the surfactant with chloride anion. The properties of the layered ATMS organosilica were investigated. The layered ATMS-Cl organosilica is stable and possesses a definite layer structure in water or ethanol. Various kinds of anions can be intercalated in the interlayer space of the layered ATMS organosilicas and the layer was expanded dependent on the intercalated anions. The structure of the layered ATMS organosilica was well retained during the intercalation processes.     

Precipitation synthesis of lanthanide hydroxynitrate anion exchange materials, Ln2(OH)5NO3·H2O (Ln=Y, Eu-Er)

Layered lanthanide hydroxynitrate anion exchange host lattices have been prepared via a room temperature precipitation synthesis. These materials have the composition Ln₂(OH)₅NO₃·H₂O and are formed for Y and the lanthanides from Eu to Er and as such include the first Eu containing nitrate anion exchange host lattice. The interlayer separation of these materials, approximately 8.5 Å, is lower than in the related phases Ln₂(OH)₅NO₃·1.5H₂O which have a corresponding value of 9.1 Å and is consistent with the reduction in the co-intercalated water content of these materials. These new intercalation hosts have been shown to undergo facile anion exchange reactions with a wide range of organic carboxylate and sulfonate anions. These reactions produce phases with up to three times the interlayer separation of the host lattice demonstrating the flexibility of these materials.     

Direct Melt Intercalation of Polylactide Chains into Nano‐Galleries: Interlayer Expansion and Nano‐Composite Structure

Summary: The polylactide‐based nano‐composites were prepared via melt extrusion method using different types of intercalants and nano‐fillers having different surface charge density. In order to understand the direct polymer melt intercalation into the nano‐galleries, the interdigitated layer structure of the organically modified layered filler (OMLF), where the intercalants are oriented with some inclination to the host layer in the interlayer space, was proposed. After polymer melt intercalation, the smaller initial interlayer opening led to the larger interlayer expansion, suggesting the large amount of the intercalation of the polymer chains. Consequently, the nano‐composite exhibited finer dispersion of the nano‐fillers when compared with the nano‐composites prepared from OMLFs with larger initial interlayer opening.

Illustration of a model of interlayer structure of the qC₁₄(OH) in gallery space of HTO.     

Incorporation of rare-earth ions in Mg-Al layered double hydroxides: intercalation with an [Eu(EDTA)] chelate

Reaction of an aqueous slurry of an Mg₂Al-NO₃ layered double hydroxide with a four-fold excess of Na[Eu(EDTA)] gives a material which analyses for Mg_0.68Al_0.32(OH)₂[Eu(EDTA)]_0.10(CO₃)_0.11·0.66H₂O. The interlayer spacing of the material is 13.8 Å, corresponding to a gallery height of 9.0 Å, which accords with the maximal dimensions (9-10 Å) of the anion in metal-EDTA complex salts as determined by single crystal X-ray diffraction. Geometrical considerations show that the charge density on the layered double hydroxide layers is too high to be balanced by intercalation of [Eu(EDTA)]⁻ alone, necessitating the co-intercalation of carbonate ions which have a much higher charge density.     

Intercalation and exchange reactions of clay minerals and non-clay layer compounds

Presently, a large variety of layered materials are synthesized that are able to intercalate neutral guest molecules or to exchange inorganic and organic ions for interlayer ions. Several of these materials are also found as minerals.The intracrystalline reactivity of a few selected compounds will be described and compared to clay minerals:

Lead tetrakis(imidazolyl)borate solids: anion exchange, solvent intercalation, and self assembly of an organic anion

The coordination polymer Pb[B(Im)(4)](NO(3))(xH(2)O), constructed by using sodium tetrakis(imidazolyl)borate and lead(II) nitrate solutions, is a layered material with the metal centers facing the interlayer spacing. As in naturally occurring layered minerals, this compound can readily undergo anion exchange and reversible intercalation of solvent water in the solid state with retention of crystallinity. We observed changes in solvent intercalation by (207)Pb solid state NMR (SSNMR) and thermogravimetric analysis (TGA). Stoichiometric exchange of (15)N nitrate for nitrate and iodide for nitrate is monitored by (15)N and (207)Pb SSNMR, and single crystals of the iodide-exchanged material Pb[B(Im)(4)]I were isolated. While the iodide compound can be obtained through facile exchange from the nitrate parent compound, the organic anion benzoate is placed in the interlayer spacing for nitrate under self-assembly conditions and forms an alternating monolayer in Pb[B(Im)(4)](C(6)H(5)COO)(0.5H(2)O). The ion exchange versus self-assembly behavior correlates with the structural differences in the three compounds. In both Pb[B(Im)(4)]I and Pb[B(Im)(4)](C(6)H(5)COO)(0.5H(2)O), the lead sites act as Lewis acids for the iodide and benzoate, respectively.     

Intercalation of Mg–Al layered double hydroxides by l-proline: synthesis and characterization

The intercalations of l-proline into Mg–Al layered double hydroxides (LDH-CO₃) have been prepared by three different methods: calcine-recovering, coprecipitation and anion exchange. The products thus obtained have been characterized by several experimental techniques: XRD, FT-IR and DSC-TG. The results show that the original interlayer carbonate ions can be replaced by the organic anions under the controlled conditions. The interlayer spaces of the materials are expanded to 0.86, 1.12 and 1.07 nm. l-proline entered into the layers as vertical and horizontal, the molecules of l-proline may stay in the layers in a bilayer with the carboxylate groups pointing towards the LDHs layers, and the structure models are shown. The crystal has a good regularity of the layered structure, which increases thermal stability of l-proline, and thermal analysis confirms that the intercalation can make l-proline stable up to 429 °C, which is 200 °C higher than that for pure l-proline.     

Synthesis of ktenasite,a double hydroxide of zinc and copper,and its intercalation reaction

Ktenasite was synthesized by the simple method of mixing ZnO powder with CuSO₄ solution at room temperature. The X-ray diffraction pattern of synthesized ktenasite was very similar to that of mineral ktenasite. The lattice parameters were determined as a=0.559, b=0.616, c=2.374 nm and β=95.63°, which agreed comparatively well with those for mineral ktenasite. The synthesized ktenasite consisted of thin rectangular particles ranging in size from 2 to 4 μm in length. TEM observation suggested the formation of a super lattice structure in the a-axis direction and significant crystal growth in the b-axis direction. The intercalation reaction of sodium dodecyl sulfate (NaDS) with ktenasite showed that the intercalation took place accompanied by the expansion of basal spacing from 1.17 to 2.70 nm. The reaction progressed by the SO₄²⁻/DS⁻ anion exchange mechanism with the dissolution of interlayer [Zn(H₂O)₆]SO₄ salt.     

Intercalative reaction of a cobalt(III) cage complex,Co(sep)3+, with magadiite,a layered sodium silicate

The cationic metal cage complex (1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]cicosane)cobalt(III), Co(sep)³⁺ has been investigated as a potential pillaring reagent for Na⁺-magadiite (Na_1.7Si₁₄O_27.9(OH)_1.9 · 7.6 H₂O) a synthetic layered sodium silicate. Reaction of Na⁺-magadiite with aqueous solutions of Co(sep)Cl₃ at 25°C resulted in the binding of Co(sep)³⁺ cations to the external crystalline surface of the layered silicate. In contrast, an intercalated product exhibiting a 17.6 Å basal spacing was generated by reaction at 100°C.²⁹Si MAS NMR and FT-IR spectroscopy indicate that Co(sep)³⁺ intercalated reaction products retain the magadiite layer structure. Moreover, scanning electron micrographs of the reaction products showed retention of the original particle morphology, suggesting a topotactic intercalation. However, during intercalation, some of the Co(sep)³⁺ was found to undergo an unusual demetalation reaction leaving a combination of Co(II) and Co(sep)³⁺ between the layers. Nitrogen surface area analysis showed that only a small amount of microporous surface existed in the Co(sep)³⁺ intercalated derivative, suggesting that most of the interlayer space is stuffed with cobalt species.     

Short-time hydrothermal synthesis and delamination of ion exchangeable Mg/Ga layered double hydroxides

The hydrothermal synthesis of magnesium-gallium layered double hydroxides (Mg/Ga LDHs) was studied under static and agitated conditions. Not only well-crystallized and large-sized Mg/Ga LDHs having hexagonal morphology were obtained but also the reaction time was comparatively decreased from 24 to 2 h by means of agitation during hydrothermal synthesis. In static conditions, mainly GaOOH and magnesite phases were formed. The elemental analysis results show that the final Mg/Ga ratio is significantly different from the initial ratio. The reason was attributed to the difference in the hydrolytic behavior of Mg²⁺ and Ga³⁺. Furthermore, the anion exchange studies with glycine, dodecyl sulfate, ferrocyanide and ferricyanide were performed to investigate the intercalation behavior of the anions into Mg/Ga LDHs. In addition, delamination of Mg/Ga LDHs was performed in formamide for the glycine exchanged forms. Large size of nanosheets thus obtained can be utilized in the fabrication of functional thin films.     

The Intercalation of 4-Aminopyridine into Layered FePS 3

A new intercalation compound,Fe_0.81PS₃(4-aminopyridineH)_0.38, issynthesized by the direct reaction of4-aminopyridine with layered FePS₃ inthe presence of acetic acid.From the XRD results it was found that there aretwo phases (Phase I and Phase II)in this intercalation compound and that4-aminopyridines as the guests adopt twodifferent orientations between theinterlayer region of the host (FePS₃).In one of them with the latticeexpansion (d) of 6.0 Å thering plane of the guest is perpendicular to thelayer and in the other with d of3.4 Å the ring plane of the guest is parallel tothe layer of the host. The IR spectraimply that the inserted guests take theprotonated form to maintain the charge balanceof the intercalation compound.Magnetic measurements indicate thatFe_0.81PS₃(4-aminopyridineH)_0.38 exhibitsparamagnetism in the range of measurementtemperature (1.8 : 300 K),where the magnetic behavior is wellin agreement with the Curie-Weiss Lawabove 55 K.     

Synthesis, structure and properties of intercalation compounds containing perfluoroalkyl groups

Synthesis, structure and properties of various layered materials containing perfluoroalkyl groups in their interlayer space were summarized. They were obtained by ion exchange method for layered materials with ion exchange capacity and by silylation technique for those possessing acidic hydroxyl groups. The orientation of perfluoroalkyl groups greatly changed depending on their contents in the layered materials. The nature of the interlayer space of them changed from hydrophilic to hydrophobic and they were well dispersed in appropriate organic solvents. Some of them formed so called nanosheet solution and film samples were prepared from it. Organic molecules were introduced into the intercalation compounds by co-adsorption or exfoliation-restacking methods. The empty space surrounded by perfluoroalky chains where organic molecules are included showed unique properties. The weak interaction between perfluoroalkyl chains and included organic molecules lead the easy diffusion of them in the interlayer space, which caused the aggregation of them or affected the distribution of isomers obtained by photochemical reaction. The low vibrational C-F bonding in perfluoroalky groups reduced radiational quenching, accordingly enhanced the fluorescence from included organic dyes.     

Synthesis and characterization of mesoporous zinc layered hydroxide-isoprocarb nanocomposite

The ion exchange method was used to intercalate a poor water-soluble insecticide, isoprocarb into zinc layered hydroxide (ZLH). PXRD analysis indicated the successful intercalation with good crystallinity for the resulting nanocomposite, with a basal spacing of 33.1 Å. FTIR analyses showing the resemblance of an absorption peak of the nanocomposite with the host and the guest anion. The thermal analysis confirmed that the nanocomposite had better thermal stability compared to the pristine isoprocarb. The nanocomposite also characterized by elemental and surface morphology analysis. The surface analyses of the host and nanocomposite showed mesoporous-type material characteristics. On the whole, the intercalation process decreased the pore size of the nanocomposite compared to the pristine host, layered zinc layered hydroxide-sodium dodecyl sulphate (ZLH-SDS). The obtained material is believed has a great potential as an environmentally friendly insecticide.     

Methotrexate intercalated ZnAl-layered double hydroxide

The anticancerous drug methotrexate (MTX) has been intercalated into an ZnAl-layered double hydroxide (LDH) using an anion exchange technique to produce LDH-MTX hybrids having particle sizes in the range of 100-300 nm. X-ray diffraction studies revealed increases in the basal spacings of ZnAl-LDH-MTX hybrid on MTX intercalation. This was corroborated by the transmission electron micrographs, which showed an increase in average interlayer spacing from 8.9 Å in pristine LDH to 21.3 Å in LDH-MTX hybrid. Thermogravimetric analyses showed an increase in the decomposition temperature for the MTX molecule in the LDH-MTX hybrid indicating enhanced thermal stability of the drug molecule in the LDH nanovehicle. The cumulative release profile of MTX from ZnAl-LDH-MTX hybrids in phosphate buffer saline (PBS) at pH 7.4 was successfully sustained for 48 h following Rigter-Peppas model release kinetics via diffusion.     

Photoactive oriented films of layered double hydroxides

The treatment of nano-ordered oriented films of layered double hydroxide (LDH) with dodecyl sulfate increased the interlayer distance from 0.4 to 1.96 nm, which allowed the intercalation of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS). The re-stacking of separated layers and the rebuilding of crystals oriented parallel to the surface of quartz slides was confirmed by X-ray diffraction and atomic force microscopy. The hybrid films contained homogeneously distributed porphyrin molecules with preserved photophysical properties such as fluorescence, triplet state formation, and energy transfer, thus forming singlet oxygen.     

Functional copolymer/organo‐MMT nanoarchitectures. III. Dynamic mechanical behavior of poly(IA‐co‐BMA)‐organo‐MMT clay nanocomposites

Functional copolymer/organo‐silicate [N,N′‐dimethyldodecyl ammonium cation surface modified montmorillonite (MMT)] layered nanocomposites have been synthesized by interlamellar complex‐radical copolymerization of pre‐intercalated itaconic acid (IA)/organo‐MMT complex as a “nanoreactor” with n‐butyl methacrylate (BMA) as an internal plasticization comonomer in the presence of radical initiator. Comparative analysis of physical structure, dynamic mechanical analysis parameters, and surface morphology of the obtained copolymers and their nanocomposites indicated that the interlayer H‐bonding and flexible n‐butyl ester linkages take place an important role in interlamellar copolymerization and intercalation/exfoliation of copolymer chains. It was found that nanocomposites' dynamic mechanical properties strongly depended on the force of interfacial H‐bonding and amount of BMA units. An increase in both of these parameters leads to enhanced intercalation and exfoliation in situ processes of copolymer chains and the formation of hybrid nanocomposites. Copyright © 2009 John Wiley & Sons, Ltd.     

Physicochemical Properties of Aqueous Solutions of Binary Mixtures of Lignin Derivatives and Sodium Dodecyl Sulfate

Physicochemical properties of aqueous solutions of binary mixtures of lignosulfonates and sodium dodecyl sulfate were studied. Introduction of sodium dodecyl sulfate into solutions of high-molecular-mass lignosulfonates at certain ratios causes macrophase separation of the systems with the formation of loose precipitates. A synergistic effect of a decrease in the surface tension is observed in the mixed solutions. This effect increases with increasing lignosulfonate molecular mass and temperature. The revealed relationships are caused by hydrophobic interactions of hydrocarbon radicals of sodium dodecyl sulfate with hydrophobic segments of lignosulfonate polymer chains with the formation of micellar associates. Aqueous solutions of binary mixtures of lignosulfonates (с_LS ≥ 0.2 g dm^–3) and sodium dodecyl sulfate (с_DSNa ≥ 0.08 g dm^–3) can be recommended for use as surfactant formulations for high-temperature autoclave leaching of polymetal ores.     

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.