超分子结构MgAl-HMBA-LDHs的组装及其紫外阻隔性能研究

以MgAl-NO3-LDHs为前驱体,采用离子交换法成功地将2-羟基-4-甲氧基二苯甲酮-5-磺酸(HMBA)阴离子插层到MgAl-NO3-LDHs层间,借助SEM、XRD、FT-IR、TG-DTA和UV-Vis等手段对样品进行了表征。结果表明,HMBA阴离子可完全取代前驱体层间的NO3-离子,并且与主体层板产生较强的超分子相互作用。MgAl-HMBA-LDHs的紫外吸收性能较HMBA客体增强,热稳定性明显提高。将MgAl-HMBA-LDHs加入至玻璃钢基体中,明显提高了玻璃钢基体的耐紫外光老化性能。     

Intercalation of Mg–Al layered double hydroxide by anionic surfactants: Preparation and characterization

The preparation and the characterization of intercalation compounds of Mg–Al layered double hydroxide (Mg–Al LDH) and various organic surfactants have been studied in detail. The preparation has been carried out following regeneration method. The aim of such organic modification is to prepare LDHs suitable for application in polymer-LDH nanocomposites. The LDH-surfactant hybrids have been characterized by wide angle X-ray scattering (WAXS) and Fourier transform infrared (FTIR) spectroscopy. The modified Mg–Al LDH materials show an increase in interlayer distance as compared to the unmodified Mg–Al LDH depending on the length of the surfactant anions. Thermal decomposition changed significantly after organic modification. The particle morphology was investigated by scanning electron microscopy (SEM).     

Inorganic layered double hydroxides as a drug delivery system—intercalation and in vitro release of fenbufen

Layered double hydroxides (LDHs), or so-called anionic clays, consist of cationic brucite-like layers and exchangeable interlayer anions. Because of their biocompatibility, some LDHs, such as Mg/Al, Zn/Al, Fe/Al and Li/Al-LDH, can be used as host materials for drug-LDH host–guest supramolecular structures. The anti-inflammatory drug fenbufen has been intercalated into layered double hydroxides for the first time by co-precipitation under a nitrogen atmosphere. The product has been characterized by powder X-ray diffraction (XRD), FT-IR spectroscopy, elemental analysis and thermogravimetry (TG) and shows an expanded LDH structure, indicating that the drug has been successfully intercalated into LDH. In addition, the dependence of the nature of the fenbufen intercalation process on conditions such as pH value and chemical composition of the host has been systematically investigated. The interlayer distance in the intercalated materials increases with increasing pH value, resulting from a change in the arrangement of interlayer anions from monolayer to interdigitated bilayer. Drug release characteristics of the pillared LDH materials were investigated by a dissolution test in a simulated intestinal fluid (buffer at pH 7.8). The results show that the drug release of supramolecular LDH materials was a slow process, especially in the case of Mg/Al intercalated materials, suggesting that these drug-inorganic hybrid materials can be used as an effective drug delivery system.     

Experimental investigation of sheet flexibility of layered double hydroxides: One-pot morphosynthesis of inorganic intercalates

The sheet flexibility of layered double hydroxides (LDHs) has been investigated experimentally using co-precipitation and urea hydrolysis methods in an aqueous solution of long-chain anion surfactant in this work. Using dodecylsulfate (DS) anion as morphology-controlling agent, layer-bended or contorted Mg/Al-LDH is obtained successfully. The morphology of bent layers is retained during either in situ decomposition of interlayer DS to SO₄²⁻ or ion exchange of interlayer DS by CO₃²⁻. The direct synthesis of the layer-distorted LDHs intercalated with small inorganic anions is quite difficult. It has been achieved using layer-bended LDHs pillared with bulky organic anions as precursors in this paper. The morphosynthesis is expanded to Co/Al and Ni/Al-LDHs, indicative of the general flexibility of this kind of anionic clays.     

Thermal characteristics of organoclay and their effects upon the formation of polypropylene/organoclay nanocomposites

Summary We have examined thermal characteristics of two types of organically modified montmorillonite (OMMT) with different alkylammonium cations and their effects upon the formation of PP nanocomposite, when using a maleic anhydride grafted polypropylene oligomer (maPP) as a compatibilizer. The microstructure of the composite has been characterized by X-ray diffraction (XRD) analysis, transmission electron microscopy and Fourier transform infrared spectroscopy. OMMT showed the decrease of the interlayer spacing at the processing temperature, due to the release of organic ion by thermal decomposition. Thermal characteristics of OMMTs depended greatly on the interlayer structure of OMMT. When the OMMT with small interlayer spacing and less organophilicity was used, PP composite resulted in the only partial exfoliation due to thermal decomposition of the clay layers. Received: 21 June 2000/Revised version: 11 August 2000/Accepted: 11 August 2000     

Effect of surfactant concentration on the stacking modes of organo-silylated layered double hydroxides

The effects of the surfactant concentration on the structure, morphology and thermal property of silylated hydrotalcites have been investigated. By in-situ coprecipitation, the surfaces of layered double hydroxides (LDHs) have been modified by using 3-aminopropyltriethoxysilane (APTS) and anionic surfactant, Na-dodecylsulfate (SDS). Two different stacking modes in the resultant materials were detected by X-ray diffraction (XRD). One has an identical structure of LDHs, in which the SDS and APTS only bond to the outside surfaces and plate edges of LDH. The other is with enlarged interlayer distance, in which SDS and APTS combined with the inside surfaces of LDH. With the increased loading of SDS and APTS, the surface of the modified LDH appeared rough as observed in the transmission electron microscopy (TEM) images. The attenuated total reflection Fourier-transform infrared (ATR FTIR) spectra of the silylated hydrotalcites showed a series of bands attributed to –NH₂ and Si–O–M (M = Mg and Al), proving that APTS has successfully been grafted onto LDH. The thermogravimetric curves (TG) showed that the silane grafted samples have less –OH concentration and less interlayer water, as a result of the –OH consumption during the condensation reaction between Si–OH and –OH on LDH surface. These nanomaterials are of potential applications including clay-based nanocomposites, adsorbents for removal of organic contaminants from water and flame retardant materials.     

Poly(N‐vinylcarbazole)–clay nanocomposite materials prepared by photoinitiated polymerization with triarylsulfonium salt initiator

A series of polymer–clay nanocomposite (PCN) materials that consist of poly(N‐vinylcarbazole) (PNVC) and layered montmorillonite (MMT) clay are prepared by effectively dispersing the inorganic nanolayers of MMT in an organic PNVC matrix via in situ photoinitiated polymerization with triarylsulfonium salt as the initiator. Organic NVC monomers are first intercalated into the interlayer regions of the organophilic clay hosts, followed by one‐step UV‐radiation polymerization. The as‐synthesized PCN materials are typically characterized by Fourier transform IR spectroscopy, wide‐angle X‐ray diffraction, and transmission electron microscopy. The molecular weights of PNVCs extracted from the PCN materials and the bulk PNVC are determined by gel permeation chromatography analysis with tetrahydrofuran as the eluant. The morphological image of the synthesized materials is observed by an optical polarizing microscope. The effects of the material composition on the optical properties and thermal stability of PNVCs and a series of PCN materials (solution and fine powder) are also studied by UV–visible absorption spectra measurements, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1904–1912, 2004     

Layered double hydroxide-derived vanadium catalysts for oxidative dehydrogenation of propane: Influence of interlayer-doping versus layer-doping

Mixed-oxide vanadium catalysts for oxidative dehydrogenation (ODH) of propane have been prepared by thermal decomposition of Mg, Al-layered double hydroxides (LDHs) containing vanadium either in the brucite layer or in the interlayer. The materials have been characterised by XRD, ICP-AES chemical analysis, XPS, BET and ESR. The catalytic performance of the samples depended on the manner of incorporation of the vanadium into the LDH structure. The sample obtained from interlayer-doped precursor was more active and more selective than mixed oxides obtained from layer-doped LDHs. The difference in the catalytic properties was attributed to the different magnesium vanadates nucleating in the calcined samples, the pyrovanadate formed from the interlayer-doped LDH giving better performance than ortho-vanadate crystallising from the layer-doped precursor. It has been suggested that one of the factors contributing to the difference in the behaviour of both types of catalysts might be the difference in the covalency of V---O in-plane bonds around the reduced V centres.     

New hybrid materials based on layered double hydroxides and antioxidant compounds. Preparation, characterization and release kinetic studies

New hybrid materials were obtained by intercalation of the antioxidant compounds vanillic acid and gallic acid in layered double hydroxides (LDHs) resulting formulations with controlled release and antioxidant activity. The hybrid materials were prepared by using two methods: coprecipitation and ion exchange. X-ray powder diffraction, infrared spectroscopy and thermogravimetric analysis confirmed that the antioxidant molecules were intercalated into interlayer spaces of LDHs. The release of the antioxidant compounds was investigated in simulated gastrointestinal solution at 37?°C and monitored using a spectrophotometric method. The results prove that these hybrid biocomposites can be classified as controlled release formulations for the antioxidant compounds under study.     

Studies on the formation of 5-aminosalicylate intercalated Zn-Al layered double hydroxides as a function of Zn/Al molar ratios and synthesis routes

The 5-aminosalicylate intercalated Zn-Al layered double hydroxides (LDHs) with variable Zn/Al molar ratios have been synthesized by both direct coprecipitation (CP) and indirect ion exchange (EX) methods. As-synthesized solids have been characterized by powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), UV-visible spectroscopy (UV-Vis), thermal gravimetric analysis (TG) and inductively coupled plasma (ICP) emission spectroscopy, and CHN elemental microanalysis. The results indicate that the supramolecular structure and the loading percentage are highly dependent on the layer charge density and the synthesis routes of the LDHs materials. Four schematic supramolecular structural models of the 5-aminosalicylate intercalates have been proposed, including the staggered dentate-like monolayer arrangement, the vertically adjacent monolayer arrangement, the vertically distant bilayer arrangement, and the vertically adjacent bilayer arrangement. The EX products present highly ordered crystallite than CP ones and the intercalates with higher layer charge density, i.e., the lower Zn/Al ratio, exhibit more ordered crystal structure and higher thermal stability than those with lower layer charge densities.     

Study on preparation of layered double hydroxides (LDHs) and properties of EPDM/LDHs composites

Abstract

The aim of this work was to study preparation and characterisation of layered double hydroxides (LDHs) and their effects on the mechanical and flame-retardant properties of ethylene propylene diene (EPDM) polymer. A series of Mg–Al, Ni–Al, and Cu–Al hydrotalcite-like compounds were prepared. The surface morphology, interlayer space, interlamellar structure, and thermal properties of these LDHs were investigated. Results showed that a best thermal stability could be obtained with Cu–Al–LDHs as the most effective components. EPDM/Cu–Al–LDHs composites were prepared by conventional compounding with EPDM and Cu–Al type of LDHs. The cure characteristics, tensile strength, wear resistant, and flame-retardant properties were investigated. The best properties were observed for 10 phr of Cu–Al–LDHs filled composite, which resulted in no obvious changes of tensile strength, increased thermal stability, 45% decrease in abrasion loss, and 53% increase in vertical burning time, respectively, compared to that of pure EPDM matrix.     

类水滑石的制备及表征

采用低饱和共沉淀法制备Zn-Al LDHs、Mg-Al LDHs、Co-Al LDHs系列水滑石,通过X射线衍射（XRD）、傅里叶红外光谱（FT-IR）、热重-差热分析（TG-DTA）等表征手段对上述样品进行分析和表征。结果表明：采用低饱和共沉淀法制备的上述水滑石结晶度较高,结构规整,具有良好的层状结构和热稳定性。     

Polymer nanocomposites based on transition metal ion modified organoclays

A unique class of nanocomposites containing organoclays modified with catalytically active transition metal ions (TMI) and ethylene vinyl acetate (EVA) copolymers was prepared. The morphology, thermal and rheological properties of these nanocomposites were studied by thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray scattering/diffraction and oscillatory shear rheometry. TMI-modified organoclays were thought to possess pillaring of multivalent TMI in the interlayer silicate gallery, leading to a notable reduction of the interlayer d-spacing. The resulting nanocomposites exhibited significantly improved thermal stability and fire retardation properties, but similar morphology (i.e., an intercalated-exfoliated structure) and rheological properties comparable with EVA nanocomposites containing unmodified organoclays. It appears that the compressed organic component in the TMI-modified organoclay can still facilitate the intercalation/exfoliation processes of polymer molecules, especially under extensive shearing conditions. The improved fire retardation in nanocomposites with TMI-modified organoclays can be attributed to enhanced carbonaceous char formation during combustion, i.e., charring promoted by the presence of catalytically active TMI.     

Preparation and Characterization of Layered Double Hydroxides – PMMA Nanocomposites by Solution Polymerization

Layered double hydroxides (LDH) – poly(methyl methacrylate) (PMMA) intercalated-exfoliated nanocomposites were synthesized by solution polymerization of methyl methacrylate (MMA) in the presence of aminobenzoate organically-modified LDH. Preparations of 4-aminobenzoate organically modified LDHs were carried out by applying a chemical co-precipitation reaction. Structural and compositional details of LDH-AB were obtained with Fourier transformed infrared (FT-IR) spectroscopy, ²⁷Al magic-angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), elemental analysis (EA), inductively coupled plasma (ICP) atomic absorption spectrometry and X-ray diffraction (XRD). The morphology of the LDH-AB in the PMMA matrix was identified by employing transmission electron microscopy (TEM), XRD, and UV/visible transmission spectroscopy. The thermal properties of the nanocomposites were enhanced and their Tg values as well as the decomposition temperatures shifted to a high temperature region as identified by the differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). For example, the Tg value and the decomposition temperature of the nanocomposites with 6.4% LDH-AB increased by 19 °C and 24 °C, respectively.     

Sorption of aqueous organic contaminants onto dodecyl sulfate intercalated magnesium iron layered double hydroxide

Dodecyl sulfate anion (DS⁻) intercalated magnesium iron layered double hydroxide (DS–Mg–Fe LDH) was firstly prepared by the co-precipitation method, and was characterized by the means of X-ray diffraction (XRD), Fourier infrared (FT-IR), Total Organic Carbon analysis (TOC), themogravimetric and differential thermal analysis (TG-DTA) and surface characteristics analysis (BET-N₂). The sorption characteristics and mechanisms of hydrophobic organic contaminants (naphthalene, nitrobenzene, acetophenone) and hydrophilic contaminant (aniline) on DS–Mg–Fe LDH were investigated, and were subsequently compared with that on the inorganic magnesium iron layered double hydroxides (CO₃–Mg–Fe LDH and NO₃–Mg–Fe LDH). The greater sorption amount of organic contaminants on DS–Mg–Fe LDH than on CO₃–Mg–Fe LDH and NO₃–Mg–Fe LDH indicated that organic modified LDHs were potential sorbents for the abatement of organic contaminants. Sorption mechanism on DS–Mg–Fe LDH varied with the types of organic contaminants. The uptake curves of naphthalene, nitrobenzene and acetophenone on DS–Mg–Fe LDH were linear, and sorption capacities for three hydrophobic compounds were in the sequence of their hydrophobicity (refers to water solubility or K_ow). These results suggested that the sorption mechanism was the partition between water and the organic interlayer phase composed of the alkyl chain of DS⁻. After eliminating the influence of the hydrophobicity, the polar compounds (nitrobenzene and acetophenone) exhibited higher affinity to DS–Mg–Fe LDH than nonpolar compound (naphthalene), which demonstrated that both the hydrophobicity and polarity benefited the sorption of hydrophobic compounds on organic LDHs. For hydrophilic compound, aniline, its uptake curve was nonlinear. The sorption process of aniline was the cooperation of the adsorption on hydroxide surface through forming the hydrogen bonding and the weak partition to the interlayer organic phase.     

Thermal degradation of organic matter in the interlayer clay–organic complex: A TG-FTIR study on a montmorillonite/12-aminolauric acid system

The storage of natural organic matter within the interlayer space of layered silicate is an important type of clay–organic association in sediment. However, the role of the interlayer space of clay minerals in the thermal degradation of organics and the generation of hydrocarbons has not been well understood. In this study, an interlayer clay–organic complex was synthesized using montmorillonite (Mt) and 12-aminolauric acid (ALA). An Mt–ALA complex in which Mt and ALA were simply mixed was also prepared for comparison. Thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) was applied to monitor the thermal events and the corresponding products during the thermal degradation of the Mt–ALA complexes. In the absence of Mt, ALA decomposed at 467 °C via the cleavage of CC bonds, producing aliphatic hydrocarbon, N-containing compounds, and carboxylic acid. The decomposition temperatures of organic matter in the mixed Mt–ALA complex and the interlayer Mt–ALA complex decreased to 402 and 342 °C, respectively. The most characteristic products of the interlayer Mt–ALA complex were NH₃ and saturated hydrocarbons. The Brønsted acid sites in the interlayer space of Mt, arising from the dissociated interlayer water, initiated the deamination of ALA via the Hoffmann elimination pathway and significantly promoted the cracking of hydrocarbons via a carbonation mechanism. Lewis acid sites had little effect on the thermal degradation of ALA. This work indicated that the interlayer space of clay minerals provided the storage space for organic matter. Moreover, the active sites within the interlayer space strongly promoted the thermal degradation of organics.     

Study on response behaviors of mixed solution of polyelectrolytes and worms under shear

In this contribution, polyvinylpyrrolidone (PVP) nanocomposites (NCs) with novel chiral diacid intercalated layered double hydroxides (LDHs) as nanofillers were prepared via ultrasonic irradiation. Chiral LDH was synthesized in one step via a co-precipitation reaction in aqueous solution under ultrasonic irradiation. The modified Mg-Al LDH shows an increase in interlayer distance as compared to the unmodified Mg-Al LDH by X-ray diffraction (XRD). Different NCs of organo-modified chiral LDHs and PVP were constructed by means of an ultrasonic process. The structures of these new materials were investigated by XRD, Fourier transform infrared, field emission scanning electron microscopy and transmission electron microscopy techniques. XRD and electron microscopy results confirmed the delaminated state of the LDH in the PVP matrix. Furthermore, thermal analysis was evaluated and the prepared NCs show significantly improved thermal stability at higher temperature because of the homogeneous and good dispersion of modified LDH in polymeric matrix.     

A Nano-Hybrid of Molybdenum Oxide Intercalated by Dithiocarbamate as an Oxidation Catalyst

A novel nano-layered material based on molybdenum oxide has been synthesized by hydrothermal method using dithiocarbamate. On the basis of the X-ray diffraction, scanning electron microscopy, thermal analysis and infrared spectroscopy results, a possible arrangement of organic ligands in the interlayer space of molybdenum oxide has been proposed. Moreover, the catalytic activity of the synthesized nanohybrid of molybdenum oxide was investigated in oxygen transfer reactions. This reagent can oxidize alkenes, alcohols, sulfides, and amines in the presence of hydrogen peroxide with high yield and selectivity.     

Adsorption of 2,4-D on Mg/Al–NO3 layered double hydroxides with varying layer charge density

Layered double hydroxides (LDHs) have high surface area and high anion exchange capacity, so they have been proposed to be an effective scavenger for contaminants. In this study, the adsorption of 2,4-dichlorophenoxyacetate (2,4-D) on Mg/Al–NO₃ LDHs with varying layer charge density was investigated with particular attention on the effect of the orientation of the interlayer nitrate. Three Mg/Al LDHs were synthesized with Al³⁺/(Al³⁺ + Mg²⁺) molar ratios of 3.3 (LDH3), 2.6 (LDH4) and 2.1 (LDH5). The results of adsorption experiments showed that LDH5 exhibited an S-type isotherm with a low 2,4-D adsorption capacity due to the low accessibility of 2,4-D to the interlayer space. The accessibility was restricted by the small basal spacing of LDH5 as a result of the parallel orientation of the interlayer nitrate with respect to the hydroxide sheet. Thus, the 2,4-D adsorption occurred mainly on the external surface of the material. On the contrary, LDH3, which has the highest layer charge density among the samples, contains nitrate with an orientation perpendicular to the hydroxide sheet of LDH3. The interlayer nitrate was readily exchanged by 2,4-D. Thus, in addition to the adsorption on the external surface, the replacement of the interlayer nitrate by 2,4-D contributed to a higher adsorbed amount of 2,4-D; the 2,4-D adsorption of LDH3 exhibited an L-type isotherm. For LDH4 that contained interlayer nitrate with both parallel and perpendicular orientations, the adsorption characteristics were between those of LDH3 and LDH5. This work has demonstrated the dependence of 2,4-D adsorption characteristics on the nitrate orientation in LDHs, as a consequence of changing layer charge density.     

Attachment of ZnO nanoparticles onto layered double hydroxides microspheres for high performance photocatalysis

In this study, ZnO nanoparticles were successfully deposited on the surface of ZnMgAl–CO₃–LDHs microspheres to form ZnO/ZnMgAl–CO₃–LDHs heterojunction photocatalysts by coprecipitation process. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV–vis diffuse reflectance spectroscopy. The results show that ZnO nanoparticles with diameters about 10–80 nm are tightly grown on the nanosheets of the ZnMgAl–CO₃–LDHs microspheres. Compared with the pristine ZnMgAl–CO₃–LDHs microspheres and pure ZnO, the photocatalytic activity of the heterojunction ZnO/ZnMgAl–CO₃–LDHs photocatalyst is significantly enhanced towards the degradation of phenol under UV light irradiation. The enhancement of the photocatalytic activity of the heterojunction catalysts can be ascribed to their improved light absorption property and the lower recombination rate of the photoexcited electrons and holes during the photocatalytic reaction. The optimal molar ratio of ZnO/ZnMgAl–CO₃–LDHs for the photocatalysis is 3. The heterojunction photocatalyst ZnO/ZnMgAl–CO₃–LDHs may be a promising photocatalyst for future application in water treatment due to its excellent performance in degradation of phenol.