层状双金属氢氧化物形成机理的研究现状

近年来,层状双金属氢氧化物（LDH）凭借特殊的层状结构、极强的可调控性能、优异的环境兼容性及显著的应用效果等特点,在环保、催化、储能、传感等领域得到广泛关注。国内外多数研究集中于LDH可控合成工艺的改进完善及LDH的应用探索,但迄今对制备LDH时涉及其组成结构形貌的变化过程,即其形成机理的关注较少,相关机制解释模糊,深入研究其形成过程对于可控制备具有独特形貌和特定组成的LDH及开发更深层次的应用具有至关重要的作用。本文介绍了LDH层板形成机理的3个主要研究方向,即以二价金属氢氧化物的存在为基础、以三价金属氢氧化物的存在为基础和拓扑相变机制,并分别进行了阐述辨析及对比分析,发现LDH层板的形成是一个极其复杂的过程,多种机制往往共同作用,总结认为固液及液液反应在初期成核阶段占据主导地位,各自作用程度及不同层板构筑机制产生的主导作用易受到外界环境因素影响,而更为普遍的LDH形成机制解释需要归纳总结更多LDH层板构筑的区别和规律,宏观和微观上探索形成过程的内在机理及科学本质,以期为LDH开发拓展提供理论基础。     

Incorporating of layered double hydroxide/sepiolite to improve the performance of sulfonated poly(ether ether ketone) composite membranes for proton exchange membrane fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) with a low sulfonation degree was blended using nanofiller layered double hydroxide (LDH, Mg₂AlCl)/sepiolite nanostructured material as additive to use as an electrolyte membrane for fuel cell application. Characterization assessments, that is, mechanical stability, thermal gravimetric analysis, ion exchange capability, swelling properties, water uptake capacities, electrochemical impedance spectroscopy analysis, and Fourier transform infrared spectroscopy of the composite membranes were conducted. The presence of LDH/sepiolite nanoarchitectured material within SPEEK was found to have the highest water retention and proton conductivity value at high temperature rather than LDH/SPEEK and pristine SPEEK membranes.     

A facile synthetic strategy for Mg-Al layered double hydroxide material as nanocarrier for methotrexate

Mg-Al layered double hydroxide nanopowders were synthesised by a facile coprecipitation technique at different pH conditions. LDH nanoparticles of higher aspect ratio with an average particle size of 26 nm were obtained at pH 9 whereas a pH of 11.3 resulted in LDH nanoparticles of average size 50 nm with lower aspect ratio and narrower size distribution. LDH-MTX organo-inorganic nanohybrid was produced with an average particle size of 53 nm after intercalation of MTX into the interlayer space of LDH, as evident from the shift of (0 0 3) peak in X-ray diffraction. This was corroborated by the transmission electron micrograph, which showed an increase in average interlayer spacing from 8.00 Å in pristine LDH to 21.4 Å in LDH-MTX nanohybrid. Thermogravimetric analyses showed ∼33.2 wt% MTX loading in the LDH structure. The MTX release profile from Mg-Al LDH-MTX nanohybrid in phosphate buffer saline at pH 7.4 follows Ritger-Peppas kinetics model which demonstrates that the release kinetics is diffusion controlled. An attempt has been made to explain the above observations based on the effect of electrical double layer repulsions on the growth of LDH nuclei, primarily considering significance of the particle morphology in drug delivery application.     

Synthesis of 5‐sulfosalicylic acid‐intercalated layered double hydroxide and its effects on wood flour/polypropylene composites during accelerated UV weathering

In this study, 5‐sulfosalicylic acid (SA) anions have been intercalated into Mg₃Al‐NO₃ layered double hydroxide (LDH) to synthesize SA‐intercalated Mg₃Al‐NO₃‐LDH (LDH‐SA) by ion‐exchange reaction. Then, the effects of LDH, SA, and LDH‐SA on the photostability of wood flour/polypropylene (WF/PP) composites during accelerated ultraviolet (UV) weathering were investigated. The surface color, surface gloss, and mechanical properties of the composites during weathering were tested, accompanied by characterizations using SEM, ATR‐FTIR, and TG. The results showed that (1) SA anions completely replaced the anions in LDH and the thermal stability of LDH‐SA was considerably enhanced; (2) composites with LDH or LDH‐SA exhibited less color change, fewer surface cracks, better thermal stability, and less losses of mechanical properties than the control group; (3) LDH‐SA showed a long‐term efficiency and alleviated the photo‐oxidation of WF/PP composites successfully; (4) LDH‐SA blocked UV light by physical shield effect of the layer sheets, as well as the chemical absorbability of the interlayer anions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44597.     

Exfoliated poly (styrene‐co‐methylstyrene) grafted‐polyaniline/layered double hydroxide nanocomposite synthesized by solvent blending method

Well defined poly (styrene‐co‐methylstyrene) grafted polyaniline/organo‐modified MgAl layered double hydroxide (LDH) was produced through solution intercalation method. After LDH nanoparticles were modified by the anion exchange reaction of MgAl (Cl) LDH with sodium dodecyl benzene sulfonate, Poly (styrene‐co‐methylstyrene) copolymers were synthesized by “living” free radical polymerization and then brominated with N‐bromosuccinimide. Afterwards, 1,4‐phenylenediamine was linked to brominated copolymers and prepared functionalized copolymer with amine. Poly (St‐co‐MSt)‐g‐PANI, has been synthesized by adding solution of ammonium persulfate and p‐toluenesufonic acid in DMSO solvent. Finally, Poly (styrene‐co‐methylstyrene) grafted‐Polyaniline/LDH nanocomposites were prepared by solution intercalation method. Characterization of these well‐defined nanocomposites included FT‐IR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimeter, transmission electron microscopy, and X‐ray diffraction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Preparation of acrylic acid and AMPS cointercalated layered double hydroxide and its application for superabsorbent

This article reports the cointercalation of acrylic acid (AA) and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) in the interlayer region of Mg₂Al layered double hydroxide (LDH) and the application of this inorganic–organic composite material in the field of water superabsorbent. The monomers of AA and AMPS were cointercalated into galleries of Mg₂Al−LDH (denoted as AA−AMPS/LDH) with various molar ratios by ion‐exchange method, which was confirmed by powder X‐ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), and elemental analysis. The polymer‐based superabsorbent was prepared through in situ free‐radical aqueous copolymerization of AA and AMPS, with AA−AMPS/LDH as additive, N,N′‐methylenebisacrylamide (NMBA) as crosslinker and potassium persulfate (KPS) as initiator. The composition of this poly(AA‐co‐AMPS)/LDH was demonstrated as a good water superabsorbent. The LDH content, water absorbency, thermal stability, and swelling rate of this superabsorbent were also investigated in detail. Results showed that the incorporation of a 5 wt % AA−AMPS/LDH into polymer matrix increased its water absorbency significantly by 27.7% (in water) and by 51.5% (in 0.9 wt % NaCl solution). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of layered double hydroxide/poly(ethylene terephthalate) nanocomposites by direct melt compounding

Thermal, rheological and mechanical properties of layered double hydroxide (LDHs)/PET nanocomposites were investigated. To enhance the compatibility between PET matrix and LDHs, organic modification of parent LDH having carbonate anion was carried out using various anionic surfactants such as dodecylsulfate (DS), dodecylbenzenesulfonate (DBS), and octylsulfate(OS) by rehydration process. Then, PET nanocomposites with LDH content of 0, 1.0, and 2.0 wt% were prepared by direct melt-compounding. The dispersion morphologies were observed by transmission electron microscopy and X-ray diffraction, indicating that LDH-DS were exfoliated in PET matrix. From the rheology study, there are some network structures owing to filler-filler and/or filler-matrix interactions in nanocomposite systems. Consequently, DS intercalated LDH provided good compatibility with PET molecules, resulting in exfoliated LDH-DS/PET nanocomposites having enhanced thermal and mechanical properties as compared to other nanocomposites as well as homo PET.     

Thermal stability of poly(vinyl chloride)/layered double hydroxide nanocomposites

Effects of nanoscale dispersed layered double hydroxides (LDHs) on thermal stability of poly(vinyl chloride) (PVC) in thermal and thermooxidative degradation processes are investigated by dynamic and isothermal thermogravimetric analysis (TGA), discoloration test, fourier transform infrared (FTIR), and ultraviolet‐visible (UV‐vis) spectroscopic techniques. During both stages of thermal degradation, the degradation temperatures, including onset degradation temperature and temperature of the maximum degradation rate, increase, and the final residue yield of the PVC/LDH nanocomposites reaches 14.7 wt %, more than double that for neat PVC. The thermooxidative degradation process is more complex. During the first two stages, the presence of nanoscale dispersed LDH particles enhances the thermal stability, whereas in the last stage accelerates the thermal degradation possibly due to the accumulation of heat released. Additionally, the studies of the isothermal thermooxidative degradation process by FTIR and UV‐vis spectra indicate that both polyene backbone formation and some carbonyl groups are simultaneously developed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of a poly(vinyl chloride)/layered double hydroxide nanocomposite with a reduced heavy‐metal thermal stabilizer

A novel poly(vinyl chloride) nanocomposite with layered double hydroxide was successfully prepared via a melt‐compounding process in which the positively charged platelets were dramatically exfoliated and homogeneously dispersed. Because of the absorption of the released hydrochloric vapor by both layered double hydroxide platelets and an organomodifier (stearate anions), the added amount of the conventional toxic heavy‐metal heat stabilizer could be reduced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Herbicide-intercalated zinc layered hydroxide nanohybrid for a dual-guest controlled release formulation

Herbicides, namely 4-(2,4-dichlorophenoxy) butyrate (DPBA) and 2-(3-chlorophenoxy) propionate (CPPA), were intercalated simultaneously into the interlayers of zinc layered hydroxide (ZLH) by direct reaction of zinc oxide with both anions under aqueous environment to form a new nanohybrid containing both herbicides labeled as ZCDX. Successful intercalation of both anions simultaneously into the interlayer gallery space of ZLH was studied by PXRD, with basal spacing of 28.7 Å and supported by FTIR, TGA/DTG and UV-visible studies. Simultaneous release of both CPPA and DPBA anions into the release media was found to be governed by a pseudo second-order equation. The loading and percentage release of the DPBA is higher than the CPPA anion, which indicates that the DPBA anion was preferentially intercalated into and released from the ZLH interlayer galleries. This work shows that layered single metal hydroxide, particularly ZLH, is a suitable host for the controlled release formulation of two herbicides simultaneously.     

Polymorphism and spherulite morphology of poly(1,4‐butylene adipate)/organically‐modified layered double hydroxide nanocomposites

A novel biodegradable poly(1,4‐butylene adipate)/organically‐modified layered double hydroxide (PBA/m‐LDH) nanocomposites are synthesized using the solution mixing process. The m‐LDH is originally prepared with magnesium nitrate hexahydrote (Mg(NO₃)₂ 6H₂O), aluminum nitrate‐9‐hydrate (Al(NO₃)₃ 9H₂O), oleic acid, and sorbitol by a novel one‐step co‐precipitation method to intercalate the organo‐modifier of oleic acid and sorbitol into the interlayer of LDH. The structure and morphology of the PBA/m‐LDH nanocomposites are characterized using X‐ray diffraction and transmission electron microscopy (TEM). It has been shown that the m‐LDH is exfoliated and well distributed in PBA matrix. The effect of m‐LDH on the polymorphic crystal and morphology of PBA at various crystallization temperatures (T_cs) would be investigated using WAXD and POM. Both data indicate that the addition of m‐LDH can change the starting formation temperature of α‐form crystals. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42526.     

In situ microwave‐assisted polymerization of polyethylene terephtalate in layered double hydroxides

The synthesis of poly(ethylene terephthalate) (PET)/layered double hydroxide (LDH) nanocomposites through microwave methods has been investigated. To enhance the compatibility between the PET polymer and the LDH, dodecyl sulfate was intercalated in the lamellar structure. The organo‐LDH structure was confirmed by powder X‐ray diffraction (PXRD) and Fourier transform infrared spectroscopy (FTIR). PET nanocomposites were prepared with 0–10 wt % of LDH content by in situ microwave‐assisted polymerization. PXRD was used to detect the formation of the exfoliated PET/LDH nanocomposites. Transmission electron microscopy was used to observe the dispersed layers and to confirm the exfoliation process. FTIR spectroscopy confirmed that the polymerization process had occurred. TG and DTA are used to study changes in thermal stability of the nanocomposites, which resulted enhanced by well dispersed LDHs layers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphological,mechanical, and thermal features of PMMA nanocomposites containing two‐dimensional Co–Al layered double hydroxide

The focus of the current study is to investigate the influence of Co–Al layered double hydroxide (LDH) on the morphological, thermal, and mechanical features of poly(methyl methacrylate) (PMMA)‐based nanocomposites. Sodium dodecyl sulfate modified Co–Al LDH was synthesized by single step coagulation method. The PMMA nanocomposites containing different loadings of nanofiller (1–7 wt %) and polystyrene‐grafted maleic anhydride compatibilizer (5 wt %) were melt intercalated via twin screw extruder and later subjected to injection molding to prepare mechanical testing samples. The different properties of PMMA nanocomposites were studied by using XRD, TEM, FTIR, DSC, TGA, tensile, flexural, impact, and flammability analysis. The result of XRD analysis suggested the exfoliated morphology of the nanocomposite while the TEM demonstrated the intercalated structure at higher loading of LDH. The thermal characterization results revealed that thermal properties were improved by the addition of Co–Al LDH, whereas the flammability test exposed that dripping was minimum at 7 wt % loading. The mechanical properties exhibited that optimum results were obtained at 1 wt % loading of Co–Al LDH. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45774.     

Numerical optimization of bipolar plates and gas diffusion layers for PEM fuel cells

This paper is devoted to the numerical optimization of the dimensions of channels and current transfer ribs of bipolar plates as well as the thickness and porosity of gas diffusion layers. A mathematical model of the transfer processes in a PEM fuel cell has been developed for this purpose. The results are compared with experimental data. Recommendations of the values of operating parameters and some design requirements to increase PEM fuel cell efficiency are suggested.This paper was originally Presented at the CHISA Congress, Prague, August 2004.An erratum to this article can be found at     

Design,synthesis, and nanoengineered modification of spherical graphene surface by layered double hydroxide (LDH) for removal of As(III) from aqueous solutions

In this study, new nano spherical graphene modified with LDH (Layered Double Hydroxide) was prepared and used to remove As(III) ion from aqueous solutions. At first, graphene oxide was synthesized from graphite using a well-known Hammer method. The obtained graphene oxide solution was sprayed in octanol solution under different temperatures and sprayed speed as influenced variables. The structure and physical characterization of synthesized spherical graphene oxide were determined by various techniques, including FT-IR, N₂ adsorption–desorption, SEM, TEM, and EDX. In the next step, the hydrothermal method was applied to deposition LDH on the spherical graphene oxide. The synthesized spherical graphene modified by LDH was used to remove As(III) as a toxic heavy metal ion. The effect of influenced variables including pH, contact time, amount of sorbent, and type eluent studied and the optimum values were as 8, 30, 50, and HCl (0.5 mol·L^-1), respectively. After optimization, the studied sorbent was shown a high adsorption capacity (149.3 mg·g^-1). The adsorption mechanism and kinetic models exhibited good agreement with the Langmuir isotherm and pseudo-second-order trends, respectively. Besides, the synthesized product was tested for seven times without significant loss in its sorption efficiency.     

Nafion-TiO2 hybrid electrolytes for stable operation of PEM fuel cells at high temperature

The fabrication and characterization of Nafion-TiO₂ hybrid electrolytes for proton exchange membrane fuel cell (PEMFC) operating at high temperature are reported. A low temperature sol-gel synthesis, based on the formation of a sol from Ti-peroxy complex, was used to effectively incorporate hydrophilic anatase TiO₂ nanoparticles into the Nafion matrix. Fuel cell testing at temperatures up to 130 °C revealed that the hybrid membranes exhibit an increasing ohmic drop with increasing TiO₂ content incorporated into the polymer. However, at high temperatures and low relative humidity (RH) the performance of fuel cells using the hybrid electrolytes was found to surpass the one of Nafion. Electrochemical impedance spectroscopy (EIS) measurements suggest that enhancement of the fuel cell performance at high temperature and low RH is related to a reduced polarization resistance, indicating that the hybrid electrolytes contribute for a better water management of the system. In addition, it was found that the inorganic phase confers stability to the polymer, allowing for the operation at high temperature and reduced RH.     

Prospects use of hybrid layered double hydroxides‐polyacrylamide as controlled release media for antibiotic molecules

Some controlled‐release media containing two commercial antibiotic molecules, viz. Amoxicillin (AMX) and Ampicillin (AMP), were prepared using layered double hydroxides (LDH) intercalated and extended by polyacrylamide. The polycarylamide was prepared in situ by polymerization of acrylamide monomer intercalated in the interlayers of LDH. The LDH‐polyacrylamide‐antibiotic hybrid nanocomposites were characterized by various techniques like Fourier transform infrared (FT‐IR), powder X‐ray diffraction (XRD), thermogravimetric analysis (TGA), and field emission scanning electron microscopy (FE‐SEM). The results from these characterizations have shown the successful incorporation of the antibiotics in the interlayers and provided important information regarding their interlayer structure. The nanocomposites showed increased thermal stability in TGA. The loading of antibiotic in the PAM/Mg‐Al nanocomposite was found to be 36.33% for AMX and 52.38% for AMP. The improved antibacterial activity of hybrid nanocomposite was evaluated against Escherichia coli using the wells diffusion technique. The aliquot samples in agar media drug release study were found to be highly effective against microorganisms. The sustained release of antibiotic drug from the hybrid nanocomposite was also verified. The release rate at pH 7.4 phosphate buffer was found slower than that at pH 4.6. It can be concluded that hybrid nanocomposites of LDH extended by in situ polymerized acrylamide are very suitable materials to host different antibiotics and their controlled release. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45442.     

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.     

Advances in layered double hydroxide (LDH)-based elastomer composites

This article reviews the advances in layered double hydroxide (LDH) materials and the synthesis of LDH-based elastomer composites. The potential of tuning the structure of LDH materials for desired properties and applications has attracted both academic and industrial interest in recent years. The modification of LDH materials and the use of such materials in the synthesis of composites with different elastomer matrices have been critically analyzed. Emphasis has been given to the use of Mg-Al LDHs and Zn-Al LDHs with different elastomers. The use of modified LDHs with elastomers substantially improves their mechanical, thermal and optical properties. Even “smart properties” of elastomers, such as reversible thermotropic optical characteristics, have been realized with the use of LDH-based multifunctional additives in rubber formulations. The flame retardance of some elastomer composites has also been enhanced with the use of modified LDHs. The possibility of replacing ZnO with LDH during rubber compounding has also been discussed, which would lead to drastic interventions in the well-established rubber processing technologies. LDH materials have also been reported to be biocompatible. Therefore, among the various possible applications of LDHs in different material development processes, their use in rubber technology offers the potential for environmentally friendly rubber products, even tires. Throughout this article, the structure, synthesis, properties and applications of elastomer/(LDH) composites are discussed, including suitable examples taken from the relevant literature.