Preparation and characterization of Mg–Al layered double hydroxides intercalated with benzenesulfonate and benzenedisulfonate

Mg–Al layered double hydroxides (Mg–Al LDHs) intercalated with benzenesulfonate (BS^–) and benzenedisulfonate (BDS^2–) ions were prepared by coprecipitation and characterized by X-ray diffraction, FT-IR spectroscopy, and chemical analyses. The intercalated BS^– and BDS^2– maintained their intrinsic molecular structures within the Mg–Al LDH interlayers. At low intercalation levels, the benzene ring of BS^– in BS · Mg–Al LDH was inclined at 30° relative to the plane of the brucite-like layers of Mg–Al LDH. With increasing BS^– content, the benzene ring adopted an additional configuration perpendicular to the Mg–Al LDH layers. In BDS-intercalated Mg–Al LDH, the benzene ring of BDS^2– was tilted at 26° relative to the plane of the Mg–Al LDH layers. Intercalation levels of BDS^2– were smaller than those of BS^– despite the greater charge density of BDS^2–, which was likely attributable to a greater degree of electrostatic repulsion between intercalated anions.     

Second staging of tartrate and carbonate anions in Mg–Al layered double hydroxide

The intercalation of tartrate was performed through ion exchange using carbonate Mg–Al layered double hydroxide (LDH) as precursor. The intermediate crystalline phase (so-called second-staging phase) was observed during the intercalation process. The pure second-staging LDH, in which alternate interlayer regions are occupied by carbonate and tartrate anions, was obtained by the deintercalation of interlayer tartrate with carbonate. It was also found that the interlayer tartrates are so stable that they are difficult to exchange by carbonate at room temperature.     

Thermal behaviour of Cu–Mg–Mn and Ni–Mg–Mn layered double hydroxides and characterization of formed oxides

Thermal behaviour of synthetic Cu–Mg–Mn and Ni–Mg–Mn layered double hydroxides (LDHs) with M^II/Mg/Mn molar ratio of 1:1:1 was studied in the temperature range 200–1100 °C by thermal analysis (TG/DTA/EGA), powder X-ray diffraction (XRD), Raman spectroscopy, and voltammetry of microparticles. Powder XRD patterns of prepared LDHs showed characteristic hydrotalcite-like phases, but further phases were indirectly found as admixtures. The Cu–Mg–Mn precipitate was decomposed at temperatures up to ca. 200 °C to form an XRD-amorphous mixture of oxides. The crystallization of CuO (tenorite) and a spinel type mixed oxide of varying composition Cu_xMg_yMn_zO₄ with Mn⁴⁺ was detected at 300–500 °C. At high temperatures (900–1000 °C), tenorite disappeared and a consecutive crystallization of 2CuO·MgO (gueggonite) was observed. The high-temperature transformation of oxide phases led to a formation of Cu^I oxides accompanied by oxygen evolution. The DTA curve of Ni–Mg–Mn sample exhibited two endothermic effects characteristic for hydrotalcite-like compounds. The first one with minimum at 190 °C can be ascribed to a loss of interlayer water, the second one with minimum at 305 °C to the sample decomposition. Heating of the Ni–Mg–Mn sample at 300 °C led to the onset of crystallization of oxide phases identified as Ni_xMg_yMn_zO₄ spinel, (Ni,Mg)O oxide containing Mn⁴⁺ cations, and easily reducible XRD-amorphous species, probably free Mn^III,IV oxides. At 600 °C (Raman spectroscopy) and 700 °C (XRD), the (Ni,Mg)₆MnO₈ oxide with murdochite structure together with spinel phase were detected. Only spinel and (Ni,Mg)O were found after heating at 900 °C and higher temperatures. Temperature-programmed reduction (TPR) profiles of calcined Cu–Mg–Mn samples exhibited a single reduction peak with maximum around 250 °C. The highest H₂ consumption was observed for the sample calcined at 800 °C. The reduction of Ni–Mg–Mn samples proceeded by a more complex way and the TPR profiles reflected the phase composition changing depending on the calcination temperature.     

层状复合氢氧化物的结构调控及其吸附重金属离子的研究进展

层状复合氢氧化物（LDHs）是具有特殊层状结构的阴离子黏土,具有化学组成可调、比表面积大及结构记忆效应独特等性质,在废水处理方面备受关注。调控LDHs自身结构,是进一步扩大其应用范围、提高其吸附性能的有效途径。该文介绍了LDHs特殊的层状结构和其自身性质;总结了LDHs最常用的制备方法,即共沉淀法、离子交换法、尿素水解法、煅烧复原法和溶胶-凝胶法等,分别介绍了各种制备方法的原理和特点;综述了LDHs的结构调控对其吸附重金属离子性能的影响,并总结了LDHs对重金属离子的吸附机理;最后,指出了目前LDHs在处理含有重金属离子废水研究中面临的挑战,并对该材料未来的研究方向和发展趋势进行了展望。     

Nanocomposites of polymer gel electrolyte based on poly(ethylene glycol diacrylate) and Mg–Al layered double hydroxides

The present paper describes the synthesis and characterization of nanocomposite materials composed of the polymer gel electrolyte and a layered double hydroxide (LDH) inorganic filler. Mg–Al LDHs were prepared with various ratios of Mg/Al. It was observed that the layered structure of Mg–Al LDH was totally exfoliated by the PEGDA. The ionic conductivity and mechanical strength were highly improved in the nanocomposite systems. In the case of the composite films having 4.5 wt% of the Mg–Al LDH, the ionic conductivity reached 1.6 × 10^?3 S cm^?1 at room temperature. The incorporation of nanoparticles into the gel resulted in a two‐ or threefold increase in the tensile modulus. Copyright © 2004 Society of Chemical Industry     

Uptake of Cu, Cd and Pb on Zn–Al layered double hydroxide intercalated with edta

Hydrotalcite-like compound [Zn₂Al(OH)₆]₂edta·nH₂O(ZnAl-edta) was obtained from the precursor [Zn₂Al(OH)₆]NO₃·nH₂O (ZnAl-NO₃), by the anion exchange method, with the aim of uptake Cu²⁺, Cd²⁺ and Pb²⁺ from the aqueous solutions by chelating process between edta and metal cations. The amount of Cu²⁺, Cd²⁺ and Pb²⁺ adsorbed was monitorized by atomic absorption technique at different contact time, pH and metal concentrations. The results indicate the very fast adsorption of the metal cations by ZnAl-edta reaching the equilibrium of the uptake reaction in two hours for Cu and Pb and 24 h for Cd. The shape of the adsorption isotherms suggests specific interaction and high host–guest affinity. At pH 5.5 and initial concentration C_i = 10 mM, the amount adsorbed was C_s = 1117, 375 and 871 μmol/g for Cu²⁺, Cd²⁺ and Pb²⁺, respectively.     

Adsorption of fluoride ions by Zn–Al layered double hydroxides

Zn–Al layered double hydroxides (LDHs) with different molar ratios Zn/Al (0, 0.17, 0.34, 0.97, 3.47, ∝) were prepared by the co-precipitation of chlorides, characterized and evaluated for their fluoride adsorption at room temperature from aqueous solutions. The fluoride adsorption of the as-synthesized LDHs was influenced by the chemical composition of the LDHs and ZA-11 (Zn/Al = 0.97) had the highest capacity for fluoride adsorption (1.14–4.16 mg/g). The adsorption increased after calcination of the LDH up to 500 °C. The equilibrium data were fitted to the Freundlich, Langmuir, and Temkin equations. The kinetics of fluoride adsorption followed the pseudo-second order model.     

Structure and analgesic properties of layered double hydroxides intercalated with low amounts of ibuprofen

Ibuprofen‐intercalated layered double hydroxides (LDH‐IBU) have been successfully synthesized via a coprecipitation method with a nominal [Al³⁺]/[Mg²⁺] ratio of 0.5 and a variable molar IBU/([Al³⁺]+[Mg²⁺]) ratio of 0, 0.15, 0.18, 0.24, 0.36, and 0.72. After an accurate determination of the composition, the nature of the intercalated species and the effective intercalation yield from to IBU, it is shown that the synthesis route used allows a good control of the quantity of intercalated IBU within the LDH framework. This results in different samples with full or partial IBU intercalation in the interlayer space in exchange of nitrate anions. The analysis of the X‐ray diffraction basal reflections reveals that the intercalation of IBU in the framework only increases the basal distances with no alteration of the brucite‐type layers. Also, a computational study used to model the positions and shapes of the basal reflections showed that the structure of the nonfully intercalated compounds follows a random interstratification scheme. Finally, three samples ranging from slightly to fully IBU‐intercalated galleries were selected for preliminary in vivo assays. These tests showed a strong tendency that after 24 hours the low yield of IBU‐intercalated compounds are almost as efficient as the fully intercalated sample.     

Desorption of Cl- from Mg-Al layered double hydroxide intercalated with Cl- using CO2 gas and water

Mg-Al layered double hydroxide intercalated with CO_3~(2-)(CO_3·Mg-Al LDH) is effective for treating HCl exhaust gas.HCl reacts with CO_3~(2-) in CO_3·Mg-Al LDH, resulting in the formation of Cl·Mg-Al LDH.We propose that CO_2 can be used for the desorption of Cl~-from Cl·Mg-Al LDH to regenerate CO_3·Mg-Al LDH.Herein,we studied the desorption of a from CI-Mg-Al LDH by adding water to Cl·Mg-Al LDH and blowing CO_2 into it.We also analyzed the effects of temperature and water addition speed on the desorption of CI~-from Cl·Mg-Al LDH.Our results show that the added water adhered to CI·Mg-Al LDH and that CO_2 in the gaseous phase was dissolved in this adhered water,thus generating CO_3~(2-).Therefore,anion exchange occurred between CO_3~(2-) and Cl~-in the Cl·Mg-Al LDH,thus desorbing Cl~-.     

Influence of M/M ratio in surface-charging behavior of Zn–Al layered double hydroxides

Zn–Al layered double hydroxides with different M^II/M^III ratios were synthesized by the coprecipitation method and the obtained solids were characterized by powder X-ray diffraction, infrared spectroscopy, acid–base potentiometric titrations, electrophoretic mobility and modeling of the electrical double layer. As general behavior, increasing hydroxyl adsorption with increasing pH and decreasing supporting electrolyte concentration takes place between pH 7 and 12. The electrophoretic mobility of the samples are in all cases positive and it decreases when the pH becomes higher than 9. A net positive charge of the particles, with a point of zero charge (PZC) around 11.8, is deduced from electrophoretic data. A modified MUSIC model, where OH⁻/Cl⁻ exchange at structural sites and proton desorption from surface hydroxyl groups are taken into account, is used to estimate the deprotonation constants, the number of surface groups, the number of sites with structural charges an the affinity constants for Cl⁻ and OH⁻ of the samples with different M^II/M^III ratios. The modeling of potentiometric titrations and electrophoresis data indicates that anions between the layers and negatively charged groups in the particle surface balance most of the structural charge at the particles surface. It shows an important variation of the number of structural sites with the M^II/M^III ratio and an important role of surface protonation–deprotonation sites to the electrical behavior and exchange properties of LDHs.     

Adsorption and photocatalytic degradation of phenol and 2,4 dichlorophenoxiacetic acid by Mg–Zn–Al layered double hydroxides

Mg–Zn–Al layered double hydroxides (LDHs) with varying amounts of zinc were prepared by the coprecipitation method. Solids were analyzed by XRD and N₂ physisorption, confirming the formation of pure LDH phase; and the production of mixed oxides with high specific surface areas (182–276 m² g⁻¹) after calcination. Band gap energy was also determined, presenting the expected decreasing tendency on increasing zinc amounts. These mixed oxides were tested both for the adsorption of 2,4 dichlorophenoxiacetic acid (2,4-d) and for the photocatalytic degradation of 2,4-d and phenol. Nearly total (97%) degradation of initial 1.45 mmol L⁻¹ of 2,4-d, with 1 g calcined LDH per liter, was accomplished in 9 h, while phenol half-life was as short as 3.5 h, with the catalyst with lowest zinc amount (5 wt.%). Langmuir adsorption isotherms are presented. Solids were also characterized by XRD and FTIR analysis after photocatalytic and adsorption activity, to determine the presence of 2,4-d. The versatility of LDH decomposition products in the elimination of different contaminants by different mechanisms puts them forward as a viable alternative for environmental remediation.     

Behavior of acrylic acid–itaconic acid hydrogels in swelling,shrinking, and uptakes of some metal ions from aqueous solution

An experimental research of the absorption properties of metal ions onto synthetic hydrogel obtained by solution polymerization of acrylic acid and itaconic acid in presence of N,N′‐methylenebisacrylamide as crosslinking agent was carried out. The swelling behavior in aqueous salt solutions was studied as a function of divalent cation concentration (Cu²⁺, Zn²⁺, Ni²⁺, Co²⁺, Cd²⁺, Pb²⁺, Hg²⁺) in the external solution ranging from 10^?5 to 1M, at 25°C. The ability of these hydrogels to bind cations was measured at different pH values and metal ion concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 530–536, 2003     

Removal of concentrated heavy metal ions from aqueous solutions using polymers with enriched amidoxime groups

Particulate and fibrous adsorbents with enriched amidoxime groups were synthesized by using a novel monomer N,N′‐dipropionitrile acrylamide. The adsorption properties of amidoximated poly(N,N′‐dipropionitrile acrylamide) [poly(DPAAm)] particles and a nonwoven fabric grafted with the same for UO₂²⁺, Pb²⁺, Cu²⁺, and Co²⁺ at high concentrations were investigated by batch process. Metal ion adsorption studies were conducted from metal ion solutions with different initial concentrations (100–1500 ppm). It was shown that particulated amidoximated poly(DPAAm) has higher adsorption capacity than amidoximated nonwoven fabrics for all metal ions, especially for uranyl ions. The results of the adsorption studies showed that the interaction between UO₂²⁺ and amidoximated groups agree with the Langmuir‐type isotherm. From the Langmuir equation, the adsorption capacities were found as 400 mg UO₂²⁺/g dry amidoximated poly(DPAAm) and 250 mg UO₂²⁺/g dry amidoximated graft polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1705–1710, 2004     

Preparation and characterization of novel hybrid of bio‐assisted mineralized Zn‐Al layered double hydroxides using chitosan as a template

The purpose of this study was to prepare and characterize a novel nanohybrid prepared from the template‐assisted mineralization of Zn‐Al Layered Double Hydroxide (LDH) onto the surface of Chitosan (CSI), with an emphasis on morphology, biocompatibility, and its use as an efficient drug carrier agent. The as prepared LDH is highly crystalline, with platelet‐like morphology and curved tactoids when nucleated onto the surface of CSI. Our results indicate that the ? OH and ? NH functional moieties on CSI can direct an ordered structure of LDH, due to the electrostatic interaction between biopolymer and inorganic lamellae. We have been successful to intercalate an anti‐inflammatory drug, Sodium Ibuprofen (Ibu), into LDH, through conventional coprecipitation method. LDHs are endowed with great potential for delivery vector because their stacked layers lead to safe reservation of biofunctional molecules or genes, and their ion exchangeability and solubility in acidic media (pH < 4) give rise to the controlled release of drug molecules. According to the cell‐growth studies, LDHs are found as cell viable up to the concentration of 500 μg/mL. This study reveals that LDH not only plays a role of a biocompatible‐delivery matrix but also facilitates a significant increase in the delivery efficiency. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hydrodechlorination of 4-chlorophenol in aqueous phase with Pt–Al pillared clays using formic acid as hydrogen source

Catalysts based on pillared clays with Al and Pt were synthesized from a commercial bentonite and tested for catalytic hydrodechlorination (HDC) using 4-chlorophenol (4-CPhOH) as the target compound and formic acid as the hydrogen source. Stable Pt–Al pillared clays were obtained, showing a high activity and a strong fixation of the active phase to the support. The influence of the method of introduction of Pt in the pillared clay (ion-exchange or impregnation) and the Pt content in the catalytic activity was checked. Likewise, operating variables such as reaction temperature, catalyst concentration and formic acid to 4-CPhOH molar ratio were studied; higher values of these variables gave rise to a higher 4-CPhOH conversion to phenol. An important deactivation of the catalyst was observed, probably due to the formation of carboneous deposits since no appreciable Pt leaching was detected.     

pH‐dependent facile synthesis of CaAl‐layered double hydroxides and its effect on the growth inhibition of cancer cells

The present communication reports a pH‐dependent facile synthesis of calcium aluminum layered double hydroxide (CaAl‐LDH), at 3 different pH conditions of 8.5, 10.5 and 12.5 respectively, by simple coprecipitation route that led to the precipitation of the same in phase pure or in mixed phase form, and their detail characterization. Interestingly, at a pH of 8.5, the precipitate obtained was 100% phase pure CaAl‐LDH, represented as sample A, whereas, at higher pH conditions, a mixed phase comprising 37% of a combination of CaCO₃ polymorphs, e.g., calcite and aragonite and 63% of the CaAl‐LDH (at pH 10.5, represented as sample B) and 43% of a combination of calcite and aragonite and the rest 57% being CaAl‐LDH (at pH 12.5, represented as sample C) respectively, were obtained. The increasing trend of the presence of carbonate anion (with reference to calcite and aragonite phases) was estimated by trace level ion‐exchange chromatography study using organic acid column. All the above samples were tested for their anticancer activity in vitro, using cancer cell lines, e.g., human colon carcinoma (HCT116) and human breast adenocarcinoma (MCF7). Interestingly, sample A only exhibited significant growth inhibition of the cancer cells as above‐mentioned. The observation as above was verified using human osteoblast precursor cells (MC3T3) as well, on which, all the samples (sample A, sample B and sample C) exhibited good cellular viability.     

Separation and recovery of gold(III) from base metal ions using melamine–formaldehyde–thiourea chelating resin

Melamine–formaldehyde–thiourea (MFT) chelating resin has been prepared. Au³⁺ ions uptake behavior and selectivity of the chelating resin were investigated by both batch and column methods. MFT resin showed higher affinity toward Au³⁺ compared with base metal ions, Cu²⁺ and Zn²⁺. The highest Au³⁺ uptake values were obtained at pH 2 and Au³⁺ adsorption capacity of the resin was calculated as 48 mg Au³⁺/g resin (0.246 mmol Au³⁺/g resin) by batch method. It was concluded that Au³⁺ ions could be selectively concentrated from the solution including Cu²⁺ and Zn²⁺ base metal ions by column method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of unsaturated polyester–styrene beads using gamma irradiation and chemical polymerization routes for use in the recovery of some alkali metal ions

Suspension polymerization of unsaturated polyester–styrene was carried out in different media using different routes of polymerization. The effects of matrix type and concentration hold up, viscosity, irradiation dose, and the agitation speed on the resultant polymer characteristics were examined. The formed beads were physically identified using scanning electron microscopy, hardness, and particle size analysis techniques. They were smooth having typical spherical surfaces; the beads diameters were in the range of about 5–200 μm. The size of the resin beads was found to decrease with increase in the concentration and viscosity of the dispersant and impeller speed. The resultant beads were applied in the recovery of Li⁺, Na⁺, K⁺, and Cs⁺ ions from acidic media. The distribution coefficients of the alkali metal ions were calculated; the order of selectivity was Li⁺ > Na⁺ > K⁺ > Cs⁺ in case of the chemically processed resin beads, while the selectivity lies in the order of Li⁺ < Na⁺ < K⁺ < Cs⁺ in case irradiation processed ones. Finally, the economics of production of the unsaturated polyester–styrene resins using different methodologies was studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1149–1160, 2007