Phase and morphological changes during thermolysis of Mg4Al2(OH)12CO3·nH2O and Zn6Al2(OH)16CO3·nH2O layered double hydroxides (LDH) and their nanocomposites with poly(styrene sulfonate) (PSS) are studied by X-ray powder diffraction (XRD), scanning and transmission electron micrography (SEM and TEM) and thermal analyses. Mg4Al2(OH)12CO3·nH2O and Mg2Al(OH)6[CH2CH(C6H4SO3)]·3H2O show comparable thermal stabilities: the layered structure is lost above 300 °C with the nucleation of the MgO phase at approximately 400 °C and the MgAl2O4 phase at approximately 800 °C Zn3Al(OH)8[CH2CH(C6H4SO3)]·nH2O undergoes complete oxidative pyrolysis of the polyanion by 500 °C. Crystalline oxide products are obtained at a temperature approximately 300 °C lower than that of thermolysis of Zn6Al2(OH)16CO3·nH2O. The SEM and TEM images show that the thermolysis of LDH carbonates produces dense aggregates containing microcrystalline particles, whereas Mg2Al(OH)6[CH2CH(C6H4SO3)]·3H2O forms a macroporous solid.

Hydrotalcite (HT) interlayered with hexacyanoferrate(II) ions ([Mg4.62Al1.52(OH)12][(Fe(CN)6)0.30-(CO3)0.29]) has been synthesized from the carbonate-HT ([Mg4.52Al1.50(OH)12][(CO3)0.77]) through double ion exchange reactions, and the products have been studied by chemical and physical methods. Mössbauer spectroscopy shows that hexacyanoferrate(II) is held rigidly in the interlayer by electrostatic forces and is characterized by a singlet at 0.01 mm s−1 at 80 K. X-ray diffraction shows an increase of the basal spacing (d003 from 0.78 to 1.1 nm following exchange. Hexacyanoferrate(II) in the interlayer was oxidized to hexacyanoferrate(III) (up to 20%) by dioxygen on dehydrating the interlayer either by drying at 70°C or by washing with nonaqueous solvents like acetone or ethanol. The CN (ν6) band of hexacyanoferrate(II) and (III) is found at 2036 cm−1 and 2112 cm−1, respectively. The presence of an absorption band at 2080 cm−1, assigned to free cyanide anions in the interlayer, suggests that the hexacyanoferrate(II,III) complexes are not inert in the interlayer, cyanide ligands being substituted with either water or hydroxyls. Oxidation and ligand exchange of the hexacyanoferrate(II) are also indicated by Mössbauer spectroscopy.

Layered double hydroxides (LDH's) interlayered with silicate anions were prepared by reaction of tetraethylorthosilicate (TEOS) with synthetic meixnerite-like precursors of the type [Mg1−xAlx(OH)2][OH−]x·zH2O, where (1 − x)/x ≈ 2, 3, or 4. TEOS hydrolysis at ambient temperature occurred readily in the galleries of the hydroxide precursors with (1 − x)/x ≈ 3 or 4, but a temperature of ∼100°C was required to achieve silicate intercalation for the LDH composition with (1 − x)/x ≈ 2. On the basis of the observed gallery heights (∼7.0−∼7.2 Å) and 29Si MAS NMR spectra that indicated the presence of Q2, Q3, and Q4SiO4 sites, the intercalated silicate anions, which are formed by condensation reactions of silanol groups and partial neutralization of SiOH groups with gallery hydroxide ions, are assigned short chain structures. Also, some O3SiOH groups become grafted to the LDH layers by condensation with MOH groups on the gallery surfaces. The LDH-silicates exhibited comparable non-microporous N2 BET surface areas in the range 59–85 m2/g, but they differed substantially in acid/base reactivities, as judged by their relative activities for the catalytic dehydration/disproportionation of 2-methyl-3-butyn-2-ol (MBOH). Under reaction conditions where the LDH structure is retained (150°C), all the silicate intercalates showed mainly basic reactivities for the disproportionation of MBOH to acetone and acetylene. However, all the LDH silicates were less reactive than the corresponding LDH carbonates. Conversion of the LDH silicates to metal oxides at 450°C introduced acidic activity for MBOH dehydration, whereas the metal oxides formed by LDH carbonate decomposition were exclusivity basic under analogous conditions.

Layered double hydroxides (LDHs) are often used as precursors for mixed-oxide catalysts and the deposition of a LDH layer on supporting materials would be advantageous because of better utilization of active components. The purpose of the present study was to investigate the formation of LDHs on Al2O3/Al supports prepared by the anodic oxidation of aluminum foil in dilute aqueous solutions of Co, Mn, and/or Ni nitrates. The LDH deposition was carried out under hydrothermal conditions at 80–180°C for periods ranging from 8 h to 7 days. In the initial stages of the reaction, a surface alumina hydration was observed. The LDH phase was detected after long-term deposition (3–7 days) at 120–160°C and only a small amount of Mn was incorporated in the LDHs deposited. In solutions containing only Co and Mn cations, scanning electron microscopy (SEM) images show a gradual growth of platy crystals resulting in the formation of discrete bulky aggregates with sizes up to several tens of micrometers. The adhesion of aggregates to the support probably decreased with increasing size and oversized aggregates fell away; none was found in SEM images of the samples obtained after prolonged reaction times. When Ni cations were present in the solution, they were incorporated preferentially into the LDH phase; an homogeneous layer was formed, with single platy crystals oriented perpendicular to the support. After calcination at 500°C, the products formed on Al2O3/Al support exhibited a shift of reduction maxima to higher temperatures in comparison with mixed oxides obtained by thermal decomposition of coprecipitated LDHs.

Over the past several decades, clay minerals have been applied in various bio-fields such as drug and drug additives, animal medicine and feed additives, cosmetics, biosensors, etc. Among various research areas, however, the medical application of clay minerals is an emerging field not only in academia but also in industry. In particular, cationic and anionic clays have long been considered as drug delivery vehicles for developing advanced drug delivery systems (DDSs), which is the most important of the various research fields including new drugs and medicines, in vitro and in vivo diagnostics, implants, biocompatible materials, etc., in nanomedicine. These applications are obviously related to global issues such as improvements in welfare and quality of life with life expectancy increasing. Many scientists, therefore, in various disciplines, such as clay mineralogy, material chemistry, molecular biology, pharmacology, and medical science, have been endeavoring to find solutions to such global issues. One of the strategic approaches is probably to explore new drugs possessing intrinsic therapeutic effects or to develop advanced materials with theranostic functions. With this is mind, discussions of examples of cationic and anionic clays with bio- and medical applications based on nanomedicine are relevant. In this tutorial review, nanomedicine based on clay minerals are described in terms of synthetic strategies of clay nanohybrids, in vitro and in vivo toxicity, biocompatibility, oral and injectable medications, diagnostics, theranosis, etc.

L-aspartic acid was intercalated into layered double hydroxides by coprecipitation. Two types of well crystallized material were obtained and were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry, differential thermal analysis and polarimetry. Schematic models of two intercalation structures with different basal spacings are given. It is proved that the optical activity of L-aspartic acid is retained during and after the intercalation process.

The formation of mixed-metal-Al layered double hydroxide (LDH) phases similar to hydrotalcite has been identified as a significant mechanism for immobilization of trace metals in some environmental systems. These precipitate phases become increasingly stable as they age, and their formation may therefore be an important pathway for sequestration of toxic metals in contaminated soils. However, the lack of thermodynamic data for LDH phases makes it difficult to model their behavior in natural systems. In this work, enthalpies of formation for Ni LDH phases with nitrate and sulfate interlayers were determined and compared to recently published data on carbonate interlayer LDHs. Differences in the identity of the anion interlayer resulted in substantial changes in the enthalpies of formation of the LDH phases, in the order of increasing enthalpy carbonate<sulfate<nitrate. Substitution of silica for carbonate resulted in an even more exothermic enthalpy of formation, confirming that silica substitution increases the stability of LDH precipitates. Both mechanical mixture and solid-solution models could be used to predict the thermodynamic properties of the LDH phases. Modeling results based on these thermodynamic data indicated that the formation of LDH phases on soil mineral substrates decreased Ni solubility compared to Ni(OH)2 over pH 5–9 when soluble Al is present in the soil substrate. Over time, both of these precipitate phases will transform to more stable Ni phyllosilicates.

The sorption of nitrate ions on calcined hydrotalcite-type compounds at 550°C (HT550), 650°C (HT650), and 850°C (HT850) from pure water solution at 25°C has been studied. The influence of the temperature was also investigated for the sample calcined at 850°C by studying the sorption process at 10 and 40°C. The experimental sorption data points were fitted to the Langmuir equation in order to calculate the sorption capacities (Xm) of the samples; Xm values range from 61.7 g kg−1 (HT550 at 25°C) to 147.0 g kg−1 (HT850 at 40°C). The values for the removal efficiency (R) obtained ranged from 70.5% for HT550 at 25°C to 99.5% for HT850 at 40°C. The sorption experiments showed that the greater the calcination temperature (850°C), the more effective the removal of nitrate. The increase in the temperature from 10 to 40°C for sample HT850 also tends to increase the sorption of nitrate from 63.3 g kg−1 to 147 g kg−1 and the corresponding removal efficiency from 71.5 to 99.5%.

Mixed FeIIFeIII hydroxides, commonly referred to as ‘green rusts’ (GRs), are important reactive phases in both man-made and natural geochemical systems. Determinations of the standard Gibbs energy of formation of GRs are needed to understand and predict the occurrence and possible reactions of GRs in these systems. Slow acid titration of crystalline green rust sulfate (${\text{GR}}_{{\text{SO}}_4}$\$\end{document}) with the formation of magnetite was used as a novel method to determine the standard Gibbs energy of formation of ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}, ${\text{Δ}}_{\text{f}}{G}^{\text{o}}\left({\text{GR}}_{{\text{SO}}_4}\right)$\$\end{document}. Aqueous suspensions of ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}, with pH slightly >8, were titrated slowly with 1 M H2SO4 until pH = 3 under strict anoxic conditions. Powder X-ray diffraction and Mössbauer analysis revealed that magnetite was the only solid phase formed during the initial part of the titration, where the equilibrium pH was maintained above 7.0. The ratio of Fe2+ release to consumption of protons confirmed the stoichiometry of dissolution of ${\text{GR}}_{{\text{SO}}_4}$\$\end{document} and the formation of magnetite at equilibrium conditions. The estimate of the absolute value of ${\text{Δ}}_{\text{f}}{G}^{\text{o}}\left({\text{GR}}_{{\text{SO}}_4}\right)$\$\end{document} was −3819.43±6.44 kJ mol−1 + y × [ΔfGo(H2O(1))], where y is the number of interlayer water molecules per formula unit. The logarithm of the solubility product, log Ksp, was estimated to be −139.2±4.8 and is invariable with y. Using the new value for ${\text{Δ}}_{\text{f}}{G}^{\text{o}}\left({\text{GR}}_{{\text{SO}}_4}\right)$\$\end{document}, the reduction potentials of several ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}-Fe oxide couples were evaluated, with the ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}-magnetite half cell showing the smallest redox potential at pH 7 and free ion activities of 10−3.

Syntheses of Fe-, Co-, and Ni-containing Mg-Al-layered double hydroxides (LDHs) are described here because Fe, Co, and Ni represent the major constituents in steel containers used for storing spent nuclear fuel. Much evidence exists for the formation of LDHs during the corrosion of such containers under repository-relevant conditions. Because of their anion-exchange properties, LDHs can be considered as materials with the potential to retain and immobilize anionic radionuclides. Evaluation of the thermodynamic properties of LDHs is essential for reliable prediction of their behavior (solubility, anion exchange properties) in geochemical environments. The impact on the thermodynamic properties of the isostructural incorporation of divalent cations into the LDH was the main focus of the present study.

Mg-Al-Cl-LDH and the Fe-, Co-, and Ni-doped LDHs were synthesized by the co-precipitation method and then characterized (using powder X-ray diffraction (PXRD), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDX), and thermogravimetric analyses (TGA)).

The PXRD and EXAFS analyses indicated that all synthesized samples were pure LDHs where Co, Ni, and Fe were incorporated isostructurally. The EXAFS and XANES results demonstrated that Ni and Co were incorporated as divalent cations and Fe as a trivalent cation. Thermodynamic calculations were performed assuming an equilibrium state between aqueous solutions and corresponding precipitates after synthesis. The first estimates of the molar Gibbs free energies for Fe-, Co-, and Ni-containing LDHs at 70ºC were provided. The calculated Gibbs free energy of the pure Mg-Al-LDH (-3629 kJ/mol) was slightly less than those for Fe-, Co-, and Ni-containing compositions (-3612±50, -3604±50, -3593±50kJ/mol).

Leaching experiments with metallic uranium-aluminum research-reactor fuel elements in repository-relevant MgCl2-rich salt brine (brine 2) were performed. A Mg-Al layered double hydroxide (LDH) with chloride as the interlayer anion was identified as a crystalline secondary-phase component. In the present study, the incorporation of Cd into the structure of the Mg-Al-Cl LDH was investigated. Synthesis by a coprecipitation method was performed and the Mg-Cd-Al-Cl LDH obtained was characterized. The sorption behavior of selenium on the LDH was investigated in water, clay pore-water (Mont-Terri-type), and brine 2. Using a LDH concentration of 10 g/L, the sorption kinetics were rapid and equilibrium was reached within 12 h. The sorption of selenium decreased with increasing amount of chloride anions in the solutions. The chloride anions acted as competing anions for the sorption of selenium. The effect of pH on selenium sorption was investigated and a large buffer capacity of the LDH was observed. For the range of selenium concentration used, linear sorption isotherms were obtained which obeyed the Freundlich and Dubinin-Radushkevich models. From these, the energies of selenium sorption were calculated to be in the range of ion-exchange processes.

Cobalt (II) and Al (III) layered double hydroxides were precipitated from homogeneous solutions using urea hydrolysis under hydrothermal conditions. The particle sizes were controlled successfully by changing the reaction temperature and period. It was found that larger particles formed by reactions at lower temperatures over longer reaction periods because the slow urea hydrolysis at lower temperatures suppresses the formation of nuclei in the solution. When the reaction was conducted at 60°C for 100 days, particles >40 µm wide were obtained.

Among the many techniques used to remove toxic dyes from the environment, layered double hydroxides (LDH) are considered to be especially environmentally friendly, but, this quality may be altered by variations in the octahedral Mg/Al molar ratios in the LDH structure. The aim of the present study was to synthesize environmentally sound LDH for use as an economically viable sorbent for the adsorption of reactive brilliant orange X-GN. Layered double hydroxides with Mg/Al molar ratios of 2:1 and 4:1 were prepared by co-precipitation. The materials obtained were characterized by powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, X-ray fluorescence spectroscopy (XRF), and surface-area analysis. Batch experiments were carried out to investigate the effects of contact time, pH, adsorbent dosage, and initial dye concentration on the adsorption behavior of the reactive brilliant orange X-GN by Mg-Al LDH. The results showed that the optimum pH value for dye adsorption was 3.0, at which the adsorption capacities of the reactive brilliant orange X-GN by the 2:1 LDH and the 4:1 LDH at 298 K were 79.370 mg/g and 83.343 mg/g, respectively. Further analysis of the dye-adsorption kinetics show that they fit the pseudo second-order model well. The adsorption equilibrium data showed that the Langmuir model provided better correlation of the equilibrium data than the Freundlich model. This result indicates that LDH provide specific homogeneous sites where monolayer dye adsorption occurs. The results of XRD and FTIR analyses of LDH before and after the dye adsorption demonstrated that the adsorption mechanisms were ion exchange and coulombic attraction.

Layered double hydroxides (LDH) are extremely important materials for industrial processes and in the environment, and their physical-chemical behavior depends in large part on their hydration state, but the characterization of these hydration effects on their properties are incomplete. The present study was designed to explore the interpolytype transitions induced by variation in the ambient humidity among LDHs. The cooperative behavior of intercalated water molecules resulted in a sudden, single-step, reversible dehydration of the [Zn-Cr-SO4] LDH. The [Zn-Al-SO4] LDH provided an interesting contrast with (1) the coexistence of the end members of the hydration cycle over the 40-20% relative humidity range during the dehydration cycle, and (2) a random interstratified intermediate in the hydration cycle. These observations showed that the [Zn-Al-SO4] LDH offered sites having a range of hydration enthalpies, whereby, at critical levels of hydration (20–40%), the non-uniform swelling of the structure resulted in an interstratified phase. The variation in domain size during reversible hydration was also responsible for the differences observed in the hydration vs. the dehydration pathways. This behavior was attributed to the distortion in the array of hydroxyl ions which departs from hexagonal symmetry on account of cation ordering as shown by structure refinement by the Rietveld method. This distortion was much less in the [Zn-Cr-SO4] LDH, whereby the nearly hexagonal array of hydroxyl ions offered sites of uniform hydration enthalpy for the intercalated water molecules. In this case, all the water molecules experienced the same force of attraction and dehydrated reversibly in a single step. The changes in basal spacing were also accompanied by interpolytype transitions, involving the rigid translations of the metal hydroxide layers relative to one another.

Because of the anisotropy in bonding, layered hydroxides crystallize with extensive structural disorder due to the incorporation of stacking faults. In contrast, the loss of crystallinity in Br−-ion intercalated layered double hydroxides (LDHs) arises due to the positional disorder of Br− in the interlayer. The structure of the interlayer in other LDHs is poorly understood due to the low X-ray scattering power of the commonly found anions such as Cl− and ${\text{NO}}_3^{-}$\$\end{document} relative to that of the metal hydroxide layers. On heating to 175°C, the Br− ion migrates from positions of lesser site degeneracy to those of greater site degeneracy as dehydration of the interlayer opens up access to positions hitherto occupied by intercalated water molecules. The new (18h) site is situated closer to the proton of the metal hydroxide layer (1.809 Å) compared to the 6c site (2.402 Å). This shows a pre-association of the bromide ion with the proton of the hydroxide layer leading to the release of HBr upon decomposition of the bromide-containing LDHs. The fact that Cl−-containing LDHs also decompose with the evolution of HCl shows that such a redistribution of the atoms in the interlayer is more common than is generally recognized.

Toxic dyes must be removed from waste water coming from the textile and paint industries. Adsorption is one possible method of removing dyes under ‘soft’ conditions, without the generation of secondary hazardous materials. The present study used the carbonate-containing layered double hydroxides (LDH), Mg-Al and Mg-Zn-Al (with a M2+/M3+ ratio of 3), as adsorbents to remove two industrial colorants, Astrazon Remazol Brilliant Blue and Direct Red, present in low concentrations in aqueous solutions. The physicochemical properties of adsorbents at the surfaces of LDH, as well as the properties of the solutions containing the dyes control how the colorants are removed. Both fresh and calcined LDH were effective in the removal experiments, with effectiveness ranging from 50 to 100%. Analysis of kinetic data demonstrated that the adsorption process fitted the pseudo-second-order model better than the pseudo-first order model, information which is useful for system design in the treatment of wastes from the textile industry. Parameters such as pH of solutions and concentration of dye in solution influenced mainly the initial adsorption rate.

Akopovaite, ideally Li2Al4(OH)12(CO3)(H2O)3, is a new hydrotalcite-supergroup mineral from the Karasu–Karavshinskoye Sn deposit, Turkestan Range, Kyrgyzstan. It occurs as white or pale yellowish rosette-like aggregates that are composed of tiny curved plates up to 20–30 μm. Akopovaite is associated with gibbsite, quartz, albite, microcline, muscovite, montebrasite, siderite, schorl and birnessite-like Fe–Mn oxides. Akopovaite has a perfect cleavage along {001}, the mineral is transparent and very soft (VHN = 24 that corresponds to Mohs hardness of ca. 1). Dmeas = 2.12(2) g/cm3 and Dcalc = 2.106 g/cm3. The Raman spectra contain bands of carbonate groups and bands of O–H stretching vibrations. The chemical composition (wt.%, electron microprobe for Al and Fe; ICP-OES for Li; CHN method for CO2 and H2O) is Li2O 6.43, Al2O3 45.79, Fe2O3 0.27, CO2 10.09, H2O 36.1, total 98.68. The empirical formula based on (Li + Al + Fe) = 6 apfu is Li1.94(Al4.05Fe0.02)Σ4.07(OH)12(CO3)1.03(H2O)3.03. The crystal structure was refined by the Rietveld method with RB = 0.006 and Rwp = 0.014. Akopovaite is monoclinic, C2/m, a = 5.0953(6), b = 8.877(1), c = 7.806(1) Å, β = 102.572(6)°, V = 344.61(8) Å3 and Z = 1. The polytype should be denoted as 1M. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 7.66(100)(001), 4.397(27)(020), 3.821(45)(002,021), 2.4881(27)(200), 2.2273(16)(201) and 1.9027(18)(202). Akopovaite is the first naturally occurring hydrotalcite-supergroup carbonate species of Al and Li; its synthetic analogue is known.

Hydrotalcites with heterogeneous distributions of anions between their layers were synthesized. Some synthesis parameters were studied to verify their influence on the anionic segregation properties of the hydrotalcites. The nature of the divalent cation and the crystallization method were most relevant. Zinc, in contrast to magnesium, assisted in discriminating carbonates and attracting nitrates to form hydrotalcites with heterogeneous distributions using microwave irradiation. Furthermore, the identification of this kind of hydrotalcite could be easily verified by determining the presence of a double reflection in the 003 X-ray diffraction (XRD) maximum, which definitively characterized a heterogeneous anion distribution. Finally, the reason as to why in some cases the hydrotalcite presented two reflections in the 003 XRD peak was elucidated.

Green rusts, GRs, can act as both sorbents and reductants towards selected pollutants. Organo-GRs are expected to combine these properties with a high affinity for hydrophobic substances. A novel organo-GR, GRLAS, was synthesized by incorporating a mixture of linear alkylbenzenesulphonates (LAS) into the interlayer space of synthetic sulphate green rust, GRSO4 . Mössbauer analysis of GRLAS indicates that the structure of the organo-GR is very similar to that of the initial GRSO4 with regard to the FeII/FeIII ratio and local coordination of Fe atoms. X-ray diffraction demonstrates that the GRLAS formed was well ordered, although a mixture of surfactant was used for intercalation. The basal spacings of the GRLAS and the kinetics of the ion-exchange process were dependent on the initial surfactant loading; basal spacings of ~2.85 nm were obtained at LAS solution concentrations >10 mM. The ratio LASadsorbed/SO42–desorbed significantly exceeded the stoichiometric ratio of 2 during the initial part of the ion-exchange process (t = 5 h). However, this ratio was reached progressively with time. GRSO4 preferentially sorbed LAS homologues with long alkyl chains over short ones. Carbon tetrachloride was successfully adsorbed into GRLAS. The adsorption isotherm was linear with a distribution coefficient, Kd, of 505±19 litre kg–1.

The increasing presence of pesticides in natural ecosystems has stimulated research to look for improved adsorbent materials which can be used to remediate and prevent soil and water contamination by these compounds. Among the different materials that have been assayed as adsorbents of pesticides are natural clay minerals, particularly 2:1 phyllosilicates and their structurally complementary synthetic analogues layered double hydroxides (LDHs). The great interest in natural clays and LDHs as adsorbent materials is mainly related to the large specific surface areas associated with their layered structure, the ease with which they are obtained or synthesized, and the possibility of modifying their surfaces to increase their affinity for specific adsorbates. This review summarizes the adsorptive properties of natural clays and LDHs for pesticides and related organic compounds. Particular emphasis is given to the surface modification of clay minerals and LDHs with organic ions as a strategy to improve the efficiency of these materials as pesticide adsorbents. Potential applications of unmodified and modified clays and LDHs as adsorbents to prevent and remediate soil and water contamination by pesticides are also discussed.