Synthesis and characterization of layered double hydroxides (LDHs) with intercalated chromate ions

Chromate intercalated layered double hydroxides (LDHs) having the formula M^II₆M′^III₂(OH)₁₆CrO₄·4H₂O (M^II = Ca, Mg, Co, Ni, Zn with M′^III = Al and M^II = Mg, Co, Ni with M′^III = Fe) have been prepared by coprecipitation. The products obtained are replete with stacking disorders. DIFFaX simulations show that the stacking disorders are of three kinds: (i) turbostratic disorder of an originally single layered hexagonal (1H) crystal, (ii) random intergrowth of polytypes with hexagonal (2H) and rhombohedral (3R) symmetries and (iii) translation of randomly chosen layers by (2/3, 1/3, z) and (1/3, 2/3, z) leading to stacking faults having a local structure of rhombohedral symmetry. IR spectra show that the CrO₄²⁻ ion is incorporated either in the T_d or in the C_3v symmetry. The interlayer spacing in the latter case is 7.3 Å characteristic of a single atom thick interlayer showing that the CrO₄²⁻ ion is grafted to the metal hydroxide slab. On thermal treatment, the CrO₄²⁻ ion transforms into Cr(III) and is incorporated into the spinel oxide or phase separates as Cr₂O₃. In the LDH of Mg with Al, Cr(III) remains in the MgO lattice as a defect and promotes the reconstruction of the LDH on soaking in water. In different LDHs, 18-50% of the CrO₄²⁻ ion is replaceable with carbonate anions showing only partial mineralization of the water-soluble chromate. The extent of replaceable chromates depends upon the solubility of the corresponding LDH, which in turn is determined by the solubility of the MCrO₄. These studies have profound implications for the possible use of LDHs for chromate amelioration in green chemistry.     

Synthesis, characterization, and controlled release anticorrosion behavior of benzoate intercalated Zn–Al layered double hydroxides

Corrosion inhibitor-inorganic clay composite including benzoate anion intercalated Zn–Al layered double hydroxides (LDHs) are assembled by coprecipitation. Powder X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectrum analyses indicate that the benzoate anion is successfully intercalated into the LDH interlayer and the benzene planes are vertically bilayer-positioned as a quasi-guest ion-pair form in the gallery space. Kinetic simulation for the release data, XRD and FT-IR analyses of samples recovered from the release medium indicate that ion-exchange is responsible for the release process and diffusion through the particle is also indicated to be the rate-limiting step. The anticorrosion capabilities of LDHs loaded with corrosion inhibitor toward Q235 carbon steel are analyzed by polarization curve and electrochemical impedance spectroscopy methods. Significant reduction of corrosion rate is observed when the LDH nanohybrid is present in the corrosive medium. This hybrid material may potentially be applied as a nanocontainer in self-healing coatings.     

Effect of intercalated aromatic sulfonates on uptake of aromatic compounds from aqueous solutions by modified Mg-Al layered double hydroxide

In this study, we utilized Mg-Al layered double hydroxide (Mg-Al LDH) modified by intercalation with three aromatic sulfonates—2,7-naphthalene disulfonate (2,7-NDS²⁻), benzenesulfonate (BS⁻), and benzenedisulfonate (BDS²⁻)—for the uptake of two aromatics—1,3-dinitrobenzene (DNB) and anisole (AS)—from aqueous solution and determined the effect of the aromatic sulfonates on the uptake of these aromatics. We found that the electron-rich aromatic ring of the intercalated aromatic sulfonates such as 2,7-NDS²⁻ undergoes strong π-π stacking interactions with the electron-poorer benzene ring of DNB in aqueous solution, and these interactions result in a higher uptake of DNB by the modified Mg-Al LDHs. In contrast, the electron-poor aromatic ring of the aromatic sulfonates such as BDS²⁻ undergoes weak π-π stacking interactions with the electron-poorer benzene ring of DNB, and these interactions result in a lower uptake of DNB by the modified Mg-Al LDHs.     

Planar defects in layered hydroxides: Simulation and structure refinement of β-nickel hydroxide

Although nickel hydroxide can be obtained by various methods in a highly ordered form, this work shows that most such preparations are not free of stacking faults. The stacking faults belong to more than one type, which differ from one another in their structure as described by the local stacking sequence. The incidence of such residual stacking faults varies in the range 1-3% depending on the method of preparation.     

High-temperature chemical and microstructural transformations of an organic-inorganic nanohybrid captopril intercalated Mg-Al layered double hydroxide

The thermal evolution of a crystalline organic-inorganic nanohybrid captopril intercalated Mg-Al layered double hydroxide (LDH) [Mg_0.68Al_0.32(OH)₂] (C₉H₁₃NO₃S)_0.130(CO₃)_0.030·0.53H₂O obtained by coprecipitation method is studied based upon in situ high-temperature X-ray diffraction, in situ infrared and thermogravimetric analysis coupled with mass spectroscopy analysis. The results reveal that a metastable quasi-interstratified layered nanohybrid involving carbonate-LDH and reoriented less ordered captopril-LDH was firstly observed as captopril-LDH heat-treated between 140 and 230 °C. The major decomposition/combustion of interlayer organics occur between 270 and 550 °C. A schematic model on chemical and microstructural evolution of this particular drug-inorganic nanohybrid upon heating in air atmosphere is proposed.     

A simple method to synthesize layered double hydroxide nanoscrolls

Layered double hydroxide (LDH) is a promising drug carrier, ion exchanger, absorbent, and catalyst or even catalyst support due to its inimitable sandwich structure. If the LDH could be synthesized into the nanoscrolls, it will be promising ion channels for the biomolecule transfer, ion exchange, or catalysis. In this report, a simple technique has been developed to prepare layered double hydroxide nanoscrolls on a large scale. The composition of LDH nanoscrolls can be conveniently adjusted through experiment conditions. We proved the “rolling mechanism” to explain the formation of LDH nanoscrolls. Moreover, we unambiguously proposed the driving force for “rolling mechanism”, which is the change of the forces between the brucite-like sheets and the interanions and between the cations and cations in the brucite-like sheets.     

Reversible thermal behavior of the layered double hydroxides (LDHs) of Mg with Ga and In

The layered double hydroxides (LDHs) of Mg with Ga and In decompose completely on heating to 500 °C to yield poorly ordered oxide residues. In the Mg-Ga system, the oxide residue has a rock-salt structure with Ga incorporated in the MgO matrix. In the Mg-In system, the oxide residue is X-ray amorphous. These oxide residues revert back to the original LDH either on standing in a water-saturated atmosphere or on hydrothermal treatment in a Na₂CO₃ solution. In contrast, the LDHs of Co with Ga and In yield the thermodynamically stable spinel oxides and the decomposition is irreversible. These results have implications for the synthesis of ‘oxide’ catalysts by thermal decomposition of the LDHs.     

Design of magnetic and fluorescent Mg-Al layered double hydroxides by introducing Fe3O4 nanoparticles and Eu ions for intercalation of glycine

We describe a novel route for the preparation of magnetic and fluorescent magnesium-aluminum layered double hydroxides by introducing Fe₃O₄ nanoparticles and Eu³⁺ ions. From the powder X-ray diffraction results, it was found that the Fe₃O₄ nanoparticles were highly dispersed in the inner void of octahedral lattice, and the Eu³⁺ ions substituted for the Al³⁺ ions and entered into hydrotalcite lattice through isomorphous replacement. Moderate introduction of Fe₃O₄ nanoparticles and Eu³⁺ ions did not change the lamellar structure of magnesium-aluminum layered double hydroxides. Glycine can also be intercalated into this magnetic and fluorescent layered double hydroxides by ion-exchange method. After intercalation of glycine, the basal spacing of magnetic and fluorescent layered double hydroxides increased from 7.6 to 8.8 Å, indicating that glycine was successfully intercalated into the interlayer space of layered double hydroxides. Magnetic measurements reveal that these novel layered double hydroxides possess paramagnetic property at room temperature, and the emission and excitation spectra indicate the layered double hydroxides exhibit fluorescent property.     

Synthesis, spectroscopic and structural characterization of poly-o-methoxyaniline and poly-o-methylaniline intercalated into layered vanadyl phosphate

We present the spectroscopic and structural characterization of poly-o-methoxyaniline and poly-o-methylaniline intercalated into oxovanadium phosphate. The influence of synthesis conditions was also investigated. Furthermore, for comparison purpose intercalation reactions between polyaniline (PANI) and the matrix also have been performed. Infrared spectra (infrared bands near 1610 and 1500 cm⁻¹ characteristic of CC stretching from quinoid and benzenic rings, respectively) suggest that the organic polymers are present in an intermediate oxidation state of emeraldine, which are in agreement with UV-Vis spectra. Under soft reaction conditions (room temperature), only aniline undergoes intercalation reaction, whereas o-methoxyaniline and o-methylaniline react under refluxing by exfoliation-reconstruction process. These different synthetic procedures (topotactic mechanism and exfoliation-reconstruction) result materials with different arrangements of polymeric species into the interlayer space.     

Synthesis of the new layered oxides NaRbLnMO5 (Ln = La, Nd, Sm, Eu, Gd; M = Nb, Ta)

The new layered transition metal oxides NaRbLnMO₅ (Ln = Nd, Sm, Eu, Gd; M = Nb, Ta) were synthesized by direct solid-state reaction. NaRbLaNbO₅ crystallizes with a tetragonal unit cell [a=5.839(6) Å, c=8.313(1) Å] analogous to that of the related compound NaKLaNbO₅, while NaRbLaTaO₅ indexes to a larger monoclinic unit cell [a=9.577(2) Å, b=5.834(1) Å, c=8.323(2) Å, β=93.00(2)]. NaRbLnNbO₅ can be prepared for Ln = Nd, Sm, Eu, Gd, and NaRbLnTaO₅ can be prepared for Ln = Nd, Sm. Both series of compounds show the expected decrease in unit cell volume as the size of the lanthanide decreases. NaRbLaNbO₅ is also amenable to ion exchange, forming Li_2−xRb_xLaNbO₅ upon reaction with molten lithium nitrate.     

Exfoliated poly(methyl methacrylate)/MgFe-layered double hydroxide nanocomposites with small inorganic loading and enhanced properties

The novel exfoliated polymer nanocomposites (PMMA/MgFe(DS)-LDH) were synthesized by in situ polymerization based on poly(methyl methacrylate) (PMMA) and dodecyl sulfate-intercalated MgFe-layered double hydroxide (MgFe(DS)-LDH). The participation of Fe³⁺ ion is found to play an important role in the improvement of thermal stability of nanocomposites with small inorganic loading and well-dispersed inorganic components. The thermal degradation mechanism was discussed.     

Oxidizing synthesis of Ni–Mn layered double hydroxide with good crystallinity

Ni²⁺–Mn³⁺ layered double hydroxide (LDHs) with good crystallinity and uniform morphology has been hydrothermally synthesized at 180 °C for 2 days using urea as hydrolysis agent and ammonium peroxodisulfate as oxidant. The obtained Ni²⁺–Mn³⁺ LDHs material has been characterized by XRD, SEM, XPS, FT-IR, and TG–DTA. Ammonium peroxodisulfate as oxidant plays an important role for the formation of Ni²⁺–Mn³⁺ CO₃²⁻ LDHs material, and Mn²⁺ ions are oxidized into Mn³⁺ ones during the precipitation of Mn²⁺ ions, giving rise to layered hydroxide with the hydrotalcite structure. Ni²⁺–Mn³⁺ LDHs material with Ni/Mn molar ratio of 4 has a layered structure with a basal spacing of 0.739 nm. The morphology, size, and uniformity of the as-prepared materials connect with the hydrothermal treatment temperatures, and uniform and regular flowerlike spheres with a mean lateral size of 3.5 μm are observed for Ni²⁺–Mn³⁺ LDHs material with good crystallinity and uniform morphology.     

Synthesis, structure, and electrochemical characteristics of LiNi1/3Co1/3Mn1/3O2 prepared by thermal polymerization

A thermal polymerization route was adopted to synthesize layered LiNi_1/3Co_1/3Mn_1/3O₂ materials. After annealing the polymer gel containing metal salts at different temperatures from 850 to 1000 °C for different time between 6 and 25 h, powders of pure α-NaFeO₂ phase were obtained. The crystal structure, morphology and electrochemical properties of the products were investigated by XRD, SEM, electrochemical cell cycling and AC impedance spectroscopy. It is found that the powder annealed at 950 °C for 15 h shows the best electrochemical property with the first specific discharge capacity of 188 mAh/g at C/10 and 87% retention after 100 cycles. It exhibits good rate capability with the specific capacity of 169 mAh/g at 1 C and 110 mAh/g at 6 C. Adopting a slowly cooling procedure during the powder annealing can improve the electrochemical performance of the LiNi_1/3Co_1/3Mn_1/3O₂ powder.     

Preparation and intercalation chemistry of magnesium-iron(III) layered double hydroxides containing exchangeable interlayer chloride and nitrate ions

Layered double hydroxides (LDHs) with Mg²⁺ and Fe³⁺ cations in the brucite-like layers and having chloride or nitrate ions in the interlayer region have been prepared and characterized by powder X-ray diffraction (PXRD), elemental analysis and thermal analysis. Thermal decomposition of the LDH-nitrate occurs in two steps, with loss of water followed by simultaneous dehydroxylation of the layers and loss of NO_x/O₂ arising from the nitrate anions. Thermal decomposition of the LDH-chloride involves an additional step, with chloride ions becoming grafted to the layers, prior to loss of HCl. The interlayer anions may be readily replaced by sulfate, thiosulfate, tartrate and vinylbenzenesulfonate ions suggesting that these materials may be useful precursors to Mg-Fe(III) LDHs intercalated with a variety of inorganic and organic anions.     

Synthesis of layered sodium lanthanum selenide through ion exchange reactions

Layered hexagonal KLaSe2 (α-NaFeO₂-type) was synthesized using the reactive flux method and analyzed by powder XRD to determine its lattice constants (space group R-3m, a = 4.40508(5) Å, c = 22.7838(5) Å). NaLaSe₂, which normally crystallizes as a disordered rock salt structure with mixed Na+/La + 3 sites, was synthesized through a solid state ion exchange reaction at 585 °C from a 1:3 molar ratio mixture of KLaSe₂:NaI. The product of this reaction was hexagonally layered NaLaSe₂ (space group R-3m, a = 4.3497(3) Å, c = 20.808(2) Å) isostructural to KLaSe₂. This product was analyzed by comparison with members of the set of solid solutions Na_(1−x)K_(x)LaSe₂ to confirm that the extent ion exchange in this reaction was complete. Cubic (disordered) NaLaSe₂ was also reacted with KI to yield the poorly crystalline hexagonally layered product with the approximate formula Na_0.79K_0.21LaSe₂.     

Synthesis of layered double hydroxides from eggshells

Ca-Al and Ca-Fe layered double hydroxides (LDHs) were successfully synthesized from chicken eggshells by an ultrasonic wave assistant method. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) techniques. XRD and TEM analyses showed that the 4Ca-Al LDHs were of high purity but other samples were not. The present study provides a simple, efficient and environmental friendly method to obtain LDHs from biowaste eggshells, in which additional alkaline solution is not required for synthesis. Moreover, eggshells provide all the requisite bivalent metal ions, which are needed to form layered double hydroxides.     

Synthesis and characterization of Ni1−xZnxFe2O4 spinel ferrites from tailored layered double hydroxide precursors

In this paper, a series of pure Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrites have been synthesized successfully using a novel route through calcination of tailored hydrotalcite-like layered double hydroxide molecular precursors of the type [(Ni + Zn)_{1 − x − y}Fe_y²⁺Fe_x³⁺(OH)₂]^x+(SO₄²⁻)_x/2·mH₂O at 900 °C for 2 h, in which the molar ratio of (Ni²⁺ + Zn²⁺)/(Fe²⁺ + Fe³⁺) was adjusted to the same value as that in single spinel ferrite itself. The physico-chemical characteristics of the LDHs and their resulting calcined products were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy. The results indicate that calcination of the as-synthesized LDH precursor affords a pure single Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrite phase. Moreover, formation of pure ferrites starting from LDHs precursors requires a much lower temperature and shorter time, leading to a lower chance of side-reactions occurring, because all metal cations on the brucite-like layers of LDHs can be uniformly distributed at an atomic level.     

Synthesis and characterization of a new layered magnesium zinc phosphate hydrate

A new layered magnesium zinc phosphate hydrate, MgZn(HPO₄)₂·H₂O, with a zinc phosphate framework isostructural with the one of Na₂Zn(HPO₄)₂·4H₂O, was prepared by the direct ambient pressure and temperature reaction between zinc 2,4-pentanedionate, phosphoric acid and hexahydrated magnesium chloride. The as-prepared sample is monoclinic (a = 8.780(7) Å, b = 13.240(7) Å, c = 11.123(0) Å and β = 116.21(2)°). The prepared solid undergoes two thermal transformations when it is heated from 110 to 600 °C. The first transformation is due to the release of intercalated water molecules and the second one is due to the HPO₄²⁻ → P₂O₇⁴⁻ transition.     

Intercalation of Ru(II) tris (1,10-phenanthroline) complex in α- and γ-zirconium dihydrogen phosphate. Synthesis, thermal behaviour and X-ray characterization

Layered inorganic systems such as ion-exchangers (α- and γ-zirconium dihydrogen phosphate) already used as hosts for larger cations, were studied for the intercalation of Ru(II) tris (1,10-phenanthroline) complex into these host matrices. The uptake of the complex occurs using the batch method; the colour of the materials changes from white to brilliant orange; the highest ion uptake is obtained in the case of the γ-phase. The materials obtained are thermally stable up to ∼350 °C and the complex decomposition occurs in two (α-phase) or three (γ-phase) steps. The complex decomposition is complete at ∼700 °C and at 550 °C (respectively for α- and γ-Ru(II) materials). As can be seen from the X-ray patterns, the Ru(II) materials are still layered and show a new phase with an increase in the interlayer distance with respect to the starting materials. The hydrogen form is always present in the case of the α-materials; whereas, in the case of the γ-materials, it is present when ≤0.12 moles of the complex/mole of exchanger are inserted. Microanalysis measurements confirm the fact that the Ru(II) complex is not modified when exchanged.     

Transformation of Dion-Jacobson phase to Aurivillius phase: synthesis of (PbBiO2)MNb2O7 (M = La, Bi)

We describe transformations of the Dion-Jacobson (D-J) phases, KLaNb₂O₇ and RbBiNb₂O₇, to the Aurivillius (A) phases, (PbBiO₂)LaNb₂O₇ (1) and (PbBiO₂)BiNb₂O₇ (2), in a metathesis reaction with PbBiO₂Cl. Oxide 1 adopts centrosymmetric tetragonal structure (a = 3.905(1) Å, c = 25.66(1) Å), whereas oxide 2 crystallizes in a noncentrosymmetric orthorhombic (A2₁am) (a = 5.489(1) Å, b = 5.496(2) Å, c = 25.53(1) Å) structure. Oxide 2 shows a distinct SHG response towards 1064 nm laser radiation. The role of La³⁺ versus Bi³⁺ in the perovskite slabs for the occurrence of noncentrosymmetric structure/ferroic property in these materials is pointed out.