Selective removal of heavy metal ions in aqueous solutions by sulfide-selector intercalated layered double hydroxide adsorbent

Remaining largely under-appreciated, a majority of metal ion sorbents are limited in their target selectivity. In this work, a 3D sulfide intercalated NiFe-layered double hydroxide (NFL-S) hierarchical sorbent has been synthesized for selective heavy metal removal. The intercalation of sulfurated groups in the interlayer of the layered double hydroxide (LDH) nanosheets endows NFL-S as a selective heavy metal ion filter; the selectivity of NFL-S for heavy metals is in the order of Pb²⁺ > Cu²⁺ ≥ Zn²⁺ > Cd²⁺> Mn²⁺, and NFL-S has high k_d values for Pb²⁺ (∼10⁶ mL/g) and Cu²⁺ (∼10⁵ mL/g). Scanning electron microscopy, X-ray photoelectron spectroscopy and powder X-ray diffraction were used to analyze the composition of the as-prepared nanoadsorbent. The selective adsorption behavior was systematically studied using batch experiments, and the performance was evaluated through kinetic and isotherm studies. Moreover, the adsorption mechanism of heavy metals by NFL-S through surface complexation was also investigated, which shows great potential for water decontamination.     

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.     

Layered double hydroxide of Zn and Al,intercalated with hexacyanoferrate(II) ions,as a sorbent for removing cesium radionuclides from aqueous solutions

Sorption of cesium radionuclides from aqueous solutions with layered double hydroxide of Zn and Al, intercalated with hexacyanoferrate(II) ions, was studied. The effect of Na⁺, K⁺, and Ca²⁺ on the degree of cesium removal from aqueous solutions was determined, and high selectivity of the sorbent was demonstrated.     

An intercalated hybrid of polyacrylamide/layered double hydroxide prepared via in situ intercalative polymerization

A new intercalated hybrid of polyacrylamide (PAM)/layered double hydroxide (LDH) prepared via in situ intercalative polymerization procedure is reported. LDH with counterion ion of nitrate or dodecyl sulfate anion was employed for comparison. The obtained PAM/LDH hybrid was characterized by X-ray diffraction, infrared spectra, differential scanning microcalorimetry and X-ray photoelectron spectrum. The results reveal that the LDH modified with dodecyl sulfate anion can be used to obtain an intercalated hybrid, whereas PAM polymer chains can not enter the interlayer space of LDH with nitrate anion as counterion ion.     

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.     

The removal and recovery of Cr(VI) by Li/Al layered double hydroxide (LDH)

Hexavalent Cr has been identified as one of the toxic metals commonly present in industrial effluents. Among the treatment techniques developed for removing Cr(VI) from waste waters, sorption is most commonly applied, due to its simplicity and efficiency. However, few adsorbents can be recycled and reused cost-effectively. In this study, the removal and recovery of Cr(VI) from water using Li/Al LDH was investigated. The removal of Cr(VI) by Li/Al LDH was evaluated in a batch mode. The results demonstrated that Cr(VI) adsorption onto Li/Al LDH occurs by replacing the Cl(-) that originally exists in the interlayer of the adsorbent. The degree of Cr(VI) adsorption observed for Li/Al LDH was relatively high and the process occurred rapidly; however, a portion of adsorbed Cr(VI) was gradually desorbed, due to the Li de-intercalation of Li/Al LDH. Lithium de-intercalation from Li/Al LDH with interlayer Cl(-) and interlayer Cr(VI) follows the first order kinetics and has the activation energies of 76.6 and 41.5 kJ mol(-1), respectively. The properties of thermal unstability and the high adsorption capacity of Li/Al LDH may lead to the development of an innovative technique for the removal of Cr(VI) from Cr(VI)-containing wastewater. That is, Li/Al LDH may be used as an effective adsorbent for the adsorption of Cr(VI) in an ambient environment. Following the adsorptive process, the adsorbed Cr(VI) may be released, using heated water to treat the Cr(VI)-containing Li/Al LDH particles. Through this hydrothermal treatment of the used adsorbent, Cr(VI) can be recovered and the solid product (gibbsite) can be recycled for further use.     

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.     

Hydrothermal crystallization of iron(III) hydroxide

The crystallization of amorphous iron(III) hydroxide during hydrothermal treatment in aqueous suspensions was studied by x-ray diffraction and transmission electron microscopy. The results demonstrate that, by varying the hydrothermal synthesis conditions (pH, temperature, duration, nature and amount of additives), one can control the phase composition, shape, and size of the forming particles. Factors that increase the concentration of soluble iron(III) hydroxocomplexes (e.g., an increase in pH) favor the formation of α-FeOOH particles, and vice versa, a reduction in the concentration of such complexes (e.g., by introducing complexing agents) leads to the formation of α-Fe₂O₃ particles.     

Preparation of meixnerite (Mg–Al–OH) type layered double hydroxide by a mechanochemical route

We have attempted to synthesize the meixnerite (Mg–Al–OH) type layered double hydroxide (LDH) by a two step milling operation of a mixture of Mg(OH)₂ and Al(OH)₃ with water. In the first-step, a mixture of the starting materials was milled for 1 h without water, and the product prepared in the first-step was milled for 2 h with water in the second-step milling operation. The milled products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), and thermo gravimetric-differential thermal analyses with mass spectroscopy (TG-DTA/MS). The surface morphology was characterized by scanning electron microscopy (SEM). Meixnerite with a small amount of carbonate was successfully synthesized mechanochemically at ambient conditions by milling for only 3 h in a planetary ball mill.     

Biocorrosion resistance and biocompatibility of Mg--Al layered double hydroxide/poly(L-lactic acid) hybrid coating on magnesium alloy AZ31

A Mg–Al layered double hydroxide (Mg–Al-LDH) coating was firstly synthesized via an in-situ steam coating growth method on the AZ31 Mg alloy, and then was modified with poly(L-lactic acid) (PLLA) via dipping and vacuum freeze-drying. The microstructure and composition of LDH/PLLA hybrid coating were analyzed by XRD, SEM, EDS and FT-IR. The biocorrosion behavior of hybrid coating was evaluated by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and hydrogen evolution test in the Hank’s solution. The results showed that LDH/PLLA coatings exhibited a much dense layer compared to the unmodified Mg–Al-LDH coating with unobvious boundary between PLLA and LDH coatings. The corrosion current density of the LDH/PLLA-10 hybrid coating decreased three orders of magnitude in comparison to its substrate. It was proven that the existence of the PLLA coating further prolonged the service life of the Mg–Al-LDH coating. What’s more, the MTT assay and live/dead staining showed that the LDH/PLLA-10 coating had good biocompatibility for Mouse NIH3T3 fibroblasts. The formation mechanism and the anti-corrosion mechanism of hybrid coatings were proposed.     

Preparation and characterization of melt processed poly(l-lactide)/layered double hydroxide nonocomposites

This work reports the fabrication and physical properties of biodegradable poly(l-lactide) (PLLA) composites containing a fraction of unmodified layered double hydroxides (LDH–NO₃) and γ-polyglutamate-modified layered double hydroxides (γ-LDH) by melt blending process. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) experimental results showed that the original LDH–NO₃ with the certain amount of aggregates was unevenly dispersed throughout the PLLA matrix. Conversely, γ-LDH allows the formation of an intercalated nanocomposite. Although the water vapor permeability of the PLLA/LDH systems was decreased with increasing the loading of LDH, the barrier property of PLLA reinforced with γ-LDH is superior to that of PLLA-L composites. The effects of both LDHs on mechanical and thermal properties of PLLA were also investigated.     

Improved thermal stability of poly(vinyl chloride) by nanoscale layered double hydroxide particles grafted with toluene-2,4-di-isocyanate

A novel interlamellar surface modification of layered double hydroxides (LDHs) via covalent bonding by toluene-2,4-di-isocyanate (TDI) has been successfully obtained, and poly(vinyl chloride) (PVC)/TDI-modified LDH nanocomposites have been prepared via solution intercalation process. After the interlamellar modification, TDI was grafted to the surface hydroxyl groups of LDHs with nitrate, dodecyl sulfate or stearate anion as counterion anion. The structures of the TDI-modified LDHs and the nanocomposites were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, and transmission electron microscopy (TEM) techniques. The enhanced thermal stability of PVC/TDI-modified LDH nanocomposites was confirmed by means of conventional Congo Red test and dynamic thermogravimetric analysis (TGA). In addition, the thermal degradation mechanism was briefly discussed on the basis of the above experimental results.     

Corrosion resistance of Zn–Al layered double hydroxide/poly(lactic acid) composite coating on magnesium alloy AZ31

A Zn–Al layered double hydroxide (ZnAl-LDH) coating consisted of uniform hexagonal nano-plates was firstly synthesized by co-precipitation and hydrothermal treatment on the AZ31 alloy, and then a poly(lactic acid) (PLA) coating was sealed on the top layer of the ZnAl-LDH coating using vacuum freeze-drying. The characteristics of the ZnAl-LDH/PLA composite coatings were investigated by means of XRD, SEM, FTIR and EDS. The corrosion resistance of the coatings was assessed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the ZnAl-LDH coating contained a compact inner layer and a porous outer layer, and the PLA coating with a strong adhesion to the porous outer layer can prolong the service life of the ZnAl-LDH coating. The excellent corrosion resistance of this composite coating can be attributable to its barrier function, ion-exchange and self-healing ability.     

Self-assembly and characterization of layered double hydroxide/DNA hybrids

The purpose of this study was to control the fabrication of new labile supramolecular assemblies by formulating associations of DNA molecules with inorganic layered double hydroxides (LDHs). The results show that LDH/DNA hybrids synthesized by a coprecipitation route involving the in situ formation of LDHs around DNA molecules acting as templates were characterized by a lamellar organization, with DNA molecules sandwiched between hydroxide layers, exhibiting a regular spacing of 1.96 nm. Our results indicate that labile complexes resulting from the association of nucleic acids and inorganic materials can be obtained not only by anion exchange but also by a direct self-assembly route.     

A comparison of corrosion inhibition of magnesium aluminum and zinc aluminum vanadate intercalated layered double hydroxides on magnesium alloys

The magnesium aluminum and zinc aluminum layered double hydroxides intercalated with NO ₃ ^- (MgAl-NO₃-LDH and ZnAl-NO₃-LDH) were prepared by the coprecipitation method, and the magnesium aluminum and the zinc aluminum layered double hydroxides intercalated with VO _x ^- (MgAl-VO _x -LDH and ZnAl-VO _x -LDH) were prepared by the anion-exchange method. Morphologies, microstructures and chemical compositions of LDHs were investigated by SEM, EDS, XRD, FTIR, Raman and TG analyses. The immersion tests were carried to determine the corrosion inhibition properties of MgAl-VO _x -LDH and ZnAl-VO _x -LDH on AZ31 Mg alloys. The results showed that ZnAl-VO _x -LDH possesses the best anion-exchange and inhibition abilities. The influence of treatment parameters on microstructures of LDHs were discussed. Additionally, an inhibition mechanism for ZnAl-VO _x -LDH on the AZ31 magnesium alloy was proposed and discussed.     

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.     

Preparation and wetting properties of layered double hydroxide colloidal nano/microspheres with tunable flower-like morphologies

Layered double hydroxides (LDHs), known as a type of multifunctional anionic layered clay, typically exhibit stability and intrinsic hydrophilicity at neutral and alkaline pH. We herein report a polymer bead-templated preparation of flower-like LDH shell microspheres with the LDH platelets tuned under different aging durations and temperatures. Thickness of LDH shell walls was tuned readily by varying preparation conditions such as aging durations and temperatures. After a simple chemical surface modification using fluorine-silane molecule, the flower-like LDH nano/microspheres show the distinctly different transitions from the intrinsic hydropholicity to the superhydrophobicity at pH 2 and neutral pH. In contrast, at alkaline condition of pH 12 small flower-like spheres were formed atop of the parent microspheres, which may be argued in terms of a process of desorption of silane molecule at the alkaline condition combined with dissolution and reassembly of LDH platelets. Our finding of the superhydrophobic LDH spheres may find useful applications in chemical and biosensors against harsh acidic conditions.     

Reconstitution effect of Mg/Ni/Al layered double hydroxide

Layered double hydroxide (LDH) having a different cation (Mg, Ni, Al) composition was successfully synthesized by the low supersaturation method. The sample was thermally decomposed and reconstituted in water and nitrate media at different temperatures. X-ray powder diffraction and X-ray fluorescence were used to investigate the differences between the obtained layered materials and those after the reconstitution process. To the best of our knowledge, there are only few studies where the influence of the third metal cation on the reconstitution process was analyzed.     

Agglomeration of magnesium oxide particles formed by the decomposition of magnesium hydroxide

The agglomeration process of MgO powder derived from Mg (OH)₂ was investigated at fixed temperatures of 600, 800, 900 and 1200° C; these temperatures were chosen as representative of four regions, i.e. below 600° C, 650 to 850° C, 850 to 1050°C and 1050 to 1200° C previously reported. At 600° C, coherent crystallites coalesced within the heating time of 60 min; on further heating till 300 min, the primary particles which consisted of crystallites grew rapidly. The original Mg (OH)₂ framework or pseudomorphs, composed of minute crystallites and primary particles, still remained in the powder. At 800° C, the pseudomorphs had disintegrated into fragments. The crystallite growth and primary particle growth were accelerated with increasing the heating times beyond 60 min. At 900° C, a further fragmentation of agglomerates occurred with increasing the heating times; the crystallite and primary particle growth in fragments brought about the pore coalescence. At 1200° C, the crystallite and primary particle growth proceeded with the coarsening of pores; on heating beyond 240 min, the crystallites and primary particles grew rapidly due to the entrapment of pores within them.