New sulfur adsorbents derived from layered double hydroxides: II. DRIFTS study of COS and H2S adsorption

H₂S and COS adsorption were studied on two calcined layered double hydroxides (LDHs), Mg_0.75Al_0.25(OH)₂(CO₃)_0.125 and Mg_0.65Al_0.35(OH)₂(CO₃)_0.175, using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a chemisorption apparatus. Both demonstrated the ability to irreversibly adsorb H₂S, corresponding to uptakes of 1.54 and 1.76 μmol/m², respectively, but Mg_0.75Al_0.25 had a significantly larger capacity for COS, 1.62 μmol/m² compared to 0.80 μmol/m² for Mg_0.65Al_0.35. Analysis of the DRIFT spectra suggests the adsorption of H₂S proceeds via the substitution of lattice oxygen with sulfur, resulting in the formation of H₂O on the surface. COS adsorption is more complicated, although it appears that a similar substitution of lattice oxygen with sulfur occurs. This results in the formation of CO₂ and subsequently bicarbonates and carbonates. The formation of hydrogen thiocarbonate is also involved, although this form is generally only observed in the later stages of adsorption and appears to form at the expense of bicarbonate. The Mg_0.75Al_0.25 LDH retained its ability to adsorb COS in the presence of propene.     

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.     

Effect of interlayer anions on chromium removal using Mg–Al layered double hydroxides:Kinetic,equilibrium and thermodynamic studies

The influence of interlayer anions such as NO3-, SO42-and Cl-on Mg–Al hydrotalcites for Cr(VI) removal from aqueous solution was studied. The structure of the prepared LDHs was characterized by XRD, SEM, FTIR, TGA, BET surface area and p Hzpc. The sorbent ability and sorption mechanisms were also investigated. The LDHs exhibit high removal for Cr(VI), and the sorbed amount depends on the nature of interlayer anion, which decreased in the following order: NO3-N Cl-N SO42-. Nitrate-containing LDH reached a Cr(VI) sorption equilibrium within only 30 min. The effects of operating conditions, including initial concentration, solution p H, agitation time and sorbent amount have been studied in batch mode. The optimum conditions were observed at an initial concentration of 100 mg·L-1, p H = 6, agitation time of 60 min and a sorbent dose of 2 g·L-1. The equilibrium data were fitted to the Langmuir, Freundlich and Dubinin–Radushkevich isotherm models. The Langmuir model was found to sufficiently describe the sorption process, offering a maximum sorption capacity of 71.91 mg·g-1. The sorption kinetic follows pseudo-second-order reaction with high accuracy. Thermodynamic parameters suggested that the sorption process is spontaneous and endothermic in nature.     

A novel gas-liquid contacting route for the synthesis of layered double hydroxides by decomposition of ammonium carbonate

Layered double hydroxides (LDHs) carbonate with the M²⁺/Al³⁺ (M=Mg or Zn) molar ratio of 2/1 has been synthesized by a gas-liquid contacting route with the decomposition of ammonium carbonate. The key feature of this method is a pH gradient germinated by the diffusion of NH₃ and CO₂ vapors in the metal salts solutions from solid (NH₄)₂CO₃ in a closed environment. The physicochemical properties of these two particles were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, simultaneous thermogravimetric and differential thermal analysis (TG-DTA), scanning electron micrograph (SEM) or transmission electron micrograph (TEM), laser particle size analysis and low-temperature N₂ adsorption-desorption analysis. The results manifested that these two particles obtained by the method present well-crystalline, uniform crystallite size and relatively high surface area. The particle sizes of MgAl-LDH and ZnAl-LDH are around 0.55 and , respectively. Both the BET surface areas of them are about .     

Simultaneous incorporation of palladium and zirconium ions in Mg-Al layered double hydroxides by co-precipitation

Simultaneous incorporation of palladium and zirconium ions in Mg-Al layered double hydroxides (LDHs) was attempted by co-precipitation. Mixed oxides were obtained by calcination at 500 °C. XRD patterns of as-synthesized samples showed the formation of well-crystallized LDHs at lower Zr contents. The CO₃²⁻ content of the solids has been determined to have information on the possible incorporation of Zr⁴⁺ into the brucite layer of the hydrotalcites. The values obtained showed that Zr⁴⁺ can incorporate into brucite sheets at Zr content lower than 10 mol%. SEM and TEM images indicated that the resulted LDHs with lower Zr content exhibited plate-like structure. Thermal calcination at 500 °C results in the formation of mixed oxides containing MgO, PdO, ZrO₂ crystallites and a solid solution formed by some of the Zr⁴⁺ cations dissolving along with Al³⁺ to MgO lattice.     

Factors influencing the hydration of layered double hydroxides (LDHs) and the appearance of an intermediate second staging phase

The hydration of layered double hydroxides (LDHs) was investigated by changing the interlayer anion species, the Mg/Al ratio of the LDH hosts and the relative humidity (RH). The anions were CO₃²⁻, Cl⁻, Br⁻, NO₃⁻, I⁻, SO₄²⁻, and ClO₄⁻ (listed in the order of ion size, small to large) and LDHs with Mg/Al = 1.90 (LDH2) and 2.91 (LDH3) were used. Their XRD profiles were measured by an XRD diffractometer while controlling the RH in the range 0–95% at 25 °C. Only I⁻, SO₄²⁻, and ClO₄⁻ LDH2s and SO₄²⁻ LDH3 showed a large step-wise basal-spacing expansion, 0.24–0.28 nm, under high RH conditions (> ca. 60%) probably due to the insertion of one water layer into the interlayer space. Such hydration occurred more favorably for the LDHs with larger anions and those with a higher layer charge (LDH2). Among them, I⁻ and ClO₄⁻ LDH2s exhibited the second staging – alternate stacking of hydrated (H) and non-hydrated (NH) interlayers – in the intermediate RH region.     

Cation composition during recrystallization of layered double hydroxides from mixed (Mg, Al) oxides

Changes in cation composition and M²⁺/M³⁺ ratio during hydrotalcite regeneration were studied. Regenerated hydrotalcites were obtained by recrystallization of mixed (Mg, Al) oxides in solutions of divalent (Mg, Zn, Co, Ni, Cu) or trivalent (Al, Fe) cations.Heating Mg–Al–CO₃ hydrotalcites with Mg/Al=2, 3 and 3.7, at 600 °C for 2 h yielded periclase-like mixed (Mg, Al) oxides (HT-P). The hydrotalcite structure was restored by dispersing oxides 48 h in water or aqueous solutions of different cations.The presence of Mg²⁺, Zn²⁺, Ni²⁺, Co²⁺, Cu²⁺ salts or of low soluble hydromagnesite increased the M²⁺/Al ratio, reaching a maximum value of 3.8. An incorporation of Zn²⁺, Ni²⁺, Co²⁺ and Cu²⁺ cations in the newly formed hydrotalcite was detected, while Mg²⁺ remained in solution. In the presence of soluble Al salts or freshly precipitated Al(OH)₃, the M²⁺/Al ratio approximated the minimal possible value of 2.The Mg/Al ratio of a hydrotalcite crystallized from a mixture of two HT-P samples with different Mg/Al ratios is equal to the weighted average value.The results obtained support the conception of the dissolution–crystallization mechanism of hydrotalcite regeneration from mixed (Mg, Al) oxides contrary to the widely accepted concept of topotactic processes.     

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。     

A new method for preparation of nanoplates of Zn-Al layered double hydroxides

Methods for preparation of nanoplates of layered double hydroxides (LDHs) have been intensively investigated for the purpose of making nanocomposites. The present study provides a new simple method of nanoplate preparation for Zn-Al LDHs. Zn-Al LDHs containing lactate or combinations of lactate and simple inorganic anions were synthesized by a coprecipitation method, and water-washed and undried LDHs were dispersed in water. Among them, suspensions of Zn-Al LDHs containing both lactate and bicarbonate were unique in that they rapidly became translucent colloidal dispersions when the molar ratio of added bicarbonate to added Al was ≤ 0.5. The resulting LDH nanoplates in the dispersions were delaminated single layers or nanoplates with a thickness of several layers, depending on the amount of bicarbonate.     

Nanocomposites based on polyethylene and Mg-Al layered double hydroxide. I. Synthesis and characterization

Low density polyethylene (LDPE)/Mg-Al layered double hydroxide (LDH) nanocomposites have been synthesized with different compositions by melt-mixing technique using maleic anhydride grafted polyethylene as compatibilizer. LDH has been modified by sodium dodecylbenzene sulfonate using reconstruction method and characterized by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The nanocomposites are characterized by different techniques such as, transmission electron microscopy (TEM), XRD and rheology. The TEM analysis shows a complex nature of particle dispersion in the polymer matrix with wide distribution of particles sizes and shapes. The rheological analysis showed significant changes in linear viscoelastic responses of the composites, even at very low concentration (2 phr) of LDH materials, in comparison to the pure polymer in low frequency regime in dynamic frequency sweep experiments. These changes are related to the LDHs-polymer chains interactions resulting in network-like structure.     

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 mechanism of humic and fulvic acid onto Mg/Al layered double hydroxides

The adsorption of humic and fulvic acids onto nitrate, chloride and carbonate intercalated layered double hydroxides with Mg/Al ratios ranging from 85/15 to 60/40 was studied by adsorption isotherms at different ionic strengths and the characterization of the preferentially adsorbed humic substance size fractions. The adsorption of humic and fulvic acids onto LDHs occurred by ion exchange with both the intercalated and surface anions of the LDH and ligand exchange reactions with surface groups. The contribution of both mechanisms to the total HA and FA adsorption was estimated. Lower molecular weight humic and fulvic acids were preferentially adsorbed because these fractions can more easily enter the mesoporous LDHs and contain more carboxylic groups, which are known to be involved in ligand exchange reactions with e.g. surface Al-OH groups. Intercalation of the entire HA or FA molecules in-between the LDH sheets is unlikely to occur.     

Ni-based supported catalysts from layered double hydroxides: Tunable microstructure and controlled property for the synthesis of carbon nanotubes

The carbon nanotubes (CNTs) with straight and helical nanostructures have been synthesized by catalytic chemical vapor deposition of acetylene over a series of Ni-based supported catalysts, which were formed from Ni–Mg–Al layered double hydroxide precursors (LDHs) synthesized through homogenous decomposition of urea under hydrothermal conditions. The materials were characterized by power X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), temperature-programmed reduction experiments (TPR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results showed that the introduction of Mg into Ni-based supported catalysts could effectively improve the catalytic activities for the growth of CNTs, mainly proceeding from the inhibition effect of spinel phases formed in calcined LDHs on the agglomeration of metallic Ni particles. Furthermore, it is found interestingly that the addition of Mg also could induce the formation of helical structured CNTs with outer diameters of 20 nm and that the higher Mg content gave rise to the more helical nanotubes. The present work provides a simple and facile way to prepare metal-supported catalysts with a good dispersion of catalytically active metal particles for the growth of straight and helical CNTs.     

Synthesis of multi-walled carbon nanotubes over tungsten-doped cobalt-based catalyst derived from a layered double hydroxide precursor

Multi-walled carbon nanotubes (CNTs) were prepared over a series of W-doped Co-based catalysts derived from layered double hydroxide precursor by catalytic chemical vapor deposition (CCVD) of acetylene. The materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption–desorption experiments and Raman spectroscopy. The effect of the proportion of W in the Co-based catalysts on the carbon yield, diameter uniformity and quality of CNTs was investigated. The results demonstrated that with the increasing W/Co molar ratio from 0 to 1.0, both the mean number of walls and the average diameter of CNT produced over catalysts increased from about 8 to 28 nm and from about 12.1 to 23.7 nm, respectively. A small amount of tungsten added to the catalyst with the W/Co molar ratio of 0.3 could facilitate the dispersion of catalytically active Co species on the surface of support, and thus uniform and high-quality CNTs with a remarkably high yield of ca. 1600% were obtained.     

Deintercalation of carbonate ions from carbonate-type layered double hydroxides (LDHs) using acid-alcohol mixed solutions

Because of the high affinity of carbonate ions (CO₃²⁻) for LDHs (layered double hydroxides), their decarbonation—deintercalation of carbonate ions and conversion into LDHs containing other anions—has been considered difficult. So far, dilute acids have been used for decarbonation with additional salt to enhance the reaction. We found that the acid resistance of the LDHs is much higher in alcohols such as methanol and ethanol than in water, and complete decarbonation was attained, yielding LDHs containing the conjugated base anions of the acids used for the decarbonation. The carbonate ions were very rapidly deintercalated (0.5-1 h) from the CO₃²⁻LDHs at room temperature (15-25 °C) without any weight loss or any appreciable selective dissolution of the metal components of the LDH layer. In contrast to decarbonation in water, for which an additional supply of anions from a neutral salt is needed, when using an acid-alcohol mixed solution, decarbonation proceeded almost quantitatively, and any additional salts were not required. Use of other polar organic solvents such as acetone, THF (tetrahydrofuran), led to similar quantitative decarbonation, but acid resistance of LDHs was less in these solvents than in alcohols.     

Intercalation of layered double hydroxides by poly(oxyalkylene)-amidocarboxylates: tailoring layered basal spacing

Mg-Al layered double hydroxides (LDHs) were intercalated with various molecular-weight poly(oxypropylene)-bis-amidoacid salts (POP-acid), synthesized from polyoxyalkylene-diamines and maleic anhydride. The intercalation involves an ionic exchange reaction of LDHs at 120 °C and under N₂ atmosphere in an autoclave to afford a series of organoclays with a maximal basal spacing of 92 Å, revealed by X-ray diffraction and transmission electron microscopy analyses. The unusually wide interlayer spacing was ascribed to the self-alignment of the hydrophobic POP backbone in the layer confinement. In contrast, the intercalation of poly(oxyethylene)-bis-amidoacids (POE-acid) afforded a low basal spacing (7.8 Å) due to their oxyethylene-backbone interaction with the layered surface. The resultant POP- and POE-acid intercalated LDHs also exhibited different dispersing properties in toluene or water. Particularly, the organically-modified and space-enlarged hybrids with a proper amount of the embedded POPs possessed an amphiphilic property of lowering the toluene/water interfacial tension.     

Adsorption of 2,4-D on Mg/Al–NO3 layered double hydroxides with varying layer charge density

Layered double hydroxides (LDHs) have high surface area and high anion exchange capacity, so they have been proposed to be an effective scavenger for contaminants. In this study, the adsorption of 2,4-dichlorophenoxyacetate (2,4-D) on Mg/Al–NO₃ LDHs with varying layer charge density was investigated with particular attention on the effect of the orientation of the interlayer nitrate. Three Mg/Al LDHs were synthesized with Al³⁺/(Al³⁺ + Mg²⁺) molar ratios of 3.3 (LDH3), 2.6 (LDH4) and 2.1 (LDH5). The results of adsorption experiments showed that LDH5 exhibited an S-type isotherm with a low 2,4-D adsorption capacity due to the low accessibility of 2,4-D to the interlayer space. The accessibility was restricted by the small basal spacing of LDH5 as a result of the parallel orientation of the interlayer nitrate with respect to the hydroxide sheet. Thus, the 2,4-D adsorption occurred mainly on the external surface of the material. On the contrary, LDH3, which has the highest layer charge density among the samples, contains nitrate with an orientation perpendicular to the hydroxide sheet of LDH3. The interlayer nitrate was readily exchanged by 2,4-D. Thus, in addition to the adsorption on the external surface, the replacement of the interlayer nitrate by 2,4-D contributed to a higher adsorbed amount of 2,4-D; the 2,4-D adsorption of LDH3 exhibited an L-type isotherm. For LDH4 that contained interlayer nitrate with both parallel and perpendicular orientations, the adsorption characteristics were between those of LDH3 and LDH5. This work has demonstrated the dependence of 2,4-D adsorption characteristics on the nitrate orientation in LDHs, as a consequence of changing layer charge density.     

Electrochemical impedance spectroscopy of electrodes modified with thin films of MgMnCO3 layered double hydroxides

The electrochemical impedance spectra of MgMnCO₃ LDH films oxidized at different dc potentials were recorded. The results were fitted to a Randles type cell by replacing the Warburg impedance with a mass transfer resistance in parallel with a constant phase element. The films charge transfer resistances decreased dramatically at the onset of manganese oxidation. In thin films, R_ct decreased from 10⁴ Ω for an un-oxidized film to a minimum of 40 Ω in a film oxidized at 0.32 V, before increasing back to 10⁴ Ω in a film oxidized at 0.5 V. Iodometry measurements show these changes correspond to increases in the manganese average valence in the films from 3.09+ prior to oxidation, to 3.80+ at 0.32 V and 3.95+ at 0.5 V. In thicker films, however, a much higher dc potential, 1.0 V, was required to return R_ct to 10⁴ Ω. There was also less change in the manganese average valence in the thicker films. Oxidation at 1.0 V only increased the manganese valence to 3.33+. For the partially oxidized films, the Nyquist plots consisted of depressed semicircles at high frequency, followed by linear regions at lower frequency where the impedance was controlled by mass transport. The effective diffusion coefficient estimated from the low frequency impedance was 1 × 10⁻⁹ cm² s⁻¹, consistent with proton diffusion in solid electrodes. The impedance spectrum of a partially oxidized film reduced at −0.2 V was similar to that of the un-oxidized film.     

The influence of the cationic ratio on the incorporation of Ti in the brucite-like sheets of layered double hydroxides

The incorporation of the tetravalent Ti⁴⁺ cations into layered double hydroxide (LDH) type materials was studied as a function of the cationic ratio in the brucite-like sheets. Therefore, Zn–Ti-LDHs with different cationic ratio were prepared by the coprecipitation method at constant pH. The X-ray diffraction patterns revealed that only for the cationic ratio of 3, the characteristic layered structure was formed. The presence and the symmetry of the interlayer carbonate anions were investigated with FTIR–PAS spectroscopy. The UV–DR shows the octahedral environment of the Ti⁴⁺ cations in the brucite-like sheets. Following the same synthesis procedure, a reference sample containing Zn²⁺ and Al³⁺ (cationic ratio of 3) was synthesized. The Zn–Al- and Zn–Ti-LDHs textural features were investigated with N₂ adsorption at 77 K and scanning electron microscopy. Incorporation of Ti⁴⁺ cations in the brucite-like sheets of LDHs lead to a material with much smaller particles, therefore more interparticle porosity and higher volume of N₂ adsorbed at high relative pressures was observed.     

Preparation of Co–Al layered double hydroxides by the hydrothermal urea method for controlled particle size

In order to control particle size and the distribution, Co–Al layered double hydroxides were prepared from aqueous glycerol solutions of cobalt chloride and aluminum chloride by urea hydrolysis under hydrothermal conditions. Effects of the synthetic conditions including heating temperature and time, and glycerol/water ratio on the particle size and its distributions of Co–Al layered double hydroxide were discussed. Particle diameter was controlled from 1.0 (glycerol/water ratio = 10 g/40 mL) to 38.3 μm (glycerol/water ratio = 0 g/40 mL, heating at 50 °C for 150 days). Narrow particle diameter distribution as low as 20% coefficient of variation was achieved under optimized synthetic conditions (glycerol/water ratio = 10 g/40 mL, heating temperature < 80 °C).