Intercalation of IR absorber into layered double hydroxides: Preparation,thermal stability and selective IR absorption

N-phosphonomethyl aminodiacetic acid (PMIDA) was intercalated into the interlayer spacing of layered double hydroxides (LDH) by an anion-exchange method. The intercalated LDHs were characterized by various techniques such as powder X-ray diffraction (XRD), FT-IR spectroscopy, elemental analysis and simultaneous thermogravimetric and mass spectrometry (TG-MS) in details. The results show the formation of Mg₂Al-PMIDA LDH based on the expansion of d-spacing from 0.89 nm to 1.22 nm and the disappearance of the characteristic IR absorption band at 1384 cm^?1 for NO₃^? anions. The incorporation of Mg₂Al-PMIDA LDH into the low density polyethylene (LDPE) as an additive enhances the selectivity of IR absorption in the main wavelength region 9–11 μm for radiant heat loss at night. Mg₂Al-PMIDA LDH as a heat-retaining additive has practical application in agricultural plastic films.     

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.     

Adsorption of cholate anions on layered double hydroxides: effects of temperature,ionic strength and pH

Layered Double Hydroxides are a class of materials that can be described as positively charged planar layers consisting of divalent and trivalent cations in the center of edge-sharing octahedra. The positive charge in the LDH layers must be compensated by anion intercalation. These materials have applications that include adsorption and/or sorption of anionic species. Cholic acid is one of the main acids produced by the liver. It promotes transport of lipids through aqueous systems. This work reports on the adsorption of Cholic acid anions in MgAl–CO₃–LDH taking ionic strength, pH, and temperature effects into account. The adsorbent was characterized by different techniques. Cholate anion adsorption was performed at two different temperatures (298 and 323 K), two different ionic strength conditions (0.0 and 0.1 M of NaCl), and two different pH values (7.0 and 10.0). The results show that the sorption of Cholate anions in calcined LDH can remove a considerable amount of these anions from the medium. Cholate anion adsorption in the LDH with no calcining also occurs, but at a lower amount.     

Mechanochemical homodisperse of Bi2MoO6 on Zn-Al LDH matrix to form Z-scheme heterojunction with promoted visible-light photocatalytic performance

In this work, a Z-scheme Bi₂MoO₆/Zn-Al LDH heterojunction photocatalyst with excellent visible light responsiveness was fabricated via a two-step mechanochemical ball-milling process, where amorphous Bi₂MoO₆ particles were homodispersed upon the surface of lamellar LDH matrix. BPA was selected as the targeted organic contaminant to quantitatively evaluate the photocatalytic capacity of Bi₂MoO₆/Zn-Al LDH, in which the optimal 30 wt%Bi₂MoO₆/LDH exhibited a degradation rate of 96% within 300 min, over 9.25 and 18.5 times higher than that of individual pristine Bi₂MoO₆ and LDH, respectively. The crystal structure, microtopography, interfacial physicochemical interaction, optical and electrochemical properties of as-fabricated hybrids were systematically evaluated, and the DFT theoretical calculation was used to confirm the electronic structural characteristics in the Bi₂MoO₆/LDH heterojunction. A possible photocatalysis reaction mechanism was interpreted through ESR where the major manner of ?O^2– proved the Z-scheme electron migration within matched band levels.     

Calcium phenylphosphonate as a host for 4-aminobenzoic acid—Synthesis, characterization, and cation adsorption from ethanol solution

Crystalline lamellar calcium phenylphosphonate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1160–695 cm⁻¹ interval confirmed the presence of the phosphonate groups attached to the inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 1532 and 1751 pm for the original and the intercalated compounds, respectively. The thermogravimetric curves of both layered compounds showed the release of water molecules and the organic moiety in distinct stages, to yield a final Ca(PO₃)₂ residue. Solid-state ³¹P nuclear magnetic resonance spectra presented only one peak for the phenylphosphonate groups attached to the main inorganic polymeric structure near 12.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 1.68 and 0.50 mmol g⁻¹ for copper and cobalt, respectively, whose average stability constants followed Co > Cu; the number of ligands was determined as four for both cations.     

Arsenic removal from water using calcined Mg–Al layered double hydroxide

Arsenic (As) in drinking water and its related toxicology are serious concerns nowadays. Development of better techniques related to removal of As from drinking water is an urgent need. Layered double hydroxide (LDH) or hydrotalcite-like compound with the general formula [M_1−x ²⁺ M _x ³⁺ (OH)₂] ^x+ A ^x−·nH₂O can be considered as a good adsorbent for the removal of toxic As from water. Due to large surface area and high anion exchange capacity of LDH, the compound may be a good adsorbent for the removal of As from contaminated water. In this study, the removal of As in aqueous solution by adsorption method based on the calcination–rehydration reaction was investigated in batch experiment at (30 ± 1)°C. Results showed the removal of 99.99% As from a solution of 0.1 ppm of As; the adsorbent required at saturation was 0.10 g/20 ml As solution with 90 min of exposure at (30 ± 1)°C. Factors like pH, adsorbent dose and shaking time influenced the rate of As removal. Experiment showed that the adsorption process follows the Freundlich-type adsorption isotherm. The explanation of adsorption phenomenon is supported by X-ray diffraction pattern.     

Hybrid inorganic/organic composites of Mg-Al layered double hydroxides intercalated with citrate, malate, and tartrate prepared by co-precipitation

Inorganic/organic composite materials composed of Mg-Al layered double hydroxides (Mg-Al LDHs) intercalated with citrate (C₆H₅O₇³⁻), malate (C₄H₄O₅²⁻), or tartrate (C₄H₄O₆²⁻) anions were prepared by a co-precipitation technique and characterized by X-ray diffraction and compositional analyses. The molecular orientation of the organic component in the interlayer space was determined. At low intercalation levels, citrate ion was inclined at an angle of 26° relative to the brucite-like layers of Mg-Al LDH. At higher solution concentrations, both the Mg(C₆H₅O₇)⁻ complex and free C₆H₅O₇³⁻ were isotropically oriented in the interlayer space. For both malate·Mg-Al LDH and tartrate·Mg-Al LDH, the organic anions were inclined at 26° relative to the Mg-Al LDH layers regardless of anion concentration.     

Preparation and gases storage capacities of N-doped porous activated carbon materials derived from mesoporous polymer

In this report, the chemical activation of mesoporous carbon derived from mesoporous polymer is used to prepare N-doped carbon materials with high surface area and narrow pores size distribution. The porous carbons derived from the activation of mesoporous carbon generally possess high surface area up to 2400 m² g⁻¹ and narrow micropores/super-micropore size distribution and exhibit H₂ uptake capacity of up to 4.8 wt% at −196 °C and 20 bar and CO₂ sorption capacity of up to 3.7 mmol g⁻¹ at 25 °C and 1 bar. The measured isosteric heat of adsorption for H₂ sorption is 10 kJ mol⁻¹ and 58 kJ mol⁻¹ for CO₂ sorption, indicating a strong interaction between the carbon surface and adsorbed hydrogen and carbon dioxide respectively.     

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion

A highly porous metal‐organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn₂(COO)₄) and tetrameric (Zn₄(O)(CO₂)₆), is successfully assembled by the reaction of a tricarboxylate ligand with Zn^II ion. Subsequently, single‐crystal‐to‐single‐crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu^II and Co^II ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation‐exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu^II and Co^II exchanged samples exhibit comparable CO₂ adsorption capability to the pristine Zn^II‐based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO₂ with epoxides into related carbonates demonstrate that Zn^II‐based MOF affords the highest catalytic activity as compared with Cu^II and Co^II exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO₂ to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs.     

Application of natural and modified hectorite clays as adsorbents to removal of Cr(VI) from aqueous solution–Thermodynamic and equilibrium study

A hectorite (H) clay sample has been modified with 2-mercaptobenzimidazole (MBI) using homogeneous and heterogeneous routes. Both modification methodologies resulted in similar products, named H_HOM and H_HET, respectively. These materials were characterized by CO₂ gas adsorption, elemental analysis, nuclear magnetic nuclei of carbon-13 and silicon-29. The effect of two variables (contact time and metal concentration) has been studied using batch technique at room temperature and pH 2.0. After achieving the best conditions for Cr(VI) adsorption, isotherms of this adsorbate on using the chosen adsorbents were obtained, which were fitted to non-linear Sips isotherm model. The maximum number of moles adsorbed was determined to be 11.63, 12.85 and 14.01 mmol g⁻¹ for H, H_HOM and H_HET, respectively, reflecting the maximum adsorption order of H_HET > H_HOM > H. The energetic effects (Δ_intH°, Δ_intG° and Δ_intS°) caused by chromium ion adsorption were determined through calorimetric titrations.     

Quaternary chalcogenides of formula MII2MV2−2yM′2yS6 and Se6

Compositions of the title formula where M^II = Ba and Sr, M^V = Ta and Nb, M′ = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rh and Ir, and y = 0.5 and 0.33 were prepared by two methods: reaction of the elements in evacuated silica tubes and reaction of M^IICO₃, M^V₂O₅, and M′ oxides with H₂S. When M^II = Ba, all members have the BaNiO₃ structure. When M′ = Mn and Cu, structural distortions are present. Some compositions have Ta or S vacancies. When M^II = Sr, compositions were prepared only with Ta, for y = 0.5 and when M′ = Cr and Fe. Electrical measurements on selected compositions showed semiconductivity.     

Anion-exchange properties of nickel–aluminum layered double hydroxide prepared by liquid phase deposition

The optimum coordination structure of Ni–fluoro complexes for the preparation of Ni–Al LDH by LPD process and the diverse anion-exchange properties of as-deposited Ni–Al on α-alumina powder were quantitatively evaluated for the industrial application of new positive material for alkali secondary batteries. The [NiF_6−x−y(NH₃)_x(OH⁻)_y]ⁿ⁺ was more suitable than [NiF₆]⁴⁻ as the precursor of the deposition of Ni–Al LDH in the LPD reaction, and the improved LPD reaction achieved the synthesis of high purity and high crystallinity Ni–Al LDH. All anion-exchanged Ni–Al LDHs for OH⁻–, Cl⁻–, SO₄²⁻–, and CH₃COO⁻–forms kept the high crystallinity and showed the enlargement of interlayer distances. The tilting angle of the intercalated CH₃COO⁻ anions was about 15°. Anion-exchange capacity remained constant at a minimum of 0.8 meq g⁻¹ in pH >10, increased as pH decreased, and reached a maximum of 8 meq g⁻¹ at pH 2. Anion-exchange of OH⁻–form of Ni–Al LDH was accelerated by the neutralization of hydroxide ions in interlayers, in addition, the anion-exchange capacity and the crystallinity of Ni–Al LDH could be controlled by the amount of doped aluminum ions.     

Comparison of the fluoride,arsenate and nitrate anions water depollution potential of a calcined quintinite,a layered double hydroxide compound

The potential for removing anionic pollutants such as F⁻, HAsO₄²⁻, and NO₃⁻ from water by mixed oxides issued from the moderate thermal treatment of quintinite (Mg₄Al₂ LDH) has been studied. This compound shows good trapping properties for F⁻ and HAsO₄²⁻, and a low potential for NO₃⁻, due to the competition with OH⁻. The competition between these three anions and CO₃²⁻ has been envisaged and shows that CO₃²⁻ is able to easily replace F⁻ and NO₃⁻, making the mixed oxides issued from MgAl LDH an inappropriate trap for F⁻ and NO₃⁻. However, only small amounts of arsenic are released after the CO₃²⁻ introduction in water. Moreover, arsenates are able to replace carbonates even at lower concentrations. This means that HAsO₄²⁻ anions present a stronger affinity than CO₃²⁻ for the LDH structure. This makes mixed oxides issued from MgAl LDH very promising materials for the removal of arsenic in polluted waters.     

Preparation and proton conductivity of poly(vinylidene fluoride)/layered double hydroxide nanocomposite gel electrolytes

Layered double hydroxide (LDH) was synthesized in the presence of sodium dodecyl sulfate. X-ray diffraction (XRD) and infrared spectrum revealed that dodecyl sulfate (DS) anions were successfully intercalated into the interlayers of LDH. Poly(vinylidene fluoride)/LDH nanocomposite membranes were prepared by mixing the DS intercalated LDH with poly(vinylidene fluoride) (PVDF) in N,N’′-dimethylformamide solution followed by the solvent evaporation. The nanocomposite membranes were further swollen with a H₃PO₄ solution in ethylene carbonate-propylene carbonate to obtain the proton conducting nanocomposite gel electrolytes. XRD and transmission electron microscope results showed that LDH particles were well-dispersed in the polymer matrix and partially intercalated by polymer chains. The proton conductivity was highly enhanced in the nanocomposite gel electrolyte systems. In the case of the nanocomposite gel electrolyte containing 7.40 wt.% LDH, the proton conductivity increased by about 2.5 times compared to pure PVDF gel electrolyte.     

Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH3 and CO2

Mg-Al hydrotalcites intercalated with five different interlayer anions—CO₃²⁻, SO₄²⁻, Cl⁻, HPO₄²⁻ or terephthalate—were synthesized by either the coprecipitation or ion-exchange method. The structure of the as-synthesized samples and the presence of intended anions in the interlayer gallery of hydrotalcites were determined by X-ray diffraction and FTIR spectroscopy. On calcination at 600 °C the materials were transformed into mixed metal oxides. The kind of the counterbalancing anions present in the parent hydrotalcite influences strongly textural parameters of the obtained Mg-Al oxides. Both temperature-programmed desorption of NH₃ and CO₂, and test reaction of 2-methyl-3-butyn-2-ol (MBOH) conversion were used to determine the acidity and basicity of the samples. The hydrotalcite derived mixed Mg-Al oxides showed the presence of Brønsted and Lewis acid and base sites. However, the strong basic character of the solids caused that acetone and acetylene were observed as the major products of MBOH conversion.     

Synthesis and adsorption properties of nanosized Mg-Al layered double hydroxides with Cl−, NO 3 − or SO 4 2− as interlayer anion

Nanosized Mg-Al layered double hydroxides (LDHs) with Cl^?, NO ₃ ^? or SO ₄ ^2? as the interlayer anion have been synthesized by a modified coprecipitation method. The obtained LDHs were confirmed to be composed of a single phase and to be highly substituted by Al (Mg/Al ratio ～1.9). The abilities of the LDHs to adsorb several harmful anions (F^?, CrO ₄ ^2? , HAsO ₄ ^2? and HSeO^3?) in aqueous solution were studied. The LDHs exhibit high adsorption abilities. The amount of adsorption onto the LDHs differed between the starting interlayer anions, and decreased in the following order of the interlayer anions: NO ₃ ^? > Cl^? > SO ₄ ^2? . The NO₃-formed Mg-Al LDH reached a CrO ₄ ^2? adsorption equilibrium state within only 30 min, much faster than those in previous reports. Thus, the nanocrystallized, highly Al substituted phase of the NO₃-formed Mg-Al LDH is found to markedly enhance the anion adsorption ability.     

One-pot synthetic method to prepare highly N-doped nanoporous carbons for CO2 adsorption

A one-pot synthetic method was used for the preparation of nanoporous carbon containing nitrogen from polypyrrole (PPY) using NaOH as the activated agent. The activation process was carried out under set conditions (NaOH/PPY = 2 and NaOH/PPY = 4) at different temperatures in 600–900 °C for 2 h. The effect of the activation conditions on the pore structure, surface functional groups and CO₂ adsorption capacities of the prepared N-doped activated carbons was examined. The carbon was analyzed by X-ray photoelectron spectroscopy (XPS), N2/77 K full isotherms, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The CO₂ adsorption capacity of the N-doped activated carbon was measured at 298 K and 1 bar. By dissolving the activation agents, the N-doped activated carbon exhibited high specific surface areas (755–2169 m² g⁻¹) and high pore volumes (0.394–1.591 cm³ g⁻¹). In addition, the N-doped activated carbons contained a high N content at lower activation temperatures (7.05 wt.%). The N-doped activated carbons showed a very high CO₂ adsorption capacity of 177 mg g⁻¹ at 298 K and 1 bar. The CO₂ adsorption capacity was found to be dependent on the microporosity and N contents.     

MgO-templated porous carbons-based CO2 adsorbents produced by KOH activation

Nanoporous (styrene–divinylbenzene)-based ion exchange resin-based carbons (MPCs) were prepared by MgO-templating synthesis and activated by KOH. MPCs were prepared from a (styrene–divinylbenzene)-based ion exchange resin by the carbonization of a mixture with Mg gluconate at 900 °C. And then, the prepared MPCs were treated with KOH at KOH/MPCs ratios ranging from 0.5 to 4 at 800 °C. Low KOH/MPCs ratios (KOH/MPCs ratio = 1) tended to favor the formation of micropores, whereas higher KOH/MPCs (KOH/MPCs ratio = 4) led to the formation of mesopores. The treated MPCs with a KOH/MPCs ratio = 1 exhibited the best CO₂ adsorption value of 266 mg g⁻¹ at 1 bar. However, the treated MPCs with a KOH/MPCs ratio = 3 exhibited the best CO₂ adsorption value of 1385 mg g⁻¹ at 30 bar. This result indicated that the CO₂ adsorption capacity of nanoporous carbons attributed to the mesopore volume fraction at higher pressure.     

Sand flower layered double hydroxides synthesized by co-precipitation for CO2 capture: Morphology evolution mechanism,agitation effect and stability

Magnesium–aluminum layered double oxides (Mg–Al-LDO) derived from calcination of layered double hydroxides (LDH) is one of the most capable candidates for CO₂ capture. LDHs with sand flower and dense layered morphology are prepared by co-precipitation method at pH = 10 under different condition with and without stirring. The sand flower LDH prepared with stirring has better CO₂ adsorption performance. Additionally, the sand flower morphology under calcination can be preserved very well, while the morphology can only remain stable below 100 °C after hydrothermal treatment and reconstruction. The formation process of the sand flower LDH is investigated in detail and the related morphology evolution mechanism is proposed. This study can provide insight into the effect of mechanical interaction on chemical reaction and give a new way to control the morphology of layered materials.     

A physicochemical study of alkaline-earth metal carbonatouranylates

Optimal procedures were developed for preparing the compounds M ₂ ^II UO₂(CO₃)₃·nH₂O (M^II = Mg, Ca, Sr, Ba; n = 0–18). The structure and thermal decomposition of these compounds were studied by X-ray diffraction, IR spectroscopy, and differential scanning calorimetry. The previously unknown standard enthalpies of formation of the compounds at 298.15 K were determined by reaction calorimetry.