Thermal decomposition of hydrotalcites with variable cationic ratios

Thermal analysis complimented with evolved gas mass spectrometry has been applied to hydrotalcites containing carbonate prepared by coprecipitation and with varying divalent/trivalent cation ratios. The resulting materials were characterised by XRD, and TG/DTG to determine the stability of the hydrotalcites synthesised. Hydrotalcites of formula Mg₄(Fe,Al)₂(OH)₁₂(CO₃)·4H₂O, Mg₆(Fe,Al)₂(OH)₁₆(CO₃)·5H₂O, and Mg₈(Fe,Al)₂(OH)₂₀(CO₃)·8H₂O were formed by intercalation with the carbonate anion as a function of the divalent/trivalent cationic ratio. XRD showed slight variations in the d-spacing between the hydrotalcites. The thermal decomposition of carbonate hydrotalcites consists of two decomposition steps between 300 and 400°C, attributed to the simultaneous dehydroxylation and decarbonation of the hydrotalcite lattice. Water loss ascribed to dehydroxylation occurs in two decomposition steps, where the first step is due to the partial dehydroxylation of the lattice, while the second step is due to the loss of water interacting with the interlayer anions. Dehydroxylation results in the collapse of the hydrotalcite structure to that of its corresponding metal oxides and spinels, including MgO, MgAl₂O₄, and MgFeAlO₄.     

Thermal decomposition of hydrotalcitewith hexacyanoferrate(II) and hexacyanoferrate(III) anions in the interlayer

The thermal decompositions of hydrotalcites with hexacyanoferrate(II) and hexacyanoferrate(III) in the interlayer have been studied using thermogravimetry combined with mass spectrometry. X-ray diffraction shows the hydrotalcites have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. XRD was also used to determine the products of the thermal decomposition. For the hydrotalcite decomposition the products were MgO, Fe₂O₃ and a spinel MgAl₂O₄. Dehydration and dehydroxylation take place in three steps each and the loss of cyanide ions in two steps.     

Thermal decomposition of hydrotalcite with chromate, molybdate or sulphate in the interlayer

The thermal decomposition of hydrotalcites with chromate, molybdate and sulphate in the interlayer has been studied using thermogravimetric analysis coupled to a mass spectrometer measuring the gas evolution. X-ray diffraction shows the hydrotalcites have a d(0 0 3) spacing of 7.98 Å with very small differences in the d-spacing between the three hydrotalcites. XRD was also used to determine the products of the thermal decomposition. For the sulphate-hydrotalcite decomposition the products were MgO and a spinel MgAl₂O₄, for the chromate interlayered hydrotalcite MgO, Cr₂O₃ and spinel. For the molybdate interlayered hydrotalcite the products were MgO, spinel and MgMoO₄. EDX analyses enabled the formula of the hydrotalcites to be determined. Two processes are observed in the thermal decomposition namely dehydration and dehydroxylation and for the case of the sulphate interlayered hydrotalcite, a third process is the loss of sulphate. Both the dehydration and dehydroxylation take place in three steps each for each of the hydrotalcites.     

Mechanism for hydrotalcite decomposition: a controlled rate thermal analysis study

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. Hydrotalcites containing carbonate, vanadate and molybdate were prepared by coprecipitation. The resulting materials were characterised by XRD, simultaneous TG-DTG-DTA and controlled rate thermal analysis (CRTA) to determine the stability and thermal decomposition pathway of the synthesised hydrotalcites. For the carbonate intercalated hydrotalcite dehydration takes place in three steps two of which are quasi-isothermal and one non-isothermal. Dehydroxylation and decarbonation occur separately over the 235-330 and 330-370 degrees C temperature range. A second non-isothermal decarbonation step is observed in the 371-541 degrees C range. In comparison the mixed carbonate-vanadate and carbonate-molybdate hydrotalcites show two dehydration steps and the dehydroxylation and decarbonation occur simultaneously. The observation of three dehydration steps is used to support the model of water molecules in three structurally distinct environments in the hydrotalcite interlayer. CRTA technology provides a mechanism for the decomposition of hydrotalcites.     

Thermal decomposition of the layered double hydroxides of formula Cu6Al2(OH)16CO3 and Zn6Al2(OH)16CO3

Zn-Al hydrotalcites and Cu-Al hydrotalcites were synthesised by coprecipitation method and analysed by X-ray diffraction (XRD) and thermal analysis coupled with mass spectroscopy. These methods provide a measure of the thermal stability of the hydrotalcite. The XRD patterns demonstrate similar patterns to that of the reference patterns but present impurities attributed to Zn(OH)₂ and Cu(OH)₂. The analysis shows that the d003 peak for the Zn-Al hydrotalcite gives a spacing in the interlayer of 7.59 ? and the estimation of the particle size by using the Debye-Scherrer equation and the width of the d003 peak is 590 ?. In the case of the Cu-Al hydrotalcite, the d003 spacing is 7.57 ? and the size of the diffracting particles was determined to be 225 ?. The thermal decomposition steps can be broken down into 4 sections for both of these hydrotalcites. The first step decomposition below 100°C is caused by the dehydration of some water absorbed. The second stage shows two major steps attributed to the dehydroxylation of the hydrotalcite. In the next stage, the gas CO₂ is liberated over a temperature range of 150°C. The last reactions occur over 400°C and involved CO₂ evolution in the decomposition of the compounds produced during the dehydroxylation of the hydrotalcite.     

Mg-Al-CO_3与Zn-Al-CO_3水滑石热稳定性差异的研究

层状双金属氢氧化物（ Layered double hydroxides,简称 LDHs）是一类近年来发展迅速的阴离子型粘土,又称水滑石,其组成通式为： [M? 1-xM? x(OH)2]x＋ Ax/nn-mH2O,其中 M?是二价金属离子, M?是三价金属离子, An－是阴离子。这种材料是由相互平行的层板组成,层板带有永久正电荷;层间具有可交换的阴离子以维持电荷平衡。通过离子交换可在层间嵌入不同的基团,制备许多功能材料,被广泛用作催化剂、吸附剂及油田化学品等,已引起人们的关 注 [1～ 4]。有关 Mg-Al-CO3与 Zn-Al-CO3水滑石的合成及性能研究国内外已有大量报道 [1…     

Thermal decomposition of Bayer precipitates formed at varying temperatures

Bayer hydrotalcites prepared using the seawater neutralisation (SWN) process of Bayer liquors are characterised using X-ray diffraction and thermal analysis techniques. The Bayer hydrotalcites are synthesised at four different temperatures (0, 25, 55, and 75 °C) to determine the effect of synthesis temperature on the thermal stability of the Bayer hydrotalcite structures and the mineralogical phases that form. The interlayer distance increased with increasing synthesis temperature, up to 55 °C, and then decreased by 0.14 Å for Bayer hydrotalcites prepared at 75 °C. The three mineralogical phases identified in this investigation are; (1) Bayer hydrotalcite, (2), calcium carbonate species, and (3) hydromagnesite. The DTG curve can be separated into four decomposition steps; (1) the removal of adsorbed water and free interlayer water in hydrotalcite (30–230 °C), (2) the dehydroxylation of hydrotalcite and the decarbonation of hydrotalcite (250–400 °C), (3) the decarbonation of hydromagnesite (400–550 °C), and (4) the decarbonation of aragonite (550–650 °C).     

Using thermally activated hydrotalcite for the uptake of phosphate from aqueous media

Hydrotalcites of formula Mg₆A₁₂(OH)₁₆(PO₄)·4H₂O formed by intercalation with the phosphate anion as a function of pH show variation in the d-spacing attributed to the size of the hydrated anion in the interlayer. The value changes from 11.91 Å for pH 9.3, to 7.88 Å at pH 12.5. No crystalline hydrotalcites with phosphate in the interlayer were formed at pH 9.3. Thermal decomposition identifies three steps namely dehydration, dehydroxylation and some loss of carbonate during the thermal treatment. The addition of a thermally activated ZnAl-HT to a phosphate solution resulted in the uptake of the phosphate and the reformation of the hydrotalcite. The technology has the potential for water purification through anion removal.     

Thermal analysis of hydrotalcite synthesised from aluminate solutions

The aluminate hydrotalcites are proposed to have either of the following formulas: Mg₄Al₂(OH)₁₂(CO₃ ²⁻)·xH₂O or Mg₄Al₂(OH)₁₂(CO₃ ²⁻, SO₄ ²⁻)·xH₂O. A pure hydrotalcite phase forms when magnesium chloride and aluminate solutions are mixed at a 1:1 volumetric ratio at pH 14. The synthesis of the aluminate hydrotalcites using seawater results in the formation of an impurity phase bayerite. Two decomposition steps have been identified for the aluminate hydrotalcites: (1) removal of interlayer water (230 °C) and (2) simultaneous dehydroxylation and decarbonation (330 °C). The dehydration of bayerite was observed at 250 °C. X-ray diffraction techniques determined that the synthesis of aluminate hydrotalcite with seawater and a volumetric ratio of 4.5 results in very disordered structures. This was shown by a reduction in the mass loss associated with the removal of interlayer water due to the reduction of interlayer sites caused by the misalignment of the metal-hydroxyl layers.     

Nitrate absorption through hydrotalcite reformation

Thermally activated hydrotalcite based upon a Zn/Al hydrotalcite with carbonate in the interlayer has been used to remove nitrate anions from an aqueous solution resulting in the reformation of a hydrotalcite with a mixture of nitrate and carbonate in the interlayer. X-ray diffraction of the reformed hydrotalcites with a d(003) spacing of 7.60 A shows that the nitrate anion is removed within a 30 min period. Raman spectroscopy shows that two types of nitrate anions exist in the reformed hydrotalcite (a) nitrate bonded to the 'brucite-like' hydrotalcite surface and (b) aquated nitrate anion in the interlayer. Kinetically the nitrate is replaced by the carbonate anion over a 21 h period. Two types of carbonate anions are observed. This research shows that the reformation of a thermally activated hydrotalcite can be used to remove anions such as nitrate from aqueous systems.     

Thermal decomposition of hydrotalcite with hexacyanoferrate(II) and hexacyanoferrate(III) anions in the interlayer

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. The thermal decomposition of hydrotalcites with hexacyanoferrate(II) and hexacyanoferrate(III) in the interlayer has been studied using controlled rate thermal analysis technology. X-ray diffraction shows the hydrotalcites have a d(003) spacing of 10.9 and 11.1 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. Calculations show dehydration with a total loss of 7 moles of water proving the formula of hexacyanoferrate(II) intercalated hydrotalcite is Mg₆Al₂(OH)₁₆[Fe(CN)₆]_0.5·7H₂O and 9.0 moles for the hexacyanoferrate(III) intercalated hydrotalcite with the formula of Mg₆Al₂(OH)₁₆[Fe(CN)₆]_0.66·9H₂O. CRTA technology indicates the partial collapse of the dehydrated mineral. Dehydroxylation combined with CN unit loss occurs in two isothermal stages at 377 and 390°C for the hexacyanoferrate(III) and in a single isothermal process at 374°C for the hexacyanoferrate(III) hydrotalcite.     

超分子结构甲基橙插层水滑石的组装及其光热稳定性研究

甲基橙是一种酸性染料,但因为它的光和热稳定性较差,使其应用范围和使用效果受到了一定限制.以Mg_0.67Al_0.33(OH)₂(CO₃)_0.165·0.58H₂OLDHs为前体,采用离子交换法,将甲基橙插入到LDHs层间,借助XRD,FTIR,UV-Vis和TG-DTA等手段对样品进行表征.结果表明,甲基橙阴离子可以完全取代前体层间的CO₃^2-离子,组装得到晶体结构良好的甲基橙插层LDHs.对其结构进行研究发现,LDHs主体层板与客体甲基橙阴离子之间存在静电吸引、氢键和其它弱化学键相互作用,具有超分子结构特征.该超分子结构材料不仅保持了甲基橙本身的颜色,而且与甲基橙相比,其耐光性和耐热性均有大幅度的提高.     

Intercalation of hydrotalcites with hexacyanoferrate(II) and (III)—a thermoRaman spectroscopic study

Raman spectroscopy using a hot stage indicates that the intercalation of hexacyanoferrate(II) and (III) in the interlayer space of a Mg, Al hydrotalcites leads to layered solids where the intercalated species is both hexacyanoferrate(II) and (III). Raman spectroscopy shows that depending on the oxidation state of the initial hexacyanoferrate partial oxidation and reduction takes place upon intercalation. For the hexacyanoferrate(III) some partial reduction occurs during synthesis. The symmetry of the hexacyanoferrate decreases from O_h existing for the free anions to D_3d in the hexacyanoferrate interlayered hydrotalcite complexes. Hot stage Raman spectroscopy reveals the oxidation of the hexacyanoferrate(II) to hexacyanoferrate(III) in the hydrotalcite interlayer with the removal of the cyanide anions above 250 °C. Thermal treatment causes the loss of CN ions through the observation of a band at 2080 cm⁻¹. The hexacyanoferrate (III) interlayered Mg, Al hydrotalcites decomposes above 150 °C.     

超分子结构水杨酸根插层水滑石的组装及结构与性能研究

以锌铝水滑石ZnAl-CO3 LDHs为前体（主体），以乙二醇为分散介质，用离子 交换法组装了水杨酸根（客体）插层水滑石ZnAl-[o-HO(C6H4)COO]LDHs，并用XRD ，FT-IR，TG-DTA等手段对样品进行了表征。结果表明，能过控制离子交换条件， 水杨酸根阴离子可取代锌铝水滑石前体层间的CO3^2-离子，组装得到晶体结构良好 的水杨酸根插层水滑石。通过研究发现，主体水滑石层板与客体以静电力和氢键相 互作用，得到的超分子结构材料紫外阻隔作用增强并具有较好的稳定性，从而成为 一种集屏蔽和吸收双重功能的新型无机-有机得合紫外阻隔材料。     

Synthesis and thermal analysis of indium-based hydrotalcites of formula Mg<Subscript>6</Subscript>In<Subscript>2</Subscript>(CO<Subscript>3</Subscript>)(OH)<Subscript>16</Subscript>·4H<Subscript>2</Subscript>O

Insight into the unique structure of layered double hydroxides (LDHs) has been obtained using a combination of X-ray diffraction and thermal analysis. Indium containing hydrotalcites of formula Mg₄In₂(CO₃)(OH)₁₂·4H₂O (2:1 In-LDH) through to Mg₈In₂(CO₃)(OH)₁₈·4H₂O (4:1 In-LDH) with variation in the Mg:In ratio have been successfully synthesised. The d(003) spacing varied from 7.83 Å for the 2:1 LDH to 8.15 Å for the 3:1 indium containing LDH. Distinct mass loss steps attributed to dehydration, dehydroxylation and decarbonation are observed for the indium containing hydrotalcite. Dehydration occurs over the temperature range ambient to 205 °C. Dehydroxylation takes place in a series of steps over the 238–277 °C temperature range. Decarbonation occurs between 763 and 795 °C. The dehydroxylation and decarbonation steps depend upon the Mg:In ratio. The formation of indium containing hydrotalcites and their thermal activation provides a method for the synthesis of indium oxide-based catalysts.     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

The thermal decomposition of Mg-Al hydrotalcites: effects of interlayer anions and characteristics of the final structure

The thermal decomposition of hydrotalcites (HTs) with different interlayer anions in the 298-523 K region has been investigated by using transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and IR, 27Al MAS-NMR and X-ray absorption near-edge structure (XANES) spectroscopy. The thermal stability of the HT with interlayer oxalate was remarkably higher than that of HTs with interlayer carbonate; the onset temperatures for decomposition were 523 K and 473 K, respectively. It is proposed that the basicity of the interlayer anion is the key factor in the onset of dehydroxylation of the brucite-like layers: the lower the basicity, the more thermally stable the HT compound. After heat treatment at 723 K, small Mg(Al)O domains (approximately 5 nm) within the HT crystallites cause broadening of the XRD reflections. The electron diffraction pattern consists of spots and rings, due to nonrandomly oriented crystalline material. Formation of disordered bonds, caused by nonideal packing between the decomposing adjacent cation layers in the (111) direction, could explain the expanded d value in the resulting MgO-like phase observed with XRD and electron diffraction. The orientation of the Mg(Al)O domains in the heat-treated material may be crucial for the so-called "memory effect" of HTs.     

Application of simplified version of advanced isoconversional procedure in non-isothermal kinetic study

Thermogravimetric analysis (TG) and powder X-ray diffraction (PXRD) were used to study some selected Mg/Al and Zn/Al layered double hydroxides (LDHs) prepared by co-precipitation. A Mg/Al hydrotalcite was investigated before and after reformation in fluoride and nitrate solutions. Little change in the TG or PXRD patterns was observed. It was proposed that successful intercalation of nitrate anions has occurred. However, the absence of any change in the d ₍₀₀₃₎ interlayer spacing suggests that fluoride anions were not intercalated between the LDH layers. Any fluoride anions that were removed from solution are most likely adsorbed onto the outer surfaces of the hydrotalcite. As fluoride removal was not quantified it is not possible to confirm that this has happened without further experimentation. Carbonate is probably intercalated into the interlayer of these hydrotalcites, as well as fluoride or nitrate. The carbonate most likely originates from either incomplete decarbonation during thermal activation or adsorption from the atmosphere or dissolved in the deionised water. Small and large scale co-precipitation syntheses of a Zn/Al LDH were also investigated to determine if there was any change in the product. While the small scale experiment produced a good quality LDH of reasonable purity; the large scale synthesis resulted in several additional phases. Imprecise measurement and difficulty in handling the large quantities of reagents appeared to be sufficient to alter the reaction conditions causing a mixture of phases to be formed.     

Reactivity of Mg–Al hydrotalcites in solid and delaminated forms in ammonium carbonate solutions

Treatment of Mg–Al hydrotalcites (LDHs, layered double hydroxides) in aqueous (NH₄)₂CO₃ at 298 K leads to composites of dawsonite, hydrotalcite, and magnesium ammonium carbonate. The mechanism and kinetics of this transformation, ultimately determining the relative amounts of these components in the composite, depend on the treatment time (from 1 h to 9 days), the Mg/Al ratio in the hydrotalcite (2-4), and on the starting layered double hydroxide (solid or delaminated form). The materials at various stages of the treatment were characterized by inductive coupled plasma-optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, infrared spectroscopy, thermogravimetry, and nitrogen adsorption at 77 K. The progressive transformation of hydrotalcite towards crystalline dawsonite and magnesium ammonium carbonate phases follows a dissolution–precipitation mechanism. A gradual decrease of the Mg/Al ratio in the resulting solids was observed in time due to magnesium leaching in the reacting medium. Dawsonite–hydrotalcite composite formation is favored at high aluminum contents in the starting hydrotalcite, while the formation of magnesium ammonium carbonate is favored at high Mg/Al ratios. The synthetic strategy comprising hydrotalcite delamination in formamide prior to aqueous (NH₄)₂CO₃ treatment is more reactive towards composite formation than starting from the bulk solid hydrotalcite.