Crystalline calcium phenylphosphonate—thermodynamic data on n-alkylmonoamine intercalations

Lamellar crystalline calcium phenylphosphonate, as anhydrous Ca(HO₃PC₆H₅)₂ and hydrated Ca(HO₃PC₆H₅)₂·2H₂O compounds, were used as hosts for intercalation of polar n-alkylmonoamine molecules of the general formula CH₃(CH₂)_nNH₂ (n=0–4, 7) in water or 1,2-dichloroethane. An increase in the interlayer distance was observed. The exothermic enthalpic values for intercalation increased with the number of carbon atoms and with increasing concentration of the amines. The intercalation followed by a titration procedure in the solid/liquid interface with Ca(HO₃PC₆H₅)₂·2H₂O and Ca(HO₃PC₆H₅)₂ gave the enthalpy/number of carbons correlations: Δ_intH=−(1.74±0.43)–(1.30±0.13)n_c and Δ_intH=−(4.15±0.15)–(1.07±0.03)n_c, for water and 1,2-dichloroethane, respectively. A similar correlation Δ_intH=−(4.27±0.80)–(1.85±0.21)n_c was obtained in water by using the ampoule breaking procedure for Ca(HO₃PC₆H₅)₂·2H₂O. The increase in exothermic enthalpic values with the increase in n-aliphatic carbon atoms is more pronounced for the anhydrous compound and also when using the ampoule breaking procedure. The Gibbs free energies are negative. Positive entropic values favor intercalation in these systems.     

Thermochemical data for n-alkylmonoamine intercalation into crystalline lamellar zirconium phenylphosphonate

Layered crystalline zirconium phenylphosphonate, Zr(O₃PC₆H₅)₂, changed its interlamellar distance of 1481 pm after intercalation of n-alkylmonoamines, CH₃---(CH₂)_n---NH₂ (n=0–6). The infrared spectra of the precursor host and the corresponding intercalated compounds presented vibrations associated with PO₃ groups in the 1163–1039 cm⁻¹ range and additional bands related to C---H stretching bands in the 2950–2850 cm⁻¹ interval were observed after amine insertion. The thermogravimetric curves showed a mass loss assigned to the phenyl group; however, the amine intercalated fraction was not quantitatively determined. A peak in the ³¹P NMR spectrum centered at −6 ppm for the host was observed. The surface area was 42.0±0.2 m² g⁻¹ and the scanning electron micrograph gave images consistent with lamellar structural features. The layered compound was calorimetrically titrated with amine in ethanol, requiring three independent operations: (i) titration of matrix with amine, (ii) matrix salvation, and (iii) dilution of the amine solution. From those thermal effects the variation in enthalpy was calculated as: −41±1.00,−33.28±0.50,−34.40±0.80,−10.40±0.40,−12.40±0.42,−16.10±0.08 and −7.0±0.04 kJ mol⁻¹, for n=0–6, respectively. The exothermic enthalpic values reflected a favorable energetic process of amine–host intercalation in ethanol. The negative Gibbs free energy results supported the spontaneity of all these intercalation reactions. The positive favorable entropic values, as carbon chain size increased, are in agreement with the free solvent molecules in the medium, as the amines are progressively bonded to the crystalline lamellar inorganic matrix at the solid/liquid interface.     

Electrical conductivity of MOXO4 (M=V, Nb; X=P, As) compounds intercalated with H2O and H3XO4

Layered compounds with the general formula MOXO₄·yH₂O (M=V, Nb; X=P, As) were prepared. The content of water y was controlled by keeping the samples in an atmosphere with various relative humidities (RH). Depending on RH, the formation of several hydrates of niobyl phosphate and arsenate was observed and their basal spacings (d) were determined, namely, NbOPO₄·H₂O, , at 11% RH and lower, NbOPO₄·2H₂O, , at 22-33% RH, NbOPO₄·3H₂O, , at 43-84% RH, and NbOPO₄·5H₂O, , at 92% RH and above; NbOAsO₄·H₂O, , at 0-16% RH and NbOAsO₄·3H₂O, at 33% RH and above. As follows from ac and dc conductivity data, NbOXO₄·yH₂O compounds are practically pure protonic conductors, whereas VOXO₄·yH₂O compounds are mixed protonic-electronic conductors and the protonic component increases with y. Two intercalates of MOXO₄·yH₂O with inorganic acids were prepared. A new intercalate of H₃AsO₄ into VOAsO₄·yH₂O with the formula VOAsO₄·0.5H₃AsO₄·yH₂O (y=0.5-0.8) has the cell parameters a=6.37 and at 0-22% RH. Above 22% RH, the intercalate decomposes and the parent VOAsO₄·yH₂O with H₃AsO₄ adsorbed on the surface is formed. Another intercalate with formula NbOPO₄·H₃PO₄·yH₂O (y=2-4 at 0-75% RH) has the cell parameters a=6.43 and at RH from 0% to 5% and a=6.48 and at RH from 33% to 75%. Both intercalates are more conductive than their MOXO₄·yH₂O hosts and their conductivity increases with increasing RH of the surrounding atmosphere. Like NbOPO₄·yH₂O, also NbOPO₄·H₃PO₄·yH₂O can be considered pure proton conductor and its conductivity at 20 °C reaches 5×10⁻³ S cm⁻¹ for y=4.     

Calorimetric study of the adducts CdBr2·nL (n = 1 and 2; L = ethyleneurea and propyleneurea)

A calorimetric study was performed for adducts of general formula CdBr₂·nL (n=1 and 2; L=ethyleneurea (eu) and propyleneurea (pu)). The standard molar reaction enthalpy in condensed phase: CdBr₂(c)+nL(c)=CdBr₂·nL(c); Δ_rH_m^θ, were obtained by reaction–solution calorimetry, to give the following values for mono- and bis-adducts: −19.54 and −34.59; −7.77 and −19.05 kJ mol⁻¹ for eu and pu adducts, respectively. Decomposition (Δ_DH_m^θ) and lattice (Δ_MH_m^θ) enthalpies, as well as the mean cadmium---oxygen bond dissociation enthalpy, DCd---O, were calculated for all adducts.     

Effects of intercalated hydrotalcite on drug release behavior for poly(acrylic acid-co-N-isopropyl acrylamide)/intercalated hydrotalcite hydrogels

The influence of positively charged intercalated hydrotalcite (IHT) in the anionic poly(acrylic acid-co-N-isopropyl acrylamide), poly(AA-co-NIPAAm)/hydrotalcite nanocomposite hydrogels on the drug release behavior for the drugs with different charges was investigated in this study. Results show that the loading amount and release ratio of indomethacin are affected by the swelling ratio in saline solution and related to the affinity in the alcohol solution, respectively. The loading amount and release ratio of caffeine are affected by the swelling ratio. The loading amount of crystal violet (CV) increased with an increase of the content of intercalating agent in IHT of the gel but the fractional release of CV in the gels decreases with increase in intercalating agent content. The result of release and loading for phenol red in the hydrogels is contrary to CV.     

Preparation and characterization of intercalated misfit-layer compounds and natural superlattices

This paper presents the preparation and characterization of the new types of misfit-layer compounds and natural superlattices consisting of Ce_xNb_1−x−y□_yS (Q′) and Ni_zNbS₂ (H) layers, where □ is an atomic deficit at a metal site. A Q′ layer is larger by about 1 Å in thickness than a CeS (Q) layer in (CeS)_1.16NbS₂. They are prepared by chemical vapor transport reaction in a closed silica tube under quasi-equilibrium conditions. The 1Q′/3H type of compound are grown as a single crystal while the 1Q′/4H type of compound is grown as composite crystals with the 1Q′/3H and 1Q/2H compounds. Natural superlattices which have a long period in a direction perpendicular to layers are found. Their chemical formulae are given by (Ce_xNb_1−x−y□_yS)_m(Ni_z)_n−m(NbS₂)_n, where m and n are integers. It is found from an X-ray-photoelectron spectroscopy (XPS) study that Nb affects the valence and the bonding of Ce in the Q′ layers. It is in a higher oxidation state than Nb in NbS₂ layers. A scanning tunneling microscope (STM) study shows that some of the superlattices form a hexagonal supercell in the (a,b)-plane and behave as a narrow-gap semiconductor so that no STM images are obtained at bias voltage less than 0.3 eV.     

Synthesis and characterization of polymer/clay nanocomposites by intercalated chain transfer agent

In situ synthesis of poly(methyl methacrylate) (PMMA) and polystyrene (PS) nanocomposites by free radical polymerization using intercalated chain transfer agent (I-CTA) in the layers of montmorillonite (MMT) clay is reported. MMT clay was ion-exchanged with diethyl octyl ammonium ethylmercaptan bromide, which acts both as suitable intercalant and as chain transfer agent. These modified clays were then dispersed in methyl methacrylate (MMA) or styrene (St) monomers in different loading degrees to carry out the in situ free radical polymerization. The intercalation ability of the chain transfer agent and exfoliated nanocomposite structure were evidenced by both X-ray diffraction spectroscopy (XRD) and transmission electron microscopy (TEM). Thermal properties and morphologies of the resultant nanocomposites were also studied.     

Synthesis, structural characterization and ferrimagnetic property of MnPS3 intercalated with nickel(II) cyclopolyamine complex cations

Two new intercalation compounds were prepared by the reactions of Ni(II) cyclopolyamine complex cations with a preintercalate Mn_1−xPS₃K_2x(H₂O)_y, respectively, through “ion exchange” process. Their structures were characterized by elemental analysis, X-ray powder diffraction and infrared spectroscopy. The lattice spacing increased 0.567 and 1.093 nm with respect to the pristine MnPS₃. Ferrimagnetism of the intercalates was confirmed by SQUID experiment with T_c at 40 and 33 K, respectively.     

Visible light photoelectrochemical activity of K4Nb6O17 intercalated with photoactive complexes by electrostatic self-assembly deposition

Electrostatic self-assembly deposition (ESD) results in the intercalation of Ru(bpy)₃²⁺ or methylene blue (MB) into the niobate layered oxide right after the cations come into contact with [Nb₆O₁₇]⁴⁻ nanosheets. Monolayers can be obtained by the exfoliation of proton exchanged K₄Nb₆O₁₇ (KNbO) in an aqueous tetrabutylammonium (TBA) solution as revealed by the atomic force microscopy micrographs. UV-vis spectra show that intercalated films are able to absorb in the visible light range. Heat-treatment of Ru(bpy)₃²⁺ resulted in the red-shift in the absorption spectra, which was assigned to the enhancement in the interaction between the complex molecules and [Nb₆O₁₇]⁴⁻ host layer. Intercalated niobate layered oxides are able to produce photocurrent as a result of the electron transfer from the excited guest molecule to the host layer under visible light illumination. Ru(bpy)₃²⁺ intercalated niobate layered oxide shows photocatalytic activity under visible light illumination to produce H₂ from water-methanol solution.     

Synthesis and characterization of layered double hydroxides (LDH) intercalated with non-steroidal anti-inflammatory drugs (NSAID)

Layered double hydroxides (LDHs) with the hydrotalcite type structure and a Mg:Al ratio of two have been prepared, with salicylate or naproxen in the interlayer. Two synthetic routes have been used: reconstruction from a mildly calcined hydrotalcite-CO₃ precursor, and a coprecipitation method with chlorides of the metals. The solids have been characterized using several physicochemical techniques, i.e., powder X-ray diffraction, FTIR and ¹³C CP/MAS NMR spectroscopies and thermal analysis (thermogravimetric and differential thermal analyses). The gallery height determined is in all cases larger than the size of the drug, 11.5 Å for salicylate and 15.8 and 16.6 Å for naproxen, depending on the specific synthesis route followed. Experimental data suggest the anion molecules form a tilted bilayer, with the carboxylate groups pointing towards the brucite-like layers. The solids are stable up to 230 °C and their evolution from 350 °C upwards is very similar to that observed for a carbonate-containing hydrotalcite, forming mostly amorphous solids with a large specific surface area.     

Enthalpies of mixing of di- n -butyl ether with isomeric butanols: Enthalpies of hydrogen-bonded complexes

The enthalpies of mixing of four isomeric butanols with di-n-butyl ether were determined at 30°C by a Calvet type microcalorimeter. All the four systems showed endothermic behaviour. The enthalpies of complex formation were calculated by the thermochemical cycle. The strength of H-bonding decreases in the order l-butanol, l-methyl-1-propanol, 2-methyl-2-propanol, 2-butanol. The results are explained on the basis of a steric effect on interaction. NCL Communication No. 4430.     

Novel hybrids of Cu2+ ternary complexes of salicylidene-amino acid Schiff base with phenanthroline（or bipyridine） intercalated in Mg/Al-NO3-layered double hydroxide

Four Cu²⁺ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline（Phen） or 2,2’- bipyridine（Bipy） were successfully intercalated in interlayer galleries of Mg/Al-NO₃-layered double hydroxide（LDH） by the swelling-restored method.The hybrids were characterized by elemental analysis,X-ray diffraction,FT-IR spectra,UV-vis DRS,TG-DTA and SEM observation.Good protection of the complexes by LDH in neutral and weak acidic solutions was revealed by UV spectra,cyclic voltammograms and luminescence spectra.     

Controlled release formulation of zinc hydroxide nitrate intercalated with sodium dodecylsulphate and bispyribac anions: A novel herbicide nanocomposite for paddy cultivation

Bispyribac (BP) anions have been successfully intercalated in the interlayer region of zinc hydroxide nitrate (ZHN) in the presence of sodium dodecylsulphate (SDS) surfactant. The physicochemical properties of the intercalation compound ZHN–SDS–BP have been characterised herein with different instrumental techniques. The intercalation of BP and SDS is clearly reflected in the PXRD analysis, based on the appearance of symmetrical, sharp and intense intercalation peaks at lower 2θ with a basal spacing of 28.2–28.6 Å. The thermal studies show that the ZHN–SDS–BP nanocomposite has better thermal stability than the pristine BP. The intercalation of BP leads to significant changes in the surface area, porosity, and morphology. Nitrogen adsorption–desorption isotherms reveal that both ZHN–SDS and ZHN–SDS–BP are of Type IV. The release and kinetic studies were also carried out on the ZHN–SDS–BP, in aqueous solution of Na₃PO₄, Na₂SO₄ and NaCl as the release media. The releases of BP in both aqueous solutions of Na₃PO₄ and NaCl were found to follow the pseudo second order kinetic model, whereas the releases of BP in the aqueous solution of Na₂SO₄ obey the parabolic diffusion kinetic model. This study shows that ZHN has the potential to be used as a host material in slowing the release of BP herbicides in the paddy cultivation sector.     

Structure and thermal decomposition of sulfated β-cyclodextrin intercalated in a layered double hydroxide

The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation.     

Intercalation compounds of γ-zirconium and γ-titanium phosphates: Kinetic study of dehydration and decomposition processes for 2,9-dimethyl-1,10-phenanthroline and its intercalated copper complex materials

γ-Zirconium and γ-titanium phosphates containing organic diamine 2,9-dimethyl-1,10-phenanthroline and its in situ formed copper complex were studied by thermal analysis and physical measurements. All the derived materials show a layered structure and their interlayer distance is increased with respect to that of their precursors. Melting, simultaneous vaporization and oxidation, as well as a decomposition process take place in the pure diamine. After dehydration, all the intercalation materials undergo a two-step decomposition. The presence of the formed copper complex between the layers of the two ion-exchangers considered shows a destabilizing effect with respect to the intercalated diamine materials, resulting in a decrease of the decomposition temperatures and the activation energy of decomposition. The application of the isoconversional Ozawa-Flynn-Wall method substantially confirms the obtained results.     

不同锌铝比水滑石的合成及其吸附脱除水中邻苯二甲酸性能

采用共沉淀法合成一系列具有不同锌铝比的水滑石,并利用X射线衍射(XRD)、扫描电镜(SEM)、热重(TG)、氮气吸脱附及电感耦合等离子体质谱(ICP-MS)等表征手段对其结构与组成进行了测试。将上述水滑石材料用于吸附脱除水中邻苯二甲酸污染物,考察了不同锌铝比水滑石吸附邻苯二甲酸性能的差异。结果表明,在较低锌铝比时,随着水滑石锌铝比的增加,其对邻苯二甲酸的吸附量逐渐增大;当锌铝比较大时(6),随着锌铝比的增加,水滑石的吸附量基本保持不变。进一步选取锌铝比为6的水滑石,分别对其吸附邻苯二甲酸的动力学和热力学进行了研究,发现其吸附等温线和吸附动力学数据分别符合Freundlich等温吸附模型和准二级动力学模型,且循环吸附性能较好。     

Hydrothermal synthesis and intercalation behavior of a layered titanium phosphate Ti2(H2PO4)(HPO4)(PO4)2 · 0.5C6N2H16, with an extended γ-phase intercalated into organic amine

With a hydrothermal technique, a layered titanium phosphate with the formula Ti₂(H₂PO₄)(HPO₄)(PO₄)₂ · 0.5C₆N₂H₁₆ (denoted TP-J2) has been prepared by treating the Ti/H₃PO₄/H₂O/1-methylpiperazine system directly. The as-synthesized products were characterized by powder X-ray diffraction, CP-MAS solid-state ³¹P NMR spectroscopy, thermogravimetric and differential thermal analyses (TG-DTA). The structure was solved by single-crystal X-ray diffraction analysis and it presents an extended γ-phase intercalated with organic amine. Crystal data: triclinic, , a = 8.106 (2) Å, b = 8.197 (2) Å, c = 11.658 (2) Å.  = 78.32 (3)°, β = 80.85 (3)°, γ = 77.90 (3)°, Z = 2. Additionally, the intercalation behavior of TP-J2 with n-alkyl monoamine (n = 2, 3, 4, 6, 8, 10 and 12) was investigated. Owing to the strong brønsted base, N,N′-dimethylpiperazine, resides in the interlayer, it presented unusual features of TP-J2 in contrast with that of γ-Tip.     

不同硅铝比Cu-ZSM-5纳米片上N2O催化分解

以双季铵盐表面活性剂为模板剂,水热条件下合成了硅铝比(nSi/nAl)为18、26和95的ZSM-5沸石纳米片,采用离子交换方法制备了铜改性的ZSM-5纳米片样品,并测试了其催化分解N_2O性能。结合X射线衍射(XRD)、N_2吸附/脱附、X射线荧光光谱(XRF)、扫描电镜(SEM)、透射电镜(TEM)、氢气程序升温还原(H_2-TPR)、氧气程序升温脱附(O_2-TPD)和原位红外漫反射光谱(CODRIFT)等表征结果 ,探讨了沸石硅铝比对于催化剂N_2O分解性能的影响及其原因。结果表明,ZSM-5纳米片硅铝比越低,CuZSM-5纳米片催化剂的活性越高。催化活性的提高归因于低硅铝比催化剂上Cu~+活性物种可还原性的增强和吸附氧脱附能力的提高。     

Synthesis and UV absorption properties of 5, 5′-thiodisalicylic acid intercalated Zn−Al layered double hydroxides

5, 5′-Thiodisalicylic acid (TDSA) has been intercalated into a ZnAl-NO₃ layered double hydroxide (LDH) by an ion-exchange reaction. After intercalation of TDSA, the basal spacing in the LDH increased from 0.89 to 1.53 nm, suggesting that the TDSA anions were arranged in the interlayer galleries of ZnAl-TDSA-LDH as a tilted monolayer arrangement of dianions. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry and differential thermal analysis (TGA-DTA), and UV-Visible spectroscopy (UV-Vis). The results show that the NO₃⁻ anions in the precursor have been completely replaced by TDSA anions to give ZnAl-TDSA-LDH having crystalline-layered structure. Detailed studies reveal the presence of a complex system of supramolecular interactions between LDH layers and TDSA anions. TGA-DTA curves suggest that the thermostability of TDSA was markedly enhanced by intercalation in the LDH host. Photostability tests show that the film of ZnAl-TDSA-LDH/PP possessed higher stability to UV radiation than either the film of TDSA/PP or pristine PP.