Synthesis and characterization of porous chromia-pillared layered lanthanum niobic acid

The first chromia-pillared layered lanthanum niobic acid was prepared by an ion-exchange route, in which n-hexylamine-pre-expanded lanthanum niobate reacted with chromium(III) acetate [Cr(OAc)₃] aqueous solution under reflux condition, and the ion-exchanged product was calcined at 450 °C in air flow. The structure of the novel pillared material was examined by means of various analytical techniques, such as powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential analysis (TG/DTA), nitrogen adsorption–desorption, and transmission electron micrographs (TEM). The chromia-pillared layered lanthanum niobic acid exhibited a porous layered structure with a BET (Brunauer-Emmett-Teller) surface area of 89 m²·g^− 1 and an interlayer distance of 1.31 nm. The layered structure could be retained up to 550 °C.     

Synthesis and room temperature photoluminescence of ZnO/CTAB ordered layered nanocomposite with flake-like architecture

Flake-like ZnO/surfactant ordered layered nanocomposite has been synthesized by self-assembly at room temperature with the presence of cetyltrimethylammonium bromide (CTAB, CH₃(CH₂)₁₅N⁺(CH₃)₃Br⁻) surfactant. The procedure described in this study is attractive since it gives high yields of ordered layered nanocomposite with flake-like architecture. XRD results showed the formation of a layered structure with two layered spacings ca. 18.56 Å. SEM and FT-IR spectroscopy were used to further characterize ZnO/CTAB nanolayered composite. The ZnO/CTAB-ordered layered nanocomposite exhibits the room temperature photoluminescence (RTPL) characteristics. It is inferred that the RTPL of ZnO/CTAB-layered nanocomposite might be induced by the interfacial effect between the ZnO and the surfactant.     

Structure and Thermal Stability of Polystyrene/Layered Silicate Nanocomposites

Polystyrene/layered silicates nanocomposites were prepared by intercalation in solution method, using CHCl₃ and CCl₄ as solvents. The clay used was organically modified by hexadecyltrimethyl–ammonium bromide (CTAB) at various surfactant loadings. It was found that intercalated nanocomposite structure was obtained using CHCl₃ as solvent while exfoliated or partially exfoliated was the predominant form in the case of CCl₄. X-ray diffraction and thermogravimetric analysis were used to characterize the nanocomposite morphology and thermal stability, respectively. Enhancement in thermal stability was observed for PS-nanocomposites compared to that of pristine polymer as indicated by TGA measurements. This increment was more prevalent for exfoliated nanocomposites prepared with carbon tetrachloride as solvent.     

Intercalation of [Pt(NH3)4]2+ ions into layered sodium silicate magadiite: a useful method to enhance their stabilisation in a highly dispersed state

Al-free layered sodium silicate magadiite has been used as the host material for the stabilisation of [Pt(NH₃)₄]²⁺ ions via intercalation and/or ion-exchange reactions. The stabilisation of Pt(NH₃)₄]²⁺ ions in between the layers of Na-magadiite was confirmed by thermogravimetric analysis (TGA), where increased decomposition temperatures were observed for the intercalated materials. The intercalation behaviour of Na-magadiite was evident from the significant uptake of Pt ions (22.2 wt%). When silica gel was used as the host matrix, negligible uptake of Pt ions (1.3 wt%) was noticed. The X-ray diffraction (XRD) measurements revealed no appreciable change in the basal spacing of the intercalated materials. Nevertheless, the decrease in the intensity of the 001 peak with increasing Pt loadings (from 13.0 to 22.2 wt%) substantiated the intercalation of [Pt(NH₃)₄]²⁺ ions within the interlayer spaces of Na-magadiite. The transmission electron microscopy (TEM) studies of the intercalated materials revealed that [Pt(NH₃)₄]²⁺ ions were homogeneously intercalated in the magadiite matrix, ranging from 2 to 3 nm. Subsequent calcination of the intercalated materials at 600 °C in air led to the formation of Pt nanoparticles supported on silica. The results of XRD and TEM indicated that Pt nanoparticles were highly dispersed on the silica support and were in the range of 5–12 nm. Moreover, chemical analyses confirmed the high loading of Pt on silica in agreement with the TGA results.     

Ab initio study of sodium intercalation into metal oxides

Using the full-potential linearized augmented plane wave (FP-LAPW) method, we have studied the effect of chemistry on the average intercalation voltage (AIV) caused by the Na ions intercalating into transition metal oxides. The effect of transition metal was systematically studied by varying M=Co, Ni and Mn in NaMO₂ and fixing the α-NaFeO₂ layered structure. The effect of the guest atoms into the host material is discussed in terms of the structural and electronic properties. Comparatively to Li intercalation, a significant electron transfer towards transition metal was found. This observation suggests that the transition metal contribute to the AIV determination and confirms the common assumption that intercalated electron reduces M⁴⁺ to M³⁺.     

Characterization, sintering and dielectric properties of nanocrystalline zinc oxide prepared by a citric acid-based combustion route

Nanosized zinc oxide has been synthesized through a novel single step solution combustion route using citric acid as fuel. The X-ray diffraction (XRD) analysis revealed that the synthesized ZnO nanopowder has the pure wurtzite structure. The phase purity of the nanopowder has been confirmed using differential thermal analysis (DTA), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The morphology and crystalline size of the as-prepared nanopowder characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the powder consisted of a mixture of nanoparticles and nanorods. The nanocrystalline ZnO could be sintered to ∼97% of the theoretical density at 1200 °C in 4 h. The dielectric constant (ε_r) and dielectric loss (ε_i) of sintered ZnO pellets at 5 MHz were 1.38 and 9×10⁻², respectively, at room temperature.     

Ultrasound-assisted fabrication of a new nanocomposite electrode of samaria and borazon for high performance supercapacitors

The fabrication of hetero structured materials with supercapacitor applications for industrial use remains a key challenge. This work reports a new supercapacitor material with high capacitance, comprising samaria and borazon (O₃Sm₂/BN) synthesized ultrasonically (40 ± 3 kHz, 200 W). The successful synthesis, probable interfaces between O₃Sm₂ and BN and thermal stability of the nanocomposite were studied by UV–Vis. and FT-IR spectroscopies, X-ray diffraction (XRD) and thermo gravimetric analyses (TGA). The morphology of nanocomposite was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Elemental mapping analysis and energy dispersive X-ray analysis (EDAX) confirmed the elements present in the material. This supercapacitor material shows a maximum discharge capacitance of 414 Fg⁻¹ at 0.25 Ag⁻¹ and an exceptional retention of specific capacitance (92.5%) in 5000 cycles. Such nanocomposite with better specific capacitance and charge/discharge rates makes it a right candidate as next generation supercapacitor, which certainly finds applications in various unconventional energy storage devices.     

Structure and electrical conductivity of a novel inorganic solid electrolyte: Na14.5[Al(PO4)2F2]2.5[Ti(PO4)2F2]0.5 (NATP)

A novel inorganic solid electrolyte with a layered framework structure stable up to 1043 K, Na_14.5[Al(PO₄)₂F₂]_2.5[Ti(PO₄)₂F₂]_0.5 (NATP), has been hydrothermally prepared and characterized by single-crystal and powder X-ray diffraction techniques, X-ray fluorescence (XRF) analysis, IR spectroscopic measurement, thermogravimetric and differential thermal analysis (TGA and DTA). NATP crystallizes in the acentric hexagonal space group P3 with a=10.448(2), b=10.448(2), , Z=1, containing a large number of Na⁺ cations in the interlamellar space and the cavities of its framework. There are six different crystallographic Na⁺ cationic sites, in which 8% Na(5) and 12% Na(6) sites are vacant. Electrical conductivity measurements show that Na⁺ cations exhibit a high mobility with two domains for the electrical conductivity versus temperature.     

Metatungstate and tungstoniobate-containing LDHs: Preparation, characterisation and activity in epoxidation of cyclooctene

Polyoxometalates (POMs) H₂W₁₂O₄₀⁶⁻ and W₄Nb₂O₁₉⁴⁻ have been intercalated between the brucite-like layers of Mg, Al and Zn, Al hydrotalcites by anion exchange, starting from the corresponding nitrate precursors. The solids have been characterised by Powder X-ray Diffraction (PXRD), Fourier Transform infrared (FT-IR) spectroscopy, N₂ adsorption-desorption at −196 °C and thermogravimetric (TG) and differential thermal analyses (DTA), and have been tested in the epoxidation of cyclooctene using H₂O₂ or t-BuOOH as oxidants. The results show that both anions are effectively located in the interlayer space maintaining their pristine structures without depolymerisation. Upon intercalation of such large anions microporosity is developed and subsequently an increase in the specific surface areas is also observed. In general, the prepared materials possess catalase and epoxidation activity, with ZnAl-intercalated H₂W₁₂O₄₀⁶⁻ giving the best results in terms of epoxide yield (17% at 24 h). Product selectivity is different for the intercalated and free POMs, the latter yielding 1,2-cyclooctanediol as the only product, whereas the former produces only the epoxide. The epoxidation reaction seems to be catalysed in homogeneous phase by the POM.     

Raman and IR spectra of K4Nb6O17and K4Nb6O17·3H2O single crystals

Polarised Raman and IR spectra of K₄Nb₆O₁₇ and K₄Nb₆O₁₇· 3H₂O single crystals were measured. The obtained spectra are discussed using the factor group approach for the orthorhombic P2₁nb space group and assignment of bands to the respective motions of atoms is proposed. In particular, we have shown that the bands above 770 cm⁻¹ can be attributed to the stretching modes of short niobium–oxygen bonds, which are present in this material due to the pronounced layered structure, whereas the potassium atoms contribute to the bands observed below 180 cm⁻¹. Our studies have revealed that intercalation of water molecules leads to shifts, broadening and changes in intensity of some bands. These changes have been attributed to slight changes in the bond lengths and angles, interactions of the water molecules with K atoms and structural disorder introduced by the intercalated water molecules. However, the main structural framework was preserved. Copyright © 2010 John Wiley & Sons, Ltd.     

Evidence for ammonia oxidation and the ionic nature of ammoniated titanium disulfide

In order to elucidate the nature of Lewis bases in layered transition metal dichalcogenides (TX₂), ammoniated titanium disulfide, (NH₃)_yTiS₂ with 0.4 ? y ? 0.6, has been synthesized using stoichiometric TiS₂ and investigated by X-ray diffraction, vapor pressure measurements, thermogravimetric analysis, differential scanning calorimetry, and SQUID magnetrometry. These intercalation compounds lose ammonia rapidly at ambient temperature to form primarily a stage II structure. Upon heating, about half of the ammonia is weakly bound (deintercalation enthalpy ?2.6 kcal/mol) and leaves the TiS₂ host at low temperatures (?75°C), whereas the other half is bound more strongly (deintercalation enthalpy ?6.3 kcal/mol) and deintercalates only at higher temperatures (?150°C). The more strongly bound ammonia is identified as NH₄⁺, and an electron is donated to the TiS₂ conduction band for each NH₄⁺-ion present. Hence, the ionic formulation (NH₄⁺)_y' (NH₃)_y'TiS₂^{y' -} best describes these materials, where the NH₄⁺ ions are analogous to alkali-metal cations M⁺ in metal-ammonia intercalation complexes. The presence of a substantial concentration of NH₄⁺ provides a simple explanation of the unusual observation that the C₃ axis of NH₃ is parallel to the TiS₂ layers. The results of this study show that redox reactions do indeed play an important role in ammonia intercalation into TiS₂ and probably also into other TX₂ hosts.     

Structure and oxygen stoichiometry of SrCo0.8Fe0.2O3−δ and Ba0.5Sr0.5Co0.8Fe0.2O3−δ

High temperature X-ray diffraction (HT-XRD), temperature programmed desorption (TPD), thermogravimetric analysis–differential thermal analysis (TGA/DTA) and neutron diffraction were combined to determine the structure and oxygen stoichiometry of SrCo_0.8Fe_0.2O_3−δ (SCF) and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) up to 1273 K in the pO₂ range of 1 to 10^− 5 atm. Formation of the vacancy-ordered brownmillerite phase, SrCo_0.8Fe_0.2O_2.5, was observed as a region of zero oxygen release in the TPD measurements and confirmed by HT-XRD and TGA/DTA. No ordering was observed in the BSCF system by any of the techniques utilized in this work. The oxygen vacancy concentration of BSCF was found to be considerably higher than that of SCF and always higher than that of the ordered brownmillerite phase of SCF, δ = 0.5. The combination of a high vacancy concentration and absence of ordering leads to higher oxygen permeation fluxes through BSCF membranes in comparison to SCF.     

Different modes and consequences of electron transfer in intercalation compounds

Intercalation reactions form one of the most versatile types of solid-state reactions known. Considering the layered host lattices they form an interesting access to artificial multilayers of very different properties. Many of these reactions are connected with redox processes. After a very short and general overview on the intercalation chemistry in layered host lattices, three different types of charge transfer accompanied with intercalation will be considered in detail and the consequence for the properties of the products will be discussed: (a) by means of electrointercalation into conducting host lattices (e.g. 2H-TaS₂) electrons are transferred to the conduction band of the host accompanied with the simultaneous uptake of cations (here organic cations like methylene blue, methylviologen) in the interlayer space. Potential vs. time curves give valuable information about two-phase regions, homogeneity ranges and deviations from equilibrium. The consequence for the superconducting properties is shown; (b) treating the graphite intercalation compound C₂₄(HSO₄)(H₂SO₄) with strong oxidants leads to graphite oxide (GO). The oxidant is directly attached to the carbon network forming C–OH and C–O–C functions. Applying ¹³C MAS NMR of GO (and derivatives) we could identify the ether function as epoxide groups. This result has strong implications for the chemical behaviour of GO and could lead to new carbon networks; (c) clay minerals containing iron in the octahedral layers can undergo changes of the oxidation state of Fe-ions. We have found in vermiculites from Spain that Fe²⁺ can be oxidized completely to Fe³⁺, whereas the degree of reduction of the Fe³⁺ is rather restricted but varies with the composition of the clay. However, the extent of reduction can be strongly increased by heating the reduced samples.     

Effect of Dy-Co on physical and magnetic properties of X-type hexaferrites (Ba2−xDyxCu2Fe28−yCoyO46)

Sol–gel method is used to make a sequence of Barium based “X-type hexagonal ferrite (X-HF)” Ba_2−xDy_xCu₂Fe_28 −yCo_yO₄₆. “X-type hexagonal ferrites” with concentrations of “x = 0.0, 0.02, 0.06, 0.1 and y = 0.0, 0.1, 0.3, 0.5” are taken and the substitution impact of trivalent Dy³⁺ and divalent Co²⁺ is observed on the physical and magnetic properties of X-HFs. The XRD result, the refinement of which is accomplished using CelRef software validates the existence of pure single phase in these ferrites. Morphological structure of the crystal grains is calculated using electron microscopy and it is found that the grain has varying size in the range of 0.75–1.001 mm. FTIR analysis is done with and without the sintering process to examine the changes relevant to the structure and the chemistry of the material and the phases existed in the material. Thermogravimetric analyzer is used to measure the TGA and DSC quantities. All FTIR, DSC, and TGA results show that they are in good harmony with the results outcomes from XRD. “Vibrating sample magnetometer (VSM)” is used to quantify the magnetic properties of the sample under observation. It is observed that with an increase in the concentration of Dy-Co, M_r (Remanence) value decreases this could be reasoned by spin canting effect. The value of coercivity (H_c) changes from 317 to 158 G which follows the inverse relation between grain size and coercivity. The future use of the material may be in the microwave absorption devices.     

Synthesis of complex oxides with garnet structure by spray drying of an aqueous salt solution

The use of spray drying to obtain powders of complex oxides with a garnet structure has demonstrated. The processes occurring during heating of the synthesized oxide–salt product, leading to the formation of a material with a garnet structure, have been investigated using DTA, TGA, XPS, and XRD. It has been shown that a single-phase garnet structure of system (Y _x Gd_(3–x))₃Al₅O₁₂ can be synthesized over the entire range of compositions.     

Preparation and characterization of polyaniline (PANI)-Mn3O4 nanocomposite

Polyaniline (PANI)-Mn₃O₄ nanocomposite was synthesized by a combination of sonochemical synthesis of Mn₃O₄ NP's and in-situ polymerization of aniline. Structural characteristics were evaluated by XRD, FT-IR, TGA, VSM, TEM and SEM analysis, and conduction characteristics were evaluated by total conductivity measurements in the temperature range of 20-100 °C and frequency range of 0.1 Hz-1 MHz. Our findings show that PANI is successfully coated on nanoparticles surface and overall conductivity of nanocomposite is approximately 50-1000 times higher than that of uncapped Mn₃O₄ or PANI base with increase in temperature. Morphology of the synthesized powder was observed to be thin nanosheets with a thickness of 2-3 nm based on SEM analysis. Room temperature magnetization curves for nanocomposite show no hysteresis, indicating the super-paramagnetic character of the sample in the region of measured field strength. σ_AC increased after polyaniline coating.     

Synthesis of lactic acid–Zr(IV) phosphate nanocomposite ion exchanger for green remediation

Lactic acid–Zr(IV) phosphate nanocomposite (LA/ZPNC) ion exchanger was synthesised by sol-gel method. The nanocomposite ion exchanger was characterized by different techniques such as Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy X-ray diffraction (XRD) and thermogravimetric analysis (TGA/DTA/DSC). LA/ZPNC was employed for different physicochemical properties such as ion exchange capacity, elution behaviour, effect of eluent concentration, pH titration and thermal stability. The ion exchange capacity of LA/ZPNC was higher as compared to their inorganic counterpart. pH results indicate the bifunctional nature of nanocomposite. A degradation efficiency of 89.47 % was attained in 4 h of illumination. The distribution coefficient (K _d) studies of LA/ZPNC ion exchanger were investigated for eight different metal ions and found more selective for Al³⁺ with higher K _d value. It was explored for photocatalytic study of methylene blue under solar illumination.     

Synthesis and structure of the monolayer hydrate K0.3CoO2·0.4H2O

The monolayer hydrate (MLH) K_0.3CoO₂·0.4H₂O was synthesized from K_0.6CoO₂ by extracting K⁺ cations using K₂S₂O₈ as an oxidant and the subsequent intercalation of water between the layers of edge-sharing CoO₆ octahedra. A hexagonal structure (space group P6₃/mmc) with lattice parameters a=2.8262(1) Å, c=13.8269(6) Å similar to the MLH Na_0.36CoO₂·0.7H₂O was established using high-resolution synchrotron X-ray powder diffraction data. The K/H₂O layer in the K-MLH is disordered, which is in contrast to the Na-MLH. At low temperatures metallic and paramagnetic behavior was found.     

CuFe2O4 magnetic heterogeneous nanocatalyst: Low power sonochemical-coprecipitation preparation and applications in synthesis of 4H-chromene-3-carbonitrile scaffolds

The paper presents the synthesis and catalytic activity of CuFe₂O₄ nanoparticles. The CuFe₂O₄ nanoparticles have been prepared by sonochemical route under low power ultrasonic irradiation (UI) and using silent stirring at room temperature only (ST) along with co-precipitation method, without using any additive/capping agent. The synthesized magnetic nanoparticles were successfully used and compared for the synthesis of 4H-chromene-3-carbonitrile derivatives. The CuFe₂O₄ nanoparticles obtained by sonochemical route exhibit higher catalytic activity because of small size (0.5–5 nm), high surface area (214.55 m²/g), high thermal stability up to 700 °C, recyclability and reusability due to its magnetic characteristics than CuFe₂O₄ nanoparticles obtained by room temperature silent stirring. The synthesized CuFe₂O₄ nanoparticles were characterized by FT-IR, SEM–EDX, HR-TEM, XRD, TGA/DTA/DTG, BET, VSM techniques. The present method is of great interest due to its salient features such as environmentally compatible, efficient, short reaction time, chemoselectivity, high yield, cheap, moisture insensitive, green and recyclable catalyst which make it sustainable protocol.     

Novel pyridyl‐substituted coumarin and its perchlorate salt–crystal structure and spectroscopic properties

The novel pyridyl‐substituted coumarin ( 1 ) and its perchlorate salt ( 2 ) have been synthesized and their structure and properties elucidated in detail spectroscopically, thermally and structurally, using single crystal X‐ray diffraction for 2 , linear‐polarized solid state IR‐spectroscopy, UV‐spectroscopy, TGA, DSC, DTA, and positive and negative ESI MS. Quantum chemical calculations were used to obtain the electronic structure, vibrational data and electronic spectra. The studied compound crystallizes in the centrosymmetric space group P‐1 and exhibits an infinite layered structure with the ions linked by means of the intermolecular N⁺H…OClO₃ (2.795 Å) interactions. The cations are disposed in a manner leading to a significant π‐stacking effect with a distance of 2.980 Å. The effects of N_py protonation on the optical and magnetic properties are elucidated by comparing the data of the protonated and neutral compounds. Copyright © 2009 John Wiley & Sons, Ltd.