Synthesis of the [Ga]-MFI under atmospheric pressure

The crystallization of the [Ga]-MFI was investigated as a function of synthesis time under atmospheric pressure. The molar composition of the reactants was 100SiO₂-Ga₂O₃-llNa₂O-llTPABr-3500H₂O. The crystallinity of the [Ga]-MFT was examined by using several analytical instruments, such as XRD, XPS, XRF, FT-IR, solid-statemas-NMR, DTG/DTA, and SEM. The [Ga]-MFI was successfully synthesized under atmospheric pressure at 97 ‡C in 72 h. It was found that the nucleation of the [Ga]-MFI took a quite long time, but the crystallization took place very fast. It is supposed that nucleation is the rate-controlling step in the [Ga]-MFI synthesis under atmospheric pressure. Consequently, if the induction period of the nucleation can be shortened, it would be possible to synthesize the [Ga]-MFI commercially under atmospheric pressure.     

Low temperature,efficient synthesis of new As(V)-silicate molecular sieves with MFI topology and their catalytic properties in oxidation reactions

New MFI type arseno-silicate molecular sieves (As(V)-MFI), synthesized for the first time, can be crystallized at lower temperature (70–90C) in 1–3 days under hydrothermal conditions. Interestingly, these As(V)-MFI molecular sieves can be synthesized even faster than the As-free silicalite-1 under identical conditions. Further, the crystallization becomes faster with the increase in As content of the reaction mixture, contrary to the observations made on all the other high silica molecular sieves, so far. These microporous As(V)-silicates exhibit significant catalytic activity in (i) phenol hydroxylation using 30% aq. H₂O₂ (ca. 55% H₂O₂ efficiency) and (ii) oxidative dehydrogenation of 2-butanol and benzyl alcohol using air under fixed bed vapor phase reaction conditions exhibiting ca. 75–85% selectivity towards 2-butanone and benzaldehyde+benzoic acid, respectively.     

The temperature-programmed desorption of hydrogen from copper surfaces

The desorption kinetics of H₂ from a Cu/ZnO/Al₂O₃ catalyst for methanol synthesis were studied under atmospheric pressure in a microreactor set-up by performing temperature-programmed desorption (TPD) experiments after various pretreatments of the catalyst. Complete saturation with adsorbed atomic hydrogen was obtained by dosing highly purified H₂ for 1 h at 240 K and at a pressure of 15 bar. The TPD spectra showed symmetric H₂ peaks centered at around 300 K caused by associative desorption of H₂ from Cu metal surface sites. H₂ TPD experiments performed with different initial coverages resulted in peak maxima shifting to higher temperatures with lower initial coverages indicating that the desorption of H₂ from Cu is of second order. The microkinetic analysis of the TPD traces obtained with different heating rates yielded an activation energy of desorption of 78 kJ mol^–1 and a corresponding frequency factor of desorption of 3×10¹¹ s^–1> in good agreement with the kinetic parameters obtained with Cu(111) under UHV conditions.     

Surface-grafted triruthenium ketenylidene clusters and their catalytic activity in co exchange and hydroformylation of ethylene

A triruthenium ketenylidene cluster [PPN]₂[Ru₃(CO)₉(CCO)] was deposited on MgO, SiO₂, and SiO₂-Al₂O₃, and the nature of surface species on the oxides were studied by an IR spectroscopic study along with catalytic performances in¹³CO exchange reaction and hydroformylation of ethylene. The IR study suggested the stoichiometric protonation of [Ru₃(CO)₉(CCO)]^2-with surface hydroxyl groups on SiO₂ and SiO₂-Al₂O₃ to give [HRu₃(CO)₉(CCO)]^– and H₂Ru₃(CO)₉(CCO), respectively. H₂Ru₃(CO)₉(CCO)/SiO_2– Al₂O₃ was active for¹³CO exchange reaction, while [Ru₃(CO)₉(CCO)]^2–/MgO showed high activity and selectivity toward propanol in hydroformylation of ethylene.     

The selective catalytic oxidation of methane to methyl bisulfate at ambient pressure

The selective catalytic oxidation of methane in 25 wt.% oleum to methyl bisulfate at ambient pressure in presence of PtCl₄ catalyst was investigated. The reaction between methane and sulfuric acid took place at atmospheric pressure if the mass transfer between gas and liquid was sufficient. The process was carried out at 130–220 °C in absorption reactor packed with glass balls 1.5–7 mm in diameter.     

Improved resistance against coke deposition of titania supported cobalt and nickel bimetallic catalysts for carbon dioxide reforming of methane

The catalytic behavior of bi-metallic Co–Ni/TiO₂ catalysts for CO₂ reforming of CH₄ to synthesis gas was investigated under atmospheric pressure with a particular attention to carbon deposition. The catalysts with optimized Co/Ni ratios showed high catalytic stability towards the reaction with very little amount of deposited carbon at a wide range of reaction temperature (773–1123 K). The results suggest that adjusting of composition of the active metals (Co and Ni) can kinetically control the elementary steps (formation of carbon species and its removal by oxygen species) of CH₄/CO₂ reaction.     

In Vivo Preclinical Assessment of β-Amyloid–Affine [11C]C-PIB Accumulation in Aluminium-Induced Alzheimer’s Disease-Resembling Hypercholesterinaemic Rat Model

Aluminum (Al) excess and hypercholesterinaemia are established risks of Alzheimer’s disease (AD). The aim of this study was to establish an AD-resembling hypercholesterinaemic animal model—with the involvement of 8 week and 48 week-old Fischer-344 rats—by Al administration for the safe and rapid verification of β-amyloid-targeted positron emission tomography (PET) radiopharmaceuticals. Measurement of lipid parameters and β-amyloid–affine [¹¹C]C-Pittsburgh Compound B ([¹¹C]C-PIB) PET examinations were performed. Compared with the control, the significantly elevated cholesterol and LDL levels of the rats receiving the cholesterol-rich diet support the development of hypercholesterinaemia (p ≤ 0.01). In the older cohort, a notably increased age-related radiopharmaceutical accumulation was registered compared to in the young (p ≤ 0.05; p ≤ 0.01). A monotherapy-induced slight elevation of mean standardised uptake values (SUV_mean) was statistically not significant; however, adult rats administered a combined diet expressed remarkable SUV_mean increment compared to the adult control (SUV_mean: from 0.78 ± 0.16 to 1.99 ± 0.28). One and two months after restoration to normal diet, the cerebral [¹¹C]C-PIB accumulation of AD-mimicking animals decreased by half and a third, respectively, to the baseline value. The proposed in vivo Al-induced AD-resembling animal system seems to be adequate for the understanding of AD neuropathology and future drug testing and radiopharmaceutical development.     

Fate of Fertilizer15N applied as urea and ammonium sulphate in opium poppy (Papaver somniferum L.) grown under greenhouse conditions

Laboratory incubation and greenhouse experiments were conducted to investigate the comparative effectiveness of urea and ammonium sulphate in opium poppy (Papaver somniferum L.) using¹⁵N dilution techniques. Fertilizer treatments were control (no N), 600 mg N pot^–1 and 1200 mg N pot^–1 (12 kg oven dry soil) applied as aqueous solution of urea or ammonium sulphate. Fertilizer rates, under laboratory incubation study were similar to that under greenhouse conditions. A fertilizer¹⁵N balance sheet reveals that N recovery by plants was 28–39% with urea and 35–45% with ammonium sulphate. Total recovery of¹⁵N in soil-plant system was 77–82% in urea. The corresponding estimates for ammonium sulphate were 89–91%. Consequently the unaccounted fertilizer N was higher under urea (18–23%) as compared to that in ammonium sulphate (9–11%). The soil pH increased from 8.2 to 9.4 with urea whereas in ammonium sulphate treated soil pH decreased to 7.3 during 30 days after fertilizer application. The rate of NH₃ volatilization, measured under laboratory conditions, was higher with urea as compared to the same level of ammonium sulphate. The changes in pH of soil followed the identical trend both under laboratory and greenhouse conditions.     

Influence of nucleation agents on crystallization and machinability of mica glass–ceramics

Effects of ZrO₂, La₂O₃, CeO₂, Yb₂O₃ and V₂O₅ on the crystallization kinetics, microstructure and mechanical properties of mica glass–ceramics were investigated by the differential scanning calorimetry (DSC), X-ray diffractometry (XRD), scanning electron microscopy (SEM) and microhardness tester. Results show that bulk crystallization can be obtained by introducing proper nucleation agents into the glass. Both Ozawa method and Kissinger method are suitable for analyzing the crystallization kinetics of mica glass–ceramic. The addition of nucleation agents has little influence on the value of n, keeping two-dimensional crystal growth mechanism. ZrO₂ and V₂O₅ are best nucleation agents in mica system. The increase of crystallization temperature is helpful for the increase of aspect ratio, and the microstructure of the glass–ceramics becomes interconnected, which contributes the improvement of the machinability of the glass–ceramics. Microhardness (H_v), cutting energy (μ¹) and machinability parameter (m) can be used for estimating the machinability of mica glass–ceramics.     

Crystallization kinetics of amorphous alumina–zirconia–silica ceramics

Crystallization kinetics of amorphous alumina–zirconia–silica ceramics was studied by nonisothermal differential scanning calorimetry (DSC). Different amorphous materials were produced by plasma spraying of near-eutectic Al₂O₃–ZrO₂–SiO₂ mixtures. Phase composition and microstructure of the amorphous materials and nanocrystalline products were analyzed. All of the investigated materials show an exothermic peak between 940 and 990 °C in the DSC experiments. The activation energies calculated from DSC traces decrease with increasing SiO₂ concentration. Values of the Avrami coefficients together with results of the microstructural observations indicate that tetragonal zirconia crystallization from materials containing more than 10 wt.% SiO₂ proceeds by a diffusion-controlled mechanism with nucleation occurring predominantly at the beginning of the process. In contrast, material with almost no SiO₂ exhibited a value of the Avrami exponent consistent with the crystal growth governed by processes at the phase boundary.     

Synthesis and characterization of mesoporous materials: Silica–zirconia and silica–titania

An experimental strategy was developed to obtain mesoporous SiO₂–ZrO₂ and SiO₂–TiO₂ mixed oxides by a sol–gel method, treating the gels hydrothermally. The solids were characterized by nitrogen physisorption, pyridine thermodesorption, ²⁹Si nuclear magnetic resonance, SEM and X-ray diffraction. The effects of ZrO₂ content, the generated pressure in the synthesis vessel and further modification of this type of procedure on the solids properties were studied. It was found that SiO₂–ZrO₂ and SiO₂–TiO₂ mixed oxides dried at atmospheric pressure developed type I isotherms. On the other hand, for the SiO₂–ZrO₂ and SiO₂–TiO₂ mixed oxides that were treated under pressure in the autoclave (at high SiO₂ content) the porosity was improved and mesoporous materials exhibiting type IV adsorption isotherms. Specific surface area and pore size distribution were a function of ZrO₂ and TiO₂ content. The materials exhibited narrow pore size distributions with pore diameters in the region of mesopores at about 4 nm and high surface areas, the highest being 481 m²/g for the 10 wt% ZrO₂ Si–Zr material. Differences in acidity as determined by pyridine thermodesorption were observed to depend on the synthesis parameters and ZrO₂ and TiO₂ concentration.     

Non-isothermal crystallization kinetics of MgO–BaO–B2O3–Al2O3–SiO2 glass

5MgO–9BaO–33B₂O₃–33Al₂O₃–20SiO₂ (mol%) glass was prepared by the melt quenching method at 1823 K for 2 h. Dilatometry and differential scanning calorimetry (DSC) curves of the glass have been investigated. Fragility index F was used to estimate glass formability. The crystallization kinetics of the glass was described by the activation energy (E) for crystallization and numerical factors (n, m) depending on the nucleation process and growth morphology. XRD and SEM analysis were also used to describe the crystals’ types and morphology precipitated from the MgO–BaO–B₂O₃–Al₂O₃–SiO₂ glass. The results show that the effective activation energy of the crystallization process E was 45.19 kJ/mol, and n up to 4.05. Two crystals phases, i.e. Al₄B₂O₉ and Al₂₀B₄O₃₆ were observed in the crystallized samples. SEM results were consistent with crystallization kinetics.     

Oriented polycrystalline mesoporous CeO2 with enhanced pore integrity

Mesoporous CeO₂ particles are synthesized using a sol–gel method involving Pluronic P123 or F127 tri-block copolymer and cerium acetate hydrate. Transmission electron microscopy reveals well defined meso-channels of about 10 nm in diameter and a wall framework consisting of highly oriented polycrystalline CeO₂. The [0 0 1] axis of the crystals is found to be aligned parallel to the meso-channels, and lattice coherency of [1 0 0] or [0 1 0] also exists in perpendicular plane to the channel. A cooperative self-assembly of the tri-block copolymer and Ce⁴⁺ species is believed to occur, along with the precipitation of nano-crystalline CeO₂ in the sol–gel process. It is proposed that the preferential orientation may result from a favored linkage of the low-order Miller indices {0 0 1} planes of CeO₂ to the PEO segment in the PEO–PPO–PEO tri-block copolymer micelles. The unique structural characteristics of meso-CeO₂ appear to contribute to maintaining the pore integrity during the synthesis as well as in a post-fabrication in situ TEM heating test.     

Ionothermal synthesis of a three-dimensional zinc phosphate with DFT topology using unstable deep-eutectic solvent as template-delivery agent

A three-dimensional zinc phosphate compound with DFT topology, designated as ZnPO₄-EU1, has been synthesized by an ionothermal approach from the system HF-ZnO–P₂O₅-choline chloride-imidazolidone. Ethylenediamine, derived from decomposition of the imidazolidone component of the deep-eutectic solvent (DES) itself, is delivered to the synthesis and serves as an appropriate template for ZnPO₄-EU1. Experiments in which the synthesis conditions were varied showed that ZnPO₄-EU1 may be prepared over a wide molar ratio of P/Zn = 0.55–13.0. Powder X-ray diffraction patterns have been obtained at intervals to track the crystallization process of this material. The experimental data show that Zn₃(PO₄)₂ · 4H₂O (a dense phase) was first isolated from the DES after reaction for 1 h. Subsequently, the pure phase of ZnPO₄-EU1 was obtained with increasing crystallization time from 12 h to 72 h. The experimental results show that the nucleation and crystallization take place with relatively low levels of solvent degradation, demonstrating that zinc phosphate with a three-dimensional framework can be synthesized by in situ generation of an appropriate template using an unstable DES at high temperatures (150–200 °C).     

A new approach to electrochemical production of benzaldehyde from toluene in an undivided cell in the presence of the couple V5+/V4+

Oxidation of toluene to benzaldehyde in the presence of the redox couple V⁵⁺/V⁴⁺ was carried out in an undivided cell where oxygen gas was continuously bubbled over the cathodic surface and the electrolyte was a mixture of aqueous H₂SO₄ solution containing V⁵⁺ and toluene. Some experimental conditions affecting the current efficiency for benzaldehyde production, such as H₂SO₄ concentration, current density, V⁵⁺ concentration and surfactants, were determined. The maximum current efficiency for benzaldehyde production at ambient temperature was 156.3% under the conditions of 11 M H₂SO₄, 2.7 × 10^–4 M CTAB, current density 1.25 mA cm^–2 and 0.0128 M V⁵⁺.     

Influencing factors on rapid crystallization of high silica nano-sized zeolite Y without organic template under atmospheric pressure

Nano-sized zeolite Y has been successfully synthesized within 4–7 h of crystallization at 100 °C at atmospheric pressure through the optimization of molar composition using 2³ factorial methods. The smallest crystal size of zeolite Y was in the range of 150–200 nm with the reaction time of 3 hrs to 4 hrs. However, solid state Si²⁹-nmr clearly shows that as aging time increases, Al seems to be more incorporated into silicate framework. Like the conventional zeolite synthesis, the alkalinity plays a critical role in the aspect of controlling the crystal size but the other two, Al₂O₃ and H₂O contents must be considered simultaneously. Therefore, the 2³ factorial methods can be a useful tool for the optimization of molar composition to synthesize nano-sized zeolite Y crystals.     

Catalytic activity of (CaO)1−x(ZnO)x solids for the N2O decomposition: relation with photoluminescence

(CaO)_1–x (ZnO) _x mixed oxides (x=0–1), heated at 1423 K under atmospheric conditions, were checked for their catalytic activity in the N₂O decomposition in the temperature range of 450–650°C. Although the catalytic activity was measured in the dark, it was found to be linearly related with the photoluminescence intensity of the catalysts.     

Influence of dopants on the crystallization of borosilicate glass

The effects of TiO₂ nucleating agent and CeO₂, ZrO₂, La₂O₃ and Y₂O₃ network modifiers on crystallization and structure of borosilicate glasses were systematically investigated. It was found that the nucleating Ti⁴⁺ ions entered [TiO₆] octahedron, participated in network formation and promoted glass crystallization, while the network modifiers induced α-quartz formation, favoring its crystallization as major crystal phase, which positively affected thermal expansion coefficient of the glass–ceramics. Network modifiers allowed strengthening glass network and conduced α-quartz-like structure, which was helpful for α-quartz crystallization.     

CO hydrogenation to iso-C4 hydrocarbons over CeO2–TiO2 catalysts

CeO₂–TiO₂ (Ce:Ti = 0.25–9, molar ratio) catalysts were synthesized by a sol–gel method and the catalytic performances were evaluated in the selective synthesis of isobutene and isobutane from CO hydrogenation under the reaction conditions of 673–748 K, 1–5 MPa and 720–3000 h⁻¹. The physical properties, such as specific surface area, cumulative pore volume, average pore diameter, crystal phase and size, of the catalysts were characterized by N₂ adsorption/desorption and XRD. All the CeO₂–TiO₂ composite oxides showed higher surface areas than pure TiO₂ and CeO₂. No TiO₂ phase was detected on the samples of CeO₂–TiO₂ in which TiO₂ contents were in the range of 10–50 mol%. Crystalline Ce₂O₃ was detected in CeO₂–TiO₂ (8:2). The reaction conditions, temperature, pressure and space velocity, had obvious influences on the CO conversion and distribution of the products over CeO₂–TiO₂ (8:2) catalyst.