A porous Ca-MOF with nano-sized {Ca11} as building unit: Structure,drug loading and release properties

A novel calcium based metal-organic framework (compound 1) was assembled from the connection of nano-sized {Ca₁₁}SBU (2.36nm) and the triple-connective triangle aromatic acid, to give the formation of 3D MOF of 1 companied with a 2D porous structure with two 1D channel (size: 10.7Å × 10.8Å and 9.4Å × 8.1Å, respectively). The framework of 1 can afford a drug loading content of 0.19g/g of guaiacol and exhibited slow release effect toward guaiacol in 15h in PBS solution.

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Catalytic asymmetric epoxidation of limonene using manganese Schiff-base complexes immobilized in ionic liquids

The asymmetric epoxidation of limonene has been performed using Jacobsen’s catalyst dissolved in 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI · BF₄) ionic liquid and with hydrogen peroxide oxidant giving high stereoselectivity. Limonene was selectively converted into 1,2-epoxi-p-ment-8-enes with a diastereoisomeric excess of 74% and conversions up to 70%. Chirality of limonene was found to play an important role in stereochemical formation of new chiral centers because the synthesis occurs with double asymmetric induction.

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Confirmation of NH species in the framework of nitrogen-incorporated ZSM-5 zeolite by experimental and theoretical studies

Nitrogen-incorporated zeolites have drawn much attention as a new family of basic solid materials and N atoms are expected to be introduced into the frameworks of zeolites. In this study, nitrogen-incorporated ZSM-5 zeolites were prepared by temperature-programmed nitridation and their physicochemical properties were characterized by means of XRD, SEM and BET techniques. Combined a detailed IR characterization with a theoretical IR simulation, the bands relating to bridging Si–N(H)–Si groups at 1151 and 985 cm^?1 were observed in the IR fingerprint region of nitrogen-incorporated zeolites. The results confirmed that N atoms have been introduced into the framework of ZSM-5 zeolites by nitridation to form basic –NH– species, which was also supported by results of ²⁹Si MAS NMR characterization. Furthermore, the basic catalytic properties of nitrogen-incorporated ZSM-5 zeolites were evaluated by Knoevenagel condensation of benzaldehyde and malononitrile and enhanced conversion of benzaldehyde was achieved.     

Enthalpy of formation and dehydration of lithium and sodium zeolite beta

Zeolite Li-BEA and Na-BEA with Si/Al = 3–4 were synthesized by alumination and ion exchange, then characterized by XRD, TG–DSC and NMR. The enthalpies of formation and dehydration of Li and Na ion exchanged zeolite beta are investigated by high temperature oxide melt solution calorimetry. For Li-BEA, the formation enthalpies of formation from oxides at 25 °C are 25.6 ± 1.7 kJ/mol TO₂ for the dehydrated zeolite and −8.45 ± 0.94 kJ/mol TO₂ for the fully hydrated zeolite; for Na-BEA they are −2.4 ± 0.6 kJ/mol TO₂ for the dehydrated and −17.8 ± 1.0 kJ/mol TO₂ for the fully hydrated zeolite. The integral dehydration enthalpy at 25 °C is 33.2 ± 1.8 kJ/mol H₂O for Li-BEA and 16.5 ± 1.1 kJ/mol H₂O for Na-BEA. The partial molar dehydration enthalpies of both Li-BEA and Na-BEA are a linear function of water content. Molecular mechanics simulations explore the cation and water molecule positions in the framework at several water contents.     

Synthesis of β-SiAlON powder by carbothermal reduction–nitridation of zeolites with different compositions

β-SiAlON was synthesized from select zeolite Y compositions with different Si/Al ratios by carbothermal reduction–nitridation (CRN), and the correlation between the starting compositions and products was investigated. The carbon content in all of the zeolite samples was fixed at 1.2 times the required stoichiometric value. Zeolite–carbon mixtures were placed in a carbon boat and fired in a furnace at 1300 °C for 0 min, and 1450 °C for 0, 120 min in a N₂ flow of 0.5 l/min. The main phase in each of the samples fired at 1450 °C for 120 min was determined from XRD results as β-SiAlON. It was also found that the ratio of β-SiAlON to minor phases such as α-Si₃N₄ and Si₂N₂O is typically higher in samples prepared from zeolites rather than from silica–alumina mixtures of the same compositions. This indicates that zeolites are ideal raw materials for the CRN synthesis of high purity β-SiAlONs by CRN with various z values.     

Synthesis of 11 Å Al-substituted tobermorite from trachyte rock by hydrothermal treatment

The alkaline hydrothermal activation of trachyte rock led to synthesis of technologically important 11 Å tobermorite. Tobermorite synthesis was studied by X-ray diffraction, scanning electron microscopy and ²⁹Si and ²⁷Al high resolution magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. The influence of the reaction conditions such as different temperatures (150–170 °C), times (5–20 h) as well as different Ca/Si ratios of 0.6, 0.9 and 1.3 on tobermorite formation were investigated. The results showed that the main rock constituents were completely converted into a well crystallized Al-substituted 11 Å tobermorite when hydrothermally activated with 3.0 M NaOH under the optimum hydrothermal conditions of 170 °C for 20 h and using Ca/Si and Al/Al + Si ratios of 0.9 and 0.17, respectively. The local structure of the synthesized tobermorites as determined by MAS-NMR spectroscopy implied an alumino-silicate mean chain length of 5.9 units with 79% of the interlayer cross-links which are of Si–O–Al configuration. The present results show that trachyte rock could be considered as a new economic resource for synthesizing Al-substituted 11 Å tobermorites.     

Carbothermal synthesis of β-sialon from mechanochemically activated precursors

Reaction mixtures of halloysite clay and fine carbon for carbothermal reduction and nitridation (CRN) synthesis of β-sialon were ground in a planetary ball mill under flowing nitrogen for varying periods before being converted to sialon by heating in nitrogen at 1200–1400 °C. After 4 h grinding the XRD reflections of the halloysite were destroyed and some of the octahedrally-coordinated Al was converted to four- and five-fold coordination. ²⁷Al and ²⁹Si MAS NMR gave no evidence of the formation of AlN or SiN bonds upon grinding. Upon subsequent heating in nitrogen, the ground samples show significant differences from the unground control, the intermediate compound mullite being replaced by β-sialon (z ≈ 2) a temperature at least 100 °C lower, but the formation of corundum (α-Al₂O₃) also occurs at a lower temperature and is more persistent than in the unground control. MAS NMR spectroscopy shows that the products from the ground mixtures contain relatively less AlON units and that the formation of SiC (a transient reaction intermediate) is also facilitated by grinding. The optimum grinding time for this system was found to be 12 h.     

Temperature effect on bonding structures of amorphous carbon containing more than 30at.% silicon

Bonding evolution of amorphous carbon incorporated with Si or a-C(Si) in a thermal process has not been studied. Unhydrogenated a-C(Si) films were deposited by magnetron sputtering to undergo two different thermal processes: i) sputter deposition at substrate temperatures from 100 to 500 °C; ii) room temperature deposition followed by annealing at 200 to 1000 °C. The hardness of the films deposited at high temperature exhibits a monotonic decrease whereas the films deposited at room temperature maintained their hardness until 600 °C. X-ray photoelectron spectroscopy and Raman spectroscopy were used to analyze the composition and bonding structures. It was established that the change in the mechanical property is closely related to the atomic bonding structures, their relative fractions and the evolution (conversion from C–C sp³ → CC sp² or CC sp² → C–Si sp³) as well as clustering of sp² structures.     

On the nature of structural disorder in calcium silicate hydrates with a calcium/silicon ratio similar to tobermorite

Four calcium silicate hydrates (CSH) with structural calcium/silicon (Ca/Si) ratios ranging from 0.82 ± 0.02 to 0.87 ± 0.02 were synthesized at room temperature, 50, 80, and 110 °C. Their structure was elucidated by collating information from electron probe micro-analysis, transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, and powder X-ray diffraction (XRD). A modeling approach specific to defective minerals was used because sample turbostratism prevented analysis using usual XRD refinement techniques (e.g. Rietveld analysis). It is shown that CSH with Ca/Si ratio of ~ 0.8 are structurally similar to nano-crystalline turbostratic tobermorite, a naturally occurring mineral. Their structure thus consists of sheets of calcium atoms in 7-fold coordination, covered by ribbons of silicon tetrahedra with a dreierketten (wollastonite-like) organization. In these silicate ribbons, 0.42 Si per bridging tetrahedron are missing. Random stacking faults occur systematically between successive layers (turbostratic stacking). Layer-to-layer distance is equal to 11.34 Å. Crystallites have a mean size of 10 nm in the a–b plane, and a mean number of 2.6–2.9 layers stacked coherently along the c* axis.     

Coarsening of nano-crystalline SiC in amorphous Si–B–C–N

The formation of nano-crystalline SiC is studied in various amorphous precursor derived Si–B–C–N bulk ceramics at temperatures between 1600 and 1800 °C. The formation process of SiC can be described by a very rapid crystallization (<15 min) of nano-sized particles with diameters between 2 and 7 nm which are embedded in an amorphous Si–B–C–N matrix. During further annealing of the material up to 40 h, particle growth due to coarsening takes place, which leads to maximum crystallite diameters of 30 nm. The kinetics of coarsening can be described by the Lifshitz–Slyozov–Wagner model. The product of the rate constant of coarsening, k_c, and of the temperature, T, follows an Arrhenius behaviour with an activation enthalpy of about 8 eV (770 kJ/mol), which is approximately the activation enthalpy of self-diffusion in Si–B–C–N, indicating diffusion controlled crystallite growth. The kinetics of coarsening is fastest for the ceramics with a low concentration of Si and N in the amorphous matrix.     

Facile synthesis of novel zinc-based infinite coordination polymer nanoparticles

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Enhanced nitridation of silicon compacts by Yb2O3 addition

The catalytic effect of ytterbium oxide (Yb₂O₃) on the nitriding reaction of Si compacts was investigated. Si powder mixtures containing Yb₂O₃ were prepared and nitrided in the form of compacts with a multi-step heating schedule over the range of 1200 °C–1450 °C. The nitriding profiles of the powder mixture with increasing temperature indicated that Yb₂O₃ clearly promoted the nitridation of Si compacts at 1200 °C compared with the pure Si compact containing no additives. The critical role of Yb₂O₃ on the nitridation of Si, was elucidated that Yb₂O₃ promotes the loss of initial SiO₂ of the raw Si powder via the measurement of the weight changes at low temperature (1100 °C) and thermogravimetric analysis under N₂ atmosphere. It was also found that the β-ratio of fully nitrided Si was closely related to the intermediate degree of nitridation at 1200 °C and 1300 °C.     

Oxidation behavior of SiC ceramics synthesized from processed cellulosic bio-precursor

Oxidation behavior of Si/SiC ceramic composite synthesized from processed cellulosic bio-precursor was studied in dry air over the temperature range 1200–1350 °C. The material was synthesized from processed bio-precursors (bleached bamboo kraft pulp in the form of flat board of bulk density 0.58 g cm^?3) and had a bulk density of 2.66 g cm^?3, porosity of 0.6 vol% and contents of Si and SiC phases of 39.1% and 60.3% (v/v) respectively. The process of oxidation could be described closely by a parabolic oxidation equation. An activation energy of 141.4 kJ/mol was obtained. Both the SiC and Si phases oxidized and the oxidation was mainly controlled by the transport of molecular oxygen through the growing oxide layer. Pre-oxidation at 1300 °C for 24 h in ambient air increased the strength of Si/SiC ceramics by around 46% because of the healing of the surface defects created during surface preparation by the oxide layer.     

Adsorption of uranyl ions on kaolinite,montmorillonite, humic acid and composite clay material

Adsorption of uranyl ions onto kaolinite, montmorillonite, humic acid and composite clay material (both clays and humic acid) was studied by measuring the system response to clay suspensions (pre-equilibrated with or without uranyl) and to perturbations of the solution chemistry. Adsorption behavior of selected materials under the frame of batch experiments was tested at high uranyl concentrations (6–1170 μg/mL; 2.5 × 10^− 2 to 4.9 μM), whereas that under flow through continuous stirred reactor experiments was tested at low concentrations (1.00 × 10^− 4 to 1.18 × 10^− 4 M). Both experiments were developed at pH 4.5 and ionic strength 0.2 mM. The adsorption experiments follow a Langmuir isotherm model with a good correlation coefficient (R² > 0.97). The calculated amount of adsorbed and desorbed uranyl was carried out by numeric integration of the experimental data, whereas the desorption rates were determined from the breakthrough curve experiments. Kaolinite with highly disordered structure adsorbed less uranyl (3.86 × 10^− 6 mol/g) than well-ordered kaolinite (1.76 × 10^− 5 mol/g). Higher amount of uranyl was adsorbed by montmorillonite (3.60 × 10^− 5 mol/g) and only half of adsorbed amount was desorbed (1.85 × 10^− 5 mol/g). The molecular interactions between kaolinite, montmorillonite, humic acid, composite material and saturated uranyl ion solutions were studied by molecular fluorescence, infrared and X-ray photoelectron spectroscopy. The Stern–Volmer constant obtained for montmorillonite (2.6 × 10³ M^− 1) is higher than for kaolinite (0.3 × 10³ M^− 1). Molecular vibrations of SiO stretching and AlOH bending related to hydroxylated groups (SiOH or AlOH) of kaolinite and montmorillonite show structural changes when uranyl ions are adsorbed. X-ray photoelectron spectroscopy shows that the U 4f_7/2 core level signals occur at 380.5 eV in either kaolinite or montmorillonite that resulted from the interaction of aluminol surface sites with the (UO₂)₃(OH)₅⁺.     

Time-resolved powder neutron diffraction study of the phase transformation sequence of kaolinite to mullite

Mullite formation from kaolinite was studied by means of high-temperature in situ powder neutron diffraction by heating from room temperature up to 1370 °C. Neutron diffractometry under this non-isothermal conditions is suitable for studying high-temperature reaction kinetics and to identify short-lived species which otherwise might escape detection. Data collected from dynamic techniques (neutron diffraction, DTA, TGA and constant-heating rate sintering) were consistent with data gathered in static mode (conventional X-ray diffraction and TEM). The full process occurs in successive stages: (a) kaolinite dehydroxylation yielding metakaolinite in the ∼400–650 °C temperature range, (b) nucleation of mullite in the temperature range ∼980–992 to ∼1121 °C (primary mullite) side by side with a crystalline cubic phase (Si-Al spinel) detected in the ∼983–1030 °C temperature interval; (c) growth of mullite crystals from ∼1136 °C, (d) high (or β) cristobalite crystallization at T > ∼1200 °C and (e) secondary mullite crystallization at T > ∼1300 °C. The calculated activation energy for the kaolinite dehydration was 115 kJ/mol; for the mullite nucleation was 278 kJ/mol and for the growth of mullite process was 87 kJ/mol; finally for cristobalite nucleation the calculated apparent activation energy was 481 kJ/mol.     

Activity of Mo(II) allylic complexes supported in MCM-41 as oxidation catalysts precursors

[Mo(η³-C₃H₅)X(CO)₂(NCCH₃)₂] (X = Br, 1a; X = Cl, 1b) complexes reacted with the bidentate ligand RNC(Ph)–C(Ph)NR, R = (CH₂)₂CH₃ (DAB, 2) affording [Mo(η³-C₃H₅)X(CO)₂(DAB)] (X = Br, 4a; X = Cl, 4b), which were characterized by elemental analysis, FTIR and ¹H and ¹³C NMR spectroscopy. The modified silylated ligand RNC(Ph)C(Ph)NR, R = (CH₂)₃Si(OCH₂CH₃)₃ (DAB–Si, 3), was used to immobilize the two complexes in MCM-41 (MCM) mesoporous silica. The new materials were characterized by powder X-ray diffraction, N₂ adsorption analysis, FTIR and ²⁹Si and ¹³C CPMAS solid state NMR spectroscopy. Both the materials and the complexes were tested in the oxidation of cyclooctene and styrene and behaved as active catalyst precursors for cyclooctene and styrene epoxidation with TBHP (t-butylhydroperoxide), leading selectively to epoxides with high conversions and TOFs. Although the homogeneous systems reach 100% conversion of cyclooctene and slightly less for styrene, the loss of catalytic activity in the heterogeneous systems is small, with a 98% conversion of styrene achieved by the chloride containing material.     

Viscosity of high-nitrogen content Ca–Si–O–N glasses

The viscosity of three high-nitrogen content Ca–Si–O–N glasses, with 30–58 e/o N and 36–39 e/o Ca, was determined by micro-indentation. The measurements were made using an automated set-up, designed and built in-house, capable of measurements up to 1200 °C with applied loads of 0.01–15 N. The viscosity increases significantly with the nitrogen content and reaches viscosity values close to reported values for rare-earth silica oxynitride glasses. The glass transition temperatures range between 878 and 995 °C and are in very good agreement with values measured by differential thermal analysis. The apparent viscosity activation energies are very high, ranging from 855 to 2170 kJ/mol. The glasses can accordingly be classified as being both very refractory and very fragile. Implications of the viscosity values and mechanical properties of the glasses for their structures are discussed.     

Sintering behaviour of a glass obtained from MSWI ash

The sintering behaviour of a glass obtained by Municipal Solid Waste Incinerator (MSWI) bottom ash (WG) was investigated and compared with a Na₂O–MgO–CaO–SiO₂ composition (CG). The sintering activation energy, E_sin, and the energy of viscous flow, E_η, were evaluated by dilatomeric measurements at different heating rates. The formation of crystalline phases was evaluated by Differential Thermal Analysis (DTA) and X-Ray Diffraction (XRD), and observed by Scanning Electron Microscopy (SEM) and Transition Electron Microscopy (TEM). In CG, the sintering started at ≈10¹³ dPa s viscosity and E_sin (245 kJ/mol) remains constant in the measured range of shrinkage, up to 9%. In WG the densification started at ≈10¹¹ dPa s, E_sin resulted to be 395 kJ/mol up to 5% shrinkage, 420 kJ/mol at 8% and 485 kJ/mol at 10% shrinkage. The sintering rate decreased due to the beginning of the pyroxene formation and the densification stopped in the temperature range 1073–1123 K after formation of 5 ± 3% and 13 ± 3% crystal phase, at 5 and 20 K/min, respectively. Higher densification and improved mechanical properties were obtained by applying the fast heating rate, i.e. 20 K/min.     

Modeling thermal and catalytic conversion of decalin under industrial FCC operating conditions

The processability of decalin, a two-fused ring cycloparaffin, in the absence and presence of USY catalysts of different zeolite crystallite sizes is investigated under actual FCC conditions. Thermal and catalytic cracking experiments using decalin are carried out in the mini-fluidized CREC riser simulator. This novel unit operates under relevant FCC process conditions in terms of partial pressures of decalin, temperatures (450–550 °C), contact times (3–7 s), catalyst–decalin mass ratios (5) and using well-fluidized catalysts. Decalin overall conversions ranged between 8–19wt% at low reaction temperatures and 14–27 wt% at high temperatures. It is found that decalin undergoes reactions such as ring opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. A heterogeneous kinetic model for decalin conversion including thermal effects, adsorption and intrinsic catalytic reaction phenomena is established. Adsorption and kinetic parameters are determined, including the heat of adsorption (?61 kJ/mol) as well as thermal and primary catalytic intrinsic activation energies, which are in the range of 56–59 kJ/mol and 74–91 kJ/mol, respectively. It is determined that hydrogen transfer reactions are more pronounced and selectively favored against other reactions at lower reaction temperatures, while ring-opening and cracking reactions predominate at higher reaction temperatures.