Acid-base properties of the surface of the α-Al2O3 suspension

The distribution of the acid-base centers on the surface of α-Al₂O₃ suspension particles was studied by potentiometric titration, and the corresponding pK spectra were constructed. It was inferred that the double electric layer created by the supporting electrolyte substantially affected the screening of the acid-base centers on the particle surface of the suspension.     

Influence of γ-radiation on the reactivity of montmorillonite towards H2O2

Compacted and water saturated bentonite will be used as an engineered barrier in deep geological repositories for radioactive waste in many countries. Due to the high dose rate of ionizing radiation outside the canisters holding the nuclear waste, radiolysis of the interlayer and pore water in the compacted bentonite is unavoidable. Upon reaction with the oxidizing and reducing species formed by water radiolysis (OH^•, e⁻_(aq), H^•, H₂O₂, H₂, HO₂^•, H₃O⁺), the overall redox properties in the bentonite barrier may change. In this study the influence of γ-radiation on the structural Fe(II)/Fe_Tot ratio in montmorillonite and its reactivity towards hydrogen peroxide (H₂O₂) was investigated in parallel experiments. The results show that under anoxic conditions the structural Fe(II)/Fe_Tot ratio of dispersed Montmorillonite increased from ≤3 to 25-30% after γ-doses comparable to repository conditions. Furthermore, a strong correlation between the structural Fe(II)/Fe_Tot ratio and the H₂O₂ decomposition rate in montmorillonite dispersions was found. This correlation was further verified in experiments with consecutive H₂O₂ additions, since the structural Fe(II)/Fe_Tot ratio was seen to decrease concordantly. This work shows that the structural iron in montmorillonite could be a sink for one of the major oxidants formed upon water radiolysis in the bentonite barrier, H₂O₂.     

Conversion of alkylmercaptans in the presence of γ-Al2O3

In the presence of -Al₂O₃ at 200–500°C methylmercaptans quantitatively transform into dimethyl sulfides with almost equilibrium degrees of conversion. 100% selectivity towards diethyl sulfide is observed when ethylmercaptan conversion amounts to about 50% of its equilibrium value. In more severe conditions, dimethyl- and diethyl sulfides convert with eliminating hydrocarbons and H₂S. Selectivity towards diisopropylsulfide is as high as 30% with isopropylmercaptane conversion up to 25%; the reaction follows a parallel-consecutive scheme.

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-Al₂O₃ 200–500°C . 100% 50% . - H₂S. 30% 25%, - .

     

Modelling, refinement and analysis of the “Type III” δ-Bi2O3-related superstructure in the Bi2O3-Nb2O5 system

The structure of the “Type III” δ-Bi₂O₃-related superstructure phase in the system Bi₂O₃-Nb₂O₅ is presented. A starting model was constructed by considering the crystal-chemistry of the system in the context of symmetry constraints determined by electron diffraction. After applying initial distortions, this could be Rietveld-refined against a combination of synchrotron X-ray and time-of-flight neutron powder diffraction data. The undistorted starting model was independently optimized using solid-state ab initio energy calculations, giving a fully optimized structure in excellent agreement with that obtained by Rietveld refinement. This dual approach both validates the structure and demonstrates the value of combining accurate total energy calculations with traditional refinement techniques for the solution of complex structures using powder diffraction data. The structure (Bi₉₄Nb₃₂O₂₂₁, Z=1, (#119), a=11.52156(18), ) consists of interacting corner-connected strings of NbO₆ octahedra along 〈110〉_F directions of the FCC subcell, and can be described as a hybrid of fluorite and pyrochlore types.     

Role of support nature （γ-Al2O3 and SiO2-Al2O3） on the performances of rhenium oxide catalysts in the metathesis of ethylene and 2-pentene

The metathesis of ethylene and 2-pentene was studied as an alternative route for propylene production over Re2O7/γ-Al2O3 and Re2O7/SiO2-Al2O3 catalysts. Both NH3 temperature-programmed desorption (NH3-TPD) and H2 temperature-programmed reduction (H2-TPR) results showed that Re2O7/SiO2-Al2O3 exhibited stronger acidity and weaker metal-support interaction than Re2O7/γ-Al2O3. At 35 60℃, isomerization free metathesis was observed only over Re2O7/γ-Al2O3, suggesting that the formation of metal-carbene metathesis active sites required only weak acidity. Our results suggest that on the Re2O7/SiO2-Al2O3, hydrido-rhenium species ([Re]-H) were formed in addition to the metathesis active sites, resulting in the isomerization of the initial 1-butene product into 2-butenes. A subsequent secondary metathesis reaction between these 2-butenes and the excess ethylene could explain the enhanced yields of propylene observed. The results demonstrate the potential for high yield of propylene from alternative feedstocks.     

Oxidative coupling of methane over Bi2O3?P2O5?K2O/Sm2O3

Oxidative coupling of methane over Bi₂O₃–P₂O₅–K₂O/Sm₂O₃ takes place giving more C₂H₄ as compared to C₂H₆. Sm₂O₃ supported Bi–P–K is a more active and selective catalyst, than TiO₂, -Al₂O₃, SiO₂ and MgO supported catalysts.

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Bi₂O₃–P₂O₅–K₂O/Sm₂O₃ , . Bi–P–K, Sm₂O₃, , TiO₂, -Al₂O₃, SiO₂, MgO.

     

Effect of Fe-modified α-Al2O3 on the properties of Pd/α-Al2O3 catalysts in selective acetylene hydrogenation

The use of nanocrystalline Fe-modified α-Al₂O₃ prepared by sol–gel and solvothermal method as supports for Pd catalysts resulted in an improved catalyst performance in selective acetylene hydrogenation. Moreover, the amount of coke deposits was reduced due to lower acidity of the Fe-modified α-Al₂O₃ supports.     

Dehydrogenation of Isobutane Over V2O5/γ-Al2O3 Catalyst

The effect of the type of the support and the amount of V₂O₅ loading on the activity of V₂O₅/γ-Al₂O₃ catalyst for the dehydrogenation of isobutane have been investigated. Based on the experimental results of TPR, XRD and ESR spectroscopy, it is suggested that there are strong interactions between vanadia and carrier and that the V⁴⁺ species on the surface is the active site of V₂O₅/γ-Al₂O₃ for this reaction. This revised version was published online in June 2006 with corrections to the Cover Date.     

Reaction of tetrahydrofuran with H2S in the presence of Na+/γ-Al2O3

Modification of -Al₂O₃ by sodium hydroxide promotes the increase of surface basicity but does not exert a strong effect on catalytic activity in the reaction of thiolane production from tetrahydrofuran and H₂S. Introduction of NaOH to -Al₂O₃ in small concentration increases the number of Lewis acid centers but decreases their strength. The activity of Na/-Al₂O₃ referred to one Lewis acid center drops.     

On the reduction of Pd2+ forms in Pd/γ-Al2O3 catalysts

The influence of the preparation method (i.e., Pd precursor and heat treatments) on the reduction pattern of Pd/-Al₂O₃ catalysts has been investigated by TPR. The role of the Cl^– ions and the effect of metal dispersity on the stability of Pd catalysts reduced at different T_r (400T_r800°C) have been discussed. Reoxidation of Pd^o occurs during exposure to the atmosphere and the formation both of easily reducible PdO forms and Cl-containign Pd²⁺ oxo-complexes, strongly interacting with alumina surface, has been pointed out.     

Effect of some parasite surface reactions on the variation of electrical conductance in the H2?Pt/Al2O3 system

The charge transfer at the interface H₂-0.5% Pt/Al₂O₃ was studied by using the transient response of the AC electrical conductance. The transient response for water and oxygen contaminated surface was of the overshoot-type.     

Pt–Sn/Al2O3 catalyst for the selective hydrodeoxygenation of esters

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Solid solubility of Yb2Si2O7 in β-, γ- and δ-Y2Si2O7

This paper examines the structural changes with temperature and composition in the Yb₂Si₂O₇-Y₂Si₂O₇ system; members of this system are expected to form in the intergranular region of Si₃N₄ and SiC structural ceramics when sintered with the aid of Yb₂O₃ and Y₂O₃ mixtures. A set of different compositions have been synthesised using the sol-gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1650 °C during different times. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of Yb₂Si₂O₇ in β-Y₂Si₂O₇ and γ-Y₂Si₂O₇. Although Yb₂Si₂O₇ shows a unique stable polymorph (β), Yb³⁺ is able to replace Y³⁺ in γ-Y₂Si₂O₇ and δ-Y₂Si₂O₇ at high temperatures and low Yb contents. IR results confirm the total solid solubility in the system and suggest a constant SiOSi angle of 180° in the Si₂O₇ unit across the system. The temperature-composition diagram of the system, obtained from powder XRD data, is dominated by the β-RE₂Si₂O₇ polymorph, with γ-RE₂Si₂O₇ and δ-RE₂Si₂O₇ showing reduced stability fields. The diagram is in accordance with Felsche's diagram if average ionic radii are assumed for the members of the solid solution at any temperature, as long as the β-γ phase boundary is slightly shifted towards higher radii.     

Hydrogenation of Cinnamaldehyde on Ir/γ-Al2O3 Catalysts. Influence of the Surface Acidity

The oxidation of methane has been studied in a flow system as a function of the chemical composition of zeolite catalyst using nitrous oxide as oxidant. It is concluded that methanol is a primary oxidation product which may undergo further oxidation to formaldehyde and to carbon oxides. However, it may also undergo conversion over the acidic catalyst to higher hydrocarbons. Reaction with nitrous oxide resulted in the production of carbon oxides, methanol, formaldehyde, C₂ - C₄ , C₅ - C₇ nonaromatics, and aromatics. The effect of Fe₂ O₃ and Al₂ O₃ , with or without, over HZSM5 on products was studied.     

Synthesis of β-peroxy-lactones using 30% H2O2

Cyclopropyl carbinols 1a-e react with H₂O₂ in the presence of concd H₂SO₄ at 0-5 °C to furnish the corresponding hydroperoxides 2a-e in 45-82% yields. This efficient trapping of cyclopropylmethyl cations by the hydroperoxy group has been exploited to prepare compounds 14-23, a new series of cyclopropyl substituted β-peroxy-lactones.     

Tuning the shell thickness of core-shell α-Fe2O3@SiO2 nanoparticles to promote microwave absorption

Various advanced microwave absorbing materials have been developed for reducing/avoiding the harm of microwave radiation.Among them,core-shell structural nanomaterials have been widely fabricated for microwave absorption.However,the“structure-performance”relationship between shell thickness and microwave absorption performance is rarely reported.In this paper,we first explored the“structureperformance”relationship between shell thickness and microwave absorption performance,based on the core-she...     

Tuning the shell thickness of core-shell α-Fe2O3@SiO2 nanoparticles to promote microwave absorption

Various advanced microwave absorbing materials have been developed for reducing/avoiding the harm of microwave radiation.Among them,core-shell structural nanomaterials have been widely fabricated for microwave absorption.However,the“structure-performance”relationship between shell thickness and microwave absorption performance is rarely reported.In this paper,we first explored the“structureperformance”relationship between shell thickness and microwave absorption performance,based on the core-she...