Modifying the functional cover of the γ-Al2O3 surface using organic salts of aluminum

A method is suggested for modifying the surface properties of alumina without changing its chemical composition. The sorption of aluminum complexes with organic acid ligands on the γ-Al₂O₃ surface is reported. The thermal decomposition of the adsorbed oxalate complexes yields supported aluminum oxide compounds on the surface of the initial support. This modifies the functional cover of the γ-Al₂O₃ surface, altering the proportions of different types of surface hydroxyl groups, reducing their total number, and lowering the concentration of weak Lewis acid sites.     

A study of the influence of the conditions of preparation of γ-aluminum oxide as a carrier for reforming catalysts on its physicochemical properties

The formation of highly imperfect γ-Al₂O₃ oxide prepared by calcining pseuodoboehmite and plasticized by organic acids was studied. The nature of the organic acid-aluminum hydroxide plasticizer was found to substantially influence the degree of γ-Al₂O₃ structure imperfection estimated qualitatively as the difference between the X-ray structural density and effective density with respect to helium and aluminum oxide. A high degree of imperfection caused an increase in the intensity of the absorption band at 3775 cm⁻¹ corresponding to OH groups localized on five-coordinate Al³⁺ and the concentration of Lewis acid centers. The adsorption and catalytic properties of systems based on these carriers were studied.     

Effect of silica on the stability of the nanostructure and texture of fine-particle alumina

The effect of the modification of aluminum oxide with silicon oxide on the stability of fine-particle Γ- and δ-Al₂O₃ phases upon heat treatment in the wide temperature range of 550–1500°C was studied. It was found that the Γ- and δ-Al₂O₃ phases modified with silica are thermally stable up to higher temperatures than pure aluminum oxide. This is due to changes in the real structure of the modified samples, specifically, an increase in the concentration of extensive defects stabilized by hydroxyl groups bound to not only aluminum atoms but also silicon atoms. It is likely that Si-OH groups, which are thermally more stable than Al-OH groups, stabilize the microstructure of Γ- and δ-Al₂O₃ to higher temperatures, as compared with aluminum oxide containing no additives. Simultaneously, an increase in the thermal stability of the modified samples is accompanied by the retention of a high specific surface area and a developed pore structure at higher treatment temperatures.     

Probing the surface acidity of modified γ-alumina with1H and15N high-resolution solid state NMR spectroscopy

¹H MAS NMR and¹⁵N NMR studies of adsorbed N₂ and N₂O molecules were used to characterize Br?nsted and Lewis acidic sites of unmodified γ-Al₂O₃ and γ-Al₂O₃ modified with NaOH. Changes in the concentrations of surface hydroxyls with the increase in the number of more “basic” OH groups for NaOH/γ-Al₂O₃ have been found by¹H MAS NMR experiments. Two different types of Lewis acidic sites in γ-Al₂O₃ have been revealed using¹⁵N NMR studies. The strongest sites are poisoned even at small NaOH concentrations (ca. 0.05 wt.%). Not only the number of electron-accepting sites but also their strength are supposed to decrease for modified γ-alumina.     

Absorption and reaction of CO2 with 2,3-epoxypropyl phenyl ether using aliquat 336 AS catalyst

A kinetic study on the absorption and reaction of carbon dioxide with 2,3-epoxypropyl phenyl ether (phenyl glycidyl ether, PGE) in benzene solution has been carried out at room temperature in the presence of tricaprylylmethyl ammonium chloride (Aliquat 336) as catalyst. A simple method of measuring the absorbed volume of CO₂ was proposed to obtain the reaction rate constant, and it was based on the film theory accompanied by a chemical reaction. The enhancement factor (β-N_CO2/N_CO2 ^o) increased with increasing bulk concentration of PGE and Aliquat 336. The flux of CO₂ was proportional to the agitation speed.     

Adsorption and catalytic properties of sulfated aluminum oxide modified with cobalt ions

The adsorption properties of sulfated aluminum oxide (9% SO ₄ ^2- /γ-Al₂O₃) and a cobalt-containing composite (0.5%Сo/SO ₄ ^2- /γ-Al₂O₃) based on it are studied via dynamic sorption. The adsorption isotherms of such test adsorbates as n-hydrocarbons (C₆–C₈), benzene, ethylbenzene, chloroform, and diethyl ether are measured, and their isosteric heats of adsorption are calculated. It is shown that the surface sulfation of aluminum oxide substantially improves its electron-accepting properties, and so the catalytic activity of SO ₄ ^2- /γ-Al₂O₃ in the liquid-phase alkylation of benzene with octene-1 at temperatures of 25–120°C is one order of magnitude higher than for the initial aluminum oxide. It is established that additional modification of sulfated aluminum oxide with cobalt ions increases the activity of this catalyst by 2–4 times. It is shown that adsorption sites capable of strong specific adsorption with both donating (aromatics, diethyl ether chemosorption) and accepting molecules (chloroform) form on the surface of sulfated γ-Al₂O₃ promoted by cobalt salt.     

Sorption behavior of γ-irradiated α-Al2O3

Irradiation of α-Al₂O₃ (Corundum) was carried out in contact with acidic media and with different doses (100-to-2500 kGy) and dose-rates (0.9, 2.6 and 6.1 kGy·h⁻¹) of γ-rays. Simultaneously parallel experiments were carried out using the same procedure, but preheated at 150°C for two days and then irradiated without acidic media. The solid thus obtained was used to determine the effect of γ-irradiation on the sorption capacities of microamounts of fission products from strongly alkaline aqueous solutions of uranium. The results revealed that the effect of γ-irradiation of α-Al₂O₃ and the acidic media in which it is immersed, is associated with a stable matrix resistant to significant changes in the composition of the surface layer; whilst it seems that the effect of γ-irradiation of preheated α-Al₂O₃, is connected with changes of surface-OH groups strongly affected by heat treatment and irradiation dose.     

Effect of phenyl group on the structure and formation of transitional alumina from Al (OPh)<Subscript>3</Subscript>

The structure of freshly prepared Al(OPh)₃, its decomposition product, the hydrolyzed products and their structural evolution were investigated employing ²⁷Al MAS NMR spectroscopy, PXRD, TGA/DTA/DSC/FTIR techniques. In the ²⁷Al MAS NMR spectrum of the aluminium phenoxide, three signals with the chemical shift at 3.78, 21 and 45 ppm were observed. The chemical shift at 3.78 and 45 ppm revealed the presence of four and sixfold coordinated aluminum. The signal at 21 ppm corresponded to fivefold coordinated aluminium. When the aluminium phenoxide was directly decomposed in air at 600 °C, it resulted in amorphous product as evidenced from the PXRD pattern. The observed signals with chemical shifts at 10.1, 42, 73.6 ppm in the ²⁷Al MAS NMR spectrum indicated the presence of 6, 5 and 4 coordination for the aluminium atoms suggesting disordered transitional γ-alumina to be the product. The hydrolysis studies of Al(OPh)₃ with excess of water at 70 °C yielded bohemite (γ-AlOOH). The alumina obtained after dehydration at 600 °C was X-ray amorphous. The dehydrated product at 600 °C showed the presence of four and six coordinated aluminium atoms in the ²⁷Al MAS NMR spectrum confirming it to be ordered γ-Al₂O₃. Crystalline γ-Al₂O₃ was obtained on further heating at 800 °C.     

Catalytic properties of Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts in the aqueous-phase reforming of ethylene glycol: Effect of the alumina support

The influence of the alumina support on the catalytic activity of Pt/Al₂O₃ catalysts in aqueous phase reforming of ethylene glycol to hydrogen was studied. The catalysts were prepared by impregnation of γ-, δ-, and α-alumina with H₂PtCl₆. The highest rate of hydrogen production (452 μmol min⁻¹ g⁻¹) obtained with the Pt/α-Al₂O₃ catalyst can be related to the highest extent of dispersion of Pt on α-Al₂O₃. XPS, TEM-EDX and TPR-H₂ measurements showed the absence of chloride-containing surface complexes in the Pt/α-Al₂O₃ catalyst. However, chloride-containing entities were found on the surface of Pt/γ-Al₂O₃ and Pr/δ-Al₂O₃ catalysts. When chloride ions are removed chlorinated Pt species facilitate the sintering of Pt crystallites and in this way affect the extent of Pt dispersion. Moreover, depending upon the particular crystalline form, alumina atoms have different coordination and alumina surfaces contain varying amounts of OH groups of different nature which affect the interaction between Pt and the support.     

XPS and SIMS Examination of Alumina Fibres Affected with Mg and MgLi Melt

 Fibre/matrix interfaces in δ-Al₂O₃/Mg8Li and δ-Al₂O₃/Mg composites have been investigated using XPS and SIMS analysis of extracted δ-Al₂O₃ fibres in context with previous XRD observations. Results obtained indicate that in MgLi based composites lithium enters preferentially the interfacial redox reactions producing Li⁺ ions that occupy vacant cation positions in the defect δ-Al₂O₃ lattice which results in a strong fibre/matrix interfacial bond. On the other hand, in Mg matrix composites the magnesium oxide appears to be the final reaction product that does not enter the solid state reaction with adjacent δ-Al₂O₃ fibre during the melt infiltration process, so that only relatively weak interfacial bond is created.     

Hydroisomerization of benzene-containing gasoline fractions on a Pt/SO 42? -ZrO2-Al2O3 catalyst: I. Effect of chemical composition on the phase state and texture characteristics of SO 42? -ZrO2-Al2O3 supports

A series of SO₄²⁻-ZrO₂-Al₂O₃ oxide supports containing from 18.8 to 89.1 wt % alumina was prepared by mixing sulfated zirconia hydrate (weight ratio ZrO₂: H₂SO₄ = 9 : 1) and pseudoboehmite followed by calcination at 650°C. For the subsequent use of the supports to optimize the acid and hydrogenating properties of bifunctional hydroisomerization catalysts of the Pt/SO₄²⁻-ZrO₂-Al₂O₃ type, the formation of these catalysts in the course of thermal treatment and their texture characteristics and phase composition were studied. It was found by chemical and thermogravimetric analysis that the addition of pseudoboehmite to sulfated zirconia hydrate resulted in a decrease in sulfur losses in the course of support production from 55.0 to 2.0% with respect to its nominal amount. As the alumina content was increased from 18.8 to 89.1 wt %, the specific surface area and the pore volume of the support increased nonadditively with respect to mechanical mixtures of sulfated zirconia and γ-alumina (from 155 to 197 m²/g and from 0.24 to 0.52 cm³/g, respectively); in this case, a maximum deviation was 18–21%. The experimental results can be explained by chemical interactions between the initial components of the supports. The results of thermogravimetric and X-ray diffraction analysis suggest that the reaction products are sulfated alumina and a sulfated ZrO₂-Al₂O₃ solid solution.     

Preparation,properties, and catalytic activity of platinum-modified plasma electrolytic oxide structures on aluminum

Catalytically active Pt-containing oxide composites on aluminum have been prepared by plasma electrolytic oxidation (PEO) and by additional modification of the resulting coating by impregnation with an aqueous solution of chloroplatinic acid followed by calcination. The oxide film/metal composites have been characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and electron microscopy. The modified films contain the γ-Al₂O₃ and Pt crystalline phases. Platinum in the surface and subsurface layers is in the Pt⁰ state. There are platinum-rich areas on the surface of the PEO films. A higher catalytic activity in CO oxidation into CO₂ is shown by the samples whose oxide film contains nickel and copper along with platinum.     

DME Synthesis From CO/H2 over Cu-Mn/?-Al2O3 Catalyst

A γ-alumina-supported copper-manganese oxide catalyst prepared by an impregnation method was used for DME synthesis from CO/H₂ (syngas). The Cu-Mn/γ-Al₂O₃ catalyst exhibits high catalytic activity in CO hydrogenation. The effect of the loading amount of Cu, the ratio of n(Cu)/n(Mn) and the reaction conditions on the activity and selectivity to dimethyl ether (DME) from CO/H₂ (syngas) were investigated. The activity was found to increase with increasing surface area of metallic copper to some extent, but it is not a linear relationship. This indicated that the catalytic activity depends on both the metallic copper area and the synergy between the copper and manganese oxide. This revised version was published online in June 2006 with corrections to the Cover Date.     

Racemization of chiral amino alcohols III: Effect of Mg or Ca addition on the activity and stability of the Co/γ-Al2O3 catalyst

The racemization of R-(-)-2-amino-1-butanol in a reaction using Co/γ-Al₂O₃ catalysts and catalysts modified by Mg or Ca was investigated in this paper. Complete racemization was achieved with a yield of over 83% at using the Mg modified Co/γ-Al₂O₃ catalyst under optimized reaction conditions of 170°C and 2.5 MPa of H₂. The catalysts were thoroughly characterized by XRD, XPS, TPR, SEM and TEM. The addition of Mg and Ca may be advantageous for dispersing and stabilizing the active species of the Co/γ-Al₂O₃ catalyst, protecting from sintering, significantly improving its catalytic activity and stability.     

Sorption behavior of Co(II) on γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in the presence of humic acid

The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions. The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations on the Co(II) sorption on γ-Al₂O₃ in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al₂O₃ in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly positive influence of HA at low pH on the Co(II) sorption on γ-Al₂O₃ was attributed to strong surface binding of HA on γ-Al₂O₃ and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO⁻) _x Co^2−x . Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al₂O₃ in the presence of HA.     

Effect of kcl on cucl2/γ-al2o3 catalyst for oxychlorination of ethane

Summary Effect of KCl on the structure and the catalytic properties of CuCl₂/γ-Al₂O₃ catalyst for ethane oxychlorination has been studied by means of solubility test, UV-vis spectroscopy, XRD, TPR, TEM and catalytic reaction. Addition of KCl decreases the interaction between active species CuCl₂ and γ-Al₂O₃ and increases the catalytic properties by accelerating the Cu(II) → Cu(I) reduction step.     

Influence of pH,humic acid,ionic strength,foreign ions,and temperature on <Superscript>60</Superscript>Co(II) sorption onto γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The sorption of ⁶⁰Co(II) on γ-Al₂O₃ was conducted under various conditions, i.e., contact time, adsorbent content, pH, ionic strength, foreign ions, humic acid (HA), and temperature. Results of sorption data analysis indicated that the sorption of ⁶⁰Co(II) on γ-Al₂O₃ was strongly dependent on pH and ionic strength. At low pH the sorption was dominated by outer-sphere surface complexation or ion exchange, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The presence of different cation ions influenced ⁶⁰Co(II) sorption, while the presence of different anion ions had no obvious influences on ⁶⁰Co(II) sorption. The presence of HA decreased the sorption of ⁶⁰Co(II) on γ-Al₂O₃. The sorption isotherms were simulated well with the Langmuir model. The thermodynamic parameters (ΔH ⁰ , ΔS ⁰ and ΔG ⁰ ) calculated from the temperature-dependent sorption isotherms indicated that the sorption of ⁶⁰Co(II) on γ-Al₂O₃ was an endothermic and spontaneous process. Experimental results indicated that the low cost material was a suitable material in the preconcentration of ⁶⁰Co(II) from large volumes of aqueous solutions.     

Preparation of γ-Alumina Membranes From Sulphuric Electrolyte Anodic Alumina and Its Transition to α-Alumina

Gamma-alumina membrane was prepared from anodic (amorphous) alumina (AA) obtained in a sulphuric acid electrolyte. The transformation scheme, i.e., the crystallization to form metastable alumina polymorphs and the final transition to α-Al₂O₃ with heating was studied by TG-DTA and X-ray diffraction (XRD) using fixed time (FT) method. When heating at a constant rate, the crystallization occurred at 900°C or higher and the final formation of α-Al₂O₃ occurred at 1250°C or higher, which temperatures were higher than the case of using anodic (amorphous) alumina prepared from oxalic acid electrolyte. Relative content of S of the products was obtained by transmission electron microscope (TEM)-energy dispersive spectroscopy (EDS). The proposed thermal change of anodic alumina membrane prepared from sulphuric acid is as follows: 1. At temperatures lower than ca 910°C: Formation of a quasi-crystalline phase or a polycrystalline phase (γ-, δ- and θ-Al₂O₃); 2. 910–960°C: Progressive crystallization by the migration of S toward the surface within the amorphous or the quasi-crystalline phase, forming S-rich region near the surface; 3. 960°C: Change of membrane morphology and the quasi-crystalline phase due to the rapid discharge of gaseous SO₂; 4. 960–1240°C: Crystallization of γ-Al₂O₃ accompanying δ-Al₂O₃; and 5. 1240°C: Transition from γ-Al₂O₃ (+tr. δ-Al₂O₃) into the stable α-Al₂O₃. The amorphization which occurs by the exothermic and the subsequent endothermic reaction suggests the incorporation of SO₃ groups in the quasi-crystalline structure. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetic Method by Using Calorimetry to Mechanism of Epoxy-Amine Cure Reaction

The thermokinetic behavior of the reaction between phenyl glycidyl ether and aniline closely resembles the analogous diepoxy diamine cure reaction in that the reactants are assembled before bond-breaking step occurs, and does not proceed through free reacting groups. The mechanism of the reaction between phenyl glycidyl ether and aniline in solventless system involves in addition to mechanism of the epoxy ring opening, structure changes accompanied by phase separation related to the self-aggregation. In an attempt to obtain further information about the reaction mechanism, the DSC heating runs of the reacted samples have been examined. These results suggest that the observed endothermic peaks are associated with additional ordering. The latter takes place only at lower temperature than reaction temperature. Since the rate constant k ₂ values for autocatalysed reaction follow of Arrhenius behavior, it is possible to calculate the activation energy, which is E=51 kJ mol^-1. Analysis of the kinetic experiments demonstrates that the heat of reaction that are detected in kinetic measurements provide correct information about the mechanism of the process. This revised version was published online in August 2006 with corrections to the Cover Date.     

Investigations on the selectivity of catalytic no reduction by ammonia

The activity and selectivity of V₂O₅/γ-Al₂O₃ catalyst were studied in the catalytic reduction of nitrogen oxide by ammonia. The activity of the catalyst monotonically increases as a function of temperature, however, its selectivity decreases. The DeNOx reaction of nitrogen oxides with ammonia can be described well by a mathematical model, which considers selectivity-decreasing side reactions as well in a wide temperature range (220–420°C).