On the promotional effect of Sn in Co–Sn/Al2O3 catalyst for NO selective reduction

NO reduction with propylene over Co/Al₂O₃ and Co–Sn/Al₂O₃ catalysts has been investigated. For the Co/Al₂O₃ catalyst, a calcination temperature exceeding 800°C led to a decrease of NO conversion. Calcination of the Co/Al₂O₃ catalyst at 1000°C resulted in the formation of -Al₂O₃ and Co₃O₄. The presence of 20% water vapor showed a significant shift for the maximum NO reduction temperature from 450 to 600°C over Co/Al₂O₃. It has been found that modification of 6 wt% Co/Al₂O₃ with 2 wt% Sn significantly enhanced the catalyst thermal stability and improved the inhibitory effect of water on NO conversion and reaction temperature. The promotional effect of Sn on the catalyst thermal stability was attributed to the suppression of the phase transformation from highly dispersed Co²⁺ species on -Al₂O₃ to -Al₂O₃ and Co₃O₄. The smaller influence of water vapor on NO reduction conversion and temperature over Co–Sn/Al₂O₃, compared to Co/Al₂O₃, was attributed to the dispersion effect of Sn species on Co²⁺ species as well as the involvement of Sn species in NO reduction at a relatively lower temperature. The synergetic effect between the octahedral Co²⁺ species and -alumina plays a significant role in the catalysis of NO selective reduction by C₃H₆.     

Characterization of MoO3–V2O5/Al2O3 catalysts for selective catalytic reduction of NO by NH3

MoO₃–V₂O₅/Al₂O₃ catalysts were characterized by B.E.T., XRD, LRS, XPS and TPR and the effect of MoO₃ addition to alumina supported vanadia catalysts on the catalytic activity for the selective catalytic reduction of NO by ammonia was investigated. Upon the addition of MoO₃, catalytic activity was enhanced and the particle size of V₂O₅ which is shown by the results of B.E.T., XRD and Raman spectroscopy decreased. This was one reason for increased catalytic activity. The results obtained by XPS and TPR showed that MoO₃ addition to alumina supported vanadia catalysts increased the reducibility of vanadia and this was the another reason for synergy effect between MoO₃ and V₂O₅ in MoO₃–V₂O₅/Al₂O₃ catalysts.     

The effect of Si–Bi2O3 on the ignition of the Al–CuO thermite

The ignition temperature of the Al–CuO thermite was measured using DTA at a scan rate of 50 °C min^?1 in a nitrogen atmosphere. Thermite reactions are difficult to start as they require very high temperatures for ignition, e.g. for Al–CuO thermite comprising micron particles it is ca. 940 °C. It was found that the ignition temperature is significantly reduced when the binary Si–Bi₂O₃ system is added as sensitizer. Further improvement is achieved when the reagents are nano-sized powders. For the composition Al + CuO + Si + Bi₂O₃ (65.3:14.7:16:4 wt.%), with all components nano-sized, the observed ignition temperature is ca. 613 °C and a thermal runaway reaction is observed in the DTA.     

Ru-Pt catalysts supported on Al2O3 and SiO2─Al2O3 for the selective ring opening of naphthenes

Alumina and silica-alumina supported Ru-Pt catalysts were evaluated for the ring opening of naphthenes. Pt, Ru, and Ru-Pt catalysts were prepared by the impregnation of inorganic precursors over γ-alumina and silica-alumina supports. The catalysts were evaluated by temperature programmed reduction (TPR), pyridine temperature programmed desorption (TPD), CO-FTIR, and by test reactions of 33DM1B isomerization, cyclohexane dehydrogenation, cyclopentane hydrogenolysis, and the ring opening of decalin. The strong interaction between the metals (Pt-Ru) was attributed to their reductions occurring simultaneously. The acidity and strength of the acid sites of the monometallic Ru catalyst were higher than those of the monometallic Pt catalyst. The total acidity (Lewis and Brønsted) and the strength of the acid sites were higher for the silica-alumina supported catalysts. The silica-alumina catalysts had 10 times more Brønsted acidity than the γ-alumina ones and an increased activity and selectivity to decalin ring opening products. Supported monometallic Ru had the best performance for the ring opening reaction.     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Origin of rate bistability in Mn–O/Al2O3 catalysts for carbon monoxide oxidation: role of the Jahn–Teller effect

Peculiarities in catalytic activity in carbon monoxide oxidation as well as some structure, electronic and magnetic properties of the three oxide catalysts, Mn³⁺–O/Al₂O₃ (1), Mn³⁺–O–Fe/Al₂O₃ (Mn-substituted spinel, 2) and -Fe₂O₃/Al₂O₃ (3), were studied by kinetic measurements and by Mössbauer spectroscopy. The catalysts 1 and 2 showed a kinetic bistability with a sharp transition towards more reactive state at 200°C (ignition point). In contrast, for catalyst 3, at 200–250°C, the behavior of reaction rate against temperature did not display noticeable hysteresis. On cooling the catalysts 1 and 2, extinction was observed at about 170 and 120°C, respectively, i.e., at 30–80°C lower than the corresponding ignition points. Proximity of activation energy for the high and low activity (15–19 kJ/mol) for both Mn-containing catalysts suggests an increase in the number of active sites at high temperature with no changes in the reaction mechanism. The considerable difference between Mn-containing catalysts 1, 2 and Fe-containing catalyst 3 may be caused by Jahn–Teller (JT) type distortions of the oxygen polyhedron around Mn³⁺. A significant spontaneous axial bond stretching within the local polyhedron seems to diminish Mn–O binding energy, facilitate the participation of surface oxygen species, O_S, in the oxidation of CO by a redox mechanism and promote oxygen vacancies at the surface that would cause considerable effect on the activity. An increase in the width of the counterclockwise hysteresis loop for the catalyst 2 compared to the catalyst 1 indicates that clusters of mixed spinel provide more active sites and more labile O_S species than clusters of the binary Mn oxide.     

Band gap tuning of Ga2O3–Al2O3 ceramics

Translucent ceramics comprising monoclinic Ga₂O₃ and non-cubic Ga₂O₃–Al₂O₃ solid solution with a composition of Ga_1.5Al_0.5O₃, GaAlO₃ and Ga_0.4Al_1.6O₃ were fabricated through two-step spark plasma sintering by using calcinated commercial mixture oxide ceramic powders. All sintered ceramics were nearly fully densified, with a relative density exceeding 99.2%. The average grain sizes decreased with increasing Al content. Band gap was tuned from 4.08 to 6.37 eV. The highest total transmittance (73.6% at 1100 nm) was measured in Ga_0.4Al_1.6O₃ ceramics with both hexagonal (rhombohedral) and monoclinic crystal structures and a minimum average grain size of 0.288 ± 0.067 μm. Defect related photoluminescence, measured under excitation by a 254 nm UV lamp in the GaAlO₃ and Ga_0.4Al_1.6O₃ ceramics, lasted more than 15 s after removal of the UV source. These translucent ceramics from Ga₂O₃–Al₂O₃ solid solution provide an alternative form of a potential transparent conducting material.     

Al2O3 loss prediction model of selective laser melting Al2O3–Al composite

The element/phase loss is undesirable but existing during selective laser melting (SLM) of materials with volatile element/phase, which not only changes the material composition but also affects the molten pool flow. In the previous researches, the effect of remelting on the element/phase loss was neglected during the SLM process, instead, laser energy density was thought to be uppermost. In fact, the SLM process fabricates the parts in a manner of line by line and layer by layer, i.e., additive character, and the remelting in the overlap zone occurs during the SLM process. In this paper, three different Al₂O₃ loss prediction models of SLM Al₂O₃–Al composite by considering the additive character of SLM and the distribution of the Al₂O₃ associated with the different molten pool driving forces were developed. By comparing with the experimental results and predicted results, it is found that the Al₂O₃ is distributed on both sides of the molten pool under the combined action of the Marangoni flow and the evaporation recoil pressure. This kind of Al₂O₃ distribution enhances the effect of the remelting on the Al₂O₃ loss, i.e., the remelting brings a logarithmic increase in the Al₂O₃ loss rate. This determines the final Al₂O₃ loss rate of the SLMed 3D samples. During this study, although the Al₂O₃ loss rate of the single-track is only 33%, the loss rate of SLMed 3D samples increases significantly to 97% when the hatching space of 60 μm and scanning speed of 200 mm/s are utilized, i.e., almost no Al₂O₃ in the 3D sample. Thus, it is more important to reduce the remelting, i.e., overlap rate for reducing the element/phase loss. This study is a benefit for understanding and reducing the element/phase loss in SLM.     

Enhanced Activity of Spinel-type Ga2O3–Al2O3 Mixed Oxide for the Dehydrogenation of Propane in the Presence of CO2

Catalytic performance of a series of Ga₂O₃–Al₂O₃ mixed oxides prepared by alcoholic-coprecipitation method for the dehydrogenation of propane in the presence of CO₂ was investigated. It is shown that the combination of Ga and Al oxides greatly improved the performance of the Ga₂O₃-based materials for catalytic dehydrogenation of propane, with the highest performance attainable at a Ga₂O₃–Al₂O₃ catalyst with a 20 mol% aluminum content. While the same tendency was observed for the specific activity normalized by BET surface area, significantly enhanced stability was achieved for Ga₂O₃–Al₂O₃ with higher aluminum content. X-ray diffraction (XRD) revealed that a homogeneous spinel-type Ga₂O₃–Al₂O₃ solid solution is uniformly formed by substitution of Ga³⁺ for Al³⁺ in the Al₂O₃ lattice. The enhanced activity of Ga₂O₃–Al₂O₃ mixed oxides was accounted for by the abundance of surface weak acid sites due to the synergetic interaction between Ga₂O₃ and Al₂O₃ in the solid solution systems.     

A Significant Role of Tb2O3 on the Optical Properties and Radiation Shielding Performance of Ga2O3–B2O3–Al2O3–GeO2 Glasses

Journal of Inorganic and Organometallic Polymers and Materials - This research article focuses on the significant role of Tb2O3 content on the optical properties and radiation shielding performance...     

Ordered mesoporous Ga2O3 and Ga2O3–Al2O3 prepared by nanocasting as effective catalysts for propane dehydrogenation in the presence of CO2

Thermally stable mesoporous gallium and gallium–aluminum (atomic ratio of Ga/Al = 4/1 and 1/4) oxides with controlled textural and structural properties were prepared by means of the nanocasting approach. All materials have uniform micron-sized particles, with a quite narrow pore-size distribution centered in the range of 6.2–6.5 nm and specific surface areas as high as 231–322 m²·g^− 1. Pure mesoporous gallium and gallium–aluminum (Ga/Al = 4:1) oxides exhibit a promising catalytic performance in the dehydrogenation of propane to propene in the presence of CO₂ (DHP-CO₂). Over the most active materials, during 4 h on stream at 823 K, propene was produced with the yield of 10–18% and high selectivity of 91–95%. Moreover, pure mesoporous gallium oxide exerted a higher resistance on deactivation during the DHP-CO₂ process in comparison with gallium oxide prepared without a hard template.     

Stability in the system CaO–Al2O3–H2O

The solubility of AH₃, CAH₁₀, C₂AH_7.5, and C₃AH₆ was determined experimentally at 7 to 40 °C and up to 570 days. During the reaction of CA, at 20 °C and above initially C₂AH_7.5 formed which was unstable in the long-term. The solubility products calculated indicate that the solubilities of CAH₁₀, C₂AH_7.5 and C₄AH₁₉ increase with temperature while the solubility of C₃AH₆ decreases. Thus at temperatures above 20 °C, C₃AH₆ is stable, while at lower temperature also CAH₁₀ and C₄AH₁₉ are stable, depending on the C/A ratio.At early hydration times, CAH₁₀ can be stable initially at 30 °C and above, as the formation of amorphous AH₃ stabilises CAH₁₀ with respect to C₃AH₆ + 2AH₃. With time, as the solubility AH₃ decreases due to the formation of microcrystalline AH₃, CAH₁₀ becomes unstable at 20 °C and above.     

Investigating the effect of WO3 on the crystallization behavior of SiO2–B2O3 – Al2O3–Na2O – CaO–ZnO high VIS-NIR reflecting glazes

White glass enamels with high solar reflectance and containing different WO₃ concentrations have been prepared and characterized with regard to their optical, mechanical and microstructural characteristics. Upon addition of WO₃ to a glass containing SiO₂, B₂O₃, Al₂O₃, Na₂O, CaO, and ZnO, the crystallization of scheelite follows a crystallization mechanism of bulk type where scheelite grows in one-dimension in a patterned morphology dominated by the heating rate and the concentration of WO₃. Octahedral bipyramids and arrow-like crystals appeared in enamels containing WO₃ concentration above 6%. The presence of scheelite crystals with different orientations also leads to slight variations in hardness and Young modulus thus obtaining Hv values between 8 and 8.8 GPa and E values between 72 and 83 GPa. Similarly, the optical properties such as whiteness, brightness and solar reflectance increase with the presence of scheelite, and the highest solar reflectance occurs for the enamel containing arrow-like and bipyramidal crystals.     

High‐activity catalyst of SO 4 2− /ZrO2 supported on γ‐Al2O3 for n‐butane isomerization

A series of Al₂O₃supported SO ₄ ^2– /ZrO₂ superacid catalysts (named SZ/Al₂O₃) were prepared by a precipitation method and their catalytic behavior for nbutane isomerization at low temperature in the absence of H₂ and at high temperature in the presence of H₂ was studied in this paper. The catalytic activities of some of these catalysts were enhanced significantly at both low and high temperatures. At 250°C after 6 h on stream, the steady activity of the most active sample, 60%SZ/Al₂O₃, is about two times higher than that of conventional SZ. The texture properties of catalysts were studied by the methods of XRD and the adsorption of N₂. Experimental evidence of IR of adsorbed pyridine indicates that the significant activity enhancements of SZ/Al₂O₃ catalysts are caused by the increasing of the amount of strong acid sites.     

Novel Pd–Au/TiO2 catalyst for the selective catalytic reduction of NOx by H2

Novel Pd–Au/TiO₂ catalyst exhibited high catalytic activity with a wide temperature window for the selective catalytic reduction of NO_x by H₂ in the presence of oxygen. The synergetic effect between Pd and Au contributes to the formation of Pd⁰ and Pd–Au alloy, thus promoting the NO_x reduction to proceed.     

Selective catalytic reduction of nitrogen oxides with hydrocarbons over Zn–Al–Ga complex oxides

Selective reduction of NO with hydrocarbons was studied using metal oxide catalysts having a spinel structure. A Zn–Al–Ga complex oxide was found to be very active and selective for the catalytic reduction of NO with both C₃H₆ and CH₄. It was revealed that the role of oxygen at the initial stage of the reaction strongly depends on the reductants; oxygen is mainly used for NO oxidation to NO₂ in the reduction with CH₄, whereas it is used both for NO oxidation to NO₂ and oxidation of C₃H₆ to an active intermediate in the reduction with C₃H₆. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mechanism of NO removal in selective catalytic reduction based on γ-Fe2O3 catalyst doped with Mg element

The doping of different elements will make the Fe₂O₃ catalyst show different catalytic characteristics and improve the activity of the Fe₂O₃ catalyst in selective catalytic reduction (SCR), mainly by increasing the types of reactive oxygen species and the specific surface area of the catalyst. In this paper, density functional theory (DFT) was used to reveal the reaction path and adsorption behaviour of the Mg-doped γ-Fe₂O₃ catalyst. The results show that the doping of Mg ions can contribute electrons and lead to electron migration on the catalyst surface, which changes the acidity of some sites on the catalyst surface. The adsorption energy of NH₃ is related to the binding sites of N atoms on the catalyst surface, and different adsorption sites will be enhanced or weakened due to Mg doping. NH₂ reacts with NO to form N₂ and H₂O, so the dehydrogenation of NH₃ to the NH₂ radical is a key step in SCR. With doping, this process becomes more likely to occur. In addition, the activation energy barrier of NH₂ formation in the aerobic environment is lower than that in the anaerobic condition, which contributes to NH₃ dehydrogenation. Therefore, doping Mg on the surface of γ-Fe₂O₃ catalyst can improve the catalytic activity of NO removal.     

The effect of CuO–ZnO–Al2O3 catalyst structure on the ethanol synthesis from syngas

CuO–ZnO–Al₂O₃ catalysts were prepared by complete liquid phase technology with different addition sequences. The results indicated that the catalyst prepared by the addition of (C₃H₇O)₃Al to Cu(NO₃)₂ and Zn(NO₃)₂ solutions shows excellent ethanol selectivity at the initial stages of reaction, reaching approximately 40%. X-ray photoelectron spectroscopy results showed that ethanol synthesis requires a higher Cu⁺ content and higher Cu/Zn ratio on the catalyst surface. The temperature-programmed reduction test revealed strong interactions between Cu species and zinc or aluminum oxide. The increase in the difficulty of catalyst reduction indicated higher ethanol selectivity.     

Effect of Al2O3 content on BaO–Al2O3–B2O3–SiO2 glass sealant for solid oxide fuel cell

The glass structure, wetting behavior and crystallization of BaO–Al₂O₃–B₂O₃–SiO₂ system glass containing 2–10 mol% Al₂O₃ were investigated. The introduction of Al₂O₃ caused the conversion of [BO₃] units and [BO₄] units to each other and it played as glass network former when the content was up to 10 mol%, accompanied by [BO₄] → [BO₃]. The stability of the glass improved first and then decreased as Al₂O₃ increased from 2 to 10 mol%, the glass with 5 mol% Al₂O₃ being the most stable one. The wetting behavior of the glasses indicates that excess Al₂O₃ leads to high sealing temperature. The glass containing 5 mol% Al₂O₃ characterized by a lower sealing temperature is suitable for SOFC sealing. Al₂O₃ improves the crystallization temperature of the glass. The crystal phases in the reheated glasses are mainly composed of Ba₂Si₃O₈, BaSiO₃, BaB₂O₄ and BaAl₂Si₂O₈. Al₂O₃ helps the crystallization of BaSiO₃ and BaAl₂Si₂O₈.     

Novel sol–gel‐derived Ag/SiO2–Al2O3 catalysts for highly selective oxidation of methanol to formaldehyde

Novel Ag/SiO₂–Al₂O₃ catalysts with low silver content prepared by the sol–gel method exhibit excellent catalytic properties in the catalytic oxidation of methanol to formaldehyde. The silver content was as low as 2% and the yield of formaldehyde was achieved as 90.3%, which is 16% higher than that of pumice‐supported silver and even 5–6% higher than that of a commercial electrolytic silver catalyst. XRD, XPS and SEM results reveal that all silver was present as Ag⁺ before catalytic reaction and was partially reduced to the metallic state after the reaction. It was also found that silver was aggregated on the surface after its reduction. This revised version was published online in July 2006 with corrections to the Cover Date.