Enhancement of oxygen storage capacity by reductive treatment of Al2O3 and CeO2–ZrO2 solid solution nanocomposite

Oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solution, Ce_xZr_(1−x)O₄, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al₂O₃ and CeZrO₄ (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m²/g) after reductive treatment at 1000 °C. The introduced Al₂O₃ facilitated the regular rearrangement of Ce and Zr ions in CeZrO₄ as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.     

Nano-gold supported on Fe2O3: A highly active catalyst for low temperature oxidative destruction of methane green house gas from exhaust/waste gases

A number of nano-gold catalysts were prepared by depositing gold on different metal oxides (viz. Fe₂O₃, Al₂O₃, Co₃O₄, MnO₂, CeO₂, MgO, Ga₂O₃ and TiO₂), using the homogeneous deposition precipitation (HDP) technique. The catalysts were evaluated for their performance in the combustion of methane (1 mol% in air) at different temperatures (300–600 °C) for a GHSV of 51,000 h⁻¹. The supported nano-gold catalysts have been characterized for their gold loading (by ICP) and gold particle size (by TEM/HRTEM or XRD peak broadening). Among these nano-gold catalysts, the Au/Fe₂O₃ (Au loading = 6.1% and Au particle size = 8.5 nm) showed excellent performance. For this catalyst, temperature required for half the methane combustion was 387 °C, which is lower than that required for Pd(1%)/Al₂O₃ (400 °C) and Pt(1%)/Al₂O₃ (500 °C) under identical conditions. A detailed investigation on the influence of space velocity (GHSV = 10,000–100,000 cm³ g⁻¹ h⁻¹) at different temperatures (200–600 °C) on the oxidative destruction of methane over the Au/Fe₂O₃ catalyst has also been carried out. The Au/Fe₂O₃ catalyst prepared by the HDP method showed much higher methane combustion activity than that prepared by the conventional deposition precipitation (DP) method. The XPS analysis showed the presence of Au in the different oxidation states (Au⁰, Au¹⁺ and Au³⁺) in the catalyst.     

Synthesis and study of a new class of red pigments based on perovskite YAlO3 structure

A red pigment has been prepared by substituting chromium ions in aluminum ion sites in YAlO₃ perovskite structure. In a first step, effect of various mineralizers on YAlO₃ formation has been investigated, which resulted in decrease of formation temperature down to 1400 °C. In the next step, a red pigment corresponding to YAl_1−yCr_yO₃ (y = 0.05), has been prepared by heating a mixture containing Y₂O₃, Al₂O₃ and Cr₂O₃ at 1500 °C for 6 h. Later, effect of the doped chromium amount on the pigment redness (a^*) has been studied. The highest redness has been obtained when y was 0.04(YAl_1−yCr_yO₃). Application of the prepared red pigment in low and high temperature glazes, demonstrated its high chemical and thermal stability.     

Improvement of thermal stability of NO oxidation Pt/Al2O3 catalyst by addition of Pd

The present work has been undertaken to tailor Pt/Al₂O₃ catalysts active for NO oxidation even after severe heat treatments in air. For this purpose, the addition of Pd has been attempted, which is less active for this reaction but can effectively suppress thermal sintering of the active metal Pt. Various Pd-modified Pt/Al₂O₃ catalysts were prepared, subjected to heat treatments in air at 800 and 830 °C, and then applied for NO oxidation at 300 °C. The total NO oxidation activity was shown to be significantly enhanced by the addition of Pd, depending on the amount of Pd added. The Pd-modified catalysts are active even after the severe heat treatment at 830 °C for a long time of 60 h. The optimized Pd-modified Pt/Al₂O₃ catalyst can show a maximum activity limited by chemical equilibrium under the conditions used. The bulk structures of supported noble metal particles were examined by XRD and their surface properties by CO chemisorption and EDX-TEM. From these characterization results as well as the reaction ones, the size of individual metal particles, the chemical composition of their surfaces, and the overall TOF value were determined for discussing possible reasons for the improvement of the thermal stability and the enhanced catalytic activity of Pt/Al₂O₃ catalysts by the Pd addition. The Pd-modified Pt/Al₂O₃ catalysts should be a promising one for NO oxidation of practical interest.     

Effect of YAG content on creep resistance and mechanical properties of Al2O3-YAG composite

Comprehensive study on effect of YAG amount on densification, creep resistance and room-temperature mechanical properties of Al₂O₃-YAG composite pressureless sintered at 1600 °C was conducted. The main goal was to optimize the amount of YAG in order to fabricate a composite with improved creep resistance and sufficiently good room-temperature mechanical properties. The composite was made by mixing a commercially available Al₂O₃ powder with fine YAG powder obtained by glycine-nitrate combustion synthesis starting from aluminum nitrate and yttrium nitrate. Increased driving force for sintering of fine YAG powder allowed fabrication of dense Al₂O₃-YAG composite with up to 30 vol% YAG. The presence of YAG was found to be very effective in improving creep resistance of Al₂O₃-YAG composite. Large Y³⁺ ions blocked diffusion along Al₂O₃ grain boundaries, reduced diffusivity and therefore enhanced creep resistance of Al₂O₃-YAG composite which continuously increased as the YAG amount increased. Тhe presence of YAG was also found to improve mechanical properties such as hardness and elastic modulus. The improvement of these properties was ascribed to increased density of Al₂O₃-YAG composites owing to high sintering activity of YAG powder. While fracture strength of the composite can be as high as that of monolithic Al₂O₃, fracture toughness of composite decreased continuously as the YAG content increased. The decrease was ascribed to transgranular fracture of both YAG and Al₂O₃ grains in samples containing larger amounts of YAG. The proper balance between fracture toughness and creep resistance was found in composite containing 18 vol% YAG which had considerably improved creep resistance accompanied by a relatively small decrease in fracture toughness.     

Preparation and electrical properties of graphene nanosheet/Al2O3 composites

Fully dense graphene nanosheet(GNS)/Al₂O₃ composites with homogeneously distributed GNSs of thicknesses ranging from 2.5 to 20 nm have been fabricated from ball milled expanded graphite and Al₂O₃ by spark plasma sintering. The percolation threshold of electrical conductivity of the as-prepared GNS/Al₂O₃ composites is around 3 vol.%, and this new composite outperforms most of carbon nanotube/Al₂O₃ composites in electrical conductivity. The temperature dependence of electrical conductivity indicated that the as-prepared composites behaved as a semimetal in a temperature range from 2 to 300 K.     

Hydroformylation of olefins by Au/Co3O4 catalysts

The hydroformylation of olefins over supported gold catalysts in an autoclave reactor under mild conditions (100–140 °C, 3–5 MPa) has been studied. Over Au/AC (activated carbon), Au/PVP (polyvinylpyrrolidone), Au/Al₂O₃, Au/TiO₂, Au/Fe₂O₃, Au/ZnO, Au/CeO₂ and Co₃O₄, 1-olefin mainly remained unchanged and the major products were isomerized olefins or hydrogenated paraffin. In contrast, Au nanoparticles deposited on Co₃O₄ led to remarkably high catalytic activities in hydroformylation reaction with selectivities above 85% to desired aldehydes. The hydroformylation of olefins proceeds preferentially at temperatures below 140 °C, above which the reactions of olefins gradually shifted to isomerization and then to hydrogenation. It appeared that the activity and selectivity of hydroformylation reaction strongly depend on the molecular structure of olefins, which could be ascribed to steric constraints as internal olefins are relatively inappropriate to form alkyl group and subsequent acyl group by insertion of CO. The Au/Co₃O₄ catalyst can be recycled by simple decantation with slight decrease in catalytic activity along with an increase in recycle times, which is a great advantage over homogeneous catalysts. The role of gold nanoparticles can be assumed to dissociate hydrogen molecule into atomic species which reduce Co₃O₄ to Co metal under mild reaction conditions.     

Influence of composition of MgAl2O4 supported NiCeO2ZrO2 catalysts on coke formation and catalyst stability for dry reforming of methane

Dry reforming of methane was studied over Ni catalysts supported on γAl₂O₃, CeO₂, ZrO₂ and MgAl₂O₄ (670 °C, 1.5 bar, 16–20 l CH₄ ml_catalyst⁻¹ h⁻¹). It is shown that MgAl₂O₄ supported Ni catalysts promoted with both CeO₂ and ZrO₂ are promising catalysts for dry reforming of methane with carbon dioxide. Within a certain composition range, the simultaneous promotion with CeO₂ and ZrO₂ has great influence on the amount of coke and the catalyst service time. XRD analyses indicate that formation of crystalline Ce_xZr_1−xO₂ mixed oxide phases occurs on double promotion. In particular, incorporation of low amounts of Zr in the CeO₂ fluorite structure provides stable dry reforming catalysis. As shown with TPR, promotion leads to a higher reduced state of Ni. SEM, XRD and TPR analyses demonstrate that highly dispersed, doubly promoted Ni catalysts with a strong metal-support interaction are essential for stable dry reforming and suppression of the formation of carbon filaments.     

Sintering mechanism and dielectric properties of LiTaO3 matrix composites with the addition of Al2O3 particles

Highly densified Al₂O₃/LiTaO₃ (ALT) ceramic composites were fabricated by hot-pressing in a nitrogen atmosphere. The addition of Al₂O₃ particles could significantly improve the densification of LiTaO₃. Sintering mechanism of the LiTaO₃ ceramic incorporated with Al₂O₃ particles is proposed. Dielectric constant of 5 vol.% Al₂O₃/LiTaO₃ (5ALT) composite ceramic was slightly increased in the range from 30 kHz to 10⁶ Hz, but the dielectric loss was lowered in the whole range from 10³ Hz to 10⁶ Hz. Piezoelectric constant (d₃₃) of the 5ALT ceramic composite is about 50% of that of LiTaO₃ single crystal.     

The influence of tetrahedral ordering on the microwave dielectric properties of Sr0.05Ba0.95Al2Si2O8 and (M = Al, Ga, M′ = Si, Ge) ceramics

The feldspars Sr_0.05Ba_0.95Al₂Si₂O₈, BaAl₂Ge₂O₈ and BaGa₂Si₂O₈ with S.G. I2/c, and BaGa₂Ge₂O₈ with S.G. P2₁/a, were studied by means of crystal structural and microstructural analyses and dielectric measurements. All the investigated densely sintered single-phase feldspars exhibited a permittivity () of 7–8 and a temperature coefficient of resonant frequency (τ_f) from −20 to −30 ppm/°C. In contrast to the and τ_f the dielectric losses were found to be dependent on the annealing conditions. In Sr_0.05Ba_0.95Al₂Si₂O₈ the Qxf values increased from 42,500 to 92,600 GHz when the annealing time at 1400 °C was increased from 1 to 162 h. Such a difference in the Qxf values as a result of various annealing conditions was attributed to different degrees of tetrahedral ordering. In contrast to aluminosilicate feldspars, Ge-containing feldspars can be sintered and ordered at low temperature. In BaAl₂Ge₂O₈ the Qxf values decreased when the sintering temperature exceeded the order-disorder I2/c ↔ C2/m phase-transition temperature. The BaGa₂Si₂O₈ and BaGa₂Ge₂O₈ feldspars exhibited a rapid decrease of Qxf values when the annealing temperature approached the melting point. However, the BaAl₂Ge₂O₈ and BaGa₂Ge₂O₈ can regain their high Qxf values by annealing at 1000 °C. The BaGa₂Ge₂O₈ stood out from the other investigated feldspars, with a sintering temperature of 1100 °C, Qxf values of 100,000–150,000 GHz and a τ_f of −26 ppm/°C.     

Fe2O3/Al2O3 catalysts for the N2O decomposition in the nitric acid industry

Fe₂O₃ catalysts supported on Al₂O₃ were used to remove nitrous oxide from the nitric acid plant simulated process stream (containing O₂, NO and H₂O). Catalysts were prepared by the coprecipitation method and were characterized for their physico-chemical properties by BET, XRD, AFM and TPR analysis. A strong influence of the post-preparation heating conditions on the structural and catalytic properties of the catalysts has been evidenced. Laboratory tests revealed 95% conversion of N₂O at temperature 750 °C and a slight decrease in activity in the presence of H₂O and NO. The catalysts were inert towards decomposition of NO. The pilot-plant reactor and real plant studies (up to 3300 h time-on-stream) confirmed high activity and very good mechanical stability of the catalysts as well as no decomposition of nitric oxide.     

AlPO4-coated mullite/alumina fiber reinforced reaction-bonded mullite composites

A precursor for reaction-bonded mullite (RBM) is formulated by premixing Al₂O₃, Si, mullite seeds and mixed-rare-earth-oxides (MREO). An ethanol suspension thereof is stabilized with polyethyleneimine protonated by acetic acid. The solid in the suspension is infiltrated into unidirectional mullite/alumina fiber-preforms by electrophoretic infiltration deposition to produce fiber-reinforced, RBM green bodies. Crack-free composites with ≤25% porosity were achieved after pressureless sintering at 1300 °C. Pre-coating the fibers with AlPO₄ as a weak intervening layer facilitates significant fiber pullout on composite fracture and confers superior damage tolerance. The bend strength is 170 MPa at 25 °C ≤ T ≤ 1100 °C. At 1200 °C, the composite fails in shear due to MREO-based, glassy phase formation. However, the AlPO₄ coating acts as a weak layer even after thermal aging at 1300 °C for 100 h.     

Low-temperature firing and microwave dielectric properties of 16CaO–9Li2O–12Sm2O3–63TiO2 ceramics with V2O5 addition

The sintering behaviors and microwave dielectric properties of the 16CaO–9Li₂O–12Sm₂O₃–63TiO₂ (abbreviated CLST) ceramics with different amounts of V₂O₅ addition had been investigated in this paper. The sintering temperature of the CLST ceramic had been efficiently decreased by nearly 100 °C. No secondary phase was observed in the CLST ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLST ceramics with small amounts of V₂O₅ addition could be well sintered at 1200 °C for 3 h without much degradation in the microwave dielectric properties. Especially, the 0.75 wt.% V₂O₅-doped ceramics sintered at 1200 °C for 3 h have optimum microwave dielectric properties of Kr = 100.4, Q × f = 5600 GHz, and TCF = 7 ppm/°C. Obviously, V₂O₅ could be a suitable sintering aid that improves densification and microwave dielectric properties of the CLST ceramics.     

In situ growth of TiC whiskers in Al2O3 matrix for ceramic machine tools

TiC whiskers have been synthesized via a carbothermal reduction technique in an α-Al₂O₃ matrix within a temperature range of 1380–1580 °C in an argon atmosphere. The raw materials consist of TiO₂, carbon, nickel and NaCl. Various mixing procedures and reaction temperatures were used. The yield of the whiskers is mainly dependent on the mixing procedures and the morphology of the synthesized composite powders is mainly dependent on the synthesis temperatures. The majority of the synthesized whiskers display an ideal aspect ratio of 10–30 with a diameter of 1–3 μm. No significant influence on the growth of the TiC whiskers by the present of the Al₂O₃ matrix powder can be noted.     

A novel solid superbase of Eu2O3/Al2O3 and its catalytic performance for the transesterification of soybean oil to biodiesel

A novel solid superbase catalyst of Eu₂O₃/Al₂O₃ was prepared and its basic strength reached 26.5 measured by indicators according to Hammett scale. The catalytic activity of Eu₂O₃/Al₂O₃ was evaluated for the transesterification of soybean oil with methanol to biodiesel in the fixed bed reactor and under atmospheric pressure. The results show that Eu₂O₃/Al₂O₃ is an excellent catalyst for the transesterification of soybean oil, and the conversion of soybean oil can reach 63.2% at 70 °C for 8 h.     

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.     

Effect of large cations (La and Ba) on the catalytic performance of Mn-substituted hexaaluminates for N2O decomposition

Mn-substituted La-hexaaluminate (LaMn_xAl_(12−x)O₁₉) and Ba-hexaaluminate (BaMn_xAl_(12−x)O₁₉) catalysts were prepared using the carbonates route and investigated for high-concentration of N₂O decomposition. It was for the first time found that the Ba-hexaaluminate exhibited higher activity than the La-hexaaluminate at a given Mn content, both of which were much more active than Mn/Al₂O₃ after being subjected to high-temperature (1400 °C) treatment. The catalytic activity varied with the Mn content and attained the best one at x = 1. X-ray diffraction (XRD) characterizations showed that a small amount of Mn (up to x = 1) promoted greatly the formation of phase-pure hexaaluminate, while excess Mn caused formation of catalytically inactive impurity phases, such as LaAlO₃, BaAl₂O₄, Mn₃O₄, and LaMnO₃, which covered partially the active sites and then led to a loss of the activity. UV–visible spectra showed that Mn²⁺ preferentially enter tetrahedral Al sites at a low Mn content (x = 0.5) for the La-hexaaluminate, which is quite different from the case of Ba-hexaaluminate where Mn³⁺ can substitute octahedral Al sites even at x = 0.5. Such a difference in the number of catalytically active Mn³⁺ sites in the octahedral position should be responsible for the higher activity of the Mn-substituted Ba-hexaaluminate.     

The influence of sintering aids for Nd(Mg0.5Ti0.5)O3 microwave dielectric ceramics properties

The influence of various sintering aids on the microwave dielectric properties and the structure of Nd(Mg_0.5Ti_0.5)O₃ ceramics were investigated systematically. B₂O₃, Bi₂O₃, and V₂O₅ were selected as liquid-phase sintering aids to lower the sintering temperature. The sintered Nd(Mg_0.5Ti_0.5)O₃ ceramics are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and microwave dielectric properties. The sintering temperature of Nd(Mg_0.5Ti_0.5)O₃ microwave dielectric ceramics is generally high, about 1500 °C. However, the sintering temperature was significantly lowered about 175 °C from 1500 °C to 1325 °C by incorporating in 10 mol% B₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (_r) value of 26.2, a quality factor (Q × f) value of 61,307 (at 9.63 GHz), and τ_f value of −45.5 ppm/°C. NdVO₄ secondary phase was observed at 10 mol% V₂O₅ addition in the sintering temperature range of 1300–1325 °C, which led the degradation in microwave dielectric properties. The microwave dielectric properties as well as grain sizes, grain morphology, and bulk density were greatly dependent on sintering temperature and various sintering aids. In this study, it is found that Nd(Mg_0.5Ti_0.5)O₃ incorporated with 10 mol% B₂O₃ with lower sintering temperature and excellent dielectric microwave properties may be suggested for application in microwave communication devices. The use of liquid-phase sintering, the liquid formed during firing normally remains as a grain boundary phase on cooling. This grain boundary phase can cause a deterioration of the microwave properties. Therefore, the selection of a suitable sintering aid is extremely important.     

Support modification to improve the sulphur tolerance of Ag/Al2O3 for SCR of NOx with propene under lean-burn conditions

Ag/Al₂O₃ catalysts with 1 wt% SiO₂ or TiO₂ doping in alumina support have been prepared by wet impregnation method and tested for sulphur tolerance during the selective catalytic reduction (SCR) of NO_x using propene under lean conditions. Ag/Al₂O₃ showed 44% NO_x conversion at 623 K, which was drastically reduced to 21% when exposed to 20 ppm SO₂. When Al₂O₃ support in Ag/Al₂O₃ was doped with 1 wt% SiO₂ or TiO₂ the NO_x conversion remained constant in presence of SO₂ showing the improved sulphur tolerance of these catalysts. Subsequent water addition does not induce significant deactivation. On the contrary, a slight promotional effect on the activity of NO conversion to nitrogen is observed after Si and Ti incorporation. FTIR study showed the sulphation of silver and aluminum sites of Ag/Al₂O₃ catalysts resulting in the decrease in the formation of reactive intermediate species such as –NCO, which in turn decreases NO_x conversion to N₂. In the case of Ag/Al₂O₃ doped with SiO₂ or TiO₂, formation of silver sulphate and aluminum sulphate was drastically reduced, which was evident in FTIR resulting in remarkable improvement in the sulphur tolerance of Ag/Al₂O₃ catalyst. These catalysts before and after the reaction have been characterized with various techniques (XRD, BET surface area, transmittance FTIR and pyridine adsorption) for physico-chemical properties.     

Preparation of in situ grown silicon carbide whiskers onto graphite for application in Al2O3-C refractories

C-SiC composite powders were prepared by salt-assisted synthesis from Si powders, graphite, and a molten salt medium (NaCl and NaF) with the molar ratio of Si/C =?1/2 at 1300?°C for 3?h. After the C-SiC composite powders part and complete replacement of the graphite, the mechanical properties, oxidation resistance and slag-corrosion resistance of the Al₂O₃-C materials were studied by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), as well as with dedicated equipment. The results indicated that SiC whiskers, with lengths of 10–50?nm, formed on the surface of the flake graphite, and the activation energy of oxidation of the C-SiC composite powder increased by 45.72?kJ?mol^?1 as compared to that of flake graphite. Furthermore, the decarburization area and slag erosion area of the Al₂O₃-C material decreased after 3?wt% of C-SiC composite powder was substituted for the flake graphite. Meanwhile, the cold modulus of rupture was maintained when 3?wt% of C-SiC composite powder was added. This improved both the oxidation and slag resistance of the Al₂O₃-C materials.