Influence of transition metals (Cr, Mn, Fe, Co and Ni) on the methane combustion over Pd/Ce-Zr/Al2O3 catalyst

The effects of transition metals (Cr, Mn, Fe, Co and Ni) on the catalytic properties of Pd/Ce-Zr/Al₂O₃ catalyst for methane combustion have been investigated. The supported Pd catalysts are characterized by BET, XRD, TEM, TPR, TPO and TPSR measurements. Activity tests in methane combustion show that Pd/Ce-Zr-Ni/Al₂O₃ has the highest catalytic activity and thermal stability among all catalysts. The results of TEM show that the addition of Ni to Pd/Ce-Zr/Al₂O₃ increases the dispersion of Pd component and inhibits the site growth. The results of TPO and TPSR show that the addition of Ni inhibits the decomposition of PdO particles and improves the reduction-reoxidation properties of the active PdO species, which increases the catalytic activity and thermal stability of the Pd/Ce-Zr/Al₂O₃ catalyst.     

X-ray photoelectron spectroscopy study of Pd oxidation by RF discharge in oxygen

The low-temperature oxidation of polycrystalline palladium by RF oxygen plasma was studied via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Detailed information about the electronic states of palladium and oxygen was obtained based on the XPS curve fitting analysis of Pd3d and Pd3p + O1s lines. The results showed that Pd oxidation by oxygen plasma was different from Pd oxidation in pure O₂ at high temperature. SEM shows well-structured submicron PdO particles result from oxidation in pure O₂, whereas plasma oxidation results in the predominant formation of two-dimensional PdO structures covering the initial crystallites of the Pd foil. Further oxidation to a three-dimensional PdO phase occurs under prolonged treatment with oxygen plasma. The formation of a PdO_x (x > 1) species, characterized by a E_b(Pd3d_5/2) = 338.0–338.2 eV value that is close to the Pd⁴⁺ oxidation state, was also observed. This PdO_x species was found to have low thermal stability (T < 400 K). It is proposed that the PdO_x species can be localized within the boundaries of crystallites.     

Promotion of surface SOx on the selective catalytic reduction of NO by hydrocarbons over Ag/Al2O3

The promotion of sulfur oxides on the selective catalytic reduction (SCR) of NO by hydrocarbons in the presence of a low concentration of sulfur oxides over Ag/Al₂O₃ has been investigated by a flow reaction test and in situ infrared spectroscopy. When the C₃H₆ (or C₁₀H₂₂) + NO + O₂ feed-flow reaction was tested, maximum NO reduction was below 30% over fresh Ag/Al₂O₃. After the addition of SO₂ to the feed flow, conversion increased slightly. Conversion increased further after SO₂ was cut-off from the feed flow. This demonstrated that the increase in NO reduction activity of the catalyst was related to SO_x adsorbed on the catalyst. SO_x adsorbed on the catalytic surface (1375 cm⁻¹) was detected by IR spectroscopy and was stable within the temperature range. NCO species, as an intermediate in NO reduction, on SO_x-adsorbed Ag/Al₂O₃ in a C₃H₆ + NO + O₂ feed flow was observed in in situ IR spectra during the elevation of the reaction temperature from 473 to 673 K, while it was only observed at 673 K on fresh Ag/Al₂O₃ under the same experimental conditions. We suggest that SO_x in low concentrations depressed the combustion of reductants by contaminating hydrocarbon combustion active sites on the catalyst, resulting in an increase in NO reduction efficiency of the reductants.     

Synthesis,crystal structure and magnetic properties of Yb8Ag18.5Al47.5, Yb2Pd2Cd and Yb1.35Pd2Cd0.65

We report the synthesis of three new Yb-based compounds, Yb₈Ag_18.5Al_47.5 (Yb₈Cu₁₇Al₄₉-type, tetragonal tI74–I4/mmm), Yb₂Pd₂Cd (Mo₂B₂Fe-type, tetragonal tP10-P4/mbm) and Yb_1.35Pd₂Cd_0.65 (MnCu₂Al-type, cubic cF16–Fm3¯m). The crystal symmetry of these compounds has been determined and the complete structural characterisation carried out by single crystal and powder diffraction techniques. Two symmetry in-equivalent sites are available for the Yb ions in Yb₈Ag_18.5Al_47.5 and Yb_1.35Pd₂Cd_0.65. The 4f levels of the Yb ions are appreciably hybridised in Yb₈Ag_18.5Al_47.5 and to a lesser extent in Yb₂Pd₂Cd as inferred from the magnetisation and heat capacity data. Signatures of heavy fermion behaviour are observed in the heat capacity data of Yb₂Pd₂Cd in which the heat capacity, C/T, increases at low temperatures attaining a value of ≈600 mJ/mol K² at 1.8 K. The electrical resistivity of Yb₂Pd₂Cd follows a linear variation with temperature, T, between 1.4 and 5 K, thus indicating a possible non-Fermi liquid behaviour. In contrast, Yb ions are trivalent in Yb_1.35Pd₂Cd_0.65 and order magnetically near 1.4 K.     

Deposition and characterization of binary Al2O3/SiO2 coating layers on the surfaces of rutile TiO2 and the pigmentary properties

Binary Al₂O₃/SiO₂-coated rutile TiO₂ composites were prepared by a liquid-phase deposition method starting from Na₂SiO₃·9H₂O and NaAlO₂. The chemical structure and morphology of binary Al₂O₃/SiO₂ coating layers were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, TG-DSC, Zeta potential, powder X-ray diffraction, and transmission electron microscopy techniques. Binary Al₂O₃/SiO₂ coating layers both in amorphous phase were formed at TiO₂ surfaces. The silica coating layers were anchored at TiO₂ surfaces via Si-O-Ti bonds and the alumina coating layers were probably anchored at the SiO₂-coated TiO₂ surfaces via Al-O-Si bonds. The formation of continuous and dense binary Al₂O₃/SiO₂ coating layers depended on the pH value of reaction solution and the alumina loading. The binary Al₂O₃/SiO₂-coated TiO₂ composites had a high dispersibility in water. The whiteness and brightness of the binary Al₂O₃/SiO₂-coated TiO₂ composites were higher than those of the naked rutile TiO₂ and the SiO₂-coated TiO₂ samples. The relative light scattering index was found to depend on the composition of coating layers.     

Chemical quenching of positronium in Fe2O3/Al2O3 catalysts

Fe₂O₃/Al₂O₃ catalysts were prepared by solid state reaction method using α-Fe₂O₃ and γ-Al₂O₃ nano powders. The microstructure and surface properties of the catalyst were studied using positron lifetime and coincidence Doppler broadening annihilation radiation measurements. The positron lifetime spectrum shows four components. The two long lifetimes τ₃ and τ₄ are attributed to positronium annihilation in two types of pores distributed inside Al₂O₃ grain and between the grains, respectively. With increasing Fe₂O₃ content from 3 wt% to 40 wt%, the lifetime τ₃ keeps nearly unchanged, while the longest lifetime τ₄ shows decrease from 96 ns to 64 ns. Its intensity decreases drastically from 24% to less than 8%. The Doppler broadening S parameter shows also a continuous decrease. Further analysis of the Doppler broadening spectra reveals a decrease in the p-Ps intensity with increasing Fe₂O₃ content, which rules out the possibility of spin-conversion of positronium. Therefore the decrease of τ₄ is most probably due to the chemical quenching reaction of positronium with Fe ions on the surface of the large pores.     

Er3+掺杂SiO2复合的Al2O3粉末结构及光致发光特性

采用溶胶-凝胶(sol-gel)工艺制备0.1 mol% Er³⁺掺杂Al₂O₃体系和SiO₂-Al₂O₃复合体系粉末. 实验结果表明：5 mol%的SiO₂复合加入Al₂O₃抑制γ→θ和θ→α相转变. 掺0.1 mol%Er³⁺:Al₂O₃体系粉末，900℃烧结，在1.47—1.63μm波段内光致发光(PL)谱为中心波长1.53 μm、半高宽56 nm的单一宽峰，1000—1200℃烧结，劈裂为多峰PL谱. 掺0.1 mol%Er³⁺:SiO₂-Al₂O₃复合体系粉末，在高达1200℃烧结，仍保持中心波长1.53 μm的单一宽峰PL谱，由于—OH更完全的脱除，PL强度较900℃烧结Al₂O₃体系，SiO₂-Al₂O₃复合体系均提高1个数量级. 关键词： 2-Al₂O₃复合体系')" href="#">SiO₂-Al₂O₃复合体系 掺铒 溶胶-凝胶工艺 光致发光     

Influence of the physico-chemical properties of CeO2-ZrO2 mixed oxides on the catalytic oxidation of NO to NO2

Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N₂ adsorption at −196 °C and XPS, and were tested for NO oxidation to NO₂. Among the different physico-chemical properties characterised, the surface composition seems to be the most relevant one in order to explain the NO oxidation capacity of these Ce-Zr catalysts. As a general trend, Ce-Zr catalysts with a cerium-rich surface, that is, high XPS-measured Ce/Zr atomic surface ratios, are more active than those with a Zr-enriched surface. The decrease in catalytic activity of the Ce-Zr mixed oxided upon calcinations at 800 °C with regard to 500 °C is mainly attributed to the decrease in Ce/Zr surface ratio, that is, to the surface segregation of Zr. The phase composition (cubic or t′′ for Ce-rich compositions) seems not to be a direct effect on the catalytic activity for NO oxidation in the range of compositions tested. However, the formation of a proper solid solution prevents important surface segregation of Zr upon calcinations at high temperature. The effect of the BET surface area in the catalytic activity for NO oxidation of Ce-Zr mixed oxides is minor in comparison with the effect of the Ce/Zr surface ratio.     

Enhanced optical activation of Er in Er-doped Al2O3 powders by Y codoping in a sol-gel method

Enhanced photoluminescence (PL) mechanism of Er³⁺-doped Al₂O₃ powders by Y³⁺ codoping at wavelength 1.53 μm has been investigated through PL measurements of 0.1 mol% Er³⁺- and 0-20 mol% Y³⁺-codoped Al₂O₃ powders prepared at a sintering temperature of 900 °C in a non-aqueous sol-gel method. PL intensity and lifetime of Er³⁺-Y³⁺-codoped Al₂O₃ powders composed of γ-(Al,Er,Y)₂O₃ and θ-(Al,Er,Y)₂O₃ phases increased with increasing Y³⁺-codoping concentration. The 10-20 mol% Y³⁺ codoping in 0.1 mol% Er³⁺-doped Al₂O₃ powders intensified the PL intensity by about 20 times, with a PL lifetime prolonged from 3.5 to 5.8 ms. A maximal increase of the optical activity of Er³⁺ in 0.1 mol% Er³⁺-Y³⁺-codoped Al₂O₃ powders about one order was achieved by 10-20 mol% Y³⁺ codoping. It is found that the improved PL properties for Er³⁺-Y³⁺-codoped Al₂O₃ powders are mainly attributed to enhanced optical activation of Er³⁺ in the Al₂O₃ by Y³⁺ codoping, and to the slightly increased radiative quantum efficiency of Er³⁺ in the Al₂O₃.     

Preparation and characterization of novel Pd/SiO2 and Ca-Pd/SiO2 egg-shell catalysts with porous hollow silica

Novel egg-shell structured monometallic Pd/SiO₂ and bimetallic Ca-Pd/SiO₂ catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl₂ and Ca(NO₃)₂·4H₂O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO₂ samples and the Pd particle size in Ca-Pd/SiO₂ was smaller than that in Pd/SiO₂ since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d_5/2 binding energies of Pd/SiO₂ and Ca-Pd/SiO₂ were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO₂ and to both oxygen and Ca in Ca-Pd/SiO₂. The activity of Ca-Pd/SiO₂ egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol_CO mol⁻¹_Pd s⁻¹ and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support.     

The improvement of Al2O3/AlGaN/GaN MISHEMT performance by N2 plasma pretreatment

This paper discusses the effect of N 2 plasma treatment before dielectric deposition on the electrical performance of a Al2O3 /AlGaN/GaN metal-insulator-semiconductor high electron mobility transistor(MISHEMT),with Al2O3 deposited by atomic layer deposition.The results indicated that the gate leakage was decreased two orders of magnitude after the Al2O3 /AlGaN interface was pretreated by N 2 plasma.Furthermore,effects of N 2 plasma pretreatment on the electrical properties of the AlGaN/Al2O3 interface were investigated by x-ray photoelectron spectroscopy measurements and the interface quality between Al2O3 and AlGaN film was improved.     

有机金属化学气相沉积法制备的Ni/Al2O3纳米复合材料的氢吸附

研究了通过有机金属化学气相沉积技术及单源分子前躯体方法制备的Ni/Al₂O₃纳米复合材料的氢吸附(存储). 在冷壁的有机金属化学气相沉积反应器中,通过降解Ni(acac)₂粉末基底上的[H₂Al(OtBu)]₂制备的Ni/Al₂O₃纳米复合材料. 通过X射线粉末衍射、扫描电镜、透射电镜以及能量色散型X射线荧光光谱等技术表征该复合材料. 采用自制Sievert's设备研究该复合材料的氢吸附(存储),可以储存约2.9%(重量比)的氢.     

Effect of TiO2/Al2O3 film coated diamond abrasive particles by sol-gel technique

The diamond abrasive particles were coated with the TiO₂/Al₂O₃ film by the sol-gel technique. Compared with the uncoated diamonds, the TiO₂/Al₂O₃ film was excellent material for the protection of the diamonds. The results showed that the incipient oxidation temperature of the TiO₂/Al₂O₃ film coated diamonds in air atmosphere was 775 °C, which was higher 175 °C than that of the uncoated diamonds. And the coated diamonds also had better the diamond's single particle compressive strength and the impact toughness than that of uncoated diamonds after sintering at 750 °C. For the vitrified bond grinding wheels, replacing the uncoated diamonds with the TiO₂/Al₂O₃ film coated diamonds, the volume expansion of the grinding wheels decreased from 6.2% to 3.4%, the porosity decreased from 35.7% to 25.7%, the hardness increased from 61.2H_RC to 66.5H_RC and the grinding ratio of the vitrified bond grinding wheels to carbide alloy (YG8) increased from 11.5 to 19.1.     

Luminescent properties of green- or red-emitting Eu-doped Sr3Al2O6 for LED

Eu²⁺-doped Sr₃Al₂O₆ (Sr_3−xEu_xAl₂O₆) was synthesized by a solid-state reaction under either H₂ and N₂ atmosphere or CO atmosphere. When H₂ was used as the reducing agent, the phosphor exhibited green emission under near UV excitation, while CO was used as the reducing agent, the phosphor mainly showed red emission under blue light excitation. Both emissions belong to the d-f transition of Eu²⁺ ion. The relationship between the emission wavelengths and the occupation of Eu²⁺ at different crystallographic sites was studied. The preferential substitution of Eu²⁺ into different Sr²⁺ cites at different reaction periods and the substitution rates under different atmospheres were discussed. Finally, green-emitting and red-emitting LEDs were fabricated by coating the phosphor onto near UV- or blue-emitting InGaN chips.     

Investigation on densification of Al2O3/B4C ceramic by ab initio calculation and experiment

Compared to experiment, the adsorption energies, bonding properties, and electronic structure of two different Al₂O₃/B₄C bridge sites with seven different Al₂O₃ surfaces are investigated by ab initio periodic density functional theory. The Al₂O₃/B₄C ceramic sintered in Ar is synthesized and measured by XRD and TEM. The calculated results reveal that the densification of O_bridge site of Al₂O₃/B₄C surface is better than that of Al_bridge. The Al₂O₃ (1 1 3)/B₄C with O_bridge is the most favorable and stable. The electronic structure shows that the electron hybridization exists between Al, O atoms and C, B atoms. The results indicate that the calculated results are in good agreement with the experiment.     

Superacid Catalyst SO42-/ZrO2-La2O3 Prepared by Ultrasonic Co-precipitation and Low Temperature Aging

低温陈化超声波共沉淀法制得SO₄^2-/ZrO^2-La₂O₃前驱体, 经H₂SO₄处理, 在不同温度下焙烧得到纳米晶催化剂SO₄^2-/ZrO^2-La₂O₃;用Hammett指示剂法测定其酸性. 用XRD、BET、TEM、IR和XPS对样品进行表征,其催化活性用醋酸和甘油的酯化反应进行了评价. 结果表明经超声波搅拌和低温(-15 ºC)陈化,650 ºC焙烧4 h得到的固体超强酸表现出较高催化活性.     

亚纳米厚的氧化铝包裹层可以显著提高负载型金纳米颗粒催化剂的热稳定性

负载型金纳米颗粒催化剂在许多催化反应中展现出非常好的催化活性,但是金纳米颗粒在高温等反应条件下容易烧结团聚,极大地限制了金催化剂的应用。利用原子层沉积技术在Au/TiO₂催化剂表面分别精确沉积了一层超薄的二氧化钛和氧化铝包裹层,并对比研究了包裹层对金纳米颗粒的热稳定性影响。原位红外漫反射CO吸附和x-射线光电子能谱数据证实了氧化物包裹层的存在。发现亚纳米厚的氧化铝包裹层能够在600 C完全避免金纳米颗粒的团聚;相反,二氧化钛包裹层对金纳米颗粒稳定性的提高没有明显效果。通过CO氧化探针反应的活性测试,发现随着煅烧温度的升高氧化铝包裹的Au/TiO₂ 催化剂的活性逐渐提高,表明高温处理可以促进被包裹金原子的暴露并表现出催化活性。提供了提高金纳米颗粒稳定性的有效方法,为拓展金催化剂在条件苛刻的反应中的应用奠定了技术基础.     

Influences of laser remelting on microstructure of nanostructured Al2O3-13 wt.% TiO2 coatings fabricated by plasma spraying

The effects of laser remelting on microstructure of nanostructured Al₂O₃-13 wt.% TiO₂ ceramic coatings prepared by plasma spraying with agglomerated powders were studied. The microstructure of the feedstock, as-sprayed and laser-remelted coatings were investigated by using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffractometry (XRD). The results indicate that the plasma-sprayed ceramic coating consists of both fully melted regions and partially melted regions. The totally ceramic coating, especially the fully melted regions, has a typical plasma-sprayed lamellar-like structure as the conventional coating, and has some pores. According to the difference of microstructures, the partially melted regions can be divided into liquid-phase sintered regions (a three-dimensional net or skeleton-like structure: Al₂O₃-rich submicron particles embedded in the TiO₂-rich matrix) and solid-phase sintered regions (remained nanoparticles). The lamellar defect of the as-sprayed coating is erased, and the compactness of the coating is improved significantly after laser remelting. The laser-remelted region composed of fine equiaxed grains, which are different from the conventional column-like crystals along the direction of the heat current. Due to the rapid solidification of laser remelting process, there are still some nanoparticles in the remelted region because of an insufficient time for grains growth.     

The electrical properties of dielectric stacks of SiO2 and Al2O3 prepared by atomic layer deposition method

We produced dielectric stacks composed of ALD SiO₂ and ALD Al₂O₃, such as SiO₂/Al₂O₃, Al₂O₃/SiO₂, and SiO₂/Al₂O₃/SiO₂, and measured the leakage currents through the stacks in comparison with those of the single oxide layers. SiO₂/Al₂O₃ shows lowest leakage current for negative bias region below 6.4 V, and Al₂O₃/SiO₂ showed highest current under negative biases below 4.5 V. Two distinct electron conduction regimes are observed for Al₂O₃ and SiO₂/Al₂O₃. Poole-Frenkel emission is dominant at the high-voltage regime for both dielectrics, whereas the direct tunneling through the dielectric is dominant at the low-voltage regime. The calculated transition voltage between two regimes for SiO₂ (6.5 nm)/Al₂O₃ (12.6 nm) is −6.4 V, which agrees well with the experimental observation (−6.1 V). For the same EOT of entire dielectric stack, the transition voltage between two regimes decreases with thinner SiO₂ layer.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.