The formation and physicochemical characterization of Al2O3-doped manganese ferrites

Mn/Fe mixed oxide solids doped with Al₂O₃ (0.32-1.27 wt.%) were prepared by impregnation of manganese nitrate with finely powdered ferric oxide, then treated with different amounts of aluminum nitrate. The obtained samples were calcined in air at 700-1000 °C for 6 h. The specific surface area (S_BET) and the catalytic activity of pure and doped precalcined at 700-1000 °C have been measured by using N₂ adsorption isotherms and CO oxidation by O₂. The structure and the phase changes were characterized by DTA and XRD techniques. The obtained results revealed that Mn₂O₃ interacted readily with Fe₂O₃ to produce well-crystallized manganese ferrite (MnFe₂O₄) at temperatures of 800 °C and above. The degree of propagation of this reaction increased by Al₂O₃-doping and also by increasing the heating temperature. The treatment with 1.27 wt.% Al₂O₃ followed by heating at 1000 °C resulted in complete conversion of Mn/Fe oxides into the corresponding ferrite phase. The catalytic activity and S_BET of pure and doped solids were found to decrease, by increasing both the calcination temperature and the amount of Al₂O₃ added, due to the enhanced formation of MnFe₂O₄ phase which is less reactive than the free oxides (Mn₂O₃ and Fe₂O₃). The activation energy of formation (ΔE) of MnFe₂O₄ was determined for pure and doped solids. The promotion effect of aluminum in formation of MnFe₂O₄ was attributed to an effective increase in the mobility of reacting cations.     

Influence of ZrO2 on Carbon Monoxide Oxidation Over Pd/Al2O3

The influence of ZrO₂ on the properties of Al₂O₃ and performances of Pd/Al₂O₃ catalyst in CO oxidation have been investigated. TPD results show that the activity enhanced is due to the increase of the adsorptive capacity of CO and the activation of C=O bond after the introduction of ZrO₂.     

Zr对CuO/ZnO/Al_2O_3前驱体物相、催化剂结构及其合成甲醇性能的影响

采用并流共沉淀法,在CuO/ZnO/Al2O3三元催化剂中加入第四组分Zr,考察了沉淀温度对四元催化剂的前驱体物相组成及浆态床合成甲醇催化活性的影响。通过XRD、DTG、TPR、FTIR、CO-TPD、XPS、HR-TEM等对所制备催化剂及其前驱体的微观结构进行了表征。研究表明:Zr促进了绿铜锌矿(Cu,Zn)5(CO3)2(OH)6物相的生成,使催化剂前驱体中绿铜锌矿含量增加,焙烧后的催化剂铜锌协同作用增强,CuO分散度提高,CuO晶粒平均直径只有4.18nm,同时还原温度显著降低为150℃,CO吸附能力增强,结果显著提高了浆态床合成甲醇催化活性和稳定性。与CuO/ZnO/Al2O3三元催化剂相比,80℃沉淀制备的含4%Zr的CuO/ZnO/Al2O3/ZrO2四元催化剂的甲醇时空收率提高了8.67%,失活率降低了65.12%。     

The Effect of MoO3 Addition to V2O5/Al2O3 Catalysts for the Selective Catalytic Reduction of NO by NH3

The effect of MoO₃ addition to alumina supported vanadia catalysts on the catalytic activity for the selective catlaytic reduction of NO is investigated. Upon the addition of MoO₃, catalytic activity is enhanced and the particle size of V₂O₅ which is shown by the results of XRD and Raman spectroscopy is decreased. The MoO₃-V₂O₅/Al₂O₃ catalyst also exhibits more resistance to SO₂ deactivation than V₂O₅/Al₂O₃ does.     

Sol-gel coatings for chemical protection of stainless steel

Sol-gel thin coatings of ZrO₂, SiO₂, 70SiO₂-30TiO₂ and 88SiO₂-12Al₂O₃ compositions (mole %) have been prepared from sonocatalyzed sols and deposited by dip-coating technique on 316L stainless steel foils. The influence of the coatings on the chemical corrosion of the substrate has been measured through potentiodynamic polarization curves in aqueous 15% H₂SO₄ solution between 25 and 50°C. The values of the corrosion potential, polarization resistance and corrosion rate have been determined. Analysis of the data combined with scanning electron microscopy studies indicate that the films act as a geometric blocking against exposure to the corrosive media and increase the lifetime of the substrate up to a factor 8.5.     

A Novel Method for Preparing Nano‐ and Microcomposite Al2O3‐ZrO2 Ceramic Coatings

Nano‐ and microcomposite Al₂O₃‐ZrO₂ coatings were deposited on various substrates in a sol‐gel ceramic paint by a supercentrifugal force and a gradual sintering process. Fine metal oxide powders were dispersed in a sol‐gel solution by superpower ball milling so as to form a uniform stable ceramic paint. High‐resolution microscopy (FE‐SEM) was used to characterize the coating, indicating that the coating is composed of composite particle clusters with an average diameter of ～1 µm. The clusters consisted of larger particles with an average diameter of ～0.5 µm in center and smaller particles of ～100 nm surrounding the larger ones. The coating was relatively dense and increasingly dense toward the substrate surface.     

Structural and spectroscopic characterization of Al2−x Cr x O3 powders obtained by polymeric precursor method

Al₂O₃ and Al_2−x Cr _x O₃ (x = 0.01, 0.02 and 0.04) powders have been synthesized by the polymeric precursors method. A study of the structural evolution of crystalline phases corresponding to the obtained powders was accomplished through X-Ray Diffraction and UV-vis spectroscopy (reflectance spectra and CIEL^*a^*b^* color data). The obtained results allow to identify the γ-Al₂O₃ to α-Al₂O₃ phase transition. The single-phase α-Al₂O₃ powder was obtained after heat treatment at 1050 °C for 2 h. The results show that the green to red color transition and ruby luminescence lines observed for the powders of Al_2−x Cr _x O₃ are related to the γ to α-Al₂O₃ phase transition and the temperature and time range for such transition depends on the chromium content.     

Chemical and electrochemical characterization of hybrid PVD + ALD hard coatings on tool steel

In the last 30 years, thin hard coatings were intensively investigated due to their high-performance characteristics: high wear resistance, low friction coefficient and good thermal stability. Performances were furthermore improved using multilayer configurations, although often limited by feasibility or cost considerations. One of the main problems to overcome was the low corrosion protection that these coatings assure to the tool steel substrates on which they are applied. To assure high performances and corrosion protection it is possible to employ a completely new approach, suitable either as a pre-treatment of the substrate or as top coating, by using materials of different nature in the form of nano-layers.Monolayer and multilayer coatings obtained by PVD (Physical Vapor Deposition, using reactive arc evaporation) and by PVD + ALD (Atomic Layer Deposition) were studied and compared. Both in-depth composition and corrosion resistance properties were investigated using SEM–EDXS, GDOES (Glow Discharge Optical Emission Spectrometry) and polarization curves in a 0.2 M NaCl solution. The coatings studied were a TiAlN/TiN bi-layer and a TiCN monolayer obtained by PVD and an Al₂O₃ nano-layer obtained by ALD.     

负载Ni催化剂上1,4-丁炔二醇加氢反应的载体效应研究

制备了Ni负载量为15%的3种催化剂Ni/Al_2O_3、Ni/SiO_2、Ni/ZrO_2,考察了其在1,4-丁炔二醇加氢反应中的催化性能,结合XRD、H_2-TPR、H_2-TPD、N_2物理吸附等表征,研究了载体性质对催化剂1,4-丁炔二醇加氢性能的影响.结果表明,Ni/SiO_2催化剂上,由于Ni与SiO_2间弱的相互作用,Ni物种主要以大晶粒形式存在,产生大量弱吸附H_2物种,有利于低温下1,4-丁炔二醇加氢,在温度50℃,氢气压力1 MPa时,反应2 h可实现1,4-丁炔二醇的完全转化,1,4-丁烯二醇和1,4-丁二醇选择性分别达到68.1%与18.2%.Ni/Al_2O_3中Ni与载体间具有强相互作用,主要存在Ni-Al_2O_3界面或溢流到Al_2O_3载体表面的强吸附H_2物种,而Ni表面的弱吸附H_2物种较少,催化加氢活性明显降低.Ni/ZrO_2中由于还原过程中ZrO_2的迁移包裹作用,Ni表面低温吸附H_2物种最少,活性最低,1,4-丁炔二醇转化率仅为8.1%,主产物为1,4-丁烯二醇.     

Preparing nanometer scaled Tb-doped Y2O3 luminescent powders by the polyol method

Sub-micrometer Tb-doped Y₂O₃ luminescent powders were prepared from nitrate precursors using the polyol method. Just after precipitation, the powders consist of agglomerates with a spherical shape and a size ranging between 400 and 500 nm. Each agglomerate is composed of ultra-small crystallites (from 3 to 6 nm) of a bcc oxide phase whose luminescence presents original features in comparison with bulk materials. Powders were further calcinated at different temperatures and for annealing below 900 °C, highly crystalline samples with the classical green ⁵D₄→⁷F₅ luminescent transitions of Tb³⁺ ions are obtained. For optimized annealing temperatures, sintering between the agglomerates is avoided and a sub-micrometric powder with a narrow size distribution and a high luminescence is obtained.     

On the surface coverage of alumina by molybdenum-oxide in nickel - and cobalt-promoted MoOx/Al2O3 catalysts

The chemisorption of CO₂ has been studied on alumina-supported Co-and Ni-promoted molybdenum-oxide (CoMo, NiMo) and, besides those, on monometallic Co and Ni. Chemisorbed amounts on the monometallic samples were equal to that on the alumina support. XPS measurements were performed with the NiMo and Ni samples. The amounts of surface Mo-and Al-ions were calculated. It could be established that molybdenum oxide forms a near to monomolecular layer on the Co-and Ni-promoted molybdena-alumina samples.     

Enhancing effect of water vapor on the reduction of lean NOx by ethanol over an Ag/Al2O3 catalyst supported on cordierite honeycomb

The Ag/Al₂O₃ catalyst supported on cordierite honeycomb (Ag/Al₂O₃/ cordierite) is highly active forthe reduction of lean NOx by ethanol. Addition of H₂O enhances the NOx reduction to CO₂ and N₂, and suppresses the formation of by-products such as CO, CH₃CHO and C₂H₄.     

CO Hydrogenation by K-Promoted Coprecipitated Co/Al2O3

Effect of K promotion on the CO hydrogenation activity and selectivity of coprecipitated Co/Al₂O₃ has been studied. K addition is found to lower total activity while enhancing C₂-C₄ olefins selectivity; kinetic data indicate that the reaction mechanism is not affected.     

微乳法合成可控粒径纳米Pt/Al2O3电催化CO氧化的尺寸效应

采用微乳法室温下合成了粒径可控Pt/Al₂O₃催化剂(1～10 nm), 以CO电催化氧化为探针反应考察了Pt微粒尺寸与催化反应性能之间的关系. 利用透射电镜(TEM), 扫描电镜(SEM), 循环伏安法(CV)等手段对催化剂进行表征, 结果表明催化剂性能与Pt粒径之间存在明显的尺寸效应, 催化剂存在最佳活性尺寸.     

Al2O3/MeSO3H (AMA) as a New Reagent for the Thia-Fries Rearrangement of Arylsulfonates to Hydroxyaryl Sulfones

A new facile method for thia-Fries rearrangement of arylsulfonates has been developed. A variety of arylsulfonates rearrange in excellent yields in the presence of Al₂O₃/MeSO₃H as a new reagent without the use of any solvent.     

Fabrication, characterization and magnetic behaviour of alumina-doped zinc ferrite nano-particles

Zinc ferrite nano-powders with a nominal composition of ZnFe₂O₄ were prepared by combustion synthesis using mixture of urea and ammonium nitrate as fuel. The influence of alumina-doping on the structural, morphological and magnetic properties of ZnFe₂O₄ nano-particles was investigated by means of X-ray powder diffraction (XRD), infrared (IR) spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and vibrating sample magnetometer (VSM). XRD and IR analyses confirm the cubic spinel phase of ZnFe₂O₄ nano-particles. The Zn ferrite presented a uniform microstructure with grain size in nano-scale. Alumina-doping brought about a change in the morphology of the as prepared ferrite from sphere-like to regular hexagon. Al₂O₃-treatment led to a decrease in the coercivity (H_c), magnetization (M_s) and magnetic moment (n_B) of the investigated system. The maximum decrease in the values of H_c, M_s and n_B due to the treatment with 1.5 wt% Al₂O₃ attained 13.5, 17.4 and 13.5%, respectively. The observed results can be explained on the basis of particle size and the Fe³⁺ concentration in the octahedral and tetrahedral sites involved in the cubic spinel structure.     

Improvement of the Pd/Al2O3 Catalyst by the Control of the Sol-Gel Preparative Parameters

In this work, the metal dispersion of the Pd/Al₂O₃ catalyst prepared by sol-gel method is improved by an adequate optimisation of the preparative variables. First, the gelation temperature and the ageing time are selected, in order to avoid the reduction of the metal precursor (palladium acetylacetonate, Pd(acac)₂) by the solvent (sec-butanol, sB). The metal sintering effect on the catalysts treated in oxygen at 500°C is then minimized when the alumina pore size is controlled by the variation of the alumium alkoxide (AsB) concentration and the acetic acid amount ([AcA]/[AsB]). The appearance of new palladium particles on the alumina surface and the matching between the particle diameters and the pore sizes were also effective for the metallic surface area improvement on the samples treated in oxygen at 800°C. Compared to the reference catalysts, the higher metal dispersion obtained on the sol-gel ones was the determinant factor for their higher catalytic activity in methane combustion.     

High-temperature dilatometer with pyrometer measuring system and rate-controlled sintering capability

An optical pyrometer is used to measure and, in conjunction with temperature programmer and controller, control the temperature of the NETSZSCH Dilatometer DIL 402 E/7 up to 2400°C. This instrument is thus suitable to investigate sintering of technical ceramic materials such as SSiC and ZrO₂. Measurements carried out on these materials containing organic additives show that the sintering range of SSiC starts at 1800°C—although its final density is not reached at 2400°C at a heating rate of 20 deg·min^?1—and that the densification of ZrO₂ occurs between 1000° and 1800°C. Using rate controlled sintering (RCS) the sintering process can be extended on a time scale, but the same densities are obtained at the same temperatures when comparing the measurements with and without RCS.     

Methane steam reforming over rhodium promoted Ni/Al2O3 catalysts

The effect of Rh addition upon catalyst characteristics and performance in methane steam reforming was investigated using Rh-promoted Ni/Al₂O₃ catalysts. The number of reduced metal atoms exposed on the surface increased for the Rh-promoted catalysts. Rh-promoted catalysts showed an increase in CH₄ reforming activity; however, constant turnover frequencies for promoted and unpromoted catalysts suggest that the increase in the number of metal surface atoms caused the activity enhancement. Rh also facilitated reduction of Ni/Al₂O₃.     

Synthesis, characterization, thermal stability and electrochemical properties of poly-4-[(2-methylphenyl)iminomethyl]phenol

In this study, the reaction conditions of poly-4-[(2-methylphenyl)iminomethyl]phenol (P-2-MPIMP) were studied by using oxidants such as air O₂, H₂O₂ and NaOCl in an aqueous alkaline medium between 50 and 90 °C. The structures of the synthesized monomer and polymer were confirmed by FT-IR, UV-vis, NMR and elemental analysis. The characterization was made by TG-DTA, size exclusion chromatography (SEC) and solubility tests. At the optimum reaction conditions, the yield of poly-4-[(2-methylphenyl)iminomethyl]phenol (P-2-MPIMP) was found to be 20% (for air O₂ oxidant), 33% (for H₂O₂ oxidant), and 74% (for NaOCl oxidant). According to the SEC analysis, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of P-2-MPIMP were found to be 3300, 4100 g mol⁻¹ and 1.242, using H₂O₂, and 4550, 5150 g mol⁻¹and 1.132, using air O₂ and 5300, 5850 g mol⁻¹ and 1.104, using NaOCl, respectively. According to TG analysis, the weight losses of 4-[(2-methylphenyl)iminomethyl]phenol (2-MPIMP) and P-2-MPIMP were found to be between 75.29% and 48.17% at 1000 °C, respectively. P-2-MPIMP was shown to have a higher stability against thermal decomposition. Also, electrical conductivity of the P-2-MPIMP was measured, showing that the polymer is a typical semiconductor. Electrochemically, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) and electrochemical energy gaps ( of 2-MPIMP and P-2-MPIMP were found to be −6.01, −6.03; −2.63, −2.82; 3.38 and 3.21 eV, respectively. According to UV-vis measurements, the optical band gap (E_g) of 2-MPIMP and P-2-MPIMP was found to be 3.40 and 2.97 eV, respectively.