Effects of genesis and ionizing radiation on the kinetics of reduction of NiO-CeO2 mixed oxides with hydrogen

The reduction of mixed oxides NiO-CeO₂ of various composition with hydrogen was studied at 290–470° by means of thermogravimetry. Some physicochemical properties of the system were also investigated and compared with earlier studied analogous samples of different “origin”. The degree of mutual interaction of the two components, the reduction kinetics and the sensitivity to the different sorts of radiation (gamma-rays, fast neutrons and electrons), applied in different doses, are strongly affected by the “pre-history” and by the composition in both compared series of mixed oxides.     

Effect of Different Treatments on the Reducibility of NiO—Y2O3 Mixed Oxides by Hydrogen

Some physico-chemical properties and reactivity in their reduction with hydrogen of NiO—Y₂O₃ mixed oxides prepared in a dry way have been studied using isothermal thermogravimetry in the range of 320–410°C and temperature-programmed reduction. It was found that addition of small amounts of chloride and acetate anions retarded the reduction of nickel oxide and accelerated the reduction of mixed oxides. The presence of oxalate and formate ions manifests itself by a small positive effect. Introduction of platinum activator or heat treatment of the samples in various atmospheres led to a pronounced increase in the reduction rate. The efficiency of the spill-over effect increases with increasing proportion of non-reducible Y₂O₃. The pre-irradiation of the samples by accelerated electrons and gamma rays at a dose of 1 MGy results in a negative kinetic effect only with the samples containing an excess of nickel oxide.This revised version was published online in November 2005 with corrections to the Cover Date.     

Physico-chemical properties and hydrogen reduction reactivity of nickel and cobalt mixed oxides of various stoichiometry

Investigations have been made of the effects of the origin and some physico-chemical parameters on the kinetics of reduction with hydrogen of two series of mixed nickel and cobalt oxides differing in the stoichiometry of the two oxides. The first series, consisting of non-stoichiometric mixed oxides NiO-Co₃O₄ of various compositions, were prepared by calcining the mass of coprecipitated hydroxides in air. High-temperature treatment of the oxides obtained led to the second series, which consisted of stoichiometric NiO and nonstoichiometric CoO. The reactivity of the mixed oxides towards reduction with hydrogen varied with the phase composition and with the amount and ratio of various forms of superstoichiometric oxygen in the systems under study.

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Zusammenfassung Es wurden Untersuchungen über den Einfluß des Ausgangspunktes und einiger physikalisch-chemischer Parameter auf die Kinetik der Reduktion zweier Reihen von Nickel- und CobaltOxidgemischen mit Wasserstoff angestellt, die sich in der stöchiometrischen Zusammensetzung der beiden Oxide voneinander unterscheiden. Die erste Reihe von nichtstöchiometrischen NiO-Co₃O₄ Oxidgemischen unterschiedlicher Zusammensetzung wurde durch Kalzinieren kogefällter Hydroxide an Luft gefertigt. Das Erhitzen der erhaltenen Oxide auf hohe Temperaturen lieferte die zweite Reihe Oxidgemische, bestehend aus stöchiometrischem NiO und nichtstöchiometrischem CoO. Die Reaktivität der Oxidgemische bei der Reduktion mit Wasserstoff verändert sich mit der Phasenzusammensetzung sowie mit Menge und Verhältnis verschiedener Formen von superstöchiometrischem Sauerstoff in den untersuchten Systemen.

     

陈化体系组成对Ce0.65Zr0.35O2储氧材料性能的影响

采用共沉淀法制备了Ce_0.65Zr_0.35O₂(CZ)储氧材料, 在传统的水陈化体系中引入了乙醇, 研究了乙醇的加入对CZ储氧材料性能的影响. 对所制备样品进行了傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)、粉末X射线衍射(XRD)、扫描电镜(SEM)、N₂吸附-脱附、储氧量(OSC)和H₂程序升温还原(H₂-TPR)的表征, 并考察了以CZ储氧材料为载体制备的单钯催化剂的三效性能. 结果表明, 乙醇引入陈化体系对样品的结构和性能有显著影响. 以醇水共存体系陈化制备的CZ储氧材料颗粒小、堆积松散、孔径分布宽、孔容大, 具有优异的储氧性能和热稳定性, 经1000 °C焙烧后, 比表面积为29.3 m²·g^-1, 储氧量仍高达520 μmol·g^-1. 以此为载体制备的单钯催化剂, 空燃比操作窗口宽, 对C₃H₈、CO、NO的转化明显优于水陈化体系制备的储氧材料所制备的催化剂.     

A Rapid Microwave-Induced Solution Combustion Synthesis of Ceria-Based Mixed Oxides for Catalytic Applications

We have been exploring the utilization of a simple and fast microwave-induced solution combustion synthesis technique for the preparation of various ceria-based mixed oxides for different catalytic applications. In our comprehensive investigation, CeO₂–SiO₂ (MWCS), CeO₂–TiO₂ (MWCT), CeO₂–ZrO₂ (MWCZ) and CeO₂–Al₂O₃ (MWCA) mixed oxides were synthesized by solution combustion synthesis method using microwave dielectric heating and employed for CO and soot oxidation applications. The intricate relationship between ceria and other supporting oxides has been explored with the help of various analytical techniques namely, X-ray diffraction (XRD), temperature programmed reduction/oxidation (TPR/TPO), temperature programmed desorption (TPD) of ammonia and CO₂, Raman spectroscopy (RS), UV–vis diffuse reflectance spectroscopy (UV–vis DRS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), BET surface area and thermogravimetry analysis (TGA) methods. XRD results revealed amorphous nature of the material in case of ceria-silica mixed oxide and formation of a specific cubic fluorite type Ce_0.5Zr_0.5O₂ solid solution in the case of ceria-zirconia mixed oxide. Ceria-titania and ceria-alumina mixed oxides exhibited diffraction lines only due to crystalline ceria. Zirconia-based mixed oxide exhibited a lower reduction temperature and better redox properties compared to other samples. TPD of ammonia and CO₂ results revealed superior acid–base properties for MWCS mixed oxide. TGA measurements indicated a complete combustion in all preparations. RS results suggested defective structure of mixed oxides resulting in the formation of oxygen vacancies. XPS results revealed that ceria-zirconia mixed oxide contained more Ce³⁺ compared to other oxides. Among all the mixed oxides, the MWCZ sample exhibited a higher oxygen storage capacity, and better CO and soot oxidation activities. All these interesting findings have been elaborated in this publication.     

Physicochemical studies on the TiO2-silica gel system

The physicochemical properties (crystal structure, surface acidity, surface area, catalytic activity and electrical conductivity) of TiO₂-silica gel mixed oxides have been investigated. A series of mixed oxides of various compositions in the range of 0–100% for each component were prepared by calcining the mixed oxides in air at temperatures of 115, 300, 600 and 1000°C. The results obtained have been discussed and correlated.     

Effect of genesis on the properties and hydrogen reducibility of NiO-ZnO mixed oxides

The physico-chemical properties and reactivity tested by hydrogen reduction have been studied for two series of NiO-ZnO mixed oxides of various composition. The solid nickel oxide or zinc oxide in interaction with the solution of nitrate of the second component were used as the precursors in each series. The differences in some physico-chemical parameters of the samples in both series were correlated with their reduction behaviour, followed both in iso- and non-isothermal regime. Moreower, the influence of various factors modifying the reactivity of mixed oxides was also investigated and the results were compared with those obtained from earlier studied analogous systems of quite different origin.This revised version was published online in November 2005 with corrections to the Cover Date.     

Oxyhydroxide Nanosheets with Highly Efficient Electron–Hole Pair Separation for Hydrogen Evolution

The facile electron–hole pair recombination in earth‐abundant transition‐metal oxides is a major limitation for the development of highly efficient hydrogen evolution photocatalysts. In this work, the thickness of a layered β‐CoOOH semiconductor that contains metal/hydroxy groups was reduced to obtain an atomically thin, two‐dimensional nanostructure. Analysis by ultrafast transient absorption spectroscopy revealed that electron–hole recombination is almost suppressed in the as‐prepared 1.3 nm thick β‐CoOOH nanosheet, which leads to prominent electron–hole separation efficiencies of 60–90 % upon irradiation at 350–450 nm, which are ten times higher than those of the bulk counterpart. X‐ray absorption spectroscopy and first‐principles calculations demonstrate that [HO?CoO_6?x] species on the nanosheet surface promote H⁺ adsorption and H₂ desorption. An aqueous suspension of the β‐CoOOH nanosheets exhibited a high hydrogen production rate of 160 μmol g^?1 h^?1 even when the system was operated for hundreds of hours.     

Catalytic combustion of ethyl acetate over ceria-promoted platinum supported on Al2O3 and ZrO2 catalysts

Platinum-supported catalysts prepared by impregnation of mixed CeO₂/Al₂O₃ and CeO₂/ZrO₂ oxides using the sol-gel method were characterized and used in the combustion of ethyl acetate. In each series, the effect of CeO₂ loading (3 and 5 wt%) was studied. Characterization data from the studied catalysts (specific area measurements, hydrogen chemisorption, programmed temperature reduction (TPR), X-ray diffraction (XRD), photoelectron spectra (XPS) and transmission electron microscopy (TEM)) revealed significant changes in porosity and metal dispersion in each series. The catalytic activity of the solids, evaluated in the total combustion of ethyl acetate, exhibited a positive effect with the addition of Ce in the zirconia series whereas no significant changes was observed in the alumina series.     

Physico-chemical properties of CuO−Bi2O3 mixed oxides and modification of their hydrogen reduction reactivity by ionizing radiation

This paper describes a study on some physico-chemical properties of CuO?Bi₂O₃ mixed oxides of various composition and their reactivity during hydrogen reduction in the range 290–460°C. Depending on the composition, the changes in the morphology of the samples, their specific surface areas, phase composition of Bi₂O₃ as well as the change in the amount of chemisorbed surface oxygen (specific surface oxidation ability) were found. The last mentioned parameter is strongly affected positively or negatively (depending on the dose absorbed) by the pre-irradiation with gamma-rays and accelerated electrons. Either reduction of CuO or consecutive reduction of both components with a maximum rate on the surface or sub-surface layers of grain, proceed in different temperature ranges. The retarding effect of liquid bismuth is partially compensated for by the sponging and trapping effects, so that the overall reduction rate changes non-monotonously with the composition of the samples. Pre-irradiation leads in all cases to the lowering of reduction rate, which can be correlated with the increase in the concentration of strongly bound oxygen forms, creating centres of donor hydrogen chemisorption. The effect of gamma-radiation appears to be function of the threshold dose absorbed.     

镁基复合氧化物催化烯烃环氧化反应

 制备了一系列镁基复合氧化物 MgM-n 样品 (M = Sn, Al, Ti, La, Ce, Zr; n 为 Mg/M 原子比), 用 X 射线衍射、N2 吸附-脱附、CO2 程序升温脱附、紫外可见漫反射光谱和电子自旋共振等手段表征了它们的结构和表面性质, 并考察了其以过氧化氢为氧化剂催化烯烃环氧化反应性能. 结果表明, MgM-n 样品表面碱量和催化性能与其中 M 的种类及含量密切相关. MgSn-4 样品的表面碱量比 MgAl-4 低, 虽两者在催化苯乙烯环氧化反应中, 苯乙烯转化率和环氧化物选择性均为 95% 左右, 过氧化氢利用率大于 80%, 但在循环使用过程中 MgSn-4 的催化性能更为稳定, 并在不同结构烯烃的环氧化反应中表现出优良的催化性能. 这除与 MgSn-4 表面碱强度适当有关外, 还与其中存在高分散的 Sn4+物种及其结构特性有关.     

Preparation, characterization and gas-sensitive properties of nano-crystalline Cr2O3Fe2O3 mixed oxides

A series of Fe₂-_xCr_xO₃(x = 0, 0.4, 0.8, 1.2, 1.6, 2.0) mixed oxides have been prepared with the chemical coprecipitation method and characterized by specific surface area, transmission electron microscopy (TEM), powder X-ray diffraction (XRD), IR and Mössbauer spectroscopy. Single-phase Fe-Cr mixed oxide nano-crystalline powders with corundum structure are obtained, and the results of the five characterization methods are well accordant with each other. Furthermore, gas-sensitive properties of the sensors made of the oxide powders have been studied.     

Highly Ordered Mesoporous Cobalt-Copper Composite Oxides for Preferential CO Oxidation

Highly ordered mesoporous cobalt-copper composite oxides were prepared by the nanocasting method with various Co and Cu ratios. The catalysts obtained were characterized by X-ray diffraction, N₂ adsorption–desorption, H₂-temperature programmed reduction, CO-temperature programmed desorption and X-ray photoelectron spectroscopy. All of the catalysts had uniform mesopores and high surface areas. The distinct catalytic properties of these well-characterized mesoporous materials were demonstrated for preferential CO oxidation. It is found that the mesoporous cobalt-copper composite oxides, exhibited the higher catalytic activity for CO conversion and selectivity compared with the mesoporous Co₃O₄ and mesoporous CuO. Among these catalysts the mesoporous cobalt-copper catalyst with Co:Cu molar ratio of 70:30, shows the best catalytic activity and the broadest operating temperature “window” for the high CO conversion in the range of 125–200^oC. The higher catalytic activity was attributed to the higher CO adsorption and oxygen vacancies.     

The Solid-State-Grinding Synthesis of Maganese-Modified Cobalt Oxides and Application in the Low-Temperature CO Preferential Oxidation in H<Subscript>2</Subscript>-Rich Gases

A series of MnOx modified cobalt oxides with different atomic molar ratios of Mn/(Mn?+?Co) were prepared by a soft reactive grinding route and investigated for CO preferential oxidation in H₂. It was found that as-prepared Mn-doped cobalt oxides exhibited superior activity compared to the single constituted oxides, other Mn–Co–O mixed oxides synthesized by solution-based route, and other grinding-derived mixed metal oxides M–Co–O (M?=?Zn, Ni, Cu, Fe). The grinding-derived MnCo10 catalyst with Mn/(Mn?+?Co) molar ration of 10% showed the best CO oxidation activity and higher selectivity at low temperature. The surface richness of Co³⁺ was not found as increasing the Mn molar ratio in the present work. However, the incoporation of MnOx with proper amount into Co₃O₄ could produce high surface area, high structure defects, and rich surface active oxygen species, while the ability to supply the active oxygen species was suggested to play the crucial role in promoting the catalytic performance of Mn–Co–O mixed oxides.     

Properties of cerium-zirconium mixed oxides partially substituted by neodymium: Comparison with Zr-Ce-Pr-O ternary oxides

CeO₂ doped with praseodymium, neodymium and/or zirconium atoms were prepared by coprecipitation and by the sol-gel method. Structural properties were investigated by in situ XRD and Raman spectroscopy while oxygen storage capacity (OSC) was measured by transient CO oxidation. All the compounds, except pure Nd₂O₃, have a fluorite-type structure as well as a Raman band at 560 cm⁻¹ characteristic of the oxygen vacancies involving non-stoichiometric oxides. The lattice parameter under hydrogen, being dependent on the temperature, revealed two reduction mechanisms: one at a low temperature at the surface and another at a high temperature in the bulk. Ce-Nd binary oxides show a strong tendency towards crystallite aggregation, which reduces accessibility to gases and OSC properties. Zirconium improves the thermal resistance to sintering of both Ce-Nd and Ce-Pr oxides. The Zr-Ce-Pr-O followed by Zr-Ce-Nd-O compounds displaying high oxygen mobility at a low temperature, appear to be very promising for practical applications such as OSC materials.     

Properties of NiO–ThO2 Mixed Oxides From Hydroxides and Their Hydrogen Reducibility Behaviour

Some physico-chemical properties of NiO–ThO₂ mixed oxides of various compositions have been investigated. The presence of strongly bound constitutional water in the hydrogel of reactive forms of thorium dioxide, determined by their origin (thermal decomposition of mixed hydroxides) caused the different reduction behaviour as compared with other mixed oxide systems containing the only, thermodynamically less stabile reducible component. The significant effects of the thermal treatment in oxygen atmosphere, pre-irradiation by the gamma rays or accelerated electrons under various conditions (in air or in water suspension) as well as of surface chemical activation with a platinum complex on the reactivity of mixed oxides or reoxidized samples during their hydrogen reduction have been also proved. This revised version was published online in August 2006 with corrections to the Cover Date.     

Investigation of Fe−Ni Mixed‐Oxide Catalysts for the Reduction of NO by CO: Physicochemical Properties and Catalytic Performance

A series of Fe?Ni mixed‐oxide catalysts were synthesized by using the sol–gel method for the reduction of NO by CO. These Fe?Ni mixed‐oxide catalysts exhibited tremendously enhanced catalytic performance compared to monometallic catalysts that were prepared by using the same method. The effects of Fe/Ni molar ratio and calcination temperature on the catalytic activity were examined and the physicochemical properties of the catalysts were characterized by using XRD, Raman spectroscopy, N₂‐adsorption/‐desorption isotherms, temperature‐programmed reduction with hydrogen (H₂‐TPR), temperature‐programmed desorption of nitric oxide (NO‐TPD), and X‐ray photoelectron spectroscopy (XPS). The results indicated that the reduction behavior, surface oxygen species, and surface chemical valence states of iron and nickel in the catalysts were the key factors in the NO elimination. Fe_0.5Ni_0.5O_x that was calcined at 250 °C exhibited excellent catalytic activity of 100 % NO conversion at 130 °C and a lifetime of more than 40 hours. A plausible mechanism for the reduction of NO by CO over the Fe?Ni mixed‐oxide catalysts is proposed, based on XPS and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses.     

Initial corrosion behavior of composite coatings obtained by co-electrodeposition of zinc with nanoparticles of Ti and Ce oxides

The present work reports the results obtained for the electrodeposition of composite Zn coatings on steel by using Ti and Ce oxides nanopowders, separately or in mixture, and a TiO₂·CeO₂ binary oxide. In an attempt to correlate the effects of nanoparticles on corrosion behavior of the composite deposits, the properties of Zn–TiO₂·CeO₂ layers were compared with those referring to similar coatings prepared by using a simple mixture of the two oxides or individual oxides. Corrosion measurements were performed in 0.2 g?L^?1 Na₂SO₄ solution (pH?=?5). The results of electrochemical measurements (open circuit potential measurements, polarization curves, and electrochemical impedance spectroscopy) were corroborated with those obtained by using X-ray diffraction, atomic force microscopy, scanning electron microscopy, and salt spray tests. The results indicate that the composite Zn–(TiO₂?+?CeO₂) coatings exhibit the highest corrosion resistance from all investigated Zn coatings.     

Characterization of the active sites in MgNiAl mixed oxides by microcalorimetry and test reaction

In this study, MgNiAl mixed oxides derived from layered double hydroxide precursors were prepared by pH-controlled co-precipitation. Three samples were prepared with a (Mg²⁺ + Ni²⁺)/Al³⁺ ratio of 2 and a Ni²⁺/Mg²⁺ with ratios of 0.22, 0.47, and 4.05. The structural, textural and redox features of the oxides were investigated by a variety of techniques, including X-ray diffraction, transmission electron microscopy, N₂ physisorption, and temperature-programmed reduction. The acid and base properties were assessed by NH₃ and CO₂ adsorption microcalorimetry, respectively. The acid–base features were also investigated by testing the catalytic behaviors of the oxides for the conversion of 4-methylpentan-2-ol under both mild and stressed conditions. The reactant alcohol can undergo dehydration into 4-methylpent-1-ene, 4-methylpent-2-ene, and skeletal isomers of C₆-alkenes, as well as dehydrogenation to 4-methylpentan-2-one and higher ketones, the product selectivity being governed by the concentration and strength of the acid and base sites. Comparison between the calorimetric and test reaction results is discussed.     

Dy2O3 as a catalyst for a Meerwein-Ponndorf-Verley reaction

Dy₂O₃ activated at high temperature is reported as a catalyst for the liquid phase reduction of cyclohexanone. The catalytic activity of Dy₂O₃ activated at 300, 500 and 800°C and its mixed oxides with alumina for the reduction of cyclohexanone with 2-propanol has been reported. The data have been correlated with the electron donating properties of the catalysts which were reported from the adsorption of electron acceptors [EA] of various electron affinity on the surface of these oxides.