State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

The state of Ni supported on HZSM‐5 zeolite, silica, and sulfonated carbon was studied during aqueous‐phase catalysis of phenol hydrodeoxygenation using in situ extended X‐ray absorption fine structure spectroscopy. On sulfonated carbon and HZSM‐5 supports, NiO and Ni(OH)₂ were readily reduced to Ni⁰ under reaction conditions (≈35 bar H₂ in aqueous phenol solutions containing up to 0.5 wt. % phosphoric acid at 473 K). In contrast, Ni supported on SiO₂ was not stable in a fully reduced Ni⁰ state. Water enables the formation of Ni^II phyllosilicate, which is more stable, that is, difficult to reduce, than either α‐Ni(OH)₂ or NiO. Leaching of Ni from the supports was not observed over a broad range of reaction conditions. Ni⁰ particles on HZSM‐5 were stable even in presence of 15 wt. % acetic acid at 473 K and 35 bar H₂.     

Formation of sulfur surface species on a commercial NO<Subscript>x</Subscript>-storage reduction catalyst

The influence of SO₂ exposure under lean (oxidizing) and rich (reducing) reaction conditions on the storage and oxidation/reduction function of a commercial NO_x storage-reduction catalyst was investigated by temperature-programmed uptake experiments and high temperature XRD. Both the storage capacity and the oxidation/reduction function of the catalyst were deactivated by SO₂ exposure under lean and rich reaction conditions. The deactivation of the storage component, i.e. the loss of the NO_x storage capacity, resulted mainly from the formation of Ba-sulfates accumulating in the bulk phase, which have a high thermal stability (>800°C) and, therefore, cannot be removed under the typical operation conditions of a NSR catalyst. For the oxidation function only a temporarily deactivation during lean reaction conditions was observed. Besides the formation of SO^2- ₄ species on the storage component at the beginning of the SO₂ exposure under rich conditions, an adsorption of SO₂ on the noble metal component was observed resulting in the formation of sulfur deposits. The oxidation of these sulfur species with a subsequent spillover of SO^2- ₄ species to the storage component during lean conditions could accelerate the deactivation of the storage capacity.     

Bent Carbon Surface Moieties as Active Sites on Carbon Catalysts for Phosgene Synthesis

Active sites in carbon‐catalyzed phosgene synthesis from gaseous CO and Cl₂ have been identified using C₆₀ fullerene as a model catalyst. The carbon atoms distorted from sp² coordination in non‐planar carbon units are concluded to generate active Cl₂. Experiments and density functional theory calculations indicate the formation of a surface‐bound [C₆₀???Cl₂] chlorine species with radical character as key intermediate during phosgene formation. It reacts rapidly with physisorbed CO in a two‐step Eley–Rideal‐type mechanism.     

Atomic‐Scale Determination of Active Facets on the MoVTeNb Oxide M1 Phase and Their Intrinsic Catalytic Activity for Ethane Oxidative Dehydrogenation

Aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) has been used to image the basal {001} plane of the catalytically relevant M1 phase in MoVTeNb complex oxides. Facets {010}, {120}, and {210} are identified as the most frequent lateral termination planes of the crystals. Combination of STEM with He ion microscopy (HIM) images, Rietveld analysis, and kinetic tests reveals that the activation of ethane is correlated to the availability of facets {001}, {120}, and {210} at the surface of M1 crystals. The lateral facets {120} and {210} expose crystalline positions related to the typical active centers described for propane oxidation. Conversely, the low activity of the facet {010} is attributed to its configuration, consisting of only stable M₆O₂₁ units connected by a single octahedron. Thus, we quantitatively demonstrated that differences in catalytic activity among M1 samples of equal chemical composition depend primarily on the morphology of the particles, which determines the predominant terminating facets.     

电感耦合等离子体原子发射光谱法测定钛酸钡纳米粉体中7种杂质元素

钛酸钡纳米粉体样品用盐酸溶解,在所得样品溶液中用电感耦合等离子体原子发射光谱法测定了以氧化物存在于样品中的7种杂质元素(包括镁、锶、钾、钠、铝、硅及铁),对测定的光谱条件进行了试验并优化达到上述各元素的测定上限为0.1%(质量分数).测得方法的检出限(3S/b)为(单位μg·L-1):2.0(铝),1.0(铁),20.0(钾),0.2(镁),4.0(钠),3.0(硅)及0.5(锶).应用此方法分析了两件实样,所得结果的相对标准偏差(n=6)小于等于2.0%,对其中4种杂质元素(镁、钾、钠和锶)同时用HG/T 3587-1999标准中的方法作分析校核,所得结果与此方法结果一致.     

A fuzzy rule based framework for noise annoyance modeling

Predicting the effect of noise on individual people and small groups is an extremely difficult task due to the influence of a multitude of factors that vary from person to person and from context to context. Moreover, noise annoyance is inherently a vague concept. That is why, in this paper, it is argued that noise annoyance models should identify a fuzzy set of possible effects rather than seek a very accurate crisp prediction. Fuzzy rule based models seem ideal candidates for this task. This paper provides the theoretical background for building these models. Existing empirical knowledge is used to extract a few typical rules that allow making the model more specific for small groups of individuals. The resulting model is tested on two large-scale social surveys augmented with exposure simulations. The testing demonstrates how this new way of thinking about noise effect modeling can be used in practice both in management support as a "noise annoyance adviser" and in social science for testing hypotheses such as the effect of noise sensitivity or the degree of urbanization.     

Continuous hydroamination in a liquid-liquid two-phase system

The direct addition of NH across a CC multiple bond (hydroamination) was efficiently catalysed in a liquid-liquid two-phase system. The latter comprised a polar catalyst phase of Zn(CF3SO3)2 in the ionic liquid 1-ethyl-3-methylimidazolium trifuoromethanesulfonate and a substrate mixture in heptane. The possibility of catalysing different hydroamination reactions continuously was demonstrated.