Alternative view of anodic surface oxidation of noble metals

The idea of underpotential oxidation of water, taking place on the surface of noble metals in the range of potentials preceding molecular oxygen evolution, is more than 40-years old. Chemisorbed oxygen atom—O_chem is considered to be the main intermediate in the underpotential oxidation of H₂O, leading eventually to chemical oxidation of noble metals and formation of anhydrous surface oxides of MeO type. This concept is still used for the evaluation of the real surface area of the noble metal electrodes and also for the interpretation of new experimental results.The existence of reversible metal-oxide electrodes demonstrated experimentally for Pt, Pd, Rh, Ir and Au electrodes, oxidized anodically in the range of potentials preceding O₂ evolution, shows that noble metals do have electrochemistry of their own. Nanometric layers of amorphous, slightly soluble hydroxides, hydrous oxides or oxides can form electrochemically on the electrode surface during the anodic process and be reduced during the cathodic one. Such alternative concept admits the reversibility of anodic and cathodic processes and changes essentially the understanding and interpretation of the phenomena of anodic oxidation of noble metals.     

碱金属和锌对高炉用SiAlON结合刚玉砖的复合侵蚀

将高炉用SiAlON结合刚玉砖制成外部尺寸为50mm×50mm,内孔尺寸为25mm×25mm的坩埚,分别加入由Na2CO3、K2CO3、ZnO和宝钢高炉现场高炉灰配制的炉渣(其w(Na2O+K2O)=2.75%,w(ZnO)=5.1%)和用K2CO3、ZnO、石墨配制的炉渣(其w(Na2O+K2O)=25%,w(ZnO)=25%),然后分别在还原气氛下于1350℃16h和1100℃40h进行侵蚀试验。将侵蚀后的试样纵向对称剖开,观察渣对试样的侵蚀和渗透情况,进行SEM和EDAX分析。结果表明:碱金属和锌含量不同的两种炉渣对SiAlON结合刚玉砖的侵蚀速度都很小;碱金属侵蚀机理主要是SiAlON与碱蒸气反应生成钾霞石,与渣反应生成铁橄榄石,并参与硅酸盐玻璃相的生成;刚玉颗粒与渣中的FeO、Na2O和K2O反应生成铁铝尖晶石和少量针状β-Al2O3;锌对该砖没有产生明显的化学侵蚀。     

Selective oxidation of ammonia to nitrogen on transition metal containing mixed metal oxides

The selective catalytic oxidation of ammonia to nitrogen (NH₃-SCO) has been studied over hydrotalcite derived mixed metal oxides containing Cu, Co, Fe or Ni. XRD, BET, NH₃-TPD and TPR techniques were used for catalysts characterization. Results of NH₃-SCO were compared with those of selective catalytic reduction of NO with NH₃ (NO-SCR). Reaction mechanism was studied by temperature-programmed surface reaction (TPSR) and activity tests with a various contact time. Catalytic performance of the studied samples depends on both kind and loading of transition metals in the mixed metal oxide system. The Cu-containing samples have been found to be the most active catalysts of the NH₃-SCO process. Transition metal loading strongly influences distribution of ammonia oxidation products. The highest selectivity to N₂ was measured for the catalysts with the lowest transition metal content.     

Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.     

Viscoelastic Effects in a Phosphate Glass-Metal Seal

A family of phosphate glasses has been developed with thermal expansion behavior in the elastic range that nearly matches the response of 304 stainless steel. Attempts to make concentric pin-shell seals consistently have yielded fractures between 400° and 300°C during cooling. Elastic stress analyses which neglect glass transitional behavior and utilize constant glassy ("elastic") thermal expansion coefficients predict a residual stress state that is compressive. However, viscoelastic computations which include the effects of structural relaxation during glass transtion show that tensile stresses sufficient to cause failure arise during cooldown of the seal.     

海泡石对废水中有机物和重金属的吸附

简述了海泡石的结构特点，及其改性方法，总结了海泡石对废水中有机物和重金属的吸附效果，分析了改性方法、pH、温度、污染物性质与浓度、海泡石用量和吸附时间等因素对吸附效果的影响．探讨了海泡石的吸附机理与等温式，展望了海泡石在废水处理中的应用前景。     

用于吸附贵重金属、有色金属、有毒金属及稀有金属的有机硅吸附剂

概述了有机硅吸附剂的结构、类型及其官能团的种类与被吸附元素的关系,详细介绍了用于吸附贵重金属、有色金属和有毒金属、稀土元素及放射性元素的有机硅吸附剂的官能团种类及其吸附特性,以及在化工废水、冶金污水、腐蚀性废水的无害化处理中的应用。     

Effect of alkali and alkaline earth metals on nitrogen release during temperature programmed pyrolysis of coal

Formation of HCN, NH₃, and N₂ during fixed-bed pyrolysis at 10K min⁻¹ has been studied using coal samples after partial demineralization followed by addition of metal hydroxides from aqueous systems. Without additives, NH₃ is the predominant product at ≤ 700°C, showing the two peaks in the formation rate profile, whereas N₂ is the only product at ≥ 800°C. The presence of NaOH, KOH and Ca(OH)₂ promotes considerable NH₃ formation between 450 and 600°C, but in contrast suppresses HCN formation in this region. The Ca shows the largest effect on both the promotion and suppression. It is likely that the NH₃ increased by Ca addition arises partly from HCN, but mainly from secondary reactions of tar-N. These hydroxides affect N₂ formation in quite different manners: the Na decreases the rate between 700 and 950°C, and the K changes it less significantly than the Na, but the Ca remarkably increases the rate in a low temperature region of 550–700°C. These different features are discussed in terms of solid-phase reactions of alkali metal carbonates with char-N and secondary decomposition reactions of tar-N on CaO particles. As a result, total conversion of coal-N to HCN, NH₃ and N₂ up to 1000°C increases in the sequence of Na < none < K < Ca.     

新型合成聚合物重金属离子吸附剂及其吸附性能

阐述了新型聚合物重金属离子吸附剂的合成与改性及其对水溶液中Cd(Ⅱ)、Pb(Ⅱ)、Cu(Ⅱ)、Hg(Ⅱ)等重金属离子的吸附性能。这些聚合物重金属离子吸附剂对低浓度的重金属离子表现出了较好的吸附能力，其中聚合物吸附剂PGHyFeO—COOH对mg／L级的Pb(Ⅱ)、Cd(Ⅱ)、Hg(Ⅱ)的最大吸附量分别为211．4mg／g、155．0mg／g、147．2mg／g。这些吸附剂的吸附速度也较快，平衡吸附时间一般在60min左右，有的甚至只有几分钟。新型聚合物重金属离子吸附剂在水处理工业中具有广阔的应用前景。     

Heavy metals contribution of non-aqueous fluids used in offshore oil drilling

A monitoring program was performed to investigate heavy metal content alteration due to exploratory drilling for oil using non-aqueous fluids (NAFs) in Brazilian offshore, 900 m deep. Fourteen elements were monitored in 54 sites and it was verified that after drilling activities the average Ba concentration was remarkably increased with respect to background level, even 1 year after the activity. A minor increase in Mn and a moderate increase in Al concentrations were verified. The Cd, Cr, Ni, As, Co, Cu, Pb, V, and Zn concentrations were at the background levels, ca. 1 year after the NAFs drilling materials deposition on the seafloor. The Al, Ba, Cd, Cr, Cu, Ni and Zn mean concentrations were significantly different (P<0.05) between the three sampling operations (cruises) performed, while As, Cd, Fe and Pb presented different mean values according to the distance of the oil well, independent of the sampling operation. Interaction between sampling operation and distance was observed for Mn. In all sediment samples the Hg concentration was below the detection limit (0.07 μg g⁻¹).