Hydrogen evolution during the oxidation of formaldehyde on Au:: The influence of single crystal structure and Tl-upd

Hydrogen evolution during formaldehyde oxidation in alkaline solution has been monitored by Differential Electrochemical Mass Spectrometry on Au(111) and polycrystalline gold. The current efficiency for hydrogen evolution increases with higher concentration and is in the same range on both, polycrystalline Au and Au(111) electrode. The onset potentials and half-wave potentials are higher on Au(111). Reaction orders for the faradaic current on the bare gold electrodes have been determined as 0.21 for higher and 0.76 for lower concentrations. Reaction orders for hydrogen evolution during formaldehyde oxidation are 1.4 times higher in each case. Tafel slopes in the range of 140-160 mV are found. This signifies that the first reaction step involving the formation of adsorbed hydrogen is largely determining the overall reaction rate. In the presence of thallium adlayers hydrogen evolution from formaldehyde oxidation is largely suppressed. On the thallium modified polycrystalline Au, formaldehyde oxidation is shifted for 100 mV to higher potentials where Tl is partially desorbed and hydroxide is coadsorbed on the modified surface. On thallium modified Au(111), a similar process takes place, but in the same potential region as the onset of formaldehyde oxidation on the bare surface and therefore the formaldehyde oxidation is only slightly shifted. Tafel slopes are decreased to 80 mV/dec in the presence of thallium. In the presence of adsorbed thallium, the first reaction step is in equilibrium, the coverage with adsorbed hydrogen is smaller and its recombination to H₂ is largely suppressed.     

高性能活性炭开发生产中的无机活化剂

无机活化剂是开发生产高性能活性炭的关键原料。综述了高性能活性炭开发生产中常用的无机活化剂;介绍了H₃PO₄、KOH、ZnCl₂、CO₂、O₂和水蒸气等无机活化剂的特点和作用机理;总结提出了新型复合活化剂的设计方法及应用。建议加快开发价格低廉的新型复合活化剂;还建议将高性能活性炭生产和酚类废弃物处理结合应用,以降低高性能活性炭生产原料成本和酚类废弃物的处理成本。     

Electrochemical and spectroscopic evidences of corrosion inhibition of bronze by a triazole derivative

The electrochemical behavior of the bronze (Cu-8Sn in wt%) was investigated in 3% NaCl aqueous solution, in presence and in absence of a corrosion inhibitor, the 3-phenyl-1,2,4-triazole-5-thione (PTS). The inhibiting effect of the PTS was evidenced for concentrations higher than 1 mM for the cathodic process whereas its effect was clearly seen with a concentration as low as 0.1 mM for the anodic process. A significant positive shift of the corrosion potential was also observed, and its inhibiting effect increased with both its concentration and the immersion time of the sample. From voltammetry and electrochemical impedance spectroscopy experiments, the inhibiting efficiency of the PTS was found to be in the 94-99% range for 1 mM concentration. Scanning electron microscopy and X-ray energy dispersion analysis of the specimen surface show the presence of sulphur on the surface. Raman micro-spectrometry study confirms the protective effect of the PTS in aqueous solution through three types of interactions with the electrode, namely the adsorption of the inhibitor in a flat configuration, the formation of copper-thiol molecules, and when copper is released, the formation of a polymeric complex.     

P450酶启发的染料后修饰铁卟啉MOF光催化氧化

受细胞色素P450酶氧化代谢的启发,将染料酸性红87（Acid Red 87）后修饰到金属有机框架PCN-222(Fe)中,构筑非均相拟酶光催化剂Acid Red 87@PCN-222(Fe),拉近染料与铁卟啉中心的距离,利用光致电子转移模拟P450的电子传递链。以1-(4-甲氧基苯基)乙醇为模板底物,对光催化氧化的条件如溶剂、电子牺牲剂、氧源等进行筛选,得到优化反应条件为高碘酸钠(53.5 mg, 0.25 mmol),2,6-二甲基吡啶三氟甲磺酸盐(64.3 mg, 0.25 mmol),Acid Red 87@PCN-222(Fe)(12.0 mg, 0.00625 mmol),乙腈(2 mL),530 nm波长LED光照反应24 h。催化剂重复使用3次后仍保持活性和晶态结构。该催化体系对苄基碳氢键氧化具有良好的底物适用范围,可应用于非甾体类抗炎药匹美诺芬的区位选择性氧化，产率为48%，该体系还可将芳基硫醚类化合物氧化至相应的亚砜，体现其在精细化工制药、工业脱硫领域的应用潜质。     

空心微珠在尼龙改性中的应用研究

利用空心微珠球型的特性，填充改性玻纤增强尼龙6。研究结果表明，空心微珠可提高材料流动性、热变形温度及改善制品外观、降低收缩率和提高制品的物理性能。     

NiFe2O4及添加TiO2的尖晶石的烧结过程

以NiO和Fe2O3为主要原料,通过添加少量TiO2粉末来改善NiFe2O4试样的烧结性能。研究了NiFe2O4和TiO2-NiFe2O4 2种样品反应烧结过程中的热力学及动力学条件,同时利用球模型推导的扩散机制的烧结方程测算出2种材料的烧结活化能。结果表明：NiO和Fe2O3固相烧结过程是固相反应和致密化过程同时进行的。添加质量分数为1％TiO2粉末,当合成温度为1250℃时,TiO2-NiFe2O4样品就已达到致密,其烧结活化能由NiFe2O4样品时的245.36kJ/mol降低为142.71kJ/mol。     

焙烧法水热合成5A沸石分子筛

焙烧活化化工原料氢氧化钙、氢氧化钠、硅酸钠和二氧化硅，探索焙烧法水热合成5A沸石分子筛的条件。并通过X射线粉末衍射(XPS)和扫描电镜(SEM)对产品进行表征。焙烧原料合成5A沸石分子筛的优化条件为焙烧温度550 ℃, 焙烧时间4 h, 晶化时间4 h。     

The linear viscoelastic properties of copolypropylene–clay nanocomposites

The linear viscoelastic properties of copolypropylene (cPP)–clay nanocomposites (cPPCNs) prepared by melt intercalating with different amounts of clay were extensively examined by rheological measurements. Meanwhile, the clay effects on the cPP confinements were first estimated by calculating the activation energy of different cPP moving units, including the whole molecular chain, the chain segment, and smaller unit such as chain link. The results showed that the stability of cPPCNs melts wrecked when the clay loading was above 5 wt %. An increase in clay loading of cPPCNs gave rise to a strong low frequency solid‐like response (G′ > G″). Unlike the matrix polymer, cPPCN5 (with 5 wt % clay) exhibited a relaxation plateau as relaxation time prolonged above 100 s, and displayed a maximal linear modulus. The variations of the activation energy of different cPP moving units revealed that the mobility of cPP molecular chains was restricted by clay layers, while these restrictions were not only related to the clay loadings but also largely depended on the clay dispersion status in the matrix. The motions of cPP chain segments were greatly limited at 3–5 wt % loading of clay, but drastically activated with the addition of 7 wt % clay due to the increasing stacks of clay layers within the matrix. However, it was found that the presence of clay had little effect on the mobility of small cPP moving units such as chain links. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1523–1529, 2006     

Activation of a Au/TiO2 Catalyst by Loading a Large Amount of Fe–Oxide: Oxidation of CO Enhanced by H2 and H2O

Catalytic activity of a 1 wt% Au/TiO₂ catalyst is markedly improved by loading a large amount of FeO_x, on which the oxidation of CO in excess H₂ is selectively promoted at temperature lower than 60 °C. Oxidation of CO with O₂ on the FeO_x/Au/TiO₂ catalyst is markedly enhanced by H₂, and H₂O moisture also enhances the oxidation of CO but its effect is not so large as the promotion by H₂. We deduced that activation of Au/TiO₂ catalyst by loading FeO_x is not caused by the size effect of Au particles but a new reaction path via hydroxyl carbonyl intermediate is responsible for the superior activity of the FeO_x/Au/TiO₂ catalyst.     

Development and characterization of silicone/phosphorus modified epoxy materials and their application as anticorrosion and antifouling coatings

Epoxy resin is chosen for our present study owing to its exceptional combination of properties such as easy processing, high safety, excellent solvent and chemical resistance, toughness, low shrinkage on cure, good electrical, mechanical and corrosion resistance with excellent adhesion to many substrates. This versatility in formulation made epoxy resins widely applied for surface coatings, adhesives, laminates, composites, potting, painting materials, encapsulant for semiconductor and insulating material for electric devices. There are numerous paint/coating systems based on epoxy resin available for corrosion and fouling prevention. They however are not completely satisfactory in field applications, where high corrosion, fouling and flame resistance are required. The demand for epoxy resin as corrosion/fouling resistant coatings is restricted mainly due to its inferior characteristics like poor impact strength, high rigidity, and moisture absorbing nature besides inadequate flame retardant properties. It is for this reason that silicones and phosphorus-based compounds are used as modifier in this work by intercrosslinking network mechanism (ICN) to obtain epoxy resin with desired properties ideally suitable for field applications for preventing corrosion and fouling with flame retardantancy. The present work involves the development of solvent free silicone/phosphorus modified epoxy coating systems, since solvent free coating systems are widely used for numerous applications due to their lower cost per unit film thickness, freedom from fire and pollution hazard and ability to provide better performance. For the development of coating systems, epoxy resin (X) serves as base material, hydroxyl terminated polydimethylsiloxane (HTPDMS) as modifier, γ-aminopropyltriethoxysilane (γ-APS) as crosslinking agent and dibutyltindilaurate (DBTDL) as catalyst. Polyamidoamine (A), aromatic amine adducts (B) and phosphorus-containing diamine (C) were used as curing agents. The study also describes the evaluation of corrosion resistant behaviour of unmodified epoxy and siliconized epoxy coatings by potentiodynamic polarization method, electrochemical impedance spectroscopy (EIS), salt-spray and antifouling tests. The results are discussed.