Effect of potential cycling on structure and activity of Pt nanoparticles dispersed on different carbon supports

Platinum particles synthesized via the Bönnemann methods were dispersed on two different Vulcan XC72 carbon supports. One was used after thermal treatment at 400 °C under nitrogen atmosphere, the other after oxidation of its surface by acid leaching using diluted HNO₃ in water (1/3). Characterization of the carbon support indicated that HNO₃ treatment leads to the decrease of the BET surface and to the increase of the surface acidity of the carbon support. After dispersion of the platinum catalyst, TEM results indicated that the mean particle size was a little higher on the non-oxidized support (Pt/XC72) than that on the functionalized one (Pt/XC72_HNO3), being 2.5 and 2.0 nm, respectively. However, potential cycles from 0.05 to 1.25 V vs. RHE led to a higher increase of the particle size when catalyst is dispersed on the functionalized support, reaching after 400 potential cycles 5.5 nm against 4.0 nm with the non-functionalized one. The effect of the upper limit (1.0 and 1.25 V vs. RHE) of the potential cycles on the active surface area and on the activity towards the oxygen reduction reaction (orr) was determined for both catalysts. Results indicated that the particle growth was not the main degradation process over the whole duration of the electrochemical experiments, but that dissolution/redeposition (Otswald ripening) was also involved. The predominant role of each degradation process depends on the number of cycles, on the upper potential limit and on the carbon surface state, and could be temporally separated. However, the lower activity towards orr was recorded for the (Pt/XC72_HNO3) cycled up to 1.0 V vs. RHE.     

Minisymposium on Endogenous Carcinogens: The Catechol Estrogen Pathway. An Introduction

Abstract

A major carcinogenic risk for many human cancers may be associated with endogenous procarcinogens that are precursors to carcinogens. If natural protective mechanisms become insufficient, these procarcinogens can be activated, giving rise to formation of endogenous carcinogens. Catechol estrogens (CE), which are metabolites of the estrogens estrone and 17β-estradiol are hypothesized to be such ubiquitous procarcinogens. Their oxidation to CE semiquinones and/or quinones can generate the DNA damage that leads to the tumor initiation process. In addition, redox cycling of CE semiquinones and quinones can generate free radicals that lead to enhancement of DNA damage. The minisymposium discussing this area of research was moderated by Pentti Siiteri and introduced by Ercole Cavalieri. It included presentations by Joachin Liehr, Judith Weisz, Cyrus Creveling and Herman Adlercreutz.     

Structural and electrochemical characterization of mechanochemically synthesized calcium zincate as rechargeable anodic materials

Hydrated calcium zincate was synthesized by mechanical ball milling of ZnO and Ca(OH)₂ in water at room temperature. The structural and electrochemical properties of this material used as rechargeable anodic material were examined by microelectrode voltammetry, charge–discharge measurements and structural analysis. The results showed that during mechanical milling, ZnO, Ca(OH)₂ and H₂O reacted rapidly to form Ca[Zn(OH)₃]₂ · 2H₂O which was subsequently transformed to a stable structure CaZn₂(OH)₆ · 2H₂O. Since this composite oxide has lower solubility in KOH solution (<35 wt %) and better electrochemical reversibility than ZnO-based negative materials, the zinc anodes using this material can overcome the problems of shape changes and dendritc formation, and therefore exhibit improved cycling life.     

Linking chemical reactivity and protein precipitation to structural characteristics of foliar tannins

Tannins influence ecosystem function by affecting decomposition rates, nutrient cycling, and herbivory. To determine the role of tannins in ecological processes, it is important to quantify their abundance and understand how structural properties affect reactivity. In this study, purified tannins from the foliage of nine species growing in the pygmy forest of the northern California coast were examined for chemical reactivity, protein precipitation capacity (PPC), and structural characteristics (¹³C NMR). Reactivity of purified tannins varied among species 1.5-fold for the Folin total phenol assay, and 7-fold and 3-fold, respectively, for the acid butanol and vanillin condensed tannin assays. There was about a 5-fold difference in PPC. Variation in chemical reactivity and PPC can be largely explained by differences in structural characteristics of the tannins determined by ¹³C NMR. In particular, the condensed versus hydrolyzable tannin content, as well as the hydroxylation pattern of the B-ring and stereochemistry at the C-2–C-3 position appear to influence reactivity. Due to the large differences in chemical reactivity among species, it is necessary to use a well-characterized purified tannin from the species of interest to convert assay values to concentrations. Our results suggest that structural characteristics of tannins play an important role in regulating their reactivity in ecological processes.     

Thermoplastic Sizing of Carbon Fibres in High Temperature Polyimide Composites

Thermoplastic sizing of various carbon fibres has been evaluated as a means of controlling the microcracking resistance, transflexural strength (TFS), and thermo-oxidative stability (TOS) of PMR-15 matrix composites. Four different fibre/thermoplastic size combinations were selected for this study, based on their higher TOS than appropriate controls. Data are presented for the transverse microcrack (TVM) density/inch, and the subsequent delamination of [0,90]_4s laminates induced by thermal cycling (-196 to 350°C for 20 cycles). Results for composite TFS, conditioned TFS (after heating in air at 350°C), and TOS (350°C and 316°C) are also reported. One fibre/thermoplastic size combination gave both good microcracking resistance, and significantly improved TOS, in composite when compared with current commercially-available material.     

用先进适用技术和高新技术提升我国传统法尿素装置(2)--传统21法

传统21法是针对我国传统法尿素工艺存在的问题,在汲取了ACES21法和NH3汽提法两流程优点的基础上组合而成的技术改造流程,属于提高第一分解回收段压力的汽提法技改方案。论述了该技改方案的技术基础、流程选择、化工过程、技术关键,以及传统21法的技术特点和工艺流程。作者提出了由传统21法工艺技术和DCS＋3个高级控制系统组合而成的提升我国传统法尿素装置的技改方案。     

估算低温下金属材料应变疲劳寿命和疲劳极限的新方法

本文建立了估算低温下金属材料应变疲劳寿命的新方法,并首次提出了金属疲劳极限的热激活模型。该模型可定量地解释温度和频率对疲劳极限的影响。研究结果表明,提出的应变疲劳公式可很好地拟合低温下金属材料应变疲劳寿命的实验结果;疲劳极限可表示成非热激活分量σ_(ai)(ε_(apc))和热激活分量σ_a~*(T,ε_p)之和;σ_(ai)(ε_(apc))是与温度和频率(或应变速率)无关的材料常数;σ_a~*(T,ε_p)与流变应力的热激活分量近似相等。最后用文献中的实验数据对本文提出的低温下就应变疲劳寿命和疲劳极限的估算方法进行了验证。     

玻璃钢复合材料在海洋环境下的抗冻耐久性能研究

采用1 000次冻融循环试验研究了189不饱和聚酯玻璃钢和MFE–2,MFE–711,MFE–W1环氧乙烯基酯玻璃钢在海水中的抗冻耐久性能。结果表明,1 000次冻融循环试验后,189不饱和聚酯玻璃钢和MFE–711环氧乙烯基酯玻璃钢的树脂基体在冻融循环产生的应力作用下发生开裂破坏,弯曲强度保留率降低至30%左右,渗入189不饱和聚酯玻璃钢和MFE–711环氧乙烯基酯玻璃钢包覆的混凝土试样表层的氯离子质量分数分别为0.08%和0.12%;MFE–2和MFE–W1环氧乙烯基酯玻璃钢在750次冻融循环后,弯曲强度保留率降至最低值65%,且不再随冻融循环次数增加而降低,1 000次冻融循环后,在MFE–2和MFE–W1环氧乙烯基酯玻璃钢包覆的混凝土试样表层未检测到氯离子渗入,它们的树脂基体在冻融循环产生的应力作用下未发生开裂破坏,具有较好的抗冻耐久性能。玻璃钢复合材料的冻融破坏是缓慢累积的过程,至少需要1 000次的冻融循环试验才能区分其抗冻耐久性能的优劣。     

铅酸蓄电池正极活性物质的研究

采用有效添加剂,提高了铅酸蓄电池正极活性物质利用率,延长了使用寿命.软化脱粉现象明显改善.通过X射线衍射分析、电子扫描显微镜分析和比表面的测定,解释了不同添加剂对PbO_2电极的组成、结构和性能的影响原因,确定了添加剂的最佳合量,从而得到较好的配方.