Circumventing the OCl versus OOH scaling relation in the chlorine evolution reaction: Beyond dimensionally stable anodes

The development of selective electrocatalysts for the chlorine evolution reaction (CER) is majorly restrained by a scaling relation between the OCl and OOH adsorbates, rendering that active CER catalysts are also reasonably active in the competing oxygen evolution reaction (OER). While theory predicts that the OCl versus OOH scaling relation can be circumvented as soon as the elementary reaction steps in the CER comprise the Cl rather than the OCl adsorbate, it was demonstrated recently that PtN₄ sites embedded in a carbon nanotube follow this theoretical prediction. Advanced experimental analyses illustrate that the PtN₄ sites also reveal a different reaction kinetics compared to the industrial benchmark of dimensionally stable anodes (DSA). A reverse Volmer–Heyrovsky mechanism was identified, in which the rate-determining Volmer step for small overpotentials is followed by the kinetically limiting Heyrovsky step for larger overpotentials. Since the PtN₄ sites excel DSA in terms of activity and chlorine selectivity, we suggest the Cl intermediate as well as the reverse Volmer–Heyrovsky mechanism as the design criteria for the development of next-generation electrode materials beyond DSA.     

Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing

The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384     

甲基丙烯酸—磷脂酰乙醇甲基丙烯酰胺共聚物LB膜的研究

制备了不同摩尔比的甲基丙烯酸-磷脂酰乙醇甲基丙烯酰胺共聚物,研究了这种共聚物在水面的表面压力(π)-分子面积(A)曲线、共聚物制成的MOS LB膜的电容(C)-电压(V)特性及此LB膜的相变温度。     

On the Ordering of a Class of Graphs with Respect to their Matching Numbers

Based on the number of k-matching m(G,k) of a graph G, Gutman and Zhang introduced an order relation of graphs: for graphs G ₁ and G ₂, if m(G ₁,k) ≥ m(G ₂,k) for all k. The order relation has important applications in comparing Hosaya indices and energies of molecular graphs and has been widely studied. Especially, Gutman and Zhang gave complete orders of six classes of graphs with respect to the relation . In this paper, we consider a class of graphs with special structure, which is a generalization of a class of graphs studied by Gutman and Zhang. Some order relations in the class of graphs are given, and the maximum and minimum elements with respect to the order relation are determined. The new results can be applied to order some classes of graphs by their matching numbers.     

Effect of the structure of titanium–magnesium catalysts on the morphology of polyethylene produced

The structure and formation of polyethylene (PE) particles on supported titanium–magnesium catalysts having different structural characteristics (sizes of microcrystallites, mesopores, and subparticles) were studied for the first time. Scanning electron microscopy was used to identify structural elements of the polymer particles formed over such catalysts and to reveal morphological changes in the growing polymer particles when the yield was increased from approximately 0.2 g PE/g catalyst to approximately 13 kg PE/g catalyst. A relationship was found between structural characteristics of the porous catalyst particles, morphology of the nascent polymer particles, and bulk density of the polymer powder. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2298–2308     

Grey relational analysis for optimization of wear parameters and surface roughness on nano composite coating

The higher wear resistance of Ni based nano composite coatings makes them potential replacement in protecting the substrate materials. The role of surface roughness of the coating along with wear parameters on the specific wear rate, pin temperature, and COF are addressed in the present study. The use of hard nano Al₂O₃ particles found significant role in increasing the resistance to wear for Ni matrix coatings on Al6061 material. The resistance to dislocation offered by these nano Al₂O₃ particles and smear out of debris with plastic deformation indicated abrasive and adhesive nature of wear mechanism in combination. The optimization of wear parameters are carried out by surface response method based grey relation analysis. The normal load applied onto the pin has significant influence on the specific wear rate and temperature rise in the pin. The surface roughness of the coating has also found instrumental in the higher pin temperature and friction coefficient.     

无箔二极管电流电压关系研究

本文给出了无箔二极管物理特性的数值模拟研究结果。研究得到了二极管电流与二极管结构参数、二极管电压以及外加磁场强度等参数的变化关系特性，并且应用这些关系特性得到了在外加磁场强度足够大情况下二极管电流的近似表达为Ib=(7.5/x)(x+(0.81-x)/(1+0.7Ld2/δr))(r2/3-1)3/2，其中Ld为阴阳极间距；Rc为阴极发射端面的外半径；Rp为漂移管管壁半径；x=ln(Rp/Rc)，δr =Rp-Rc。这一表达式在大量二极管结构参数和二极管电压参数情况下与数值模拟结果在10％误差范围内相一致，能够比较准确的表达无箔二极管的电流电压关系。     

补偿效应研究的一个新视角

补偿效应与Arrhenius方程关系密切。本文为补偿效应研究提供了新视野。用几何图象分析了Arrhenius方程,指出过去认为此方程只表示速率与温度关系是不全面的,忽视了速率常数与活化能关系的研究。从图形看出,指前因子与活化能本身就具有互补关系,虽仅限于每两个不同活化能的情况。反应是一自组织过程。补偿效应的成立有必要条件和充分条件。欲实现补偿效应,从协同学角度考虑,E/T作为参变量必需小于一阈值,以使反应起活。并有一自变量做系列改变,以使A、E随其相似地连续变化,从而连通所有A、E的内在联系,1/T-lnk图中诸直线交于一点。指数分布是非均匀体系最具有普遍意义的分布函数。概率分析指出,补偿效应是A、E在固体表面和内部均呈相似指数分布的产物。对催化反应与非催化反应有普适性。在速率常数中体现为结构分布概率因子及能量分布概率因子。     

硫醇和硫醚的沸点与分子结构之间关系的拓扑化学研究

根据分子拓扑学原理, 用染色因子标识原子性质的差异, 发展了一种适用于含原子分子体系结构性能关系研究的新方法。据此探讨了硫醇和硫醚的沸点与分子结构之间的关系, 提出一个既能合理表征结构性能关系, 又能预测沸点的定量关系式。     

Entanglement conditions for four-mode states via the uncertainty relations in conjunction with partial transposition

From the Heisenberg uncertainty relation in conjunction with partial transposition, we derive a class of inequalities for detecting entanglements in four-mode states. The sufficient conditions for bipartite entangled states are presented. We also discuss the generalization of the entanglement conditions via the Schrödinger-Robertson indeterminacy relation, which are in general stronger than those based on the Heisenberg uncertainty relation.