金属有机框架CPL-1填充柱气相色谱分析氢同位素

金属有机框架(MOFs)材料CPL-1的比表面积大、孔径均一,在低温条件下对氢同位素具有良好的量子筛分效应,是气相色谱固定相潜在的应用材料。采用CPL-1填充制备了长0.5 m、内径1 mm的微孔填充柱,借助单晶Al_2O_3颗粒间隙构建了色谱载气流通路径,在低温条件下探索研究了CPL-1填充柱的氢同位素分析性能。结果表明,在77 K时CPL-1对H_2和D_2的吸附量接近4 mmol/g,优于MnCl2/γ-Al_2O_3和γ-Al_2O_3,CPL-1填充柱在取样量0.25~2 mL范围内对低浓度氢同位素样品的检测具有良好的线性关系,检测的相对误差小于4%。CPL-1填充柱具有线性范围宽、重复性好、准确度高等优点,在氢同位素色谱分析中具有潜在的应用价值。     

Z箍缩驱动聚变-裂变混合堆氚燃料循环系统氚盘存量与氚自持初步分析

为研究氚自持条件,建立了Z-FFR氚分析模型,基于理论方程和氚平均滞留时间方法进行计算,得到稳态运行时排灰气处理系统、氚增殖提取系统、同位素分离系统、水去氚化系统的氚质量流分别为52.30,25.40,81.30,3.60 g/day,对应的氚盘存量为52.30,25.40,8.13,1.80 g。同时以氚质量流推导出氚自持判断条件,分析了设计参数能够满足氚自持要求,同时获得了燃烧效率、氚增殖率、提取效率与氚自持的互补关系,三者作为关键参数相互依存,于临界值、设计值、理想值之间分析了氚的自持情况。     

DMFC两相流及其对传质影响的研究

采用自制的实验系统对液态进料直接甲醇燃料电池(DMFC)阳极交叉指状流道内的两相况功特性进行了可视化实验研究.自制的DMFC单电池带有透明窗口,采用镀金的不锈钢阴极极板和透明的聚碳酸脂阳极流场板,电解质为Nafion117膜.实验过程中燃料电池的进口总管和出口总管是水平的,进口流道和出口流道是竖直的.实验发现,出口流道中典型的两相流流型是泡状流、而出口总管中的典型流型是弹状流.进口流道中的气弹和气柱导致了阳极传质恶化.     

Measurement and modeling of the sooting propensity of binary fuel mixtures

The sooting behaviour of binary fuel mixtures was evaluated both experimentally and through computer simulations. The soot volume fraction in laminar diffusion flames of mixtures of ethylene/propane, methane/ethylene, methane/propane, methane/ethane, methane/butane, ethane/propane and ethane/ethylene fuels was measured using 2-dimensional line of sight attenuation. A synergistic effect was observed for the ethylene/propane, methane/ethylene, methane/ethane and ethane/ethylene mixtures. The synergistic effect translated into a higher soot concentration for a mixture fraction than could be yielded by the added contribution of both pure fuels. Such an effect was not observed for the methane/propane, methane/butane and ethane/propane mixtures. Through experiments in which the flame temperature was kept constant, it was determined that the synergistic effect in the methane/ethylene mixture is very temperature dependent whereas, that in the ethylene/propane mixture is not. This phenomenon was further studied through the modeling of the ethylene/propane mixture. Numerical simulations were carried out using two different soot models. The simulations confirmed the presence of a synergistic effect. It was found that the effect could be directly correlated to a synergistic effect in the concentration of n-C₄H₅ and n-C₄H₃, which could be traced back to an interaction between ethylene and methyl radical species. These results yield further insight into the pathways to soot formation and highlight the importance of further analyzing binary fuel mixtures as a means of understanding soot formation in practical devices using industrial fuels.     

生物添加剂对汽油机燃油经济性及废气排放影响的研究

将一种棕榈油提取物作为添加剂,加入汽油中以研究其对汽油机燃油经济性和排放品质的影响。针对市场上正使用的辛烷值为93#的高清洁汽油和乙醇汽油,通过发动机台架试验对加剂前后的汽油机性能指标进行了对比和分析．结果表明:加入此种添加剂后对各种汽油的燃油经济性有大幅改善作用,对乙醇汽油的效果尤甚。加剂后可以使乙醇汽油的燃油经济性与普通汽油完全一样。对于93#高清洁汽油,除了未燃碳氢(HC)略有上升外,其他排放物如氮氧化物 (Nox)、一氧化碳等有所减少, CO2排放有明显的改善。对于乙醇汽油,则HC和CO2略有上升。     

Highly alkaline stable anion exchange membranes from nonplanar polybenzimidazole with steric hindrance backbone

The anion exchange membranes (AEMs) with both high ionic conductivity and alkali stability are always the research focus of the AEM fuel cells. Here, a novel nonplanar polymer for AEMs manufacture, mPBI‐TP‐x‐R, with excellent hydroxide stability and satisfactory processability is reported for the first time. The serial mPBI‐TP‐x resins with steric hindrance were prepared by copolymerization among 3,3′,4,4′‐tetraaminobiphenyl, isophthalic acid and tetraphenyl‐terephthalic acid (TP) in different ratios under microwave condensation. The copolymers mPBI‐TP‐x were quaternized at N1/N3‐sites of benzimidazole unit in backbone with alkyl groups (R?CH₃, C₂H₅, n‐C₃H₇, or n‐C₄H₉) to prepare soluble ionomers, and the corresponding membranes in hydroxyl ion form were prepared by a solution casting method and subsequent ion‐exchange process. The chemical structure of all membranes was characterized using FTIR and ¹H NMR spectroscopy. The properties of ion exchange capacity, water uptake, swelling ratio, tensile strength, ionic conductivity, and alkaline stability were measured. Among the prepared membranes, the mPBI‐TP‐15%‐(n‐Bu) exhibited the excellent alkaline stability (only degradation ca. 5% under 1M NaOH aqueous solution at 60 °C for 800 h) and satisfactory OH^? conductivity (46.66 mS/cm at 80 °C). The current research provides a useful exploration to commercial application of alkaline fuel cell. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1087–1096     

Synthesis and Characterization of Phenolphthalein‐Containing Sulfonated Poly(arylene ether phosphine oxide)s by Direct Polycondensation for Proton Exchange Membrane

A series of novel phenolphthalein‐containing sulfonated poly(arylene ether phosphine oxide)s (sPAEPP) with various sulfonation degrees were synthesized by direct polycondensation. The structure of sPAEPP was confirmed by ¹H‐NMR, ¹³C‐NMR, and IR spectroscopy. The high‐molecular weight of these polymers was determined by gel permeation chromatography (GPC). The transparent, tough, and flexible membranes could be achieved by solution casting. The macroscopic properties and microstructure of the obtained membranes were investigated in detail. The results showed that these sPAEPP membranes displayed excellent properties in terms of swelling, proton conductivity, and methanol permeability. For example, sPAEPP‐100 membrane exhibited an appropriate water uptake of 33.1%, a swelling ratio of only 11.7% (lower than 20.1% of Nafion 117), a proton conductivity of 0.11 S cm^?1 (similar to that of Nafion 117) at 80 °C, and a methanol permeability of 4.82 × 10^?7 cm² s^?1. Meanwhile, it also presented outstanding oxidative stability. Atomic force microscope (AFM) micrographs showed that the hydrophilic domains of the sPAEPP‐100 membrane formed connected and narrow ionic channels, which contributed to its high proton conductivity and good dimensional stability. As a result, sPAEPP‐100 membrane displays excellent application prospect for fuel cells. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1097–1104     

Bioinspired Transition-Metal Complexes as Electrocatalysts for the Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) is one of the most important reactions in life processes and energy conversion systems. To alleviate global warming and the energy crisis, the development of high-performance electrocatalysts for the ORR for application in energy conversion and storage devices such as metal–air batteries and fuel cells is highly desirable. Inspired by the biological oxygen activation/reduction process associated with heme- and multicopper-containing metalloenzymes, iron and copper-based transition-metal complexes have been extensively explored as ORR electrocatalysts. Herein, an outline into recent progress on non-precious-metal electrocatalysts for the ORR is provided; these electrocatalysts do not require pyrolysis treatment, which is regarded as desirable from the viewpoint of bioinspired molecular catalyst design, focusing on iron/cobalt macrocycles (porphyrins, phthalocyanines, and corroles) and copper complexes in which the ORR activity is tuned by ligand variation/substitution, the method of catalyst immobilization, and the underlying supporting materials. Current challenges and exciting imminent developments in bioinspired ORR electrocatalysts are summarized and proposed.     

Double-Shelled C@MoS2 Structures Preloaded with Sulfur: An Additive Reservoir for Stable Lithium Metal Anodes

The growth of Li dendrites hinders the practical application of lithium metal anodes (LMAs). In this work, a hollow nanostructure, based on hierarchical MoS₂ coated hollow carbon particles preloaded with sulfur (C@MoS₂/S), was designed to modify the LMA. The C@MoS₂ hollow nanostructures serve as a good scaffold for repeated Li plating/stripping. More importantly, the encapsulated sulfur could gradually release lithium polysulfides during the Li plating/stripping, acting as an effective additive to promote the formation of a mosaic solid electrolyte interphase layer embedded with crystalline hybrid lithium-based components. These two factors together effectively suppress the growth of Li dendrites. The as-modified LMA shows a high Coulombic efficiency of 98 % over 500 cycles at the current density of 1 mA cm⁻². When matched with a LiFePO₄ cathode, the assembled full cell displays a highly improved cycle life of 300 cycles, implying the feasibility of the proposed LMA.