Experimental Boosting of the Oxygen Reduction Activity of an Fe/N/C Catalyst by Sulfur Doping and Density Functional Theory Calculations

向Fe/N/C非贵金属催化剂中再引入S掺杂是进一步提高其氧还原催化活性的有效方法。为了探究活性提高的原因,本文以三聚氰胺-甲醛树脂为前驱体,氯化; 钙为模板,氯化铁为铁源,通过添加硫氰化钾(KSCN)来控制热解催化剂的S掺杂量。通过对比分析催化剂的物化性质,结合密度泛函理论(DFT)计算,分; 析S掺杂促进Fe/N/C催化剂氧还原活性的原因。透射电子显微镜(TEM)和N_2吸脱附等温线测试结果表明,S元素可抑制含铁纳米粒子的形成,促使形; 成多孔碳结构,提高比表面积。X射线光电子能谱(XPS)结果表明,适量S前驱体可实现较高的S掺杂含量,得到最优的活性,过量的S反而会导致Fe和S的; 掺杂量同时降低,影响活性。DFT计算结果表明在Fe-N_4大环中引入S掺杂,可增强O_2分子和中间体OOH与Fe-N_4结构中的Fe的相互作用,; 促进形成Fe―O键,从而导致O―O键的键能显著降低,为后续反应O―O键的断裂提供可能,促进ORR反应的进行。S doping in Fe/N/C non-precious metal catalysts is an effective approach to further improve their catalytic activity for the oxygen reduction reaction (ORR). However, the enhancement mechanism is not yet clear. Here, we synthesized an Fe/N/C catalyst using melamine-formaldehyde resin as the N and C precursors, CaCl2 as the template, and FeCl3 as the Fe precursor. The effects of S doping on the morphology, textural property, composition, and ORR catalytic activity were investigated by adding various amounts of KSCN as a precursor. Transmission electron microscopy (TEM) and N-2 adsorption-desorption isotherm results revealed that S prevented the growth of Fe-containing nanoparticles, and facilitated the formation of a porous structure, which increased both the catalyst surface area and mass transfer rate. X-ray photoelectron spectroscopy (XPS) results indicated that a suitable amount of S precursor led to a high doping level of S and provided the highest ORR activity. However, too much S in the precursor decreased the doping levels of both Fe and S, due to the formation of FeS, which could be completely removed by acid leaching. Density functional theory (DFT) calculations showed that the addition of S in an Fe-N-4 macrocycle could enhance the interaction strength of the Fe-O bond between the O-2 molecule or the intermediate OOHspecies and Fe in the Fe-N-4 structure, resulting in a significant decrease in the O-O bond energy, and may help in bond breaking in subsequent reactions, facilitating the ORR process.National Natural Science Foundation of China [21373175, 21621091

Development of the facility for model scramjet testing

A hypersonic propulsion test facility has been constructed in IMCAS (Institute of Mechanics, Chinese Academy of Sciences) in order to provide a high enthalpy hypersonic flow for a model scramjet testing. The vitiated air is produced by a hydrogen/air and oxygen replenishment combustion heater with flow rate of 3.5kg/s, total pressure of 5MPa and total temperature of 2000K in maximum, and accelerated up to Mach 5.6 by a two-dimensional nozzle. Test chamber of the facility is evacuated by a one-stage central air ejector. The preliminary facility performance tests showed that the vitiated air heater could provide the high enthalpy flow as expected. A copper model scramjet without cooling is ready for testing. © 2001 The American Institute of Aeronautics and Astronautics Inc. All rights reserved

Large eddy simulation of ignition and combustion of ethylene/air turbulent jet diffusion flame with reduced kinetic mechanism

In this paper, unsteady process of ignition and combustion of turbulent plane-jet diffusion flame of ethylene/air at varied fuel/air ratios is numerically simulated with Large Eddy Simulation (LES) and a reduced kinetic mechanism of ethylene. The kinetic mechanism consisting of 25species and 131steps is reduced from a 71species/395steps detailed mechanism via the method of error-propagation-based directed relation graph (DRGEP) and sensitivity analysis. The LES results of height of flame lift-up and averaged temperature profiles at different downstream locations are compared with the DNS result of Yoo (2011) and satisfactory agreements are found. Unsteady processes of ignition and combustion of ethylene plane-jet diffusion flame are simulated with varied fuel injection velocities. Dynamic evolutions of temperature field as well as CH2 and OH radicals are obtained, which are found to be strongly related to turbulence eddies caused by jet/air mixing layer. The present numerical study shows that LES method with reduced mechanism of hydrocarbon fuels can effectively simulate temporal and spatial evolution of ignition and combustion process. © 2015, AIAA American Institute of Aeronautics and Astronautics. All rights reserved

关于菲律宾提起的“南海仲裁案”的法理分析

2016年7月12日,在中方缺席的情况下,应菲律宾阿基诺政府单方请求建立的南海仲裁案仲裁庭(以下简称"仲裁庭")就该案做出了实体问题的裁决。这是一场由某些域外国家导演的披着法律外衣的政治闹剧,其目的是损害中国在南海的领土主权和海洋权益。针对上述所谓裁决,中国政府先后发表了一系列声明和相关文件,表明了我国不参与、不接受、不承认的严正立场,并重申了中国在南海的领土主权和海洋权益。中国法学会也于2016年7月13日发表了《关于菲律宾共和国单方面提起的南海仲裁案的声明》,从法律层面有力地支持了我国政府的观点和立场。2016年7月21日,中国法学会联合中国国际法学会、中国海洋法学会共同举办了"南海仲裁案法律专家座谈会",组织国内60余位知名海洋法、国际法专家学者,对南海仲裁案严重损害中国领土主权和海洋权益的所谓裁决做进一步法律评析。专家们在座谈中指出,无论是基于《联合国海洋法公约》(以下简称《公约》)的宗旨、原则和规定、国际社会公认的基本法理,还是基于基本的历史事实,菲律宾单方面提起仲裁和仲裁庭强行推进有关程序均是违法、无效的。现将座谈会中较有代表性的专家观点以笔谈形式刊发,以期能够引领更多的相关研究。中国法学会课题“我国南海岛礁所涉重大现实问题及其对策”(项目批准号:CLS(2015)ZDWT54)的阶段性成果之

Environmental Behavior and Risk Assessment of Organic Phosphorus Pesticides at Water from Jiulong River Estuary

利用SPE GC FPD测定了九龙江口水体中 1 7种有机磷农药的浓度 ,总有机磷农药 (1 7种 )的含量范围是1 3 4 8～ 3 5 4 6ng/L ,平均 2 2 7 2ng/L .对其各组分的含量与行为特征进行分析表明 ,5种有机磷农药 (甲胺磷、敌敌畏、马拉硫磷、氧乐果、乐果 )在各站位均占主要部分 ,其行为受复杂的来源输入及河口的水动力影响 .对九龙江口水体中的有机磷农药的含量与其他地区进行比较 ,评价了该河口水体中有机磷农药的污染水平及风险概率Organic phosphorus pesticides (OPPs) were determined by SPE-GC-FPD. The contents of the total seventeen OPPs ranged from 134.8ng/L to 354.6ng/L (the mean was 227.2ng/L) at water in Jiulong River Estuary (JLRE). The distribution and behavior characteristics of OPPs indicated that five main OPPs (Methamidophos, Dichlorvos, Malathion, Omethoate, Dimethoate) were predominant of the total OPPs, which were affected by the complicated hydrological kinetics. When compared with other areas, the OPPs concentration level in JLRE was some moderate. But the risk evaluation of OPPs in JLRE indicated that some kinds of OPPs (Methamidophos, Dichlorvos, Omethoate) had threat to the ecological environment and human health.海洋环境科学教育部重点实验室开放基金项目(MEL0 10 4);; 中国博士后科学基金项目 ( 2 0 0 2 466

闽江口水、间隙水和沉积物中有机氯农药的含量

[摘要]：利用GC2ECD 和GC2MSD 对1999 年11 月闽江口水、间隙水和沉积物中的有机氯农药进行了研究. 结果显 示,闽江口水中有机氯农药的含量范围是01532～1182μg/ L ,间隙水中有机氯农药的含量为4154～1317μg/ L ,沉 积物(干重,以下讨论到的沉积物,无特别说明都是干重表示) :28179～52107μg/ kg ;与其他河口如珠江口、九龙江 口相比,闽江口的污染水平居中. 间隙水的污染物浓度普遍高于其上覆水的浓度,而沉积物中的浓度大于间隙水、 表层水,是由于有机污染物在水体中倾向于吸附在沉积物颗粒,并且通过再悬浮从底层向上迁移. 对水体中有机 氯农药各组分的含量及特征进行了分析,发现有机氯农药的主成分为:β2HCH ,DDE ,Heptachlor (七氯) ,Endosulfan Ⅱ(硫丹) ,Methoxychlor (甲氧滴涕) . DDE、β2HCH、Endosulfan Ⅱ分别占DDTs、HCHs 和硫丹的主要部分;有机氯 农药各组分间有正相关性,表明其河口有机氯农药陆源的土壤输入与相似的环境行为;对该河口的污染水平进行 了初步的评价,HCHs 符合国家海水水质一级标准,DDTs 则超过该标准.[Abstract]:The concentrations of 18 organochlorine pesticedes in water , pore water and surface sediment from Minjiang River Estuary were analyzed by GC2ECD , and confirmed by GC2MSD. The range of organochlorine pesticides was 01532～1182μg/ L at water , 4154～1317μg/ L at pore water , and 28179～52107μg/ kg at sediment . Compared with the results of other estuaries and gulfs (Pearl River Estuary , Jiulong River Estuary and so on) , it showed that the pollu2 tion of organochlorines in Minjiang was some moderate. The concentration difference in surface water , middle water , bottom water , pore water and sediment , due to the higher affinity of these hydrophobic compound for sedimentary phase than to water and a potential flux of pollutants from sediment to overlying water. The predominance ofβ2HCH ,DDE , Heptachlor , Endosulfan Ⅱand Methoxychlor in all water , pore water and sediment were clearly observed. On average , DDE、β2HCH、Endosulfan Ⅱoccupied the most part of total DDTs , HCHs and Endosulfans respectively , indicated the fate of these parent compounds or congeners. At the same time , it was found that thepositive relationship among the in2 dividual organochlorine components (HCHs , DDTs and Endosulfans) , which indicated that the similar of the source and behavior for organochlorine pesticides.海洋环境科学教育部重点实验室开放基金与教育 部重点基金联合资

2D C/SiC复合材料高温蠕变损伤的显微CT分析

利用显微CT针对自愈合2DC/SiC复合材料高温蠕变试验前后的内部孔隙率进行了分。析结果表明,显微CT技术能较好地探测高温蠕变前后2DC/SiC复合材料内部孔隙率变化,从孔隙率的变化初步证实了BxC组元对2DC/SiC复合材料有一定的自愈合作用。利用显微CT技术证实了高温下的拉伸应力不会导致2DC/SiC复合材料中新的裂纹产生

Micro-CT analysis of high temperature creep damage of 2D C/SiC composites

利用显微CT针对自愈合2dC/SIC复合材料高温蠕变试验前后的内部孔隙率进行了分。析结果表明,显微CT技术能较好地探测高温蠕变前后2dC/SIC复合材料内部孔隙率变化,从孔隙率的变化初步证实了bXC组元对2dC/SIC复合材料有一定的自愈合作用。利用显微CT技术证实了高温下的拉伸应力不会导致2dC/SIC复合材料中新的裂纹产生。We report a micro-CT experiment that permits us to assess void growth and microstructure development in self-healing 2D C/SiCcomposites subjected to high temperature creep.The results reveal that the micro-CT is a promising facility to detect the evolution of voidsin 2D C/SiC composites,and the BxC composition plays a positive role in the self-healing behavior of the composites subjected to hightemperature.In addition,the results show that high temperature creep will not lead to new cracks in the composites,which may be caused bythe self-healing of matrix cracks.国家自然科学基金重点项目(90405015

CVI B-C基体改性2D C/SiC在低温湿氧中的自愈合行为

针对C/SiC低温氧化易失效的不足,研究了CVI B-C基体改性2D C/SiC在700℃湿氧中100MPa下加载至60h的氧化行为,利用SEM和TEM观察了改性材料不同服役时间的微结构特征,揭示了演变规律.研究表明,CVI B-C基体改性使C/SiC低温抗氧化能力显著提升.基体裂纹及其在应力加载下的开裂均为氧化气体提供进入通道,而后可被B-C氧化产物B2O3封填,抑制内部C消耗.CVI B-C与其氧化产物一同参与缺陷愈合.在60h内,B-C改性层愈合能力尚未完全发挥,可服役更长时间

C/SiC表面SiC涂层氧化的显微CT无损检测与分析

对C/SiC复合材料表面SiC涂层在1300℃干氧和湿氧环境中退火处理60 h,利用显微CT技术对高温氧化后的SiC涂层进行无损检测。通过重构SiC涂层不同深度的氧化形貌,并利用SEM、EDS和XRD进行辅助验证,得到沿SiC涂层表面和厚度方向的氧化形貌。结果表明:显微CT能有效地检测氧化后SiC涂层中存在的氧化产物SiO2及其氧化深度,其在表面及深度方向均呈非均匀分布;在干氧环境中SiC涂层的氧化面积沿着涂层的深度方向呈减少趋势,而在湿氧环境中SiC涂层的氧化面积沿着涂层的深度方向呈先增加后递减的趋势,验证了C/SiC复合材料表面SiC涂层在干氧和湿氧中不同的氧化机制