三维有序介孔铈钴铜催化剂的制备及其降解邻二甲苯的机制

以PMMA为模板,通过聚乙二醇(PEG400)和柠檬酸辅助的溶胶凝胶法制备三维有序介孔铈钴铜(3DOM 3C)催化剂,应用BET、SEM、XRD和XPS等对不同煅烧温度的3DOM 3C催化剂进行表征分析,研究了催化剂活性及其影响因素,并利用FT-IR和GC-MS对降解产物进行分析,推测出催化降解邻二甲苯的机理.结果表明,煅烧温度500℃时制备的3DOM 3C催化剂表面具有三维介孔结构,且分散均匀,表面的晶体氧化物最少,存在大量的Cu~(2+)、Ce~(3+)和表面氧,催化剂表面存在更多的固溶体、表面活性位点和氧空位,有利于提高催化活性.在邻二甲苯初始浓度600 ppm、空速16000 h~(-1)、50%O_2条件下,煅烧温度500℃时制备的3DOM 3C催化效果最佳,在260℃时,3DOM 3C催化剂对邻二甲苯的转化率达98%,T_(90)为250℃. 3DOM 3C对邻二甲苯的转化率随着初始浓度、空速和相对湿度的升高而呈下降趋势,随着O_2含量的增加而增加.气流中混入150 ppm的乙酸乙酯能够提高邻二甲苯的转化率,提高其低温催化性能.邻二甲苯催化反应后催化剂表面的O—H、■、C—H和金属—氧键都相应的减少,降解中间产物主要有邻甲基苯甲醛和邻甲基苯甲酸.邻二甲苯降解反应涉及Mars Van Krevelen机理(MVK),先被氧化成邻甲基苯甲醛,再进一步氧化成邻甲基苯甲酸,最终生成CO_2和H_2O.     

Improving photostability and efficiency of polymeric luminescent solar concentrators by PMMA/MgO nanohybrid coatings

MgO nanocrystals were synthesized and doped with different concentrations in poly(methylmethacrylate) (PMMA) to prepare hybrid organic-inorganic coatings based on polymer nanohybrid thin films. The nanoparticles were found to be spherical with 62 nm diameter as determined by X-ray diffraction (XRD) and atomic force microscope (AFM). The coatings were characterized by spectroscopic tools such as optical absorption, transmission and fluorescence spectroscopy. The prepared nanohybrid films were spin-coated on cost-effective luminescent PMMA substrates doped with highly efficient luminescent dyes luminescent solar concentrators (LSCs). The outdoor photostability tests demonstrated enhanced protection against UVA radiation for coated LSCs compared to bare LSC substrates. The current–voltage characteristics of commercially produced LSC prototypes showed that the poor UV response of monocrystalline silicon solar cell can be improved by for LSCs coated by PMMA/MgO nanohybrid films which act as luminescent down shifting layer (LDSL).     

ZnO-PMMA复合材料光催化去除水中低浓度氨氮

通过水热法制备纳米ZnO,采用热粘固法成功地将其负载于聚甲基丙烯酸甲酯(PMMA)微球表面,并对ZnO-PMMA复合材料光催化去除水中低浓度氨氮的能力进行了考察.同时,探究了负载比例、初始氨氮浓度、催化剂浓度和pH对低浓度氨氮去除效率的影响.实验结果显示,PMMA改善了纳米ZnO的分散性和光催化能力,ZnO-PMMA能够有效地催化去除氨氮废水.在汞灯照射下,当pH=12、温度为30℃时,1 g·L~(-1)的催化剂(ZnO-PMMA)对50 mg·L~(-1)的氨氮废水去除率达到66%,且反应产物硝氮和亚硝氮含量较低,体现了该催化剂具有将氨氮转化为N2的良好的光催化降解能力.同时,纳米材料可以简单方便地回收,减轻了对环境的潜在影响,符合绿色化学的原则.     

McCaffrey等估计轰燃前火灾温度方法的改进

在估计室内轰燃前火灾温度的多种方法中，McCaffrey等人提出的方法比较典型。该文根据内衬材料的热惯性对室内火灾的重要影响，在大量实验数据的基础上，对McCaffrey等人提出的这一方法进行了初步和理论上的改进；结合室内火灾的控制因素，对有机玻璃火灾的回归结果进行了进一步改进，提出了估计室内轰燃前火灾温度的新方法。     

振荡辐射下PMMA 热解与着火过程研究

采用正弦波变化振荡的辐射热流,对热厚PMMA(聚甲基丙烯酸甲酯)的热解和着火过程进行研究,同时采用数值模拟,对实验结果进行验证和补充。结果表明,表面温度和深度温度随着时间而增加,温度由于周期性的辐射而发生振荡,而振荡幅度随着深度的增加而衰减;表面温度与深度温度振荡存在时间延迟;着火时间随着热流振荡周期的增大而减小,主要由于平均热流密度随着周期增大而增大。     

羟肟酸功能化PMMA/AM/HOA的合成及对Hg2+和Cd2+的吸附性能

用悬浮聚合法合成了甲基丙烯酸甲酯（MMA）与丙烯酰胺（AM）的共聚物PMMA/AM,再经羟胺改性制备了含羟肟酸功能基的改性PMMA/AM/HOA 树脂。通过红外光谱（FTIR）和热重分析（TG）对PMMA/AM/HOA树脂的结构和稳定性进行了表征。以PMMA/AM/HOA为吸附剂,考察了温度、吸附时间、pH值和金属离子浓度等条件对Hg2+、Cd2+两种金属离子吸附性能的影响。结果表明,改性树脂对Hg2+、Cd2+具有良好的吸附能力,其实验吸附量分别为0.822和0.384 mmol·g-1。改性树脂对Hg2+和Cd2+的吸附过程符合拟二级动力学方程,25℃时其二级动力学吸附速率常数分别为5.301×10-2和3.582×10-2 g·（mmol·min）-1;改性树脂对Hg2+和Cd2+的吸附量随温度的升高有所增大,吸附过程符合Langmuir和Freundlich吸附等温式。     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

阴离子黏土(层状双氢氧化物)对鲱鱼精DNA在重金属作用下的保护作用研究

用X射线衍射(XRD)、傅立叶红外光谱(FTIR)、扫描电镜(SEM)、循环伏安法、紫外光谱法等方法,研究了在重金属Cd2+、Pb2+作用下,阴离子黏土(LDH)对鲱鱼精DNA的保护作用.实验表明,LDH层间距由0.76 nm增大到2.30 nm,DNA-LDH复合体上出现了DNA分子中骨架和碱基上的CO(1 534 cm-1和1 488 cm-1),C—O伸缩振动峰(1 228 cm-1),P—O对称伸缩振动(1 096 cm-1),说明DNA已通过离子交换插入LDH的层间.然而DNA分子并没有完全交换出LDH层中NO3-(DNA部分嵌入),未交换到层间的DNA分子通过吸附作用固定于LDH表面上.循环伏安曲线显示,DNA-LDH复合体中的DNA还原峰与原始DNA保持一致,两个还原峰出现在EP=-1.2 mV和EP=-2.4 mV位置,也没有产生阴极凹陷.这表明当DNA固定在LDH上时,Cd2+、Pb2+就不能插入DNA沟槽之中,与碱基或其它基团的发生缔合作用.研究结果表明,一方面,LDH吸附溶液中的Cd2+、Pb2+于外表面上从而固定Cd2+、Pb2+,另一方面,LDH层板为DNA提供了保护空间,阻止Cd2+、Pb2+进入层间域与DNA作用从而保护DNA分子.     

航空有机玻璃热老化失重分析和暴露时间估计方法

对YB-DM-11航空有机玻璃在4个温度点下进行了热老化试验,每个温度点的试验分别设定4个不同的暴露时间。通过试验得出该材料在不同热环境下的质量保持率、温度和暴露时间。在此基础上,通过回归分析确定质量保持率和时间对数的关系,进而得出了质量保持率一定时时间对数与热力学温度倒数关系的回归方程。最后利用回归方程得到了在所选温度下达到给定质量保持率的估计时间。     

Effect of superfine KHCO3 and ABC powder on ignition sensitivity of PMMA dust layer

In order to evaluate the flame-retardant capacity of KHCO₃ and ABC on the ignition of PMMA dust layer accumulation on hot surfaces, the ignition time and critical heating temperature of PMMA/KHCO₃ and PMMA/ABC dust layer were experimentally investigated. The thermal stability of the mixed dust, the condensed phase products and gas phase products of the mixed dust combustion were analyzed to reveal the flame-retardant mechanism. The ignition time of 30 μm PMMA was obviously longer than that of 5 μm PMMA, and the critical heating temperature was close to that of 5 μm PMMA. KHCO₃ and ABC could greatly extend the ignition time of the PMMA dust layer and increase the critical heating temperature of the dust layer. ABC was more effective than KHCO₃. The decomposition of KHCO₃ and ABC absorbed the heat and inhibits the pyrolysis of PMMA. The HPO₃ and P₂O₅ generated by the decomposition of ABC would cover the surface of PMMA aggregates or particles and act as a physical barrier. The main light combustible gas produced by PMMA pyrolysis were CO and C₂H₄. The CO₂ generated during the decomposition of KHCO₃ could dilute the combustible gas in the ambient to inhibit the combustion of PMMA.