TiO2/Schwertmannite nanocomposites as superior co-catalysts in heterogeneous photo-Fenton process

The heterogeneous photo-Fenton reaction is an effective technique in combating organic contaminants for both soil and water remediation,and extensive studies have focused on enhancing its efficiency and reducing its costs.In this work,we developed novel photoFenton catalysts by simply milling commercially available TiO_2(P25)with Schwertmannite(Sh),a natural iron-oxyhydroxysulfate nanomineral.We expect that the photo-generated electrons from TiO_2could continuously migrate to Sh,which then could enhance the separation of electron-hole pairs on TiO_2and accelerate the reduction of Fe(III)to Fe(II)on Sh,leading to high degradation efficiency of the target organic contaminants.SEM and TEM results showed the distribution of TiO_2on Sh surface for the nanocomposites(TiO_2/Sh).Under simulated sunlight irradiation,the much higher content of Fe(II)was determined on TiO_2/Sh than on Sh via a common method in the iron ore,and the consumption of H_2O_2and the production of·OH were more significant in the TiO_2/Sh system than those in the TiO_2and Sh systems.These results well support our hypothesis that the photo-generated electrons could migrate from TiO_2to Sh on the composites,and can also explain the much higher degradation efficiency of Rhodamine B(RhB)in the TiO_2/Sh system.Besides,TiO_2/Sh had lower Fe dissolution as compared with Sh,and retained high catalytic stability after four repeated cycles.Above merits of the TiO_2/Sh composites,in combining with their simple synthesis method and low-cost property,indicated that they should have promising applications as heterogeneous photo-Fenton catalysts.     

高原城市室内灰尘对人角膜上皮细胞损伤研究

收集高海拔城市昆明不同功能区室内灰尘,利用等离子发射光谱仪分析不同粒径（F1~F4：100~2000,75~100,63~75,45~63μm）灰尘中Pb,Cu,Cd,Zn,Cr,Ni,Co,As和Mn的含量,借助人工泪液提取的方法,测定目标重金属的可溶出率（生物可给性）,并分析室内灰尘人工泪提取液对人角膜上皮细胞的毒性效应.结果表明,办公室灰尘中Ni,Mn,Zn显著高于家庭及学生宿舍（P<0.01）,且Cd,Ni,Zn的含量高于昆明市土壤背景值的39.3、9.5、12.3倍.居民住宅Co（10.6%）、办公室As（16.1%）及学生宿舍Mn（36.0%）溶出率最高.重金属元素在粒径分布规律上表现出不同特征,办公室及宿舍灰尘重金属易在63~100μm粒径范围内富集.人角膜上皮细胞经室内灰尘人工泪提取液暴露24h后,低浓度（20μg/mL）、高浓度（1280μg/mL）分别促进和抑制细胞增殖,与对照组相比较均具有统计学意义（P<0.05）.细胞炎症因子IL-1β和TNF-α相对表达量显著增加,提示昆明室内灰尘暴露有诱发角膜炎症疾病发生的风险.     

微介复合固体酸β分子筛催化芳烃硝化合成研究

研究了多级孔道β分子筛催化剂对芳烃(氯苯)的硝化反应,显示具有优异的催化作用。在以硝酸为硝化剂,氯苯∶催化剂=3∶1,60℃反应2 h条件下,对比传统β分子筛,自制多级孔道β分子筛的催化活性较高,且氯苯的对位选择性均有所提高,对位/邻位比分别从0.5提高到1.2。多级孔道β分子筛催化剂重复使用5次,催化活性保持稳定,且随着孔道比表面积增加,催化剂稳定性更好。     

弹药殉爆试验与反应等级评估探讨

目的获取弹药在殉爆情况下发生反应的特征行为,为不敏感弹药的评定以及弹药安全性的评估提供技术支撑。方法参照北约STANAG4396标准,开展某型弹药殉爆试验。采用超压测量、见证板变形破坏情况观测、破片速度测量等传统测试方法,结合先进的激光干涉测速技术(Photonic Doppler Velocimetry—PDV)测量被发弹药及主发弹药反应后壳体膨胀速度。结果被发弹药侧见证板比主发弹药侧见证板产生了更严重的变形。11 m和14 m处超压测量结果分别达到306 kPa和177 kPa,与两枚弹药爆轰后产生的超压相当。被发弹药和主发弹药的壳体膨胀速度相当,达到约3500 m/s。结论在试验条件下,被发弹药发生了爆轰反应,该弹药不属于不敏感弹药。在殉爆试验中,主发弹药和被发弹药的壳体膨胀速度可作为判断被发弹药反应等级的关键参量。     

某四组元复合推进剂的热分解规律研究

目的研究某四组元推进剂的热分解特性。方法进行差示扫描量热(DSC)和热重分析(TG)实验。结果分别得到了推进剂在不同温度下的DSC和TG曲线,以及同一温度下推进剂各单组分的DSC和TG曲线,并计算得到了不同升温速率下的反应动力学参数。结论推进剂的热失重主要分为三个阶段,150～220℃的范围主要为RDX的热分解,220～375℃的范围主要为AP热分解,375～515℃的范围主要为部分AP高温分解和橡胶分解。同时推进剂在200～237℃和337～385℃各出现了一个放热峰,在240～248℃出一个吸热峰。推进剂的吸热峰为推进剂中AP晶型转变的吸热峰,推进剂中两个放热峰分别是由于RDX热分解和AP的高温分解产生的。同时计算得到推进剂样品的活化能,推进剂的表观活化能在1.6×10~5～2.1×10~5J/mol的范围之间,随着热分解的进行,活化能先降低后升高。     

环境水对FeMnO3和NiMnO3室温催化氧化甲醛的影响

环境水会影响催化剂的性能,设计合成耐湿的锰复合氧化物催化剂用于甲醛氧化具有重要实用意义 . 采用共沉淀法合成了 FeMnO₃和NiMnO₃催化剂,研究了不同湿度条件（RH=0、40%、65% 和 90%）对 FeMnO₃和 NiMnO₃催化剂室温催化氧化甲醛活性及稳定性的影响 . 结果表明,在相对湿度为 40% 和 65% 时,水的加入在催化剂表面形成缔结吸附水,提高了甲醛室温催化氧化的转化率 . 在反应10h后,FeMnO₃和NiMnO₃催化剂上甲醛的转化率都大于 15%. 在相对湿度为 40% 时,水的加入有利于增加催化剂表面高价态 Fe 和 Ni 金属及表面氧物种含量,并且有利于生成易于分解成 CO₂和 H₂O 的碳酸盐中间物种 . 该研究可为制备甲醛催化氧化的耐湿催化剂提供参考及加深人们对环境水影响下甲醛催化氧化机理的理解 .     

初始pH值对连续投加铝盐混凝去除小分子有机物的影响机制

以污水厂二级出水中小分子有机物强化混凝去除为目的,提出了连续投加混凝工艺(CDC),并以水杨酸为模型小分子有机物,研究了初始pH值对CDC工艺去除效果的影响以及铝离子与水杨酸的络合特性.结果表明,初始pH值6时CDC工艺的去除率最高,比常规混凝工艺提升了13.8%.但是初始pH值5和7时CDC工艺的提升效果较小.三维荧光结果表明,不同pH值下水杨酸和铝离子的络合特性不同.X射线光电子能谱和电喷雾质谱结果表明,pH值5时CDC工艺前期主要生成1:1络合物Al(OH)(C₇H₄O₃)(H₂O)₂.其络合作用强烈,稳定性较高,难以从水中去除.pH值6时前期主要生成中等聚合铝(如原位Al₁₃),其与水杨酸形成的络合物可以参与到铝离子的生长过程,最终生成表面崎岖形态松散的珊瑚礁状絮体,强化了水杨酸的去除.pH值7时,主要生成不定形氢氧化铝,通过絮体表面吸附小分子有机物.     

地下水人工回灌水化学因素对生物堵塞的影响

通过室内砂柱实验及扫描电镜,红外光谱,光电子能谱等技术,研究回灌水中离子强度及回灌过程中水-岩作用对细菌在饱和多孔介质中迁移及滞留的影响,揭示回灌过程中离子强度对介质生物堵塞演化规律及其作用机理的影响.结果表明,适宜的离子强度刺激细菌的生长及胞外聚合物（EPS）的生成,导致介质渗透性下降幅度达到99%,离子强度过高或过低都会抑制微生物的生长;Na⁺可以中和介质与细菌表面的负电荷,通过压缩双电层及减少静电斥力,进而增强细菌在介质表面的附着能力;介质中的碳酸盐矿物水解可导致环境pH值升高,诱导介质中的微量SiO₂,Al₂O₃等矿物溶解,促使介质孔隙度增大,延缓生物堵塞的发生时间并缓解堵塞程度;外源Na⁺及内源介质溶解产生的Ca²⁺,Mg²⁺,Al （III）,刺激细菌产生更多的EPS,同时化学离子与EPS的官能团以新的官能团和化学键结合,形成新的物质,对堵塞的发生和演化起促进作用;溶解产生的Mg²⁺,Ca²⁺与细菌呼吸产生的CO₂,在微碱性条件下反应形成新的沉淀,也对堵塞产生促进作用.     

Novel electrochemical half-cell design and fabrication for performance analysis of metal-air battery air-cathodes

Metal-air batteries (MABs) are considered promising candidates for sustainable energy storage & conversion applications. Air-cathodes have been identified to be the major challenge towards the commercialization of MAB technology. In development of air-cathodes effectively, a method, or a device is desired for cathode evaluation at operating conditions that are as close as possible to that of an actual battery. In this paper, for diagnosing, evaluating and analyzing the electrochemical performance of MAB air-cathodes, a novel electrochemical half-cell has been designed and fabricated. This half-cell is a three-electrode system, in which the air-cathode is used as the working electrode, a platinum wire with large area as the counter electrode and a saturated calomel electrode (SCE) as the reference electrode. The working electrode is designed to allow the surface of gas diffusion layer to be exposed to the air and the catalyst layer to be exposed to the electrolyte. This half-cell is validated by commercially available and in-house made air cathodes using electrochemical linear scan voltammetry (LSV) method in both neutral and alkaline solutions at various temperatures, enabling the in-situ performance evaluation and analysis of air-cathodes in an environment much closer to that of a primary aqueous metal-air battery while offering a more controlled laboratory environment and economic way for down-selecting and optimizing the air-cathodes.     

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L^?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C₃H₃Cl₂ as most abundant fragment.