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。     

磁性氮掺杂碳材料活化过硫酸盐降解酸性橙7

采用一步水热碳化法制备出微米级磁性氮掺杂碳材料（Magnetic N-doped Carbonaceous Materials,MNC）作为过硫酸盐（Persulfate,PDS）活化剂,以生成的活性氧化物质降解偶氮类染料酸性橙7（Acid Orange 7,AO7）.同时,利用扫描电镜（SEM）、比表面积与孔径测定仪（BET）、振动样品磁强计（VSM）等对MNC进行表征,考察了MNC投加量、PDS浓度、初始p H值和无机阴离子对活化PDS降解AO7的影响,并采用紫外-可见光谱分析、淬灭实验和电子顺磁性共振（Electron Paramagnetic Resonance,EPR）初步探讨了AO7的降解机理.结果表明,MNC呈微米级球状,表面富含含氧基团和氨基等活性点位;饱和磁化强度为12.7 emu·g^-1,能在外加磁场条件下实现固液分离.AO7去除率随MNC投加量、PDS浓度的增加而增加,但初始p H对AO7降解的影响呈相反规律,随p H升高而降低.3种无机阴离子对AO7降解抑制程度大小顺序为HCO₃^->SO     

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.     

Anthraquinone acted as a catalyst for the removal of triphenylmethane dye containing tertiary amino group: Characteristics and mechanism

Herein, we found that anthraquinone (AQ) acted as a catalyst for the rapid and effective removal of triphenylmethane dye containing tertiary amino group (TDAG). Results showed that AQ had an enhanced catalytic reactivity towards the removal of TDAG compared to hydro-quinone, which was further proved and explained using density functional theory (DFT) calculations. AQs could achieve a TDAG removal efficiency and rate of approximately 100% and 0.3583 min⁻¹, respectively, within 20 min. Quenching experiments and electron paramagnetic resonance (EPR) tests indicated that the superoxide radical (O₂^•−) generated through the catalytic reduction of an oxygen molecule (O₂) by AQ contributed to the effective removal of the TDAG. In addition, it was found that the electrophilic attack of the O₂^•− radical on the TDAG was the driving force for the dye degradation process. Decreasing the pH led to protonation of the substituted group of AG, which resulted in formation of an electron deficient center in the TDAG molecule (TDAG-EDC⁺) through delocalization of the π electron. Therefore, the possibility of the electrophilic attack for the dye by the negative O₂^•- radical was significantly enhanced. This study revealed that the H⁺ and the O₂^•− generated by the catalytic reduction of O₂ have synergistic effects that led to a significant increase in the dye removal rate and efficiency, which were higher than those obtained through persulfate oxidation.     

FeS-Fe0纳米复合材料活化过硫酸盐降解双酚S的研究

双酚S(BPS)是一种新兴的内分泌干扰物,在环境中广泛存在,并对自然环境和人体健康有严重危害。制备了FeS-Fe⁰纳米复合材料作为催化剂,明确了FeS-Fe⁰纳米复合材料活化PS体系(FeS-Fe⁰/PS体系)的反应条件对去除BPS的影响,包括材料中FeS与Fe⁰摩尔比、材料投加量、PS浓度、溶液初始pH值等,并应用X射线衍射分析、X射线光电子能谱分析等技术表征该复合材料,通过反应体系对比实验、Fe离子溶出实验、PS的消耗实验、猝灭实验、电子顺磁共振波谱检测,探究了FeS-Fe⁰纳米复合材料的活化机理。实验结果表明:FeS-Fe⁰/PS体系降解BPS的最优条件为溶液初始pH=3、FeS与Fe⁰摩尔比1∶25、材料投加量0.10 g/L、PS浓度1.0 mM;FeS-Fe⁰/PS体系中产生的硫酸根自由基(SO₄^·-)和羟基自由基(HO·)可降解BPS,且HO·占主导作用;FeS-Fe⁰纳米复合材料表面的FeS促进了铁离子的溶出和循环,因此其活化能力优于纳米零价铁。     

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.     

Instantaneous char reaction of biomass particles in a hot gas flow with fluctuating temperature

Char reaction is an important stage of the combustion processes of biomass particles. It dominates the burnout of biomass particles. The instantaneous char reaction processes of biomass particles in a hot gas with temperature fluctuation are studied. Two types of biomass fuels, i.e. pine and thistle, are chosen for the present investigation. The instantaneous mass variations of biomass particles with initial diameters of 100, 200, and 300 μm are calculated under different conditions. The gas temperature fluctuation leads to faster mass loss for both pine and thistle particles. The char reaction of biomass particles is further enhanced by increase in the fluctuation amplitude of gas temperature.