Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

The thermal transformation mechanism of chlorinated paraffins: An experimental and density functional theory study

The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.     

烟颗粒对太赫兹波衰减特性的影响研究

太赫兹成像系统相对于普通红外线成像系统而言,其受温度和烟雾密度的影响较小,将其引入火场环境侦测中能较好地解决火场环境能见度低的问题.但太赫兹波在火场烟气环境中传播时,会受到烟颗粒的吸收和散射作用影响,造成其传播特性发生变化,因此有必要开展烟颗粒对太赫兹波衰减特性的影响研究.采用离散偶极子近似法进行模拟运算,结合烟颗粒分...     

连续流2450MHz电磁波剩余污泥脱水与溶出效果研究

利用连续流2450MHz的电磁波污泥脱水装置,对2种不同的污泥进行均匀性试验,得到加载功率270W、加载时间200s、加载泥量150mL工况最优.该工况下,污泥离心含水率、沉降含水率、SV分别由原泥的90.46%、96.35%、88%下降到87.32%、95.55%、76%,比阻由2.37?109m/kg升高至1.22?1010m/kg ,在同等离心条件下,经过2450MHz电磁波处理的污泥体积比不经电磁波处理的体积减少了25%.加载后,TN、TP、SCOD的最大溶出倍数分别达到了17.69、9.50和40.11,EPS降低61.9%,与现有的微波加载实验结果对比发现,在原泥比阻值较低情况下,连续流状态下比阻值未降反增,但污泥胞内物质的溶出倍数明显更大,能有效降低EPS,改善污泥脱水性能,表明了2450MHz电磁波动态污泥脱水的效果更好.     

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

•Addition of hindered amine increased thermal stability and viscosity of TTTM. •Addition of hindered amine improved the CO₂ absorption performance of TTTM. •Good the CO₂ absorption of recycled solvents after two regenerations. •Important role of amine group in CO₂ absorption of TTTM confirmed by DFT analysis. Is it possible to improve CO₂ solubility in potassium carbonate (K₂CO₃)-based transition temperature mixtures (TTMs)? To assess this possibility, a ternary transition-temperature mixture (TTTM) was prepared by using a hindered amine, 2-amino-2-methyl-1,3-propanediol (AMPD). Fourier transform infrared spectroscopy (FT-IR) was employed to detect the functional groups including hydroxyl, amine, carbonate ion, and aliphatic functional groups in the prepared solvents. From thermogravimetric analysis (TGA), it was found that the addition of AMPD to the binary mixture can increase the thermal stability of TTTM. The viscosity findings showed that TTTM has a higher viscosity than TTM while their difference was decreased by increasing temperature. In addition, Eyring’s absolute rate theory was used to compute the activation parameters (ΔG*, ΔH*, and ΔS*). The CO₂ solubility in liquids was measured at a temperature of 303.15 K and pressures up to 1.8 MPa. The results disclosed that the CO₂ solubility of TTTM was improved by the addition of AMPD. At the pressure of about 1.8 MPa, the CO₂ mole fractions of TTM and TTTM were 0.1697 and 0.2022, respectively. To confirm the experimental data, density functional theory (DFT) was employed. From the DFT analysis, it was found that the TTTM+ CO₂ system has higher interaction energy (|ΔE |) than the TTM+ CO₂ system indicating the higher CO₂ affinity of the former system. This study might help scientists to better understand and to improve CO₂ solubility in these types of solvents by choosing a suitable amine as HBD and finding the best combination of HBA and HBD.     

综合管廊燃气舱结构形式对燃气爆炸超压的影响*

为研究地下综合管廊燃气舱结构形式对燃气爆炸超压的影响,采用数值模拟的方法,改变燃气舱高度,通风分区长度和局部开口大小,分析不同情况下的燃气爆炸超压变化规律。结果表明:冲击波传播速度随燃气舱高度的增加而减小,随着高度的增加,超压峰值曲线由“驼峰状”逐渐变为两端高中间低的“盆形”,爆炸过程产生的最大超压与高度成反比关系。超压峰值在340 m处接近0 kPa,延长通风分区并不会增加超压峰值,可以在考虑防火的要求下根据实际情况适当延长通风分区的长度。局部开口的存在使得爆炸气流能够自由泄压,超压峰值与开口的大小成反比关系。     

爆炸冲击波作用下圆形通风设施的动态破坏特性

为了研究瓦斯爆炸对通风设施造成的严重破坏及其导致的通风系统紊乱与灾情迅速扩展问题,基于LS-DYNA有限元软件,模拟研究巷道中瓦斯爆炸冲击波作用下圆形通风设施的动态破坏特性,分析应力、应变、速度、位移的动态特征及其破坏过程,并对圆形通风设施动态破坏机理进行初步探索。研究结果表明:爆炸冲击波作用下,圆形通风设施正、反面出现压应力与拉应力分布圆环,且压应力与拉应力峰值处于在外部受约束边界径向圆环附近区域与圆心位置,应变、速度和位移最大值均分布在次区域;爆炸冲击波作用下,通风设施表面形成多圈的正向和反向的应变相互交替,呈现W型的褶皱变形;爆炸冲击波作用下,环向裂纹集中在受约束的边界区域附近,发生脆性破坏,其他区域会出现较多的径向裂纹,可发生韧性破坏,整个断裂过程是脆性与韧性断裂的混合型断裂。     

轮式装甲车整车外流场热管理浅析

某改进的轮式装甲车在使用过程中,发动机附近环境的温度比原车高。针对这一问题,通过FLUENT软件对装甲车外形流场进行三维模拟计算,找到了故障发生的原因,并根据计算结果提出了最佳改进方案。通过对原车和改进整车的发动机冷却系统进行热平衡道路试验对比,验证了改进方案的合理性。     

张北地震序列的尾波Qc值研究

采用尾波单次散射模型,选取张北地震序列70条波形记录,计算了张北地区t=58.88s时的尾波QC值:QC(f)=132.6±20f0.96±0.14。研究中发现,随流逝时间的增加QC逐渐增大,当流逝时间>120s时,出现逆转,QC迅速减小。文中采用频率域方法计算QC值,尾波功率谱计算自t>2ts开始,选用垂直向波形记录,取时间窗长为5.12s,步长2.56s向前滑动,每个时间窗两端5%的数据与余弦函数相乘,然后做FFT变换,分别计算9个中心频点各时间窗的能量密度谱,尾波流逝时间取各时间窗的中心点。当信号的能量密度<4倍的背景噪声能量密度时,尾波能量密度取值结束。求得能量密度谱后,线性拟合可求得不同流逝时间各频点的QC值。     

拟合水工设计反应谱的人工地震波的生成与Huang变换校正

根据非平稳输入下建立的功率谱与均值反应谱之间的关系,合成基于水工设计反应谱的人工地震波,并对其幅值进行修正,降低了高频区误差作用;为了解决加速度时程积分后的速度、位移时程的零线漂移现象,利用Huang变换得到加速度时程的固有模态函数,由Huang变换方法得到的最低频率固有模态函数分量通常情况下代表原始信号的趋势或均值,对去掉均值后的加速度时程进行积分得到的速度、位移时程不存在零线漂移问题。