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.     

低温等离子体协同催化降解废气污染物的研究进展

阐述了低温等离子体协同催化工艺流程与反应机理,探讨了反应温度、废气进口组分、废气中水蒸气含量、气体流速、气溶胶等因素对降解效果的影响。分析认为:一段式低温等离子体协同催化可改变低温等离子体特征及催化剂催化特性,但尚未解决尾气臭氧逃逸、副产物产生及放电稳定性等问题;两段式低温等离子体协同催化可提高污染物分子降解效率并减少尾气臭氧逃逸,但未能有效利用等离子体的能量,气体中的水蒸气、粉尘及反应过程中产生的气溶胶均能影响后置催化剂的催化性能;两段式低温等离子体协同催化已具备工程应用条件,还需配套高效预处理单元以降低废气中水蒸气、粉尘等对催化剂的影响。     

Synergistic effect of F and triggered oxygen vacancies over F-TiO2 on enhancing NO ozonation

Oxidation-absorption technology is a key step for NO_x removal from low-temperature gas. Under the condition of low O₃ concentration (O₃/NO molar ratio = 0.6), F-TiO₂ (F-TiO₂), which is cheap and environmentally friendly, has been prepared as ozonation catalysts for NO oxidation. Catalytic activity tests performed at 120°C showed that the NO oxidation efficiency of F-TiO₂ samples was higher than that of TiO₂ (about 43.7%), and the NO oxidation efficiency of F-TiO₂-0.15 was the highest, which was 65.3%. Combined with physicochemical characteristics of catalysts and the analysis of active species, it was found that there was a synergistic effect between F sites and oxygen vacancies on F-TiO₂, which could accelerate the transformation of monomolecular O₃ into multi-molecule singlet oxygen (¹O₂), thus promoting the selective oxidation of NO to NO₂. The oxidation reaction of NO on F-TiO₂-0.15 follows the Eley-Rideal mechanism, that is, gaseous NO reacts with adsorbed O₃ and finally form NO₂.     

有机物分子结构与光催化氧化反应活性的关系

从正辛醇－水分配系数与Ｈａｍｍｅｔｔ常数，光催化氧化过程中的光解作用，表面活性剂的微环境效应及取代基的诱导效应等方面，探讨了有机物分子结构与其光催化氧化反应性之间的关系。     

粉煤灰综合利用—制无烟型煤

粉煤灰,又称“烟道灰”,是从燃烧装置的烟道气中收集而得到的细灰.目前,国内外对粉煤灰的综合利用极为重视,但大部分都着眼于建材、建筑和农业等方面,而本发明是将粉煤灰作为型煤的掺合料配制型煤,即将粉煤灰与烟煤、褐煤和泥炭混配,再加入适量的添加剂,混匀后经压力成型制成各种形状的无烟燃料.实践证明,只要灰质、煤质和掺比相匹配,可压制成合格的掺灰型煤,达到“煤掺灰,灰代煤、效益高”的效果.该掺灰型煤,具有反应活性高,燃烧效果好,基本无烟等特点,投资少,见效快,效益高,节约能源等.经试烧证明,燃烧排烟中的各种污染物可消减50%以上,节约煤炭约30%以上,并且,每吨掺灰型煤(按售价每吨100元计算)可增收15—20元.     

Decomplexation of Cu-1-hydroxyethylidene-1,1-diphosphonic acid by a three-dimensional electrolysis system with activated biochar as particle electrodes

The feasibility of decomplexation removal of typical contaminants in electroplating wastewater, complexed Cu(II) with 1-hydroxyethylidene-1,1-diphosphonic acid (Cu-HEDP), was first performed by a three-dimensional electric reactor with activated biochar as particle electrodes. For the case of 50 mg/L Cu-HEDP, Cu(II) removal (90.7%) and PO initial pH 7, acid-treated almond shell biochar (AASB) addition 20 g/L, and reaction time 180 min, with second-order rate constants of 1.10 × 10⁻³ and 1.94 × 10⁻⁵ min⁻¹respectively. The growing chelating effect between Cu(II) and HEDP and the comprehensive actions of adsorptive accumulation, direct and indirect oxidation given by particle electrodes accounted for the enhanced removal of Cu-HEDP, even though the mineralization of HEDP was mainly dependent on anode oxidation. The performance attenuation of AASB particle electrodes was ascribed to the excessive consumption of oxygen-containing functionalities during the reaction, especially acidic carboxylic groups and quinones on particle electrodes, which decreased from 446.74 to 291.48 µmol/g, and 377.55 to 247.71 µmol/g, respectively. Based on the determination of adsorption behavior and indirect electrochemical oxidation mediated by in situ electrogenerated H₂O₂ and reactive oxygen species (e.g., •OH), a possible removal mechanism of Cu-HEDP by three-dimensional electrolysis was further proposed.     

Experimental and theoretical studies on NO selective catalytic oxidation over α-MnO2

Based on the experimental and theoretical methods, the NO selective catalytic oxidation process was proposed. The experimental results indicated that lattice oxygen was the active site for NO oxide over the $\mathrm{\alpha }$-MnO₂(110) surface. In the theoretical study, DFT (density functional theory) and periodic slab modeling were performed on an $\mathrm{\alpha }$-MnO₂(110) surface, and two possible NO oxidation mechanisms over the surface were proposed. The non-defect $\mathrm{\alpha }$-MnO₂(110) surface showed the highest stability, and the surface O_s (the second layer oxygen atoms) position was the most active and stable site. O₂ molecule enhanced the joint adsorption process of two NO molecules. The reaction process, including O₂ dissociation and O=N-O-O-N=O formation, was calculated to carry out the NO catalytic oxidation mechanism over $\mathrm{\alpha }$-MnO₂(110). The results showed that NO oxidation over the $\mathrm{\alpha }$-MnO₂(110) surface exhibited the greatest possibility following the route of O=N-O-O-N=O formation. Meanwhile, the formation of O=N-O-O-N=O was the rate-determining step.     

Hazard evaluation for chlorination and amination reactions of fluorocytosine production process

Reaction thermal runaway is one of the most important reasons leading to chemical accidents. With the rapid development of the chemical industry in the world, especially the fine chemical industry, various safety accidents also occur frequently. Therefore, it is necessary to study the exothermic behavior of the reaction process. In this study, reaction calorimeter was used to study the exothermic phenomena during the chlorination reaction and amination reaction. Differential scanning calorimetry was performed on the reactants, and thermogravimetric experiments were performed on the products. In addition, adiabatic experiment was performed to study the thermal runaway behavior of amination products under adiabatic conditions. The results showed that the target reactions generated a large amount of heat in the initial stage. The maximum temperature of amination reaction is higher than the initial decomposition temperature of the amination product under adiabatic condition. The pyrolysis of amination product was divided into three stages. The product had a high apparent activation energy at the beginning of decomposition, and the apparent activation energy decreased as the decomposition progressed.     

水中脲类除草剂Chlortoluron氯化产物鉴定、降解途径探究

对不同pH下Chlortoluron氯化后生成的非挥发性中间产物和挥发性产物进行了研究。对Chlortoluron氯化后的非挥发性中间产物的UPLC-ESI-MS鉴定发现了m/z为213、229、263、281、和247的离子,分析表明它们分别是Chlortoluron及其一羟基、一氯羟基、二氯和一氯衍生物。对Chlortoluron氯化后的挥发性产物采用吹扫补集-GC-MS进行分析鉴定发现了三氯甲烷(CF)、二氯硝基甲烷(DCNM)、二氯乙腈(DCAN)、1,1-2-二氯丙酮(1,1-DCP)、三氯硝基甲烷(TCNM)和1,1,1-2-三氯丙酮(1,1,1-TCP)六种消毒副产物。根据本研究中的实验结果分析和推测,在Chlortoluron的氯化过程中,苯环上和脲基链上都经历了羟基化、氧化和取代反应,接着苯环被打破,随后生成了更为有害的副产物,基于此,本文推断了Chlortoluron的氯化降解途径。     

活性焦联合脱硫脱硝技术及发展方向

本文介绍了活性焦特点、活性焦联合脱硫脱硝技术的反应机理及工艺流程、活性焦联合脱硫脱硝技术的优缺点及发展方向。指出了活性焦联合脱硫脱硝工艺具有可以实现同时脱除S02、NOx和粉尘,脱除效率高,投资小等优点,通过加热再生活性焦,可获得高浓度的SO2气体,用于生产硫酸、液体二氧化硫或硫磺,有效回收硫资源。该技术具有流程简单、占地面积小、无二次污染、费用低、应用范围广等特点。