层状氧化物NaCo_2O_4热催化H_2O_2降解亚甲基蓝

采用固相烧结法制备了NaCo_2O_4催化剂,构建了NaCo_2O_4-H_2O_2热催化体系降解亚甲基蓝(MB)。XRD和SEM表征结果显示,合成的NaCo_2O_4催化剂具有良好的稳定性。NaCo_2O_4对H_2O_2具有良好的热催化性能,反应温度越高,反应速率常数k越大,该催化反应符合一级动力学方程。NaCo_2O_4-H_2O_2体系对MB具有较好的降解效果,在反应温度为50℃、NaCo_2O_4加入量为50 mg、MB溶液加入量为100 mL、MB初始质量浓度为30 mg/L、H_2O_2加入量为1.00 mL的最优条件下,反应340 min时,MB降解率达87.00%;催化剂重复使用三次,MB降解率仍可达85%以上;经捕获剂效果对比实验发现,催化反应体系中存在h~+、·OH等催化活性物种。     

垃圾焚烧烟气中HCl与消石灰的反应机理研究

测试了两种消石灰与垃圾焚烧烟气中HCl的反应率,得出了消石灰的反应率与反应时间的反应曲线,分析了消石灰与HCl的反应机理及影响消石灰最终反应率的因素。试验结果表明,消石灰与HCl反应初期按灰层扩散控制进行,两种消石灰的最终反应率分别为16％和36％。     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

铁铜双金属有机骨架MIL-101(Fe,Cu)活化双氧水降解染料性能

针对非均相芬顿传质效率低和Fe（Ⅲ）Fe（Ⅱ）转化慢导致活性低等问题,采用溶剂热法制备铁铜双金属有机骨架材料[MIL-101（Fe,Cu）],并研究了材料界面性质、催化降解染料（亚甲基蓝）性能以及活化催化机制.结果表明,MIL-101（Fe,Cu）晶体结构完整且呈三维八面体形状;比表面积和平均孔径分别为667.2 m² ·g^-1和1.9 nm,可充分暴露反应活性位点.MIL-101（Fe,Cu）在广谱pH范围可活化H₂ O₂高效降解亚甲基蓝.当pH=5、反应20 min,MIL-101（Fe,Cu）/H₂ O₂对20 mg ·L^-1亚甲基蓝的去除率为100%,较MIL-101（Fe）/H₂O₂和单独H₂ O₂分别提高43.1%和88.9%.自由基猝灭实验与反应前后铁和铜价态变化结果表明,羟基自由基（·OH）是MIL-101（Fe,Cu）/H₂ O₂催化降解亚甲基蓝的主要活性物种;Cu（Ⅱ）掺杂引入新的活性位点,且Cu（Ⅱ）/Cu（Ⅰ）循环和Fe（Ⅲ）/Fe（Ⅱ）循环可协同产生·OH,进而提高催化效率.MIL-101（Fe,Cu）作为新型非均相类芬顿催化剂,无需复杂pH调节即可获得良好催化效果,在工业废水处理上具有较好地应用前景.     

MnFe2O4磁性纳米棒非均相Fenton催化降解水中四环素的研究

采用水热合成法成功制备出MnFe₂O₄磁性纳米棒（s-MnFe₂O₄）,并考察了商品化的Fe₃O₄、MnFe₂O₄和合成的s-MnFe₂O₄纳米棒这3种磁性纳米颗粒作为非均相Fenton催化剂降解水中四环素抗生素的性能.同时,采用X射线衍射（XRD）、透射电镜（TEM）、N₂吸附-脱附、振动样品磁强计（VSM）及X射线光电子能谱（XPS）等技术对催化剂的理化性质进行了表征.非均相Fenton催化降解四环素的结果表明,s-MnFe₂O₄具有最高的催化活性,反应180 min,四环素的去除率可以达到87.6%,TOC的去除率达到47.5%.自由基捕获试验证实了羟基自由基（·OH）是非均相Fenton氧化过程中的主要活性物种.s-MnFe₂O₄磁性纳米棒的高催化活性归因于其表面拥有较高含量的Mn³⁺和Fe²⁺物种,它们的存在能加速界面电子的转移效率,从而促进·OH的生成.合成的s-MnFe₂O₄催化剂具有良好的稳定性,循环使用6次,四环素的去除率仅从87.6%降低到80.2%,且氧化过程中活性组分的流失很少.     

铝系混凝剂优势形态分析及其混凝特性

聚合氯化铝（PACl）是常用的水处理混凝剂,在应用过程中通常表现出比传统铝盐更为优异的效果.研究表明,这种优异性能主要得益于其特殊的组成,特别是高分子聚合物Al₁₃和Al₃₀独特的物化特性.Al₁₃和Al₃₀是铝离子水解过程中的中间产物,在地球科学和环境化学等领域有着重要的研究价值.于水处理而言,二者的结构和分子特性是研究者关注的重点,大量研究基于此展开,很多重要的发现为实际应用奠定了基础.基于对PACl及其组成性质的研究,本文对PACl的混凝特性及其优势形态分子的分析进行了综合阐述.     

深圳市秋季大气臭氧立体分布特征

利用大气O₃探测激光雷达在深圳市东部生态区和西部城区同步开展垂直观测,探究了2018年深圳市O₃立体分布在秋季光化学污染活跃期至冬季非活跃期的演变过程.结果表明：光化学反应活跃的10月,东部地面O₃浓度相对于西部地面高出约128%;地面向上至450m,O₃浓度在东部生态区发生快速降低,而在西部城区由于存在“滴定效应”,O₃浓度随高度升高而升高;450m~2km,东、西部O₃浓度均随高度升高而降低,西部城区O₃浓度水平超过东部生态区约30%;2km以上高空,东、西部O₃浓度趋同（70μg/m³）,并保持稳定,为具深圳市秋季O₃污染过程提供了较高的大气背景浓度.高污染期间,深圳市大气边界层内O₃浓度变化较为一致,西部高空的O₃区域传输作用更加显著.秋季至冬季光化学反应逐渐减弱,深圳市O₃浓度的水平和垂直空间差异逐渐减小,冬季的深圳市O₃污染基本受大气背景控制.     

苯醌对聚合硅酸铁多相UV-Fenton体系的增效机制

通过构建苯醌增效聚合硅酸铁多相UV-Fenton体系,讨论了体系中橙Ⅱ的脱色和降解途径.在研究苯醌浓度对聚合硅酸铁铁离子的释放、Fe²⁺与Fe³⁺之间的转化、H₂O₂分解和·OH生成影响的基础上,提出了苯醌对聚合硅酸铁多相UV-Fenton体系的增效机制.结果表明,随苯醌浓度的增加,其紫外光下光解还原聚合硅酸铁并释放Fe²⁺的程度增大、H₂O₂分解速度加快、产生·OH浓度峰值增高且出现的时间提前;苯醌增效体系释放于溶液中的Fe²⁺可以通过Fenton反应转化成Fe³⁺,反应结束后聚合硅酸铁能重新吸附Fe³⁺并使其浓度降低,避免了增效体系铁离子的二次污染.本研究将为多相催化剂催化过程的调控提供新的视角,为多相光助-芬顿反应在有机废水资源化中的应用提供理论依据和技术支持.     

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.     

新型Fe3O4@α-MnO2活化过一硫酸盐降解水中偶氮染料

采用两步水热法制备了新型磁性纳米Fe₃O₄@α-MnO₂复合材料作为催化剂,用于活化过一硫酸盐（PMS）产生强氧化性的硫酸根自由基（SO₄^-·）氧化降解偶氮染料活性黑5（RBK5）.采用透射电子显微镜（TEM）,X射线粉末衍射仪（XRD）和振动样品磁强计（VSM）对制备的催化剂进行表征,证明成功合成了纳米α-MnO₂包覆Fe₃O₄形态的Fe₃O₄@α-MnO₂催化剂,催化剂的饱和磁化强度为39.89emu/g.Fe₃O₄@α-MnO₂催化剂活化PMS与单一的Fe₃O₄和α-MnO₂活化PMS相比,具有更高的催化效率,说明铁锰双金属存在协同作用.同时研究了催化剂的投加量、PMS的浓度和初始pH值等各种因素对RBK5的降解效率以及反应动力学的影响.实验结果表明,Fe₃O₄@α-MnO₂催化剂活化PMS降解RBK5的过程符合准一级反应动力学,在催化剂投加量为1.2g/L,PMS的浓度为4mmol/L,初始pH值为7.0,反应时间为60min的情况下,浓度为30mg/L的RBK5的降解效率可达到91%,此时RBK5的降解速率常数也达到最高值0.023min^-1.此外,通过加入自由基淬灭剂甲醇、叔丁醇和硝基苯判断了Fe₃O₄@α-MnO₂/PMS体系中起主要氧化降解作用的活性物种为SO₄^-·.