大气环境中OH自由基测定

采用自旋捕集技术和电子自旋共振法结合测定大气环境中ＯＨ自由基，首先用自旋捕集剂将ＯＨ自由基捕集，生成比较稳定的自然旋加合物，，然后带回实验室处理测定，该法为开展大气光化学研究提供了一种采样方便，利于实测的方法，据３个采样点的实测结果表明，相对误差约为３５％，比文献所示结果略大。     

极谱催化波法测定痕量亚硝酸根的研究

在含稀硫氰酸盐的底液中 ,在单扫示波极谱仪上 ,有一灵敏的亚硝酸根催化波。峰电位为 -0 .47V( vs·SCE)。阳极化二阶导数峰高与亚硝酸根浓度在 1× 10 - 7～ 5× 10 - 5mol/L 之间成线性关系。检测限达 5× 10 - 5mol/L( 2 .3ppbNO - 2 )。试验了多种共存离子对测定的影响 ,表明该法具有较好的选择性 ,尤其是大量硝酸根不干扰。应用该法测定了许多样品中的亚硝酸根 ,并对该波的机理进行了研究 ,结果证明该波是 [SCN· NO]催化溶液中的溶解氧还原所致     

硫酸根自由基对活性炭吸附刚果红的影响

本研究通过研究硫酸根自由基（SO₄^-·）对活性炭吸附性能的影响来探究SO₄^-·活化再生活性炭的可行性.结果证实,当刚果红溶液浓度为100mg/L,活性炭加入量为1.25g/L时,活性炭对刚果红的吸附量为62mg/g.体系pH值、KH₂PO₄和K₂HPO₄对活性炭吸附刚果红效果影响较小.当体系中过硫酸钠加入量为刚果红浓度的12倍时,过硫酸钠联合活性炭对刚果红去除率仅比活性炭单独吸附的对照处理提高5%;然而,在水浴锅加热条件下,70℃热活化过硫酸钠在30~120min对刚果红的去除率可达94%~99%;70℃热活化过硫酸钠联合活性炭处理在对应时间段对刚果红的去除率为91%~94%,紫外光活化过硫酸钠联合活性炭处理在对应时间段对刚果红的去除率仅为86%~90%.由此可知,热活化和紫外光活化过硫酸盐产生SO₄^-·对活性炭的吸附性能影响较小,基于硫酸根自由基的高级氧化技术再生活性碳的可能性不大.     

电凝聚臭氧化耦合工艺的二级出水处理特性与机理研究

构建电凝聚臭氧化耦合工艺对城市污水处理厂二级出水进行深度处理,研究了不同初始pH值、臭氧投加量和电流密度对二级出水处理效果的影响.结果表明,当初始pH值为5、臭氧投加量为1.5 mg·mg^-1、电流密度为15 mA·cm^-2时,该工艺处理效果达到最佳,二级出水中溶解性有机物的去除率可达到58.6%.与单独电絮凝和臭氧氧化工艺相比,耦合工艺对有机物有更好的去除效果.由于金属盐水解产物可以作为臭氧化的催化剂,为了甄别其活性点位,将磷酸盐引入体系中,结果表明磷酸盐占据了混凝剂水解产物表面的羟基,从而阻碍了臭氧与水解铝盐混凝剂之间的反应,使得有机物的去除率降低,傅立叶红外（FT-IR）分析的结果进一步证明表面羟基是产生的铝盐混凝剂催化臭氧化的活性点位.为了进一步明确该耦合工艺去除溶解性有机物的机理,选择对氯苯甲酸（pCBA）探针法间接证明和电子顺磁共振（EPR）实验直接证明体系中羟基自由基（·OH）的存在,结果表明,电凝聚臭氧化耦合工艺较单独臭氧氧化工艺产生了更多的·OH,说明电絮凝产生的铝盐混凝剂水解产物可以作为催化剂催化臭氧产生·OH,提升体系对有机物的去除效率.     

城市污水二级处理出水中不同种类PPCPs的臭氧氧化效果与机制研究

研究了臭氧氧化对城市污水二级处理出水中15种典型药品和个人护理品（PPCPs）的去除效果及O₃分子氧化和·OH自由基氧化的贡献.结果表明,PPCPs的臭氧氧化去除效果与其亲核官能结构特性相关,芳香胺结构为主的PPCPs易降解,烷基胺结构为主的PPCPs可部分降解,亲核特性较弱的双键为主的PPCPs难降解;在臭氧投加量为5.5 mg·L^-1条件下,这3类PPCPs的去除率为分别为大于95%、57%~68%和39%~57%.臭氧氧化过程中,O₃分子氧化和·OH自由基氧化均起重要作用.易降解PPCPs的氧化机制以O₃分子氧化为主,贡献率为82%~91%;可降解和难降解PPCPs的氧化机制以·OH自由基氧化为主,贡献率分别为48%~71%和66%~94%.二级出水中臭氧氧化过程中,UVA₂₅₄去除率可呈单线性或分段线性指示PPCPs的去除效率.     

碳纳米管负载纳米四氧化三铁多相类芬顿降解亚甲基蓝

在课题组前期研究的基础上,以碳纳米管(MWCNTs)为载体制备了Fe3O4/MWCNTs复合物并作为催化剂,以染料亚甲基蓝(MB)为降解对象,研究了该催化剂催化H2O2对亚甲基蓝溶液的降解特性及其影响因素,并考察了催化剂的重复使用效果,探讨了催化反应的机理.结果表明,在pH值3~8的范围内,催化反应体系都能有效降解MB,最佳pH值为3.5.随着催化剂投量的增加,MB的降解率明显提高,500 mg·L-1催化剂投量条件下,MB的降解率最高.随着H2O2初始浓度的增加,MB的降解率增加,10 mmol·L-1时MB的降解率最高.溶液中共存的阴离子会降低MB的降解率.在最佳条件,即温度25℃、H2O2浓度10 mmol·L-1、催化剂浓度500 mg·L-1的条件下,0.20 mmol·L-1MB在30 min内的降解率达到99.1%.催化剂重复使用后仍然具有较好的催化活性,说明Fe3O4在MWCNTs表面负载比较牢固,催化剂具有反复使用的能力.催化反应机理是催化剂催化H2O2产生羟基自由基,高活性的羟基自由基氧化MB.     

Heterogeneous Fenton-like degradation of 4-chlorophenol using iron/ordered mesoporous carbon catalyst

Ordered mesoporous carbon supported iron catalysts(Fe/OMC) were prepared by the incipient wetness impregnation method and investigated in Fenton-like degradation of 4-chlorophenol(4CP) in this work. XRD and TEM characterization showed that the iron oxides were well dispersed on the OMC support and grew bigger with the increasing calcination temperature. The catalyst prepared with a lower calcination temperature showed higher decomposition efficiency towards 4CP and H2O2, but more metals were leached. The effect of different operational parameters such as initial pH, H2O2 dosage, and reaction temperature on the catalytic activity was evaluated. The results showed that 96.1% of 4CP and 47.4% of TOC was removed after 270 min at 30°C, initial pH of 3 and 6.6 mmol/L H2O2. 88% of 4CP removal efficiency was retained after three successive runs, indicating Fe/OMC a stable catalyst for Fenton reaction. 4CP was degraded predominately by the attack of hydroxyl radical formed on the catalyst surface and in the bulk solution due to iron leaching. Based on the degradation intermediates detected by high performance liquid chromatography, possible oxidation pathways were proposed during the 4CP degradation.     

Combination of heterogeneous Fenton-like reaction and photocatalysis using Co-TiO2 nanocatalyst for activation of KHSO5 with visible light irradiation at ambient conditions

A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction（SR-Fenton） and visible light photocatalysis（Vis-Photo）, for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50 mg/L Rhodamine B（Rh B） degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the Ti O2 lattice is the reason for the visible light photocatalytic activity of Co–Ti O2. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability,and almost no dissolution of Co2＋was found.     

Herbicide Roundup® and its main constituents cause oxidative stress and inhibit acetylcholinesterase in liver of Carassius auratus

Roundup® is a glyphosate-based herbicide containing a mixture of surfactants. This paper evaluates the toxic effects of Roundup® and its main constituents on the goldfish, Carassius auratus, after 7 days exposure. Fish were exposed to 0.16, 0.032 and 0.0064 mg/L of Roundup® [containing 41% isopropylamine salt of glyphosate (G.I.S) and 18% polyoxyethylene amine (POEA)], G.I.S, and POEA. Their livers were taken for determining reactive oxygen species (ROS), superoxide dismutase (SOD) activity, malondialdehye (MDA) content and acetylcholinesterase (AChE) activity. Hydroxyl radical (·OH) could be induced by exposing Roundup® at a rate of 43%–111%, G.I.S at 90%–124% and POEA at142%–157%. A decreased SOD activity was observed in fish exposed to G.I.S and POEA. The contents of MDA significantly increased when exposed to Roundup® at all concentrations, 0.16 mg/L G.I.S and 0.032 mg/L POEA. The exposure led to an inhibition of AChE in livers overall during the experimental periods. POEA was more toxic than Roundup® or G.I.S during this experiment. AChE and ·OH are supposed to be sensitive biomarkers of the exposure of Roundup® and its main constituents to C. auratus.