纳米Fe3 O4-H2 O2 非均相Fenton反应催化氧化邻苯二酚

由四氧化三铁(Fe3O4)-过氧化氢(H2O2)构成的非均相Fenton体系主要利用H2O2分解产生的羟基自由基氧化去除难降解有机污染物.研究了邻苯二酚在纳米Fe3O4-H2O2构成的非均相Fenton体系中的催化氧化特征,同时对实验室制备的纳米级Fe3O4和商品微米级Fe3O4两种催化剂的催化活性进行比较,并考察了H2O2初始浓度对邻苯二酚的催化氧化的影响.结果表明,自制纳米Fe3O4-H2O2体系较商品Fe3O4-H2O2体系,能更快速地去除溶液中的邻苯二酚和总有机碳(TOC),邻苯二酚的去除率接近100%,同时能迅速催化H2O2分解.邻苯二酚的催化氧化反应遵循准一级反应动力学方程,H2O2的分解反应能用三级反应动力学方程较好拟合.此外,反应过程中铁释放低于0.3 mg.L-1,不足以启动均相Fenton反应,反应机制为由界面反应控制的非均相反应机制.     

Photocatalytic degradation of C. I. Reactive Red 24 solution with K6SiW11O39SnII

Environmental friendly materials, K₆SiW₁₁O₃₉Sn (SiWSn), was synthesized. SiWSn photocatalytic decomposition of C. I. Reactive Red 24 (RR24) with the UV-lamp (253.7 nm, 20 W), Xenon lamp filtered less than 390 nm light (500 W) and sun light was investigated. The results showed that RR24 solution could be effectively decolorized with the SiWSn photocatalyst. The photocatalytic degradation efficiency of RR24 with SiWSn was affected by the initial concentration of RR2 solution, the amount of SiWSn and the photolysis time. It is demonstrated that the process of photodegradation of RR24 with SiWSn is a pesudo first-order reaction, which can be described by Langmuir-Hinshelwood equation. Hydroxyl radicals and holes are both the main oxidants in the photocatalytic reaction of RR24 with SiWSn.     

微米炭介导下4-硝基氯苯的还原-氧化耦合修复

针对土壤和地下水中难以去除的污染物4-硝基氯苯(4CNB),本文提出了微米级活性炭(MAC)介导的先还原后氧化的耦合修复工艺.通过序批实验、密度泛函分析、电子顺磁共振分析等手段研究了MAC表面性质、温度对强化硫化物还原4CNB的影响,探究了4CNB还原-氧化反应机理.结果表明在MAC介导下,4CNB可能发生了热力学有利的双电子还原过程,并且MAC对污染物的吸附富集作用减轻硫化物对过硫酸盐氧化过程的影响,高效去除了难以被硫化物还原和过硫酸盐氧化的4CNB.MAC强化下,4CNB还原速率相比单独硫化物作还原剂时提高8～82倍,35℃以上反应4h其降解率超99%.当4CNB还原为4-氯苯胺(CAN)后在炭表面经自由基氧化和过硫酸盐直接氧化去除.本研究提出了一种新的微米炭介导的4CNB还原-氧化耦合修复路线,为利用热处理工艺余热,实现低能耗、低成本修复4CNB污染土壤和地下水提供了新的思路.     

Intrinsic chemiluminescence production from the degradation of haloaromatic pollutants during environmentally-friendly advanced oxidation processes: Mechanism, structure–activity relationship and potential applications

The ubiquitous distribution of halogenated aromatic compounds(XAr) coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes(AOPs) have been considered as an"environmentally-friendly" technology for the remediation and destruction of such recalcitrant and highly toxic XAr. During our study on the mechanism of metal-independent production of hydroxyl radicals(UOH) by halogenated quinones and H_2O_2, we found, unexpectedly, that an unprecedented UOH-dependent two-step intrinsic chemiluminescene(CL) can be produced by H_2O_2 and tetrachloro-p-benzoquinone, the major carcinogenic metabolite of the widely used wood preservative pentachlorophenol. Further investigations showed that, in all UOH-generating systems, CL can also be produced not only by pentachlorophenol and all other halogenated phenols, but also by all XAr tested. A systematic structure–activity relationship study for all 19 chlorophenolic congeners showed that the CL increased with an increasing number of Cl-substitution in general. More importantly, a relatively good correlation was observed between the formation of quinoid/semiquinone radical intermediates and CL generation. Based on these results, we propose that UOH-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual CL production; and a rapid, sensitive,simple, and effective CL method was developed not only to detect and quantify trace amount of XAr, but also to provide useful information for predicting the toxicity or monitoring real-time degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on halogenated aromatic persistent organic pollutants.     

生物淋滤联合类Fenton反应去除污染土壤中重金属的效果

针对我国南方地区广泛存在的土壤重金属污染问题,以广东韶关铅锌矿周边污染农田土壤为研究对象,探讨利用生物淋滤方法与生物淋滤联合类Fenton反应对土壤Cu、Zn、Cd和Pb的去除效果,并采用序列化学提取(SEC)方法,分析不同处理对土壤中4种重金属形态分布的影响.结果表明,经12 d生物淋滤Cu、Zn、Cd和Pb的去除率分别达到66.5%、55.1%、72.8%和35.6%,其中无机结合态重金属去除效果最好,固相中剩余重金属主要以稳定的残渣态形式存在.2 d生物淋滤联合类Fenton反应在优化的H_2O_2浓度(5 g·L-1)下,对上述4种重金属的去除率分别为55.6%、50.6%、60.7%和30.5%,低于12 d生物淋滤处理,但显著高于H_2SO_4酸化、2 d生物淋滤、化学Fenton反应等对照处理.生物淋滤联合类Fenton反应可以实现原土壤中残渣态、有机结合态和无机结合态等较稳定态重金属的有效去除,使处理后土壤中4种重金属Cu、Zn、Cd和Pb的含量分别低于50、200、0.3和250 mg·kg~(-1)的标准限值.该方法兼具生物淋滤高去除效率和Fenton反应快速处理等优势,对于修复重金属Cu、Zn、Cd和Pb等复合污染的土壤具应用前景.     

Heterogeneous reaction of SO2 on CaCO3 particles: Different impacts of NO2 and acetic acid on the sulfite and sulfate formation

Despite the heterogeneous reaction of sulfur dioxide (SO₂) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO₃) combined with NO₂ and acetic acid to investigate their effects on the heterogeneous reaction of SO₂ on CaCO₃ particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO₂ or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO₂ and SO₂ that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO₂ that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO₂ with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.     

油污土壤呼吸作用强度的测定

通过土壤呼吸作用强度可以考察油污染物被微生物降解的情况,因此进行了土壤呼吸作用强度测定方法的研究。方法原理是用ＮａＯＨ溶液吸收土壤呼吸释放出的ＣＯ２,然后再用酸滴定剩余的ＮａＯＨ,从而计算出ＣＯ２释放量。测定结果说明添加菌和营养物的油污土壤呼吸作用强、释放的ＣＯ２量大、油降解量大。     

碳纳米管修饰泡沫镍空气扩散电极电-Fenton法降解水中对硝基酚

采用涂覆焙烧法制备碳纳米管修饰泡沫镍空气扩散电极,并用环境扫描电子显微镜和循环伏安法对其表面形貌和氧化还原特性进行了表征。考察了该电极还原O2产生H2O2的性能及对水中对硝基酚的降解性能。表征结果表明:碳纳米管修饰泡沫镍空气扩散电极具有多级孔道结构;在-0.6 V处具有较强的氧双电子还原峰。实验结果表明:当电流为150 m A、反应时间为120 min时,产生的H2O2的质量浓度为321.38 mg/L;在外加0.1 mmol/L Fe SO4形成的电-Fenton体系中,反应30 min后对硝基酚去除率可达95.90%;且该电极重复使用10次的对硝基酚去除率为92%~96%。     

水溶液中4-氯酚的微波辅助光化学降解

研究了微波辅助无极紫外灯(MW/UV)光化学降解4-氯酚(4CP)模拟废水;为了考察溶液中4CP的降解效果,用紫外可见分光光度法(UV-VIS)和离子色谱法(IC)测定了溶液中4CP的降解率和Cl^-浓度.结果表明,MW/UV体系中30mg/L 4CP反应120min的降解率由紫外(UV)光解体系的21.56%提高到52.40%.提高溶液的pH值、向体系通入氧气、增强光照度以及外加氧化剂H₂O₂均能增加水溶液中4CP的降解率.微波辅助光化学降解4CP服从一级反应动力学方程.     

A位掺杂LaSrCoO4对CO和C3H8氧化性能研究

采用聚丙烯酰胺溶胶-凝胶法制备了A位掺杂(Cu、Ce)LaSrCoO4复合氧化物催化剂,考察了它们对CO和C3H8的催化氧化活性,并运用XRD,TPR和TPD等手段对催化剂进行了表征。结果表明,不同稀土掺杂对LaSrCoO4复合氧化物的CO和C3H8氧化活性的影响不同,Cu掺杂能增加Co3+、化学吸附氧和晶格氧的数量,提高复合氧化物的活性,而Ce则相反。