纳米材料对环境中微生物活性的影响研究

研究纳米材料对环境中微生物细胞活性的影响可为纳米材料的生物安全性评价提供一定的理论基础.以大肠杆菌和枯草芽孢杆菌为受试生物,采用电导率仪测定细菌培养液电导率变化,分别研究了纳米TiO2、纳米ZnO、纳米Fe3O4、纳米SiO2、纳米二氧化钛载银、纳米磷酸锆载银、纳米棕色银对细菌细胞膜通透性的影响.结果表明,纳米材料对革兰氏阳性枯草芽孢杆菌细胞活性影响更大;同种纳米材料,粒径越小,对细菌的细胞活性影响越强;对细菌细胞活性影响最大的是纳米棕色银,对细菌细胞活性影响最小的是纳米SiO2和Fe3O4.     

Accumulation and elimination of iron oxide nanomaterials in zebrafish (Danio rerio) upon chronic aqueous exposure

A 52-day continuous semi-static waterborne exposure (test media renewed daily) regimen was employed to investigate the accumulation and elimination profiles of two iron oxide nanomaterials (nano-Fe₂O₃ and nano-Fe₃O₄) in zebrafish (Danio rerio). Adult zebrafish were exposed to nanomaterial suspensions with initial concentrations of 4.0 and 10.0 mg/L for 28 days and then were moved to clean water for 24 days to perform the elimination experiment. Fe content was measured in fish body and feces to provide data on accumulation and elimination of the two iron oxide nanomaterials in zebrafish. The experiment revealed that: (1) high accumulation of nano-Fe₂O₃ and nano-Fe₃O₄ were found in zebrafish, with maximum Fe contents, respectively, of 1.32 and 1.25 mg/g for 4.0 mg/L treatment groups and 1.15 and 0.90 mg/g for 10.0 mg/L treatment groups; (2) accumulated nanoparticles in zebrafish can be eliminated efficiently (the decrease of body burden of Fe conforms to a first-order decay equation) when fish were moved to nanoparticle-free water, and the elimination rates ranged from 86% to 100% by 24 days post-exposure; and (3) according to analysis of Fe content in fish excrement in the elimination phase, iron oxide nanomaterials may be adsorbed via the gastrointestinal tract, and stored for more than 12 days.     

无缝钢管生产酸性废水治理

针对无缝钢管管坯酸洗废水pH值低、氧化铁含量高等特殊性 ,提出一套完整的治理工艺。实践运行证明 ,该处理工艺技术先进、可靠 ,处理效果好 ,处理后的水回用于生产     

Fe_3O_4/石墨烯活化过硫酸盐降解罗丹明B废水的研究

利用水热法合成石墨烯负载Fe3O4催化剂,利用X-射线衍射、红外光谱、比表面积等对其进行表征。以Fe3O4/石墨烯为催化剂,活化过硫酸钾降解罗丹明B,考察了石墨烯与Fe3O4配比、催化剂用量、氧化剂浓度、pH值和温度等因素对其降解性能的影响。石墨烯的加入可以显著提高罗丹明B的降解率,氧化剂用量的增加有利于降解反应,弱酸性条件有利于降解;温度升高对罗丹明B降解有利。在该反应体系中存在的自由基以SO-4为主,·OH和O-2为辅。     

磁性微球负载光催化剂的吸附特性研究

在TiO2/SiO2/Fe3O4物化特性的研究中,通过测定方法的改进首次获得光照反应阶段TiO2/SiO2/Fe3O4吸附量与溶液残余量间的定量关系(以苯酚为例,结果表明:在光照及无光照条件下TiO2/SiO2/Fe3O4遵循不同的吸附规律,以后者取代前者存在明显缺陷;揭示了凝聚现象是导致TiO2/SiO2/Fe3O4光活性降低的主要原因。     

Recovery of heavy metals from electroplating sludge and stainless steel pickle waste liquid by ammonia leaching method

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固液界面NOM吸附中疏水效应的影响研究

文章以腐殖酸和纳米Fe2O3为对象,着重研究了腐殖酸分子在纳米Fe2O3表面的吸附过程中的疏水效应,借助红外光谱和热重等分析方法研究了腐殖酸吸附前后的疏水性随溶液环境变化的规律。结果表明,当离子强度为0、0.005、0.01和0.05 mol/kg,pH值从7变到12时,纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的热失重量随着pH值的升高先减小后增大。当pH值从7升高到10时,亲水性降低,疏水性增强;当pH值从10升高到12时,亲水性增强,疏水性降低。当离子强度为0.001 mol/kg,pH值从7变到12时,复合体的热失重量随着pH值的升高而减小,亲水性降低,疏水性增强。当pH值为定值,离子强度变化时,纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的热失重量随着离子强度的增加不断变化,曲线呈现出波动趋势,亲、疏水性在交替变化。红外光谱分析结果说明,对纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的亲疏水性起主要影响的官能团可能是亲水性的羟基-OH、羰基C=O和疏水性的CH2烷烃。     

TiO2/PS/Fe3O4 光催化剂的低温制备及其光催化和磁回收性能

以聚苯乙烯(PS)包覆油酸修饰过的纳米Fe3O4为磁核,在低温(90℃)、中性(pH=7左右)条件下,制备了以PS为惰性隔离层的磁载TiO2光催化剂.用X射线衍射仪(XRD)、透射电子显微镜(TEM)、傅里叶红外分光光度计(FT-IR)、振动样品磁强计(VSM)对催化剂的物相组成、形貌、表面性质、磁学性质进行了表征.以苯酚为模拟污染物,考察了其光催化活性,以自制的磁回收装置,考察其回收特性.结果表明,低温制备的TiO2为锐钛矿结构,平均粒径为2～5 nm,催化剂TiO2/PS/Fe3O4[其中物质的量比为n(TiO2)∶n(St)∶n(Fe3O4)=60∶2.5∶1]具有结构完整的壳/壳/核结构,TiO2在PS/Fe3O4表面负载牢固;光催化降解苯酚遵循一级反应动力学方程,TiO2/PS/Fe3O4[n(TiO2)∶n(St)∶n(Fe3O4)=60∶2.5∶1]的反应速率常数K=0.025 8,与纯TiO2的活性接近(K=0.026 2);循环使用5次后,反应速率常数仅降低0.003 4.所制催化剂具有较强的磁感应强度,平均回收率可达到92%以上.该低温水解法制备的磁载TiO2光催化剂具有良好的应用前景.     

仿酶催化剂制备及催化降解PAEs类污染物

采用超声辅助反向共沉淀法制得磁纳米Fe3O4颗粒,然后以磁纳米Fe3O4颗粒为种子采用种子乳液聚合法制得羟基功能化的磁纳米复合物微球,再以三聚氯氰为桥联剂键合氯化血红素制得仿酶催化剂。利用傅里叶变换红外光谱仪(FT-IR)、配置积分球的紫外-可见(UV-Vis)分光光度计、透射电子显微镜(TEM)、热重分析仪(TGA)和振动样品磁强计(VSM)对催化剂进行了表征。结果表明,催化剂粒径大小为10¹2 nm,粒度均一,分散性好,在300 K下具有一定顺磁性,饱和磁化强度为21.61 emu/g,磁性物质含量为52.50 wt%。催化剂在紫外光照和H2O2存在下对水中邻苯二甲酸二甲酯(DMP)有较高的氧化降解活性,且重复使用效果较好,因此对其反应机理进行了探讨。     

聚合多巴胺包覆的磁性微球吸附Cr(Ⅵ)

用聚合多巴胺(PDA)包覆溶剂热法制备Fe_3O_4磁性微球,得到Fe_3O_4@PDA复合材料,并采用红外光谱、扫描电镜、透射电镜对复合材料进行表征。同时,对Fe_3O_4@PDA吸附溶液中六价铬(Cr(Ⅵ))的性能进行研究,考察了溶液pH对其吸附性能的影响。结果表明:Fe_3O_4@PDA在溶液pH为3.0时对Cr(Ⅵ)有较好的吸附性能,其吸附动力学数据符合伪二级动力学方程,等温吸附符合Langmuir吸附模型,最大吸附容量达到108.8 mg/g,热力学实验计算出的吉布斯自由能为负值,表明Cr(Ⅵ)在Fe_3O_4@PDA的吸附为自发过程。     

纳米磁粉复配混凝剂深度处理木薯酒精废水研究

将纳米Fe_3O_4颗粒与无机混凝剂FeCl_3复配,用于木薯酒精废水的强化混凝处理;探索了磁复配前后混凝剂的除浊、除有机物和脱色效果,并对絮体和出水分别进行了红外和三维荧光光谱分析。结果表明:相较于普通FeCl_3,磁复配混凝剂的浊度去除率达98.5%,除浊效果有明显提高;而溶解性有机物和致色物质的去除主要依赖于FeCl_3的作用,由于木薯酒精好氧处理出水存在木质素分解产物和类黑精,大量羟基和酰胺键易与Fe~(3+)形成金属配位键。     

Fe-N co-doped coral-like hollow carbon shell toward boosting peroxymonosulfate activation for efficient degradation of tetracycline: Singlet oxygen-dominated non-radical pathway

Fe-N co-doped coral-like hollow carbon shell (Fe-N-CS) was synthesized via a simply impregnation-pyrolysis method. The Fe-N-CS showed an excellent ability for activating peroxymonosulfate (PMS), which could degrade about 93.74% tetracycline (20 mg/L) in 12 min. The Fe-N-CS/PMS system exhibited a good anti-interference capacity of various pH, inorganic anions, HA and different water qualities. More importantly, the Fe nanoparticles were anchored uniformly in the carbon layer, effectively limiting the metal leaching. The quenching tests and electron spin resonance (ESR) manifested that non-radical singlet oxygen (¹O₂) was the main reactive oxygen species (ROS) for TC degradation. The mechanism study showed that Fe nanoparticles, defect and graphite N played a key role in activating PMS to produce ROS. Moreover, three probable degradation pathways were proposed by using LC-MS measurements. Generally, this work had a new insight for the synthesis of heterogeneous Fe-N-C catalysts in the advanced oxidation process based on PMS.     

Double catholyte electrochemical approach for preparing ferratealuminum：a compound oxidant—coagulant for water purification

Ferrate is an excellent water treatment agent for its multi-functions in oxidation,disinfection,coagulation and adsorption,but its coagulation ability depends on its dosage and is after its oxidation.This paper focuses on preparing a new kind of ferrate combined with alum to enhance its coagulation function for water purification.An effective electrolysis reactor was designed and employed in the test.Some key parameters in the process of electrolysis concerning the prepar\ation efficiency,such as the current density,temperature and alkalinity were also investigated.The proper conditions for ferrate-alum preparation were determined.Under the condition of 5V given voltage,6h electrolyzing interval,below 2% alum concentration (in weight),a combined liquid ferrate-alum products was successfully prepared,which contained 0.0294 mol/L FeO4^2- and 0.0302 mol/L total soluble ferron with 2% Al2O3.There was no insoluble ferron produced by controlling an optimum electrochemical condition.     

绿色合成纳米氧化铁对污染土壤中镉的钝化研究

虽然绿色合成纳米材料已成功地用于去除废水中的重金属,但利用绿色合成纳米材料钝化土壤中重金属的报道很少.本文利用植物叶提取液制备纳米氧化铁(GION),并将其用于钝化土壤中重金属镉的研究,观察中、短培养周期下对镉钝化的稳定性.实验室条件下设置50%田间最大持水量培养,对照、1%、3%、9%GION 4个处理.分别于第60、120 d采样分析土壤中镉、pH、铁、酶等相关指标的变化.结果表明,GION对土壤中镉有较好的钝化效果,60 d与120 d之间有效态镉的含量无显著差异,说明GION对土壤中镉的钝化作用随时间增长相对稳定.120 d的数据显示,相比对照组,1%、3%、9%GION处理下有效态Cd(0.1 mol·L~(-1) CaCl_2)分别降低了19.1%、16.7%、66.7%,交换态Cd(Tessier法)分别降低了12.5%、18.8%、56.3%.GION能够显著提高土壤的pH和铁的含量.pH提高能够显著降低Cd的有效性.(NH_4)C_2O_4-Fe则分别增加了0.7、1.1、1.9倍,DCB-Fe分别增加了0.4、2.9、6.0倍.另外,随培养时间的延长,(NH_4)C_2O_4-Fe和DCB-Fe增加而HCl-Fe~(2+)含量降低.说明GION影响土壤中铁物种的活性,增强其生物化学过程而转化为更加稳定的形态,该过程将改变镉在土壤中的赋存形态.通过扫描电镜-能谱(SEM-EDS)发现,GION处理残渣态中Fe的含量远高于对照组,说明镉可能随铁进入残渣态.土壤中脲酶和转化酶活性升高而过氧化氢酶则没有显著的变化.该结果说明GION降低了土壤中镉的生物有效性,土壤得以恢复,从而提升了土壤酶活性.综上所述,GION具有环境友好的特点,且对镉具有稳定的钝化作用,可作为一种良好的中低污染重金属污染土壤的修复剂.     

Effects of different sludge disintegration methods on sludge moisture distribution and dewatering performance

A key step in sludge treatment is sludge dewatering. However, activated sludge is generally very difficult to be dewatered. Sludge dewatering performance is largely affected by the sludge moisture distribution. Sludge disintegration can destroy the sludge structure and cell wall, so as change the sludge floc structure and moisture distribution, thus affecting the dewatering performance of sludge. In this article, the disintegration methods were ultrasound treatment, K2 Fe O4oxidation and KMn O4 oxidation. The degree of disintegration(DDCOD), sludge moisture distribution and the final water content of sludge cake after centrifuging were measured. Results showed that three disintegration methods were all effective, and K2 Fe O4oxidation was more efficient than KMn O4 oxidation. The content of free water increased obviously with K2 Fe O4and KMn O4 oxidations, while it decreased with ultrasound treatment. The changes of free water and interstitial water were in the opposite trend. The content of bounding water decreased with K2 Fe O4oxidation, and increased slightly with KMn O4 oxidation, while it increased obviously with ultrasound treatment. The water content of sludge cake after centrifuging decreased with K2 Fe O4oxidation, and did not changed with KMn O4 oxidation, but increased obviously with ultrasound treatment. In summary, ultrasound treatment deteriorated the sludge dewaterability, while K2 Fe O4and KMn O4 oxidation improved the sludge dewaterability.     

二氧化铈纳米催化剂的制备及臭氧化应用

分别以Ce(NO3)3.6H2O和(NH4)2Ce(NO3)6作为铈源,通过简便的化学沉淀法,制备了二氧化铈纳米材料,考察了铈源对所得纳米结构、表面特征的影响。并将纳米材料应用于降解废水用臭氧化催化剂。结果表明,铈源的不同,导致纳米材料的表面态不同,从而引起二者的催化性能具有显著差异。其中,以Ce(NO3)3.6H2O为铈源获得的样品显示了较好的催化活性,以臭氧化反应60 min降解苯酚为例,苯酚降解效率提高了70%,开拓了纳米氧化铈作为臭氧化催化剂的新应用,为臭氧化水处理技术提供了新的选择。     

Enhanced remediation of Cr（Ⅵ）-contaminated groundwater by coupling electrokinetics with ZVI/Fe3O4/AC-based permeable reactive barrier

Although widely used in permeation reaction barrier（PRB） for strengthening the removal of various heavy metals, zero-valent iron（ZVI） is limited by various inherent drawbacks, such as easy passivation and poor electron transfer. As a solution, a synergistic system with PRB and electrokinetics（PRB-EK） was established and applied for the efficient removal of Cr（Ⅵ）-contaminated groundwater. As the filling material of PRB, ZVI/Fe₃O₄/activated carbon（ZVI/Fe₃O₄     

磁性微球负载光催化剂失活特性及再生方法研究

TiO2/SiO2/Fe3O4在连续使用过程中存在失活现象并表现出吸附能力的降低,在实验基础上提出了超声波在线再生的解决方案;测试结果表明,TiO2/SiO2/Fe3O4在重复使用10次及连续使用130h条件下可保持其催化活性不变。     

纳米Fe、Si体系对3,3′,4,4′-四氯联苯的脱氯降解

研究了纳米Fe、Si体系降解3,3′,4,4′-四氯联苯(PCB77)的动力学差异.结果表明,纳米Fe0、纳米Fe3O4和纳米Si0对PCB77均有降解作用,该降解为还原脱氯反应.降解过程符合准一级反应动力学,反应速率常数Kobs分别为0.0177,0.0038,0.0045h-1.PCB77初始浓度为5mg/L,纳米材料投加量为5g/L,溶液pH4.5条件下,纳米Fe0体系对PCB77降解效果最为显著,64h时PCB77残留率仅为19.83%,氯离子浓度为50.3μmol/L,反应体系pH值从4.5升至5.26.纳米双元体系Fe0和Si0、Fe3O4和Si0对PCB77降解过程也符合准一级反应动力学,反应速率常数Kobs分别为0.0114,0.004h-1,其中纳米Fe0和Si0体系降解效果优于纳米Fe3O4和Si0体系.PCB77残留率分别为34.91%和66.62%,氯离子浓度分别为40.07,20.47μmol/L,反应体系pH值变化不明显.随着溶液初始pH值增加,纳米Fe0、纳米Fe3O4降解PCB77效果明显降低,但溶液pH值升高有利于纳米Si0对PCB77的降解.两组纳米双元体系对PCB77的降解效果受pH值影响小.     

纳米四氧化三铁对2,4-D的降解研究

采用纳米Fe3O4降解溶液中的2,4-D,考察了2,4-D初始浓度、纳米Fe3O4的投加量、溶液pH对2,4-D降解效率的影响,并探讨了2,4-D的降解机理。实验结果表明,Fe3O4对2,4-D有明显的降解作用,纳米Fe3O4的降解效果优于微米级Fe3O4,降解过程中溶液中的氯离子浓度随着2,4-D的降解而升高,Fe3O4对2,4-D的降解机理是还原脱氯。当2,4-D初始浓度在0～10mg/L、纳米Fe3O4投加量0～300mg/L的范围内,2,4-D降解率随初始浓度和纳米Fe3O4投加量的增加而增大。在2,4-D初始浓度为10mg/L、pH3.0、纳米Fe3O4投加量300mg/L时降解效率最高,48h内2,4-D的降解率可达40%。