天然黏土材料附着纳米TiO2对 电解锰渣中锰的吸附固定

采用机械球磨法对膨润土、硅藻土、高岭土3种天然黏土材料进行预处理,通过超声法将纳米TiO_2附着于其上制得复合材料,考察了不同复合材料加入量及养护时间条件下复合材料对电解锰渣中Mn的吸附固定效果。3种天然黏土材料中,硅藻土的平均粒径最小,比表面积和总孔隙度最大,对水中Mn的吸附量也最大。黏土材料附着纳米TiO_2后对电解锰渣中Mn的吸附固定效果较单纯黏土材料有明显改善。在养护时间为12 d、硅藻土附着纳米Ti O_2复合材料加入量为10%(w)的最佳条件下,Mn的TCLP浸出量较原电解锰渣下降了83.04%。     

A comparative study on emergent pollutants photo-assisted degradation using ruthenium modified titanate nanotubes and nanowires as catalysts

Several methods have been used to tailor nanomaterials structure and properties.Sometimes,slight changes in the structure outcomes expressive improvements in the optical and photocatalytic properties of semiconductor nanoparticles.In this context,the influence of the metal doping and the morphology on a catalyst performance was studied in this work.Here,ruthenium doped titanate nanotubes(RuTNT) were synthesised for the first time using an amorphous Ru-containing precursor.Afterwards,the photocatalytic performance of this sample was compared to the one obtained for ruthenium titanate nanowires(RuTNW),recently reported.Two samples,RuTNW and RuTNT,were produced using the same Ru-containing precursor but distinct hydrothermal methodologies.The powders were structural,morphological and optical characterized by X-ray diffraction and fluorescence,transmission electron microscopy,Raman,X-ray photoelectron and photoluminescence spectroscopies.Distinct variations on the structural and optical properties of the RuTNT and RuTNW nanoparticles,due to ruthenium incorporation were observed.Their potential use as photocatalysts was evaluated on the hydroxyl radical photo-assisted production.Both samples were catalytic for this reaction,presenting better performances than the pristine counterparts,being RuTNT the best photocatalyst.Subsequently,the degradation of two emergent pollutants,caffeine and sulfamethazine,was studied.RuTNT demonstrated to be better photocatalyst than RuTNW for caffeine but identical performances were obtained for sulfamethazine.For both catalysts,the degradation mechanism of the pollutants was explored through the identification and quantification of the intermediate compounds produced and several differences were found.This indicates the importance of the structural and morphological aspects of a material on its catalytic performance.     

改性黏土矿物修复重金属污染底泥的稳定化试验研究

为控制河流污染底泥中重金属的迁移和生物有效性,将膨润土、硅藻土和海泡石分别进行改性得到有机膨润土、Mn-硅藻土和酸改性海泡石,按照10%的比例添加至污染河流底泥中,进行稳定化实验。结果表明:在2种浸提剂作用下,有机膨润土和酸改性海泡石对Cu、Pb、Cr的释放皆具有抑制效果,Mn-硅藻土对Pb和Cr的释放皆具有一定控制作用。重金属形态分布结果显示,3种稳定化剂对Pb具有良好的修复效果,分别使其稳定态增加92.85%、75.62%、71.02%,提升了Pb的稳定性;有机膨润土和酸改性海泡石使弱酸提取态Cu降低了39.05%和10.35%,Mn-硅藻土和酸改性海泡石则对含Cr底泥具有一定修复作用,使其不稳定态降低了22.25%和35.71%,二者的生物有效性均得到控制。     

2种四环素类抗生素在凹凸棒石黏土中的吸附研究

通过静态吸附实验,探究凹凸棒石黏土对四环素和土霉素的吸附动力学;采用准一级动力学、准二级动力学和颗粒内扩散模型拟合实验数据,分析吸附过程。测定凹凸棒石黏土对四环素和土霉素的动态吸附曲线和吸附容量,研究凹凸棒石黏土对水溶液中四环素和土霉素的动态吸附性能。探讨初始质量浓度对穿透曲线的影响,采用Thomas模型对动态试验数据拟合,获得相关参数。结果表明,凹凸棒石黏土能够有效去除水中的四环素和土霉素,且四环素的吸附容量高于土霉素,在初始浓度为400mg/L时,对四环素的饱和吸附量达74.5mg/g,对土霉素的饱和吸附量达69.2mg/g。穿透曲线呈S型,且随着初始浓度的增大,穿透点向左移,穿透时间缩短,平衡吸附量增加。     

钛负载纳米Pd粒子电极的电化学催化性能研究

采用电化学沉积法将纳米钯粒子负载在钛板上,制备钛负载纳米钯粒子的NanoPd/Ti电极.利用循环伏安法和线性扫描伏安法对比研究NanoPd/Ti电极与Ti电极的电化学性能,以及分别对氯苯和硝基苯模拟废水电化学催化性能,表明NanoPd/Ti电极循环伏安过程出现新的氧化峰和还原峰,反应电位明显正移,反应过程峰电流也明显增大.通过降解实验,NanoPd/Ti电极可以在更低电压,更短时间内达到更好CODcr去除效果.     

蒙脱土原位生长MoS2复合材料光催化降解罗丹明B的机理研究

通过在Na⁺-MMT表面生长MoS₂来提高窄带隙半导体光生电子分离速率及稳定性.利用阳离子填充法及水热法成功制备了复合光催化剂Na⁺-MMT/MoS₂,并通过FT-IR、SEM、TEM、Raman、XRD、TG、XPS、UV-DRS和ESR等表征进一步证明了材料的成功负载及光、电化学性能. 同时,以有机染料罗丹明B为待降解染料来评价光催化剂的催化性能,发现其在80 min可有效降解罗丹明B,降解率达96%.经过5次循环使用后,Na⁺-MMT/MoS₂复合光催化剂仍具有较好的光催化性能.因此,利用MMT的表面电负性及稳定的片层结构负载MoS₂,可形成光生电子迁移通道进一步提高电荷迁移速率及光催化剂的稳定性.本研究可为黏土材料调控窄带隙半导体制备环境友好型光催化剂提供新思路.     

纳米零价铁耦合黏土修复污染土壤的研究进展

黏土负载型nZVI具有低成本、易制备、环境相容性好、综合性能优越的特点.本文在归纳nZVI改性策略的基础上,比较了黏土种类对nZVI形貌和性能的影响,提出了理想黏土载体的优选顺序,分析了复合材料的铁含量、比表面积、nZVI尺寸等与去除性能之间的关系,对nZVI耦合黏土在修复土壤重金属、卤代有机物、硝酸盐、新型污染物等方面的研究进行了总结,并概述了nZVI技术在土壤修复中的负面效应,最后对nZVI耦合黏土修复污染土壤的未来方向进行了展望.     

Acid-assisted hydrothermal synthesis of nanocrystalline TiO2 from titanate nanotubes: Influence of acids on the photodegradation of gaseous toluene

In order to efficiently remove volatile organic compounds(VOCs) from indoor air, onedimensional titanate nanotubes(Ti NTs) were hydrothermally treated to prepare Ti O2 nanocrystals with different crystalline phases, shapes and sizes. The influences of various acids such as CH3 COOH, HNO3, HCl, HF and H2SO4 used in the treatment were separately compared to optimize the performance of the Ti O2 nanocrystals. Compared with the strong and corrosive inorganic acids, CH3 COOH was not only safer and more environmentally friendly, but also more efficient in promoting the photocatalytic activity of the obtained Ti O2. It was observed that the anatase Ti O2 synthesized in 15 mol/L CH3 COOH solution exhibited the highest photodegradation rate of gaseous toluene(94%), exceeding that of P25(44%) by a factor of more than two. The improved photocatalytic activity was attributed to the small crystallite size and surface modification by CH3 COOH. The influence of relative humidity(20%–80%) on the performance of Ti O2 nanocrystals was also studied. The anatase Ti O2 synthesized in 15 mol/L CH3 COOH solution was more tolerant to moisture than the other Ti O2 nanocrystals and P25.     

铜胁迫对黄芪幼苗的生理学毒性与凹凸棒黏土的缓解作用

为探究黄芪幼苗对铜离子（Cu²⁺）胁迫的耐性机理以及凹凸棒黏土对Cu²⁺污染的缓解作用,研究了不同浓度CuSO₄（2~20mmol/L）胁迫对黄芪幼苗的生理学毒性与凹凸棒黏土的缓解作用.结果表明,2mmol/L CuSO₄胁迫使得根系Cu²⁺含量、H₂O₂（过氧化氢）含量、MDA（丙二醛）含量分别较对照显著上升1.82倍、1.04倍、2.14倍.CuSO₄胁迫浓度达8mmol/L时,根系SOD（超氧化物歧化酶）活性、根尖膜损伤程度和叶片Cu²⁺含量分别较对照显著上升1.13倍、1.12倍和2.62倍;同时,叶片PS Ⅱ（光系统II）实际光化学效率[Y（II）]、光化学淬灭系数（qP）、PSⅡ电子传递速率（ETR）和叶绿素含量较对照分别显著降低22.88%、24.44%、21.49%和28.31%,而NPQ和qN（非光化学荧光猝灭系数）则较对照分别显著上升2.35倍和1.58倍.根系POD（过氧化物酶）和CAT（过氧化氢酶）活性、可溶性糖和可溶性蛋白含量在8mmol/L CuSO₄处理下达到最高值后呈下降趋势.CuSO₄浓度为15~20mmol/L时,根系APX活性和叶片光适应下PS II潜在最大光化学效率（F_v'/F_m'）,以及幼苗全株鲜重、全株干重、地下部鲜重、地下部干重较对照显著下降.在非CuSO₄胁迫条件下,基质中凹凸棒黏土的存在使得幼苗根系MDA含量较对照显著降低15.93%,但未对其它所测生理学指标产生显著影响;在20mmol/L CuSO₄胁迫条件下,基质中凹凸棒黏土的存在使得幼苗根系和叶片中Cu²⁺含量分别显著下降30.78%和23.12%;同时显著缓解了20mmol/L CuSO₄胁迫对根系活性氧水平、抗氧化酶活性、膜脂质过氧化程度、根尖膜损伤程度、可溶性蛋白和可溶性糖含量,叶片PS II光化学活性和叶绿素含量的不良影响,以及对幼苗生长的抑制作用.研究结果表明,培养基质中凹凸棒黏土的存在能够显著降低幼苗组织中Cu²⁺的生物有效性,继而缓解CuSO₄胁迫对黄芪幼苗的生理学毒性作用.     

接种丛枝菌根真菌对露天矿区不同配比沙土与黏土的培肥效应分析

在室内盆栽条件下,研究沙土和黄土配比联合接种AM真菌对根际土壤养分、有机质含量,植物叶片营养元素含量等的影响。结果表明:接种AM真菌后玉米的生物量和叶片营养元素含量均呈现不同程度的提高,沙土与黄土质量比为1∶1和3∶1中接菌处理的提高作用较为显著;接菌后土壤中的速效磷和速效钾含量降低的同时有机质含量增加。将黄土和沙土进行优化配比可以显著提高菌根侵染率和玉米的生物量,提高土壤速效磷和有机质的含量,提升玉米叶片的营养元素含量。相关性分析表明,菌根侵染率与土壤各理化指标之间存在相互的正效应,菌根侵染后对植物营养吸收具有协同作用。