酸性土壤条件下纳米氧化锌长期暴露对蕹菜生长和叶绿素荧光参数的影响

为了探明酸性土壤条件下纳米氧化锌（nano-ZnO）长期暴露对蕹菜的生理生态效应，通过盆栽实验，设置7个浓度系列的nano-ZnO，70 d后测定相对叶绿素含量、生长参数和叶绿素荧光参数。结果显示，随nano-ZnO浓度升高，蕹菜相对叶绿素含量和生长参数先缓慢增加后显著下降。nano-ZnO对蕹菜生物量在根部和冠部间的分配无显著影响。相对叶绿素含量与nano-ZnO浓度呈显著负相关（r=-0.879,p<0.001）。在nano-ZnO质量比为160 mg/kg时，光合有效辐射190μmol/(m²·s)诱导的激发能过剩，但过剩激发能可通过热耗散保护机制消耗，以避免发生光损伤。酸性土壤条件下，弱光诱导的蕹菜叶绿素荧光参数对nano-ZnO长期暴露不敏感，但蕹菜的生物量累积易受nano-ZnO长期暴露的影响。     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

纳米材料对斑马鱼的氧化损伤及应激效应研究

以斑马鱼(Daniorerio)为受试动物,研究了纳米及常规TiO2、ZnO悬浮液对其鳃、消化道及肝脏的氧化损伤及应激效应,同时对纳米及常规TiO2、ZnO悬浮液中的颗粒形貌特征及·OH生成量进行了测定.结果发现,虽然纳米TiO2、ZnO颗粒与其常规颗粒在溶液中的粒径分布接近,但50mg/L纳米TiO2、ZnO悬浮液中·OH产生量(96h光照下,分别为2.17mmol/L、0.72mmol/L)远远高于50mg/L常规颗粒(未检测到).50mg/L纳米TiO2处理下,斑马鱼肝脏中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、还原型谷胱甘肽(GSH)、蛋白质羰基含量分别为对照的70.2%、65.4%、53%、178.1%;消化道中SOD活性及GSH、丙二醛(MDA)含量分别为对照的149.6%、212.9%、217.2%;鳃中MDA含量为对照的160.9%.而50mg/L常规TiO2悬浮液对斑马鱼没有产生毒理效应.5mg/L纳米及常规ZnO对斑马鱼肝脏的氧化伤害最强,其中5mg/L纳米ZnO处理组中SOD、CAT活性及GSH、MDA含量分别为对照的62.9%、53.1%、45.2%、204.2%,5mg/L常规ZnO处理组中SOD、CAT活性及GSH、MDA含量分别为对照组48.3%、51.8%、34.6%、289.6%;虽然斑马鱼鳃及消化道也受到明显氧化应激效应(p0.05),但并没有受到氧化损伤.研究表明,团聚作用对不同化学组成纳米颗粒的毒性影响程度不同;且不同化学组成纳米颗粒在生物体内可能通过不同机制产生了不同种类的ROS,从而对不同细胞组分产生的氧化损伤及应激效应是其重要的毒理机制.     

Explosion characteristics of micron- and nano-size magnesium powders

Explosion characteristics of micron- and nano-size magnesium powders were determined using CSIR-CBRI 20-L Sphere, Hartmann apparatus and Godbert-Greenwald furnace to study influence of particle size reduction to nano-range on these. The explosion parameters investigated are: maximum explosion pressure (P_max), maximum rate of pressure-rise (dP/dt)_max, dust explosibility index (K_St), minimum explosible concentration (MEC), minimum ignition energy (MIE), minimum ignition temperature (MIT), limiting oxygen concentration (LOC) and effect of reduced oxygen level on explosion severity. Magnesium particle sizes are: 125, 74, 38, 22, 10 and 1 μm; and 400, 200, 150, 100, 50 and 30 nm. Experimental results indicate significant increase in explosion severity (P_max: 7–14 bar, K_St: 98–510 bar·m/s) as particle size decreases from 125 to 1 μm, it is maximum for 400 nm (P_max: 14.6 bar, K_St: 528 bar·m/s) and decreases with further decrease of particle size to nano-range 200–30 nm (P_max: 12.4–9.4 bar, K_St: 460–262 bar·m/s) as it is affected by agglomeration of nano-particles. MEC decreases from 160 to 30 g/m³ on decreasing particle size from 125 to 1 μm, its value is 30 g/m³ for 400 and 200 nm and 20 g/m³ for further decrease in nano-range (150–30 nm). MIE reduces from 120 to 2 mJ on decreasing the particle size from 125 to 1 μm, its value is 1 mJ for 400, 200, 150 nm size and <1 mJ for 50 and 30 nm. Minimum ignition temperature is 600 °C for 125 μm magnesium, it varies between 570 and 450 °C for sizes 38–1 μm and 400–350 °C for size range 400–30 nm. Magnesium powders in nano-range (30–200 nm) explode less violently than micron-range powder. However, likelihood of explosion increases significantly for nano-range magnesium. LOC is 5% for magnesium size range 125–38 μm, 4% for 22–1 μm, 3% for 400 nm, 4% for 200, 150 and 100 nm, and 5% for 50 and 30 nm. Reduction in oxygen levels to 9% results in decrease in P_max and K_St by a factor of 2–3 and 4–5, respectively, for micron as well as nano-sizes. The experimental data presented will be useful for industries producing or handling similar size range micron- and nano-magnesium in order to evaluate explosibility of their magnesium powders and propose/design adequate safety measures.     

Producing biodiesel from waste animal oil by modified ZnO

Biodiesel produced by transesterification of waste animal oil is a promising green fuel in the future. ZnO-Al₂O₃ and ZnO/Zn₂Al composition oxides were prepared by co-precipitation method and impregnation method, respectively. The above catalysts were characterized by X-ray diffraction (XRD), Brunauer--Emmett--Teller (BET) and CO₂ adsorption and temperature-programmed desorption (CO₂-TPD) and show that the high activity for the catalyst is attributed to its high alkalinity. The reaction parameters were optimized and the results show that the transesterification ratio of waste animal oil can reach 98.7% with 10% ZnO/Zn₂Al catalyst after 2 h. Moreover, 10%ZnO/Zn₂Al compound oxides can be active for the successive cycles. The glycerol as a predominant by-product after transesterification is of high purity with high use value.     

人造沸石负载纳米氧化镁同步脱氮除磷的研究

氮、磷是引发水体富营养化的限制性因素,控制水体中的氮、磷总量可以有效抑制水体富营养化的产生。以人造沸石为研究对象,探究不同改性方法对人造沸石同步去除水中氮、磷的影响。主要工艺为高温碱(NaOH)浸改善沸石结构,高温盐浸(MgCl)负载纳米态氧化镁。结果表明改性的最佳条件为:两阶段的烘干温度45℃;NaOH溶2+3-液浓度0.5 mol/L;MgCl溶液的浓度1 mol/L。对NH-N和PO的去除效率分别可达到83.76%和74.24%。对人造沸石2 4 4的热稳定性进行了实验,其烧失量达40.6%。最后,对吸附饱和的人造沸石进行脱附实验,脱附剂的选择为NaCl、KCl以及+3-两者的混合液。NaCl对NH4+-N和PO43-都有较为明显的脱附效果,脱附率分别可达84.54%和59.35%。     

Enhanced photocatalytic activity of quantum-dot-sensitized one-dimensionally-ordered ZnO nanorod photocatalyst

An efficient photocatalyst was fabricated by assembling quantum dots （QDs） onto one-dimensionally-ordered ZnO nanorods, and the photocatalytic properties for Methyl Orange degradation were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-Vis-NIR absorption spectroscopy and photoluminescence. The results indicate that the catalyst with assembled QDs is more favorable for the degradation than the pristine ZnO nanorods. The QDs with core-shell structure lower the photocatalytic ability due to the higher carder transport barrier of the ZnS shell layer. Besides its degradation efficiency, the photocatalyst has several advantages given that the one-dimensionally-ordered ZnO nanorods have been grown directly on indium tin oxide substrates. The article provides a new method to design an effective and easily recyclable photocatalyst.     

天然水体中多壁纳米碳管对纳米氧化锌颗粒团聚与沉降行为的影响

研究了淡水湖泊水体中氧化多壁纳米碳管(Oxidized-multiwalled carbon nanotubes,o-MWCNTs)对纳米氧化锌(ZnO nanoparticles,nZnO)颗粒团聚与沉降行为的影响,探讨了天然胶体及o-MWCNTs的浓度对nZnO颗粒团聚粒径、团聚速率及沉降行为的作用.结果表明,nZnO在天然水体中会发生明显沉降,相比去除天然胶体的天然水而言,天然胶体的存在显著减少了nZnO的沉降.这主要归因于nZnO-天然胶体颗粒间的作用能垒高于nZnO-nZnO颗粒间的作用能垒,使得天然胶体的存在降低了nZnO-nZnO之间的颗粒碰撞效率,从而促进nZnO悬浮.o-MWCNTs对nZnO在天然水体中沉降行为的影响与天然胶体密切相关.相比于nZnO的单独沉降,在不过膜天然水中(含天然胶体),低浓度o-MWCNTs的存在增加了颗粒间的团聚速率,从而促进nZnO的沉降,而高浓度o-MWCNTs降低了颗粒间的团聚速率和团聚体粒径,从而降低了nZnO的沉降.而在过膜天然水中(不含天然胶体),o-MWCNTs的存在显著降低了颗粒间的团聚粒径和团聚速率,从而降低了nZnO的沉降,且o-MWCNTs的浓度越高,对nZnO悬浮稳定性的促进作用越明显.     

ZnO-PMMA复合材料光催化去除水中低浓度氨氮

通过水热法制备纳米ZnO,采用热粘固法成功地将其负载于聚甲基丙烯酸甲酯(PMMA)微球表面,并对ZnO-PMMA复合材料光催化去除水中低浓度氨氮的能力进行了考察.同时,探究了负载比例、初始氨氮浓度、催化剂浓度和pH对低浓度氨氮去除效率的影响.实验结果显示,PMMA改善了纳米ZnO的分散性和光催化能力,ZnO-PMMA能够有效地催化去除氨氮废水.在汞灯照射下,当pH=12、温度为30℃时,1 g·L~(-1)的催化剂(ZnO-PMMA)对50 mg·L~(-1)的氨氮废水去除率达到66%,且反应产物硝氮和亚硝氮含量较低,体现了该催化剂具有将氨氮转化为N2的良好的光催化降解能力.同时,纳米材料可以简单方便地回收,减轻了对环境的潜在影响,符合绿色化学的原则.     

不同磷水平下丛枝菌根真菌对纳米氧化锌生物效应的影响

纳米ZnO颗粒是应用最为广泛金属型纳米颗粒(nanoparticles,NPs)之一,对作物和土壤微生物的影响值得关注.丛枝菌根(arbuscular mycorrhizal,AM)是自然界中普遍存在的植物-真菌共生体,对各种环境胁迫具有一定的抵御能力,但菌根效应受土壤和植物磷含量的影响.分别设置0、20、50、100 mg·kg~(-1)这4个磷水平,在接种或不接种AM真菌Funneliformis mosseae、添加或不添加纳米ZnO(500 mg·kg~(-1))条件下在温室中利用玉米进行土壤盆栽试验.结果表明,纳米ZnO没有显著影响玉米生长,但不利于菌根侵染和磷素吸收,并引起锌在植物体内的积累.纳米ZnO和高磷降低玉米菌根侵染,但AM真菌在所有磷水平下均显著促进植物生长.施磷和接菌均可使土壤p H升高、降低纳米ZnO源锌的生物有效性,从而降低锌向玉米地上部分的转运和积累,体现出一定保护作用.接菌在多数情况下显示出积极的菌根效应,尤其在低磷、添加纳米ZnO条件下更为显著.结果首次表明,AM真菌、磷肥均有助于减轻纳米ZnO引起的土壤污染及其所产生的生态和健康风险.