用EXAFS研究Zn在水锰矿上的吸附-解吸机理

用延展X光吸收精细结构光谱(EXAFS)研究了重金属Zn(Ⅱ)在水锰矿(γ-MnOOH)上吸附产物的微观结构及其吸附机理.结果表明,Zn(Ⅱ)-水锰矿体系中(pH 7.5,0.1mol/LNaNO₃介质,25℃),Zn²⁺主要是通过共用水合Zn²⁺的O原子及水锰矿表面上的O原子形成Zn-O键,从而结合到水锰矿固体表面上的.平均Zn-O原子间距为1.998±0.010 A(n=3).这个Zn-O键键长是六配位的Zn(H₂O)²⁺₆及其水解产物四配位的Zn(OH)₂或Zn(OH)₄^2-各以一定比例混合吸附于水锰矿表面而形成的.同时,对第二配位层(Zn-Mn相互作用)的EXAFS图谱分析证明存在2个典型的Zn-Mn原子间距,即R₁=3.08±0.024A(n=3)和R2=3.54±0.018 A(n=3).这2个Zn-Mn原子距分别对应于水锰矿结构单元MnO6八面体与Zn水合离子ZnO多面体结合的2种方式,即共用2个O原子的边-边结合与共用1个O原子的角-角结合.边-边结合是较强的吸附位,Zn-Mn原子距较短(R₁=3.08A),吸附较不可逆.角-角结合是较弱的吸附位,Zn-Mn原子距较长(R₂=3.54A),吸附较为可逆.这一结果从微观上证明了亚稳平衡态吸附理论(MEA理论)的基本假设,即具有相同吸附密度的同一吸附质由于吸附力强弱以及微观构型的不同可具有不同的化学位,因而证明了修正传统吸附热力学的基本假设(吸附密度为热力学状态函数)的必要性.宏观的吸附-解吸热力学实验表明Zn(Ⅱ)在水锰矿上的吸附是不可逆的,EXAFS结果指出这种不可逆性主要是由Zn水合离子中ZnO多面体与水锰矿结构单元MnO₆八面体之间的边-边结合所导致的.     

生物沸石床污水脱氮效果及机理

研究了生物沸石床对模拟村镇生活污水中各形态氮及COD等污染物的去除效果结果表明,生物沸石床对NH₃^--N去除效果明显且稳定,去除率大于95%,对NO₃^--N的去除则受水力停留时间的影响较大从机理分析,生物沸石对NH₃-N的去除主要依靠化学吸附、离子交换以及生物硝化的协同作用,而对NO₃^--N的去除主要依赖反硝化作用.生物沸石的硝化作用明显,并受溶解氧浓度限制,沸石床中部沸石硝化强度只有表层沸石的1/2;其反硝化能力则随实验条件中C/N的不同而变化明显,当COD/TN=5时,反硝化作用最强,在时间变化规律上,前6h反硝化速率最大.     

磁性吸附材料CuFe2O4吸附砷的性能

根据Cu(Ⅱ)和Fe(Ⅲ)都对砷有较强的亲和性,制备了同时含有Cu(Ⅱ)和Fe(Ⅲ)的、可用磁分离方法进行分离回收的磁性吸附材料CuFe₂O₄,并对其进行了表征及吸附砷的性能研究.结果表明,该吸附剂对砷的吸附能力与溶液pH有关,在弱酸性及中性条件下,吸附砷的能力最强,而对As(V)的吸附能力比对As(Ⅲ)更强些,在平衡浓度为10μg/L时,其吸附容量可达10mg/g左右,可以很容易地将水中浓度为1～20mg/L的As(V)降到10μg/L以下.实验考察了几种无机阴离子对吸附砷的影响,表明较高浓度(砷浓度的20倍)的硫酸盐对As(Ⅲ)和As(V)的吸附均有一定影响,盐酸盐及磷酸盐则影响不明显;负载的As(V)可较容易地用0.1mol/L NaOH洗脱下来,使吸附剂再生,而As(Ⅲ)则难以洗脱,这与2种价态砷的吸附机理不同有关.     

化学解耦联剂对活性污泥工艺中污泥产率的影响

采用3,3′,4′,5-四氯水杨酰苯胺(TCS)作为代谢解耦联剂添加到活性污泥工艺中,连续曝气分批培养实验结果表明,TCS在浓度高于1.0mg/L时是一种有效的化学解耦联剂,能显著地降低污泥产率.当TCS浓度为6.0mg/L时,污泥产率可降低约50%.在40d的运行期间,隔天分别在3个反应器中添加TCS 2.0、2.8和3.6mg/L,基质的去除能力和出水氨氮及总氮浓度均未受影响,污泥的SOUR值和脱氢酶活性相应增加,污泥的沉降性能也未见有明显影响.镜检发现,对照反应器中的污泥经40d运行后仍有丝状菌存在,而添加解耦联剂反应器中的污泥几乎无丝状菌的存在.以上结果表明,可以应用TCS来降低活性污泥工艺中的剩余污泥产量.     

过电流故障铝导线熔痕部位与组织特征关联性研究

为深入研究过电流故障铝导线熔痕部位与组织特征之间的关联关系,本文模拟2.5 mm2BLV铝导线通25～ 187.5 A电流时的发热、熔断和燃烧过程,研究过电流铝导线发热形变与熔痕形成的内在关联,根据各部位熔痕受热形成过程,分类识别典型组织特征.研究结果表明:随着电流值升高,铝导线先后出现线芯发热、绝缘热解、熔断拉弧、绝...     

Effects of alfalfa coverage on runoff, erosion and hydraulic characteristics of overland flow on loess slope plots

An evaluation of the interactions between vegetation, overland and soil erosion can provide valuable insight for the conservation of soil and water. An experiment was conducted to study water infiltration, runoff generation process, rate of sediment erosion, and hydrodynamic characteristics of overland flow from a sloping hillside with different draw-off discharges from alfalfa and control plots with 20° slope. The effect of alfalfa on runoff and sediment transport reduction was quantitatively analyzed. Alfalfa was discussed for its ability to reduce the overland flow scouring force or change the runoff movement. Compared to the bare-soil plots, alfalfa plots generated a 1.77 times increase in infiltration rate. Furthermore, the down-slope water infiltration rate for the bare soil plots was higher than in the up-slope, while the opposite was found in the alfalfa plots. In addition, alfalfa had a significant effect on runoff and sediment yield. In comparison to the control, the runoff coefficient and sediment transportation rate decreased by 28.3% and 78.4% in the grass slope, respectively. The runoff generated from the alfalfa and bare-soil plots had similar trends with an initial increase and subsequent leveling to a steady-state rate. The transport of sediment reduced with time as a consequence of the depletion of loose surface materials. The maximum sediment concentration was recorded within the first few minutes of each event. The alfalfa plots had subcritical flow while the bare-soil plots had supercritical flow, which indicate that the capability of the alfalfa slope for resisting soil erosion and sediment movement was greater than for bare soil plots. Moreover, the flow resistance coefficient and roughness coefficient for the alfalfa plots were both higher than for the bare-soil plots, which indicate that overland flow in alfalfa plots had retarded and was blocked, and the flow energy along the runoff path had gradually dissipated. Finally, the ability to erode and transport sediment had decreased.     

Low-temperature CO oxidation over Au-doped 13X-type zeolite catalysts: preparation and catalytic activity

Au-supported 13X-type zeolite (Au/13X) was synthesized using a common deposition–precipitation (DP) method with a solution of sodium carbonate as a precipitate agent. Further testing was conducted to test for catalytic oxidation of CO. A study was conducted on the effects of different preparation conditions (i.e., chloroauric acid concentration, solution temperature, pH of solution, and calcinations temperature) on Au/13X for CO oxidation. In respect to the catalytic activity, the relationship between different the preparation conditions and gold particles in 13X zeolite was analyzed using X-ray diffraction, TEM and XPS. The activity of Au/13X catalysts in CO oxidation was dependent on the chloroauric acid concentration. From XRD results, a higher chloroauric acid concentration induced larger gold nanoparticles, which resulted in lower catalytic activity. Results revealed that higher temperatures induced higher Au loading, homogeneous deposit, and smaller gold clusters on the support of 13X, resulting in higher CO activity. Furthermore, a pH of 5 or 6 generated greater amounts of Au loading and smaller Au particles on 13X than at a pH of 8 or 9. This may be a result of an effective exchange between Au(OH)2Cl2- and Au(OH)₃Cl^- on specific surface sites of zeolite under the pH’s 5 and 6. The sample calcined at 300°C showed the highest activity, which may be due to the sample’s calcined at 200°C inability to decompose completely to metallic gold while the sample calcined at 400°C had larger particles of gold deposited on the support. It can be concluded from this study that Au/13X prepared from a gold solution with an initial chloroauric acid solution concentration of 1.5 × 10^-3 mol·L^-1 gold solution pH of 6, solution temperature of around 90°C, and a calcination temperature of 300°C provides optimum catalytic activity for CO oxidation.     

Environmental dispersivity in free-water-surface-effect dominated wetland: multi-scale analysis

Distinct from the case with width-dominated shallow wetland flows, the longitudinal evolution of contaminant concentration in the most-typical pattern of wetland as dominated by free-water-surface-effect is characterized by a multi-scale analysis in the present study. An environmental dispersion model for the evolution of the mean concentration is deduced as an extension of Taylor's classical formulation by Mei’s multi-scale analysis. Corresponding environmental dispersivity is found identical to that determined by the method of concentration moments.     

Influence of Polyol Plasticizers on the Properties of Polyvinyl Alcohol Films Fabricated by Melt Processing

In this work, high-alcoholysis polyvinyl alcohol (PVA) films were fabricated by melt processing and the plasticizing effect of compound polyol plasticizers on PVA were investigated with X-ray diffraction (XRD), differential scanning calorimetry (DSC), rheological measurements, mechanical tests etc. Hydrogen bonding interactions occurred between PVA and plasticizer. With the increase of plasticizer, the flowability of PVA was improved and reached the maximum value at the plasticizer of 20%. Glass transition temperature (T _g) and melting point (T _m) decreased with the increase of plasticizer content. For the heterogeneous nucleation effect of plasticizer, new polymorph of PVA formed. The viscosity was sensitive to the shear rates. The incorporation of plasticizers into PVA resulted in the increase of elongation at break and impact strength, as well as the decrease of tensile strength.     

Removal of methylene blue by coupling black carbon adsorption with TiO2 photodegradation

In this study, the removal of methylene blue (MB) by the coupling of black carbon (BC) and TiO₂ was investigated. The effects of different parameters such as catalyst dose, sorbent, initial concentrations of dye, pH of the solutions, recycles on discoloration, and chemical oxidation demand (COD) reduction of MB were monitored to optimize the reaction conditions. The discoloration and COD conversation rate of MB obtained by the coupling process were 100% after 90?min irradiation. The synergistic effect of MB-adsorption on BC followed by degradation through TiO₂ photocatalysis was proved by FT–IR spectrophotometer. The BC as by-product of natural materials is a promising adsorbent for waste water treatment.