适于工业应用的TiO2纳米管的阳极氧化法制备

通过阳极氧化法制备了适于工业应用的大尺寸二氧化钛纳米管阵列.考察了电极形状和面积、氧化电压、氧化时间、预处理等因素对阳极氧化法制备二氧化钛纳米管阵列形貌的影响.结果显示,电极形状对纳米管的制备没有影响;阳极氧化前打磨与否对纳米管也没有影响;氧化电压、氧化时间和电极面积对纳米管的影响较大,只有在合适的电压和时间下才能制成纳米管阵列.电极面积影响电流密度,从而影响纳米管的形貌,试验中电极最大面积为360cm2.通过试验得出工业化制备二氧化钛纳米管阵列的最佳条件是电压20V,电解时间30min,反应前不用进行打磨.实验结果显示制成的纳米管阵列对强酸强碱的耐受力强,完全可以适应工业化废水的pH变化.     

利用碳氮共掺杂二氧化钛纳米管阵列实现同时降解甲基橙和产氢

本研究结合阳极氧化和超声辅助沉积的方法合成碳氮共掺杂的二氧化钛纳米管阵列,并采用XRD、FESEM、UV-vis、XPS等技术对材料进行表征.光电化学(PEC)体系中,碳氮共掺杂二氧化钛纳米管阵列作为阳极,甲基橙溶液作为光电催化氧化的对象,对光催化剂的氧化性能进行了考察,与此同时,在阴极实现光解水产氢,最终在PEC体系中实现同时降解甲基橙和产氢.XRD、FESEM、UV-vis、XPS及TEM等表征结果表明,碳氮成功地掺入到了二氧化钛纳米管阵列中,并未破坏其多孔有序的结构,而且比二氧化钛纳米管阵列具有更高的光催化活性.光电催化降解甲基橙的实验当中,在酸性溶液条件下,二氧化钛纳米管阵列的催化氧化效率较高,降解效率达到了100%,其速率常数为2.3×10-3s-1(p H=4),同时也具有较高的产氢速率(0.95 mmol·h-1),因此,该实验体系在光电催化降解污水中的有机污染物同时产氢方面有应用前景.     

氧气热处理的TiO2纳米管阵列光电催化降解亚甲基蓝的研究

采用原位阳极氧化法在Ti基底上制备了高度有序的TiO2纳米管阵列薄膜,SEM图像表明TiO2纳米管定向排列整齐,分布均匀,其管径范围在70～100 nm.XRD结果证明,阳极氧化法制备的TiO2纳米管为无定型晶型,经退火后为具有良好光催化活性的锐钛矿型.以亚甲基蓝（methylene blue）为目标物研究了TiO2纳米管光电催化性能及影响因素,结果表明,以0.1 mol/L NaCl为电解质,在氧气热处理气氛下,外加偏压为0.5 V、pH=3.25、光照强度为1 000μW/cm2、纳米管薄膜表面积为2 cm×2 cm且MB初始浓度为10 mg/L的条件下,TiO2纳米管阵列薄膜光电催化降解MB的降解效率可达99.56%.电化学阻抗谱分析显示,光电催化降解过程的速控步骤均为表面反应步骤,外加偏压减小了界面电荷转移阻抗,提高了光生载流子的分离效率.     

石墨烯修饰的二氧化钛纳米管电极光电催化去除铜氰络合物研究

首先采用阳极氧化法制备了二氧化钛纳米管电极,进一步通过电化学循环伏安法制备了石墨烯(GO)修饰的二氧化钛纳米管电极.同时,采用SEM对电极的形貌进行了表征分析.光电化学测试分析结果表明,石墨烯修饰二氧化钛纳米管电极的电极光电响应性能得到了提高.最后,采用制备的电极为光阳极,通过光电催化氧化方法对铜氰络合物进行了去除研究.结果表明:在电压为2.0 V的条件下,采用二氧化钛纳米管电极,反应120 min后,剩余总氰的含量及铜的回收率分别为4.0%和96.3%;采用石墨烯修饰的二氧化钛纳米管,反应60 min后,剩余总氰的含量及Cu的回收率分别为0.3%和99%.可以看出,经石墨烯修饰的二氧化钛纳米管显示出了较好的光电催化去除铜氰络合物的效果.     

Bi-TiO2纳米管阵列电极对水中硝酸盐的去除

为研究电化学技术对硝酸盐氮的去除作用,本实验以TiO₂纳米管（TiO₂-NT）为基体,利用电沉积法制备了Bi-TiO₂纳米管阵列电极（Bi-TNA）.同时,采用X-射线衍射仪（XRD）、扫描电子显微镜（SEM）对电极涂层表面形貌和晶体结构进行表征,并分析了电流密度、pH、初始浓度对硝态氮去除、亚硝态氮和氨氮转换、总氮去除及氮气选择性的影响.最后分析了Bi-TNA电极对硝态氮去除的动力学模型.结果表明,在单因素水平下,最佳操作条件为：硝态氮浓度为50 mg·L^-1,电流密度为30 mA·cm^-2,pH值为8.5.Bi-TNA电极对硝态氮的还原过程都遵循一级反应动力学.     

TiO_2纳米管修饰电极处理反渗透浓水研究

研制了新型的TiO2纳米管修饰电极,应用于反渗透膜浓水的电化学氧化处理;利用扫描电镜和线性极化曲线对电极进行了表征;考察了电解时间、电流密度和pH值因素对电化学氧化处理反渗透膜浓水的影响;并分析了电极对反渗透浓水中各有机物组分的去除效果。实验结果表明TiO2纳米管修饰电极对反渗透浓水具有较高的电催化性能。     

SiO_2-TiO_2纳米管的制备及其光催化性能的研究

文章采用水热法制备SiO2-TiO2纳米管,通过扫描电镜(SEM)和透射电镜(TEM)考察了该纳米管的结构形态,并用X-射线衍射考察其晶体结构。实验结果表明所制得的纳米管是锐钛晶型,其两端开口,具有多层管壁;管径为8nm左右,管壁厚1～2nm。光催化降解酸性橙Ⅱ实验表明:SiO2-TiO2纳米管光催化速率比TiO2纳米管高出10%。这可能是因为Si元素的存在增大了钛纳米管的比表面积,同时SiO2的存在能降低光生电子和空穴的复合率。     

SiO-TiO2纳米管的制备及其光催化性能的研究

文章采用水热法制备SiO2-TiO2纳米管,通过扫描电镜(SEM)和透射电镜(TEM)考察了该纳米管的结构形态,并用X-射线衍射考察其晶体结构.实验结果表明所制得的纳米管是锐钛晶型,其两端开口,具有多层管壁;管径为8 nm左右,管壁厚1～2 nm.光催化降解酸性橙Ⅱ实验表明:SiO2-TiO2纳米管光催化速率比TiO2纳米管高出10%.这可能是因为Si元素的存在增大了钛纳米管的比表面积,同时SiO2的存在能降低光生电子和空穴的复合率.     

臭氧/TiO_2纳米管工艺处理水中2,4-二氯酚的效能研究

采用水热合成法制备TiO2纳米材料,用BET、XRD、TEM技术对样品进行表征,结果表明,制备出来的样品均为纳米管,随着煅烧温度的增加,晶型从锐钛矿变成金红石相。实验考察了体系参数对臭氧/TiO2纳米管工艺降解2,4-二氯酚废水影响,结果表明:随着臭氧投加量的增加,废水COD的去除效率随之增加,初始浓度的增加会抑制降解效率,中性或弱碱性水环境有利于反应的进行。另外,通过研究叔丁醇对反应体系的影响,表明实验反应遵循羟基自由基的反应机理。     

基于传感器阵列的可燃混合气体RBF网络分析

为克服传感器阵列在混合气体检测中的交叉敏感现象,采用具有最佳逼近和全局最优性能的RBF神经网络对传感器阵列的输出信号进行分析。建立了多种可燃气体分析的数学模型,并对CO,H2和CH4的混合气体样本进行了实验。结果表明,传感器阵列和RBF神经网络处理单元构成的气体分析系统可以较好地实现对可燃混合气体的分析,误差不大于2%。     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.