磁溅射法制备TiO2/PTFE复合膜及其性能研究

目的研究磁控溅射法在聚四氟乙烯(PTFE)微孔膜上负载TiO_2,制备TiO_2/PTFE复合膜。方法利用接触角、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、拉伸强度等对复合膜亲水性、元素、形貌和机械强度进行测试,通过控制变量法研究了溅射时间、溅射功率对膜性能的影响及对复合膜对甲基橙的降解性能。结果在溅射功率为40 W,溅射时间为90 s时,TiO_2/PTFE复合膜的亲水性和拉伸强度相对较好,甲基橙的去除率达97%,降解效果好。结论通过实验可以优化出磁控溅射的工艺参数,制备出物理性能优异,并具有较高的光催化活性的负载型纳米催化剂。     

二氧化钛介孔微球的纳米金修饰及对其催化性能的影响

染料污染和大气中CO排放已成为日益严重环境问题,研发染料污染物的降解技术及低温CO催化氧化有助于解决上述问题。利用高分辨透射电子显微镜(HRTEM)和X射线衍射(XRD)等技术,该文比较了二氧化钛(TiO_2)介孔微球修饰金(Au)纳米颗粒前后的形貌、结构与组成的变化及催化染料降解和低温CO氧化的性能。结果表明,应用沉积-沉淀法可将Au纳米颗粒均匀地修饰在TiO_2介孔微球表面,颗粒直径约为4.5 nm。XRD结果显示Au~(3+)被还原为单质Au,且还原过程没有破坏TiO_2载体的晶体结构;电感耦合等离子体质谱(ICP-MS)测试得出Au含量仅为3.12%。氮气吸附-脱附等温曲线测试出Au/TiO_2比表面积为103.6 m~2/g,相应的Barret-JoynerHalenda(BJH)孔径分布测试出平均孔径为9.3 nm。有机染料罗丹明B(Rh B)的光催化降解结果显示,Au/TiO_2复合催化剂催化下的降解速率为6.63×10-5s-1,而单一TiO_2催化下的降解速率为5.18×10~(-5)s~(-1)。亚甲基蓝(MB)光降解实验显示出相同的结果,进一步证明Au/TiO_2复合催化剂具有较高的活性。低温催化CO氧化测试结果表明,单一TiO_2不具有催化活性,Au/TiO_2催化作用时在室温下CO转化率达48%,升温至50℃时CO转化率可达到99%,显示出很高的催化活性和热稳定性,并且可重复利用。可见,纳米Au/TiO_2复合催化剂在处理有机染料污染和低温CO氧化方面具有潜在的应用价值。     

rGO/TiO_2复合光催化剂的制备及光催化性能

用Hummers法制备氧化石墨烯(GO),以柠檬酸作为钛酸四丁酯的水解抑制剂和氧化石墨烯的表面活性剂制备G0/TiO_2前驱体溶胶,经过干燥、热处理后用NaBH_4还原得到还原氧化石墨烯/TiO_2(rGO/TiO_2)复合光催化剂.利用X射线衍射(XRD)、透射电镜(TEM)、荧光光谱(PL)对其进行表征分析;研究了GO的引入量、光催化剂的投入量对甲基橙降解性能的影响.结果表明:柠檬酸的加入能有效改善纳米TiO_2在rGO表面的分散情况;rGO/TiO_2复合光催化剂的光催化活性明显高于纯TiO_2;GO的加入量为10%且催化剂用量为0.1g时催化效果最佳.     

氧化物载体对Ni-V催化剂催化燃烧二氯甲烷的影响

以Al₂O₃,TiO₂,ZrO₂ 3种氧化物为载体,通过溶胶凝胶法制备以Ni-V双金属氧化物为活性组分催化剂,在固定床反应器上研究了催化剂的二氯甲烷（DCM）催化燃烧性能.并通过XRD、BET、FTIR-Pyridine和H₂-TPR表征分析催化剂的物理化学特性,结果表明催化剂的氧化还原性能与酸性存在一定的协同能力促进DCM的催化氧化.10% Ni-V/Al₂O₃和10% Ni-V/TiO₂催化剂表面大量的酸性位点和强氧化性使得催化剂在催化燃烧DCM时拥有较好的活性,其中10% Ni-V/Al₂O₃在252℃时就有90%的转化率,但其在低温时易产生含氯有机副产物的CH₃Cl,并且50h连续稳定性测试发现其有失活现象.而10% Ni-V/TiO₂催化剂达到90%转化率时温度为274℃,且其在DCM降解中并没有CH₃Cl的产生,稳定性测试中也没有失活现象发生,这可能是与其拥有更多中强度B酸以及较强氧化还原能力有关.     

混合单体对等离子体法改性PTFE膜微生物亲和性能的影响

膜材料氧传质性能和微生物亲和性对MABR（膜曝气生物膜反应器）的稳定运行及处理效果有重要影响,为探究混合单体对等离子体法改性PTFE（聚四氟乙烯）膜微生物亲和性能的影响,采用两步等离子体法分别在PTFE膜表面接枝聚合DOPA（左旋多巴）/GMA（甲基丙烯酸缩水甘油酯）、Lys（赖氨酸）/GMA、BA（苯胺）/GMA和DEA（乙二胺）/GMA四种混合单体,测定改性前、后PTFE膜的微生物亲和性,并进一步确定最佳混合单体改性PTFE膜的氧传质性能.结果表明:与未改性PTFE膜和仅接枝聚合GMA单体改性复合膜相比,DOPA/GMA、Lys/GMA、BA/GMA和DEA/GMA混合单体改性复合膜表面的微生物亲和性均有提高;Lys/GMA混合单体改性复合膜表面的微生物亲和性最佳,显著高于未改性PTFE膜,膜表面的生物量用ρ（DNA）和ρ（TOC）表示,分别为9.67 ng/μL和103.44 mg/L,比未改性PTFE膜高出34.7%和286.0%,同时其膜表面的生物量增加速度最快;DOPA/GMA和DEA/GMA混合单体改性膜表面的微生物亲和性相近,且高于BA/GMA混合单体改性膜;Lys/GMA混合单体改性复合膜的最大氧传质系数为1.17 m/d（操作压力为35 kPa）,显著高于未改性PTFE膜的0.48 m/d（操作压力为11 kPa）.研究显示,两步等离子体法接枝聚合的混合单体改性能够同时改善PTFE膜的微生物亲和性和氧传质性能,更适合于制备MABR复合膜,可为开发MABR专用膜材料提供理论基础和技术支持.      

燃料电池碳载PtSn纳米复合催化剂的研究

本文以SnO、Pt(NO3)2为原料,通过直接热分解途径制备Pt的质量分数为20%的PtSn/C催化剂。XRD表征催化剂的结构,并与ETEK公司20%Pt/C催化剂的XRD进行比较,同时利用电化学方法研究了PtSn/C催化剂中不同形态的Sn对其催化性能的影响。结果表明:扫描初期,PtSn/C催化剂的表面处于富Sn状态时,峰电流密度较小;随着扫描圈数的增加,催化剂表面暴露出大量的PtSn合金,PtSn协同效应明显,导致0.47V处催化剂对乙醇氧化的峰电流密度快速增大;但随着扫描圈数的继续增加,合金态的Sn溶解,催化剂的电催化性能下降;继续增加扫描次数,催化剂表面Pt原子发生了重组,氧化峰电流密度减小。     

g-C_3N_4/TiO_2瓷砖的制备及其性能研究

采用空压机在瓷砖表面喷涂了以钛酸四丁酯为钛前驱体,三聚氰胺为氮源制备的g-C_3N_4/TiO_2复合光催化剂。通过扫描电子显微镜(SEM)、透射电镜(TEM)、傅里叶红外光谱(FT-IR)、紫外可见漫反射光谱(DRS)等对材料的结构与性能进行表征。附着力测试显示g-C_3N_4/TiO_2薄膜附着力良好,达到5B级别。分别以罗丹明B和大肠杆菌进行了降解和杀菌实验,结果显示g-C_3N_4/TiO_2瓷砖在白炽灯(照度(10 000±1 000)Lux)下光照6 h罗丹明B的脱色率达到45.1%,光照5 h大肠杆菌灭菌率约为99.7%。重复性试验证明,其稳定性较好。说明制备的g-C_3N_4/TiO_2瓷砖具有较好的自清洁和杀菌性能。     

可见光响应GO/g-C3N4改性平板膜的制备条件及其表面性能

以氧化石墨烯(GO)与石墨相氮化碳(g-C_3N_4)为改性剂,采用界面聚合与超滤抽吸结合,对PVDF平板超滤膜(简称原膜)进行表面改性,得到可见光响应的纳米复合改性膜(简称:GO/g-C_3N_4改性膜),研究改性膜的制备条件及其表面性能.结果表明:(1)最佳制备条件为:g-C_3N_410 mg、g-C_3N_4/GO比值为80、苯胺(An)浓度0.5%、An浸泡时间4 h、过硫酸铵(APS)浓度0.8 g·L~(-1)、APS浸泡时间3 h;(2)GO/g-C_3N_4改性膜表面亲水性与抗污染性能显著提高,表面接触角下降55.1%,通量衰减率下降46.3%,经水力冲洗后膜通量恢复率增加51.5%;(3)改性膜的机械强度与拉伸强度增强,拉伸弹性模量增加;(4)GO/g-C_3N_4改性膜表面具有较强的可见光活性,最大吸收边带为495 nm,表面改性功能层的禁带宽度(Eg)值为2.5 e V.改性膜对罗丹明B(Rh B)的可见光催化降解去除率达到81.2%,而原膜对Rh B吸附去除率仅为42.2%.     

光催化复合超滤膜的制备与催化性能

经金属Fe掺杂改性的TiO_2纳米粒子与PSF铸膜液共混,采用L-S浸没相转化法制备了分散均匀的Fe-TiO_2/PSF光催化复合超滤膜,测试该复合超滤膜的形貌、表面官能团、亲水性能、超滤性能、机械性能、热稳定性能、光催化性能,考察了纳米Fe-TiO_2光催化剂的含量对膜结构和性能的影响.结果表明:当Fe-TiO_2与PSF质量比为0.20时,Fe-TiO_2/PSF复合膜对罗丹明B(RhB)的去除率(61%)明显高于纯聚砜膜(33%);通过添加光催化剂,可使复合膜在模拟太阳光下具有光响应;同时,催化剂的适量添加,可提高聚砜膜的亲水性和物化性能,拓宽膜的应用领域.     

介孔炭基复合阴极的制备及其产H2O2性能研究

近年来,气体扩散电极因可以使氧气/空气从外部供应到阴极表面,而不需要在电解质中溶解,在提高H₂O₂的电化学合成效率方面得到了广泛的关注。该文以介孔炭为催化层材料,购买的商业碳黑和石墨作为扩散层材料制备电极。从产H₂O₂量和电流效率可以看出,当催化层为介孔炭且与PTFE乳液的比例为2∶1,扩散层为碳黑且与PTFE乳液的比例为1∶3时,在鼓气速率为18 L/h、电解质为200 mL 0.5 mol/L的Na₂SO₄溶液、电流密度为10 m A/cm²、初始p H值为11.0的条件下,能高效生成H₂O₂,60 min产H₂O₂量为47 mmol/L,且制作的空气扩散电极在数次使用之后,仍能保持良好的产H₂O₂能力。     

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.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

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.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

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

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