碳纳米管接枝聚乙二醇负载ZnO的制备与表征

利用聚乙二醇接枝的多壁碳纳米管（MWNT-g-PEG）作为介质,在低温下,通过溶胶-凝胶法在PEG修饰后的MWNT表面负载花瓣状的纳米氧化锌（ZnO）。通过X射线衍射、红外波谱、扫描电镜和透射电镜对MWNT-g-PEG/ZnO纳米复合材料进行表征和分析。结果表明ZnO纳米粒子和MWNT之间结合紧密,ZnO的尺寸比较均一,推测了ZnO纳米粒子在MWNT表面的生长机理。MWNT表面的PEG对ZnO的负载起着重要的作用,它是ZnO原位生长的活性点。     

钛基石墨烯复合材料的制备及其光催化还原Cr（VI）的研究

通过改进的Hummers法制备氧化石墨烯(GO),再将氧化石墨烯和钛酸四丁酯作为初始反应物,利用溶剂热法制备Ti O_2/RGO纳米复合材料.利用SEM、TEM、XPS、XRD等分析手段对Ti O_2/RGO纳米复合材料进行表征,考察其在可见光照射条件下光催化还原水中Cr(Ⅵ)的效能,并对光催化还原机制进行了初步探讨.结果表明,Ti O_2/RGO复合材料的光催化还原能力与单一Ti O_2(P25)相比有了显著提高;复合材料中RGO含量、溶液p H值、催化剂投加量、Cr(Ⅵ)初始浓度均对光催化还原过程有所影响,当复合材料中RGO含量比例为2%、溶液p H值为2,催化剂投加量为40 mg时,光催化还原Cr(Ⅵ)的效率可达98%.光催化还原Cr(Ⅵ)的过程是吸附过程和光催化还原过程的共同作用结果,RGO不但提高了复合材料的吸附能力,还作为复合材料的电子导体,抑制了光生电子-空穴对的复合,增强了复合材料的光催化性能.经过5次循环使用后,复合材料的光催化还原效率仍然保持在90%左右.     

Pt负载暴露(001)晶面Bi2WO6催化剂合成及光催化性能

通过水热法制备了暴露（001）晶面的Bi₂WO₆纳米片,利用光还原法将Pt纳米颗粒负载于其表面.选择苯甲醇氧化和罗丹明B（RhB）降解为探针反应,评价了催化剂的光催化性能.在苯甲醇氧化实验中,Pt负载暴露001晶面的Bi₂WO₆样品的苯甲醇转化率为20.7%,约为未负载样品的2倍.在RhB降解实验中,Pt负载样品在光照40min后对RhB的矿化率可达81.1%,而未负载样品RhB矿化率仅为55.8%,表明Pt负载样品具有更优的降解速率和矿化能力.催化剂性能的提升归因于高能晶面暴露和Pt负载的协同作用.Pt纳米颗粒的负载作为助催化剂增加了催化剂表面的活性位点,同时提高了晶面光生电子空穴对的分离和迁移效率.     

Pt负载暴露(001)晶面Bi2WO6催化剂合成及光催化性能

通过水热法制备了暴露（001）晶面的Bi₂WO₆纳米片,利用光还原法将Pt纳米颗粒负载于其表面.选择苯甲醇氧化和罗丹明B（RhB）降解为探针反应,评价了催化剂的光催化性能.在苯甲醇氧化实验中,Pt负载暴露001晶面的Bi₂WO₆样品的苯甲醇转化率为20.7%,约为未负载样品的2倍.在RhB降解实验中,Pt负载样品在光照40min后对RhB的矿化率可达81.1%,而未负载样品RhB矿化率仅为55.8%,表明Pt负载样品具有更优的降解速率和矿化能力.催化剂性能的提升归因于高能晶面暴露和Pt负载的协同作用.Pt纳米颗粒的负载作为助催化剂增加了催化剂表面的活性位点,同时提高了晶面光生电子空穴对的分离和迁移效率.     

纳米ZnO胁迫下SBBR污染物去除性能及微生物群落响应

为探究生物膜处理系统对纳米ZnO的耐受性能,构建序批式生物膜反应器（SBBR）开展纳米ZnO对生物膜的胁迫试验.计算纳米ZnO在生物膜中的累积量,研究其对有机物、氮、磷的去除性能影响,判定SBBR对纳米ZnO的耐受阈值.通过测定生物量、微生物活性及群落结构变化,分析微生物群落对纳米ZnO的响应.结果表明：低浓度（1~10mg/L）纳米ZnO对COD、NH₄⁺-N、溶解性磷（SOP）去除无显著影响,但5mg/L纳米ZnO对微生物代谢速率和生物活性产生促进作用.纳米ZnO浓度逐增至50mg/L,对生物量、微生物活性抑制作用增强,COD、NH₄⁺-N、SOP去除率分别下降26.45%、57.83%和43.50%.纳米ZnO的胁迫对SBBR中COD去除性能影响最小,对NH₄⁺-N影响较大.COD所指示SBBR的纳米ZnO耐受阈值为911.49mg,而NH₄⁺-N、SOP所指示的耐受阈值为579.83mg.纳米ZnO的胁迫降低了系统中微生物群落的多样性,改变了群落结构组成,Proteobacteria和Chlorofiexi相对丰度由21.09%和7.03%分别降至8.00%和2.60%,致使NH₄⁺-N去除受到显著抑制;Patescibacteria丰度由9.33%突增至56.64%,为有机物的去除起到至关重要的作用.污染物去除性能及微生物活性表明,SBBR生物膜系统对纳米ZnO的耐受性强于活性污泥法.     

GO/AC/Ti复合电极的制备及其对甲基橙的吸附电解性能

吸附和电解是2种去除水中有机物的有效方法,为发挥吸附和电解对有机物的协同作用,将具有优良吸附导电性能的还原氧化石墨烯（RGO）与活性炭（AC）复合得到复合材料并将其黏附在Ti极片上,得到RGO/AC/Ti复合电极用于电解水中的甲基橙。利用SEM、FT-IR、BET、XRD、C-V、EIS等对复合材料及电极进行表征,考察了Ti、RGO/Ti和RGO/AC/Ti对甲基橙的电化学性能。结果表明:与RGO相比,RGO/AC的比表面积由318.1 m2/g增加到405.1 m2/g。相对于RGO/Ti,RGO/AC/Ti电极比电容值略有下降,但电容保持率提升。在电解质浓度为0.15 mol/L,极距为15 mm,电流为100 mA,pH为6时,Ti、RGO/Ti和RGO/AC/Ti电极对甲基橙的去除率分别达到48.1%、79.5%和88.8%,去除效果较好。     

有机凹凸棒石负载纳米零价铁去除水中六价铬

以黏土为载体负载纳米零价铁（nZVI,nanoscale zero-valent iron）可改善零价铁颗粒的团聚行为,增强其反应性.在负载过程中铁和黏土用量比例不同,对nZVI颗粒团聚和反应性的影响也不同.以有机凹凸棒石（CTMAB/A）为载体,采用液相还原法在1：3和1：5两种铁土质量比条件下制备负载型纳米零价铁复合材料CTMAB/A-nZVI-3和CTMAB/A-nZVI-5.利用X射线衍射仪（XRD）和扫描电子显微镜（SEM）表征了两种负载样品和不添加黏土载体时nZVI的分散差异,并通过X射线光电子能谱仪（XPS）分析样品与Cr（VI）反应后的产物分布.结果表明：降低负载反应时的铁土比能明显改善nZVI粒子的团聚现象、减小nZVI平均粒径、提高小粒径颗粒占比、增强其反应活性.小于10nm的nZVI颗粒在CTMAB/A-nZVI-3和CTMAB/A-nZVI-5负载nZVI总数中占比分别为3.60%和7.60%,在不负载的nZVI样品中占比为0.铁的投加量同为0.75g/L时,CTMAB/A-nZVI-5中铁对Cr（VI）去除率为86.20%,CTMAB/A-nZVI-3中为78.00%.     

粉煤灰基多孔材料负载纳米铁的制备及其对龙胆紫的去除效果

为制备新型可再生吸附反应材料,以工业废弃物粉煤灰、棕榈壳等为主要原料,烧结制备FAP（粉煤灰基多孔材料）,并以FAP为载体负载纳米零价铁,制备FAP/nZVI（粉煤灰基纳米零价铁多孔材料）,以散失率、龙胆紫去除率、纳米零价铁负载量等为指标,确定FAP及FAP/nZVI的最佳制备条件,并考察二者对染料龙胆紫的去除特性.结果表明:① FAP的最佳制备条件为m（粉煤灰）:m（膨润土）:m（棕榈壳）=190:95:15,升温速率10℃/min,烧结温度800℃,保温时间30 min.② FAP/nZVI最佳制备条件为m（Fe）/m（FAP）1:3,振荡时间1 h,选用抗坏血酸为稳定剂,过程中无需使用惰性气体;SEM结果表明纳米零价铁被成功负载于FAP上.③ FAP/nZVI对200 mg/L龙胆紫的去除率为94.8%,FAP同条件下的去除率仅为26.2%,FAP/nZVI对龙胆紫的去除同时存在物理吸附和化学还原作用,并且纳米零价铁的还原占主导作用.④ FAP/nZVI再生10次后30 min内对100 mg/L龙胆紫去除率高达97.6%.研究显示,FAP可将纳米零价铁氧化产物Fe2+固定在表面,经还原后可再生为纳米零价铁,具有良好的再生性能.      

过硫酸盐协同光催化纳米ZnO降解盐酸四环素的影响机制

以水葫芦为原料,制备了负载纳米ZnO的生物炭材料（ZnO-BC）,研究了单独光催化ZnO-BC和过硫酸钠（PS）协同ZnO-BC/UV体系氧化降解盐酸四环素（TC）.结果表明,PS协同ZnO-BC /UV体系的降解反应速率比单独光催化ZnO-BC时有显著提高,120min后降解率达到89.48%.PS可作为强氧化剂,利用纳米ZnO的光生电子产生SO₄^-·和·OH协同光催化反应.TC的反应过程可分为两个阶段：暗吸附阶段和光催化反应阶段.影响因素和响应面试验结果得出的影响顺序为PS浓度 > 紫外灯功率 > 初始pH值 > 纳米ZnO质量浓度.猝灭试验表明,在TC的降解中,SO₄^-·和·OH是参与反应的主要自由基.起氧化作用的自由基一部分在溶液中产生,另一部分由生物炭材料表面含氧官能团的作用和紫外光激发纳米ZnO产生.在此基础上,探讨了在TC降解过程中,PS与ZnO-BC的协同机理和协同作用的规律.     

纳米零价铁/生物炭材料吸附Cr(Ⅵ)的研究

为治理工业废水中重金属铬污染,该文以梧桐叶为原料、绿茶滤液为绿色还原剂制备出纳米零价铁/生物炭复合材料,对材料的微观形貌、所含官能团、元素组成等理化性质进行表征,考察其对水中Cr（Ⅵ）的吸附去除性能。结果表明：纳米零价铁颗粒均匀附着于光滑舒展的生物炭表面,材料含有酚类、烯烃、芳香化合物和醇类等多种有机化合物,负载纳米零价铁后生物炭本身的石墨结构无显著变化,XRD谱图具有零价铁的特征峰。600℃热解制备生物炭,Fe/C负载比为1∶24的负载纳米零价铁生物炭材料,投加量2.0 g,对50 mL初始浓度为10 mg/L Cr（Ⅵ）溶液吸附60 min后,最大去除率为58.72%。     

Ag–AgBr/TiO2/RGO nanocomposite: Synthesis, characterization, photocatalytic activity and aggregation evaluation

Ag–AgBr/TiO_2 supported on reduced graphene oxide(Ag–AgBr/TiO_2/RGO) with different mass ratios of grapheme oxide(GO) to TiO_2 were synthesized via a facile solvothermal-photo reduction method. Compared to the single-, two-and three-component nanocomposites,the four-component nanocomposite, Ag–AgBr/TiO_2/RGO-1 with mass ratio of GO to TiO_2at 1%, exhibited a much higher photocatalytic activity for the degradation of penicillin G(PG)under white light-emitting diode(LED-W) irradiation. The PG degradation efficiency increased with the increase of mass ratio of GO to TiO_2 from 0.2% to 1%, then it decreased with the increase of mass ratio of GO to TiO_2 from 1% to 5%. The zeta potentials of RGO-nanocomposites became more negative with the presence of humic acid(HA) due to the negatively charged HA adsorption, resulting in the shift of points of zero charge to lower values of pH. The aggregations of nanocomposites were more significant due to the bridging effect of HA. Furthermore, the aggregated particle sizes were larger for RGO-nanocomposites compared to other nanoparticles, due to the bindings of the carboxylic and phenolic functional groups in HA with the oxygen-containing functional groups in the RGO-nanocomposites.The microfiltration(MF) membrane was effective for the nanocomposites separation. In the continuous flow through submerged membrane photoreactor(sMPR) system, backwashing operation could efficiently reduce membrane fouling and recover TiO_2, and thus indirectly facilitate the PG removal.     

Highly efficient reduction of aqueous Cr(VI) with novel ZnO/SnS nanocomposites through the piezoelectric effect

In this work, novel ZnO/SnS nanocomposites were successfully synthesized via a hydrothermal approach, which is developed for piezoelectric catalytic reduction of hexavalent chromium (Cr(VI)) in an aqueous solution. The constructed ZnO/SnS nanocomposites exhibited higher catalytic efficiency for Cr(VI) reduction under a mechanical force (e.g., ultrasonic vibration) compared to pristine ZnO and SnS. In particular, the ZnO/SnS (with 30 wt.% of SnS) heterojunctions revealed an optimal degradation activity among all the prepared samples, which completely removed the Cr(VI) (20 mg/L) solution within 35 min. Moreover, the piezoelectric catalytic activity of ZnO/SnS remained stable after four consecutive cycling experiments. The results of the morphology observations indicated that the SnS nanoparticles adhere to the surface of the ZnO nanorods. The improved piezoelectric catalytic performance of the ZnO/SnS heterojunctions can be attributed to the formation of an intimate interfacial between ZnO and SnS, which effectively inhibits the electron-hole recombination and speeds up the rate of charge transfer. The study reveals a new design of ZnO/SnS heterojunctions as a high-performance and eco-friendly piezoelectric catalyst and provides a promising strategy for addressing environmental problems and energy crises.     

RGO/TiO2光催化降解2,4-二氯苯氧乙酸研究

通过Hummers法及紫外光/热还原工艺制得还原氧化石墨烯(RGO),采用溶胶-凝胶-煅烧法,以RGO和钛酸酊脂为前驱体制备出RGO/TiO2光催化复合材料,并利用XRD、FT-IR等对其进行了表征.对RGO/TiO2光催化降解性能的研究发现,复合光催化剂RGO/TiO2对2,4-二氯苯氧乙酸(2,4-D)的光催化降解活性显著优于纯TiO2,并且发现负载量和pH值对光催化降解性能有较大的影响:RGO/TiO2投加量为1.2g·L~(-1)、RGO负载量2%、pH为3、初始浓度为50 mg·L~(-1)反应12 h,2,4-D去除率达到98.75%;2,4-D降解率随着RGO/TiO2投加量的增大先增大后减小;RGO/TiO2对2,4-D的降解为脱氯还原和催化氧化过程,产生氯酚、苯酚等中间产物.     

A nanofilter composed of carbon nanotube-silver composites for virus removal and antibacterial activity improvement

We have developed a new nanofilter using a carbon nanotube-silver composite material that is capable of efficiently removing waterborne viruses and bacteria.The nanofilter was subjected to plasma surface treatment to enhance its flow rate,which was improved by approximately 62%.Nanoscale pores were obtained by fabricating a carbon nanotube network and using nanoparticle fixation technology for the removal of viruses.The pore size of the nanofilter was approximately 38 nm and the measured flow rate ranged from 21.0 to 97.2 L/(min·m~2)under a pressure of 1–6 kgf/cm~2 when the amount of loaded carbon nanotube-silver composite was 1.0 mg/cm~2.The nanofilter was tested against Polio-,Noro-,and Coxsackie viruses using a sensitive real-time polymerase chain reaction assay to detect the presence of viral particles within the outflow.No trace of viruses was found to flow through the nanofilter with carbon nanotube-silver composite loaded above 0.8 mg/cm~2.Moreover,the surface of the filter has antibacterial properties to prevent bacterial clogging due to the presence of 20-nm silver nanoparticles,which were synthesized on the carbon nanotube surface.     

MnO2@Fe3O4/石墨烯复合材料对水中Pb(Ⅱ)的吸附

以氧化石墨烯（GO）为原料制备MnO₂@Fe₃O₄/石墨烯（RGO）,考察吸附过程中MnO₂@Fe₃O₄/RGO投加量、溶液pH值、初始浓度和吸附时间等因素对Pb（Ⅱ）的去除率和吸附量的影响,并运用BET比表面积测试法计算MnO₂@Fe₃O₄/RGO的比表面积和平均孔径,采用扫描电子显微镜（SEM）,振动样品磁强计（VSM）,X射线衍射（XRD）和X射线光电子能谱（XPS）等对样品进行表征.结果表明：MnO₂@Fe₃O₄/RGO的比表面积为89.164m²/g,孔容为0.284cm³/g;随着pH值在2~10范围内增加,复合材料对Pb（Ⅱ）的去除率先增大后减小,pH=6时达到最大值.通过4种等温吸附模型（Langmuir、Freundlich、Temkin、D-R模型）和4种吸附动力学模型（伪一级动力学、伪二级动力学、Elovich、颗粒内扩散模型）拟合发现,MnO₂@Fe₃O₄/RGO对Pb（Ⅱ）吸附符合伪二级动力学模型.吸附等温线更符合Langmiur模型,属于典型的单分子层吸附,以化学吸附为主,最大吸附量为265.3mg/g.     

氧化锌纳米颗粒对膜-生物反应器运行性能的影响

考察了城市污水中典型浓度的氧化锌(ZnO)纳米颗粒对膜-生物反应器(MBR)运行、活性污泥性质以及膜污染的影响.结果表明,ZnO纳米颗粒不利于微生物对有机物的去除,但是不会影响微生物对氨氮的去除.由于微滤膜的截留作用,ZnO纳米颗粒对MBR的出水没有影响.ZnO纳米颗粒的投加导致溶解性微生物产物(SMP)浓度从17.9mg/gVSS上升到35.0mg/gVSS左右,污泥粒径由162.9μm下降到105.2μm,引起了外部阻力的上升,造成了膜污染的加剧.ZnO纳米颗粒会抑制微生物活性和改变活性污泥中微生物的种群结构,这主要与ZnO纳米颗粒释放的Zn2+有关.