Pd/GO/Ni电极的制备及对2,4-二氯酚的降解研究

为去除持久性氯代有机污染物2,4-二氯酚(2,4-DCP),利用电化学沉积法制备了一种新型钯/氧化石墨烯/泡沫镍(Pd/GO/Ni)电极,并通过电化学法降解2,4-二氯酚,取得良好的效果。通过扫描电镜等表征手段观察其表面形貌。结果表明:氧化石墨烯浓度为10 mol/L是制备Pd/GO/Ni电极的最佳浓度,p H为3时,Pd/GO/Ni电极对2,4-二氯酚的去除率达到90.7%。     

CMC改性的纳米Fe/Cu双金属去除2,4-二氯苯酚的研究

为解决纳米零价金属在水中暴露出的极易聚集与氧化的问题,本研究使用铜作为纳米零价铁(NZVI)的复合金属,制得纳米Fe/Cu双金属,并用羧甲基纤维素钠(CMC)对其包覆改性.使用扫描电子显微镜、X射线衍射以及氮气吸附/脱附等温线对改性前后的双金属进行表征.结果表明,改性之后的材料具有更大的尺寸以及比表面积,且抗氧化性得到显著增强.材料的沉降实验以及对2,4-二氯苯酚(2,4-DCP)降解实验的结果揭示,CMC的包覆比对改性后双金属的分散性与反应活性影响较大.当包覆比为80%时,双金属的分散稳定性最强,释放的活性位点个数最多,表现为最高的反应活性.此时脱氯效率达到90.3%,且脱氯过程和产物发生明显改变.     

EDTA优化纳米Pd/Fe对2,4-D的催化脱氯研究

采用EDTA优化纳米Pd/Fe催化脱氯水中2,4-二氯苯氧乙酸(2,4-D),并考察了EDTA投加浓度、pH、钯化率、温度等因素对2,4-D还原的影响.结果表明,EDTA的加入络合了纳米Pd/Fe在催化脱氯过程中生成的铁离子,抑制纳米Pd/Fe颗粒表面钝化层的形成,提高了体系的反应活性.适宜的EDTA浓度、低pH、高钯化率、低温等有利于2,4-D的还原脱氯.当EDTA浓度为25.0 mmol·L-1,纳米铁含量为1.0 g·L-1,初始pH=4.3、钯化率为0.5%,温度为25.0℃,搅拌速率为200 r·min~(-1)时,反应50 min,10.0 mg·L-1的2,4-D去除率及苯氧乙酸(PA)生成率均达到100%.     

不同pH下纳米铁镍颗粒对生物降解苯酚的影响

研究不同pH(8.0、6.0和3.0)下金属纳米颗粒(Fe和Fe/Ni)对纺锤芽孢杆菌(BFN)降解苯酚的影响.实验结果发现pH在8.0和6.0时投加2种金属纳米颗粒(Fe和Fe/Ni)对BFN降解苯酚有促进作用,其原因主要是纳米颗粒在水中持续腐蚀产生H2,为BFN降解苯酚提供电子,促进BFN的生长.但在pH=3.0时,只有BFN-纳米Fe耦合体系才使苯酚得到部分降解,主要是因为纳米Fe颗粒与水反应产生OH-,使pH值有所升高,更适宜BFN的生长,同时提供电子供体H2促进BFN对苯酚的利用.扫描电镜(SEM)和能谱分析(EDS)数据证实金属纳米颗粒(Fe和Fe/Ni)在反应后附着在微生物表面,但微生物的表面形态并未发生显著改变.因此,纳米金属颗粒虽然通过附着影响微生物的活性,但其在腐蚀过程中产生的H2将作为电子供体而被BFN所利用,综合作用的结果是有利于BFN的生长进而提高苯酚的降解速率.     

镍/铁二元金属对莠去津脱氯特性的影响

为了考察Ni/Fe二元金属对莠去津的催化还原特性,分别以Fe粉和Ni/Fe体系作为还原和催化剂,在酸性条件下对莠去津的脱氯特性进行比较,并讨论了pH值,Ni/Fe配比以及金属添加量等因素对莠去津脱氯效率的影响.结果表明:与Fe粉比较,Ni/Fe体系对莠去津具有很明显的催化脱氯特性.在pH=2时,1.22%(W/W)Ni/Fe体系30min对莠去津的脱氯效率大于90%,相同条件下用Fe粉还原时,90min脱氯效率仅为22.21%通过Fe粉和Ni/Fe表面形态的比较以及实验结果的分析,对Ni/Fe体系的催化还原脱氯机理进行了初步探讨.     

Catalytic reductive dechlorination of p–chlorophenol in water using Ni/Fe nanoscale particles

Nanoscale bimetallic Ni/Fe particles were synthesized from the reaction of sodium borohydride （NaBH4） with reduction of Ni^2＋ and Fe^2＋ in aqueous solution. The obtained Ni/Fe particles were characterized by TEM （transmission electron microscope）, XRD （X-ray diffractometer）, and N2-BET. The dechlorination activity of the Ni/Fe was investigated using p-chlorophenol （p-CP） as a probe agent. Results demonstrated that the nanoscale Ni/Fe could effectively dechlorinate p-CP at relatively low metal to solution ratio of 0.4 g/L （Ni 5 wt%）. The target with initial concentration ofp-CP 0.625 mmol/L was dechlorinted completely in 60 rain under ambient temperature and pressure. Factors affecting dechlorination efficiency, including reaction temperature, pH, Ni loading percentage over Fe, and metal to solution ratio, were investigated. The possible mechanism of dechlorination ofp-CP was proposed and discussed. The pseudo-first- order reaction took place on the surface of the Ni/Fe bimetallic particles, and the activation energy of the dechlorination reaction was determined to be 21.2 kJ/mol at the temperature rang of 287-313 K.     

CMC改性纳米Fe/Cu双金属模拟PRB去除地下水中2,4-二氯苯酚

使用羧甲基纤维素钠（CMC）对纳米零价铁（NZVI）改性,并将铜（Cu）作为复合金属,制得改性纳米Fe/Cu双金属.同时采用模拟反应柱模拟可渗透反应墙（PRB）去除地下水中2,4-二氯苯酚（2,4-DCP）的反应过程.改性前后材料的表征以及沉降实验结果表明,改性后的材料有更强分散性.通过考察污染物浓度、材料投加量、Cu的负载率、pH值、流量等因素对降解2,4-DCP的影响,结果表明：反应过程符合一级动力学模型,较低的pH值与较小的流速以及10%的Cu负载率有利于2,4-DCP脱氯,过多的材料投加量和过高的初始2,4-DCP浓度不利于其脱氯.     

纳米Pd/Fe双金属对2,4-二氯酚的脱氯机理及动力学

采用纳米Pd Fe双金属对2,4 二氯酚(2,4 DCP)进行了催化还原脱氯处理.结果表明,纳米Pd Fe双金属具有较高的比表面积和反应活性,对2,4 DCP具有较好的脱氯效率.当纳米Pd Fe用量在6g·L-1时,2,4 DCP脱氯率达到90%以上;脱氯效率与pH值、温度、钯化率、Pd Fe投加量等因素有关.2,4 DCP在脱氯过程中先生成邻氯酚和对氯酚,而后继续脱氯生成苯酚,或由2,4 DCP直接降解成苯酚.2,4 DCP降解符合拟一级反应动力学.2,4 DCP催化还原脱氯反应的活化能为139 7kJ·mol-1.     

膨润土负载纳米铁/镍还原阿莫西林的环境影响因素研究

采用液相还原法制备膨润土负载纳米铁/镍(Bent-Fe/Ni)用于还原阿莫西林,研究了不同浓度的阴离子(SO2-4、HCO-3)和阳离子(Ca2+、Cu2+)对Bent-Fe/Ni还原阿莫西林的影响.结果表明,SO2-4、HCO-3浓度对Bent-Fe/Ni还原阿莫西林的影响较大,当其浓度分别为0和500mg·L-1时,阿莫西林的去除率分别为93.7%和21.5%(SO2-4),以及93.7%和5.8%(HCO-3);Ca2+对Bent-Fe/Ni还原阿莫西林起到抑制作用,当其浓度为0和500 mg·L-1时,阿莫西林的去除率分别为93.7%和77.8%;低浓度的Cu2+对Bent-Fe/Ni还原阿莫西林起到促进作用,而高浓度的Cu2+对Bent-Fe/Ni还原阿莫西林起到抑制作用,当其浓度为0、10和100 mg·L-1时,阿莫西林的去除率分别为93.7%、94.8%和86.7%.     

针铁矿、磁铁矿和石膏对2,4-二氯苯酚厌氧降解的影响

2,4-二氯苯酚(2,4-dichlorophenol,2,4-DCP)常用于农药生产,在水体和土壤中广泛分布,具有难降解、高毒性的特点.通过模拟自然过程,在厌氧反应体系中投加铁氧化物和硫酸盐矿物,重点考察了不同矿物对2,4-DCP降解的影响.结果发现,厌氧体系中针铁矿、磁铁矿和石膏对2,4-DCP均没有明显的吸附作用;质量衡算结果表明所有反应体系中仅发生2,4-DCP向4-氯苯酚(4-chlorophenol,4-CP)的转化;与无外加碳源组相比,乙酸钠的加入使得2,4-DCP的还原脱氯反应速率增大一倍.分析表明针铁矿和磁铁矿加入可刺激脱氯功能菌的生长或活性,进而提高微生物的电子传递能力和2,4-DCP的降解速率;石膏加入强烈抑制脱氯功能菌的生长或活性,进而抑制2,4-DCP的降解.研究结果对认识难生化降解卤代酚在厌氧环境中的迁移转化及环境工程中此类物质的处理具有潜在意义.     

EDTA对Pd/Fe体系还原脱氯2,4-D的影响

针对Pd/Fe体系对含氯有机物催化还原脱氯过程中,零价铁易腐蚀并在颗粒表面形成钝化层,阻碍目标污染物的进一步脱氯去除,本研究利用乙二胺四乙酸(EDTA)与Fe2+和Fe3+的络合作用,消除Pd/Fe颗粒表面的钝化层,使还原脱氯过程得到持续进行.实验考察了EDTA的投加方式和投加量、p H、钯负载率、温度等因素对2,4-二氯苯氧乙酸(2,4-D)还原脱氯的影响.结果表明:1EDTA浓度为25.0 mmol·L-1、投加速率为20 m L·h-1时,苯氧乙酸(PA)生成率在20 min达到了90.7%.而未加EDTA的反应体系,反应210 min后,PA的生成率仅为74.5%;2EDTA可以络合Pd/Fe体系在催化脱氯过程中生成的Fe2+和Fe3+,防止或减缓了Pd/Fe颗粒表面钝化层的形成,提高了反应活性;3适宜的2,4-D催化脱氯条件为:浓度25.0mmol·L-1的EDTA溶液,投加速率20 m L·h-1、初始p H为4.2、钯负载率0.050%、温度30.0℃、搅拌速率200 r·min-1,反应210 min,20.0 mg·L-1的2,4-D几乎可完全转化为PA;42,4-D催化脱氯的中间产物主要是2-氯苯氧乙酸及微量的4-氯苯氧乙酸,最终产物为苯氧乙酸.     

微塑料PES与2,4-DCP复合污染对厌氧污泥胞外聚合物与微生物群落的影响

考察了聚醚砜(PES)微塑料及2,4-二氯苯酚(2,4-DCP)对厌氧颗粒污泥疏松胞外聚合物(LB-EPS)和紧密胞外聚合物(TB-EPS)组分的影响,并利用高通量测序技术对厌氧颗粒污泥的微生物群落及基因功能变化进行了分析.结果 表明,2,4-DCP以及PES +2,4-DCP实验组COD去除率分别为35％和37％,与...     

纳米Ni/Fe用于去除染料生产废水二级生物处理出水中AOX和色度的研究

用纳米Ni/Fe材料深度处理染料生产废水的生物处理出水,考察了不同Ni负载量(质量分数0~5%)、废水初始p H值(4.1~10.0)、Ni/Fe投加量(1~5 g·L-1)、反应时间(0.5~96 h)下对可吸附性有机卤代物(absorbable organic halogens,AOX)的去除率和脱色率.结果表明,AOX和色度去除率随Ni负载量的增加先升高后减少,随废水初始p H值的降低和Ni/Fe投加量的增加而持续提高.最优化条件为Ni负载量1%、废水初始p H 4.1和Ni/Fe投加量3 g·L-1,该条件下AOX和色度的24 h去除率分别为29.2%和79.6%,96 h去除率分别为50.6%和80.7%.GC-MS分析表明经材料处理后废水中氯代苯胺类、对硝基苯胺、4-甲氧基-2-硝基苯胺及卤代烷烃等有毒有害物质得到高效去除.     

纳米级Fe3O4-Pd/Fe复合材料催化脱氯2,4-D研究

采用共沉淀法制备纳米级Fe_3O_4,将其包覆在纳米Pd/Fe颗粒表面制成纳米级Fe_3O_4-Pd/Fe复合材料,并用于2,4-二氯苯氧乙酸(2,4-D)的催化脱氯.同时,采用透射电镜(TEM)、扫描电镜(SEM)等方法对复合材料的结构进行分析,并考察了初始pH、钯化率、反应温度、纳米Fe_3O_4投加量等实验参数对n Fe_3O_4-Pd/Fe复合材料催化脱氯2,4-D的影响.结果发现,纳米Fe_3O_4粒径小于Pd/Fe纳米颗粒,具有一定的磁性,包覆于纳米Pd/Fe表面,提高了纳米材料的稳定性及分散性,并有利于复合材料的回收和循环利用.此外,纳米Fe_3O_4具有一定的导电性,可作为良好的电子通道为纳米Pd/Fe颗粒传递电子,促进反应的进行,增强2,4-D的去除效果.实验结果表明,较高的钯化率、反应温度、Fe_3O_4∶Fe质量比及中性pH条件均有利于反应的进行.当纳米Fe投加量为1.0 g·L-1,m(Fe_3O_4)∶m(Fe)为1∶1,初始pH为7.0,钯化率为0.15%,反应温度为25.0℃时,反应90 min后,40.0 mg·L-1的2,4-D的去除率达到100%,苯氧乙酸(PA)的生成率达99.8%.     

Enhanced activity of ZnS(111) by N/Cu co-doping:Accelerated degradation of organic pollutants under visible light

High-efficiency photocatalysts are of great significance for the application of photocatalytic technology in water treatment.In this study,N/Cu co-doped ZnS nanosphere photocatalys(N/Cu-ZnS) is synthesized by a hydrothermal method for the first time.After doping,the tex ture of nanosphere becomes loose,the nanometer diameter is reduced,making the specific surface area of catalyst increased from 34.73 to 101.59 m²/g.The characterization results show that more ZnS (111) crystal planes a...     

A high activity of Ti/SnO2-Sb electrode in the electrochemical degradation of 2,4-dichlorophenol in aqueous solution

Electrochemical degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution was investigated over Ti/SnO₂-Sb anode. The factors influencing the degradation rate, such as applied current density (2-40 mA/cm²), pH (3-11) and initial concentration (5-200 mg/L) were evaluated. The degradation of 2,4-DCP followed apparent pseudo first-order kinetics. The degradation ratio on Ti/SnO₂-Sb anode attained > 99.9% after 20 min of electrolysis at initial 5-200 mg/L concentrations at a constant current density of 30 mA/cm² with a 10 mmol/L sodium sulphate (Na2SO4) supporting electrolyte solution. The results showed that 2,4-DCP (100 mg/L) degradation and total organic carbon (TOC) removal ratio achieved 99.9% and 92.8%, respectively, at the optimal conditions after 30 min electrolysis. Under this condition, the degradation rate constant (k) and the degradation half-life (t_1/2) were 0.21 min^-1 and (2.8±0.2) min, respectively. Mainly carboxylic acids (propanoic acid, maleic acid, propanedioic acid, acetic acid and oxalic acid) were detected as intermediates. The energy efficiencies for 2,4-DCP degradation (5-200 mg/L) with Ti/SnO₂-Sb anode ranged from 0.672 to 1.602 g/kWh. The Ti/SnO₂-Sb anode with a high activity to rapid organic oxidation could be employed to degrade chlorophenols, particularly 2,4-DCP in wastewater.     

Preparation and characterization of Pd/Fe bimetallic nanoparticles immobilized on Al2O3/PVDF membrane: Parameter optimization and dechlorination of dichloroacetic acid

Using a liquid–solid phase inversion method, a hybrid matrix poly(vinylidene fluoride)(PVDF) membrane was prepared with alumina(Al2O3) nanoparticle addition. Pd/Fe nanoparticles(NPs) were successfully immobilized on the Al2O3/PVDF membrane, which was characterized by Scanning Electron Microscopy(SEM) and Transmission Electron Microscopy(TEM). The micrographs showed that the Pd/Fe NPs were dispersed homogeneously. Several important experimental parameters were optimized, including the mechanical properties, contact angle and surface area of Al2O3/PVDF composite membranes with different Al2O3 contents. At the same time, the ferrous ion concentration and the effect of hydrophilization were studied. The results showed that the modified Al2O3/PVDF membrane functioned well as a support. The Al2O3/PVDF membrane with immobilized Pd/Fe NPs exhibited high efficiency in terms of dichloroacetic acid(DCAA) dechlorination. Additionally, a reaction pathway for DCAA dechlorination by Pd/Fe NPs immobilized on the Al2O3/PVDF membrane system was proposed.     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.     

人工合成铁、铝矿物和镁铝双金属氧化物对土壤砷的钝化效应

应用室内模拟培养的方法,研究了人工合成铁、铝矿物和镁铝双金属氧化物对砷超标土壤中砷的钝化效果.每种钝化剂均设置0.1％、0.5％、1.0％、2.5％和5.0％五个添加量处理.结果表明,添加水铝矿明显降低了土壤pH值,其中,添加5％水铝矿的处理降幅最大,达到1.20;而添加镁铝双金属氧化物则显著提高了土壤pH值,5％镁铝双金属氧化物的处理土壤pH值由5.04最高可提高至8.09.添加铁铝矿物均降低了土壤有效砷的含量,下降幅度为1.89％～64.15％;而添加镁铝双金属氧化物则使土壤有效砷含量增加;添加水铁矿和针铁矿处理对提高土壤中残留态砷含量的作用较为明显.总体看来,两种人工合成铁矿较镁铝双金属氧化物和水铝矿对土壤中砷有更好的钝化效果,可以作为钝化剂应用于土壤中砷的钝化.     

纳米Fe0粒子对产乙烯脱卤菌群脱氯性能和多样性影响研究

为探讨纳米Fe0粒子对产乙烯脱卤菌群脱氯性能和物种多样性的影响,采用纳米Fe0粒子与产乙烯脱卤菌群联合脱氯,并通过气相色谱、PCR-DGGE和TEM等技术手段进行相关表征.结果表明:当纳米Fe0粒子浓度为0~0.50 g·L-1时,体系的脱氯速率提高较小,低于40%,且菌种数量无明显变化;当其浓度为0.50~1.00 g·L-1时,体系的脱氯速率由0.31μmol·h-1提高到0.77μmol·h-1,体系的脱氯速率提高了60%,部分DGGE条带消失,多样性减少.TEM结果显示,产乙烯脱卤拟球菌在与纳米Fe0粒子接触部位有轻度破损,但细胞没有破裂.纳米Fe0粒子浓度较高时对产乙烯脱卤菌群的脱氯有明显的促进作用,但会使产乙烯脱卤菌群物种多样性减少.