TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应

以内分泌干扰物阿特拉津为模型污染物,研究了TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应.结果表明,在H2O2存在条件下,金红石TiO2经可见光激发可持续稳定地产生.OH自由基,在Fe3+协同作用下,.OH自由基生成量急剧增加;TiO2能可见光催化H2O2降解阿特拉津,金红石TiO2显示出较锐钛矿TiO2及混晶TiO2(TiO2P25)更高的催化活性,反应60 min,阿特拉津的降解率可达40%;以Fe3+协同TiO2可见光催化H2O2降解阿特拉津时,反应效率显著加快,反应5 min即对阿特拉津的降解率达到100%,而金红石TiO2显示出更为明显的协同效应.     

Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.     

Photocatalytic degradation of phenanthrene on soil surfaces in the presence of nanometer anatase TiO2 under UV-light

The effect of nanometer anatase TiO₂ was investigated on the photocatalytic degradation of phenanthrene on soil surfaces under a variety of conditions. After being spiked with phenanthrene, soil samples loaded with different amounts of TiO₂ (0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, and 4 wt.%) were exposed to UV-light irradiation for 25 hr. The results indicated that the photocatalytic degradation of phenanthrene followed the pseudo first-order kinetics. TiO₂ significantly accelerated the degradation of phenanthrene with the half-life reduced from 45.90 to 31.36 hr for TiO₂ loading of 0 wt.% and 4 wt.%, respectively. In addition, the effects of H₂O₂, light intensity and humic acid on the degradation of phenanthrene were investigated. The degradation of phenanthrene increased with the concentration of H₂O₂, light intensity and the concentration of humic acids. It has been demonstrated that the photocatalytic method in the presence of nanometer anatase TiO₂ was a very promising technology for the treatments of soil polluted with organic substances in the future.     

钯掺TiO2光催化降解全氟辛酸

全氟辛酸(perfluorooctanoic acid,PFOA)以其分布广泛性、生物蓄积性、生物毒性强而成为全球关注的一种新型持久性有机污染物.采用化学还原法制备钯掺二氧化钛(Pd-Ti O2)催化剂,利用XRD、FESEM、UV-vis DRS对催化剂进行表征,并考察其在365 nm紫外光照射下对PFOA的光催化降解效果.结果表明,化学还原的制备方法使Ti O2粒径减小、比表面积增大且对紫外光的吸收性能增大,但并不引起PFOA光催化效果的改变.而Pd掺杂后大大增强了PFOA的降解效果,反应7 h后溶液中氟离子浓度为6.62 mg·L-1,是Ti O2(P25)的7.3倍.投加俘获剂与通入氮气的实验证明,在PFOA的降解过程中·OH起重要作用,氧气的存在可促进PFOA的降解.采用UPLC-QTOF-MS对产物进行鉴定分析,PFOA的可能降解过程是经h+氧化后发生脱羧基反应,产生的全氟烷烃自由基(·CnF2n+1)被·OH氧化,脱氟生成短链全氟羧酸.Pd能作为电子(e-)捕获剂、加速e-向O2等电子受体的转移,从而缓解e-累积,提高对PFOA的降解效果.     

2,4,4'-三溴联苯醚的光降解研究

以固相微萃取(SPME)结合气相色谱(GC)、气相色谱-质谱联用(GC/MS)技术作为分析检测手段,研究光源、有机溶剂、无机盐与腐殖酸对BDE-28光降解的影响,实验结果表明,光源是影响其降解的主要因素,其次,丙酮、铜离子和腐殖酸对其降解的影响较显著.光源对BDE-28光降解速率的影响为300 W汞灯500 W金卤灯100 W汞灯500 W氙灯;有机溶剂对BDE-28降解速率的影响为甲醇/水(1∶1)甲醇己烷甲苯乙腈丙酮;无机离子的影响各有差别:K+、Na+、SO2-4、NO-3、Cl-对BDE-28降解影响不明显,而Fe3+、NH+4促进BDE-28的降解,Fe2+、Cu2+、Br-抑制BDE-28的降解;腐殖酸抑制BDE-28的降解.     

TiO2光催化降解PFOA的反应动力学及机制研究

全氟辛酸(PFOA)是一种新的持久性有机污染物,其处置技术是研究的热点.以UV254 nm紫外灯为光源,采用商品TiO2(P25)对PFOA进行光催化降解实验,并考察pH、TiO2用量、初始浓度、反应气氛对降解的影响.结果表明,反应符合准一级动力学方程,pH对反应有重要影响,氧气存在下能提高反应效率.在pH为3,TiO2用量为1.5 g·L-1,通入空气条件下反应7 h实现基本降解,速率常数为0.4206 h-1.投加俘获剂实验表明,空穴(h+)是主要的活性物质,其对反应速率贡献率为66.1%;羟基自由基(·OH)也参与PFOA的降解过程;投加NaF实验表明,PFOA在TiO2上吸附是反应发生的首要条件.UPLC-QTOF/MS分析表明,PFOA光催化降解逐级生成短链全氟羧酸(PFCAs).     

莠去津降解菌HB-5的最佳产酶培养基及发酵条件

从农药厂废水中分离到一株降解莠去滓的节杆菌(Arthrobacter sp.)HB-5,以从该菌中提取到的降解酶对莠去津的降解率为指标,进行最佳产酶培养基及发酵条件的优化研究,对其产酶量进行了评价.通过正交试验和均匀试验,对细菌HB-5的发酵培养基进行了优化研究.运用SAS软件进行结果分析,所获优化培养基配方为:蔗糖3.0g·L-1,莠去津0.38g·L-1,K2HPO40.5g·L-1,KH2PO41.2 g·L-1,MgSO4·7H2O 1.2g·L-1,NaCl 0.1g·L-1,微量元素溶液3.8mL·L-1.得到菌株培养的最佳优化条件为:菌株发酵液培养时间为48h.接种量为2%,发酵液初始pH值为9,250mL三角瓶中装液量为80mL经优化后,降解酶对莠去津的降解率(91.64%)比原培养基(40.67%)提高了125%.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well. Translated from Acta Scientiae Circumstantiae, 2005, 25(6): 816–820 [译自: 环境科学学报]     

铜绿假单胞菌对DBP的降解特性研究

采用小容量全萃取方法,研究了1株铜绿假单胞菌对BDP的降解特性.结果表明,该菌株对DBP具有高效降解能力,当DBP浓度为400 mg/L,投菌量为2 g/L时,t_1/2为3.60　d;其降解过程完全符合一级反应动力学.DBP作为该菌生长的唯一碳源时,其降解过程包括快速生物吸附、解析、降解等几个阶段.实验还确认了存在邻苯二甲酸单丁酯和邻苯二甲酸2种中间产物,从而验证了DBP在双加氧水解酶作用下2步水解变为邻苯二甲酸的历程.     

活性炭负载纳米TiO2对腐殖酸光催化降解动力学

采用溶胶-凝胶法制备了以颗粒活性炭(GAC)为载体的纳米TiO2/AC复合催化剂,并将其用于腐殖酸的光催化降解.动力学研究表明,TiO2/AC光催化降解腐殖酸过程可用Langmuir-Hinshelwood(L-H)动力学模式表示.L-H表观反应速率常数KLH=0.1124mg·L-·1min-1,吸附平衡常数K*=0.3402L·mg-1.活性炭负载TiO2对腐殖酸的光催化降解过程,体现了活性炭与TiO2的协同作用,活性炭的吸附作用提高了光催化反应速率.     

Adsorptive behaviors of humic acid onto freshly prepared hydrous manganese dioxides

This study focused on the adsorptive behaviors of humic acid onto freshly prepared hydrous MnO₂(s) (δMnO₂), and investigated the feasibility of employing δMnO₂ for humic acid removal from drinking water. Effects of such parameters as molecular mass of humic acid, kinds of divalent cations on adsorptive behaviors and possible mechanisms involved were investigated. This study indicated that humic acid with higher molecular mass exhibited more tendency of adsorbing onto δMnO₂ than that with lower molecular mass. Ca²⁺ facilitated more humic acid adsorption than Mg²⁺; UV-Vis spectra analysis indicated higher capabilities of Ca²⁺ coordinating with acidic functional groups of humic acid than that of Mg²⁺. Additionally, ζ potential characterization indicated that Ca²⁺ showed higher potential of increasing gz potential of δMnO₂ than Mg²⁺. Ca²⁺ of 1.0 mmol/L increased ζ potential of δMnO₂ from −37 mV (pH 7.9) to +7 mV (pH 7.2), while 1.0 mmol/L Mg²⁺ increased to lower value as −9 mV (pH 6.5), correspondingly. Fourier transform infrared (FTIR) spectra demonstrated the adsorption of humic acid onto δMnO₂, showing the important roles of-COO⁻ functional groups and surface Mn-OH in the adsorption of humic acid onto δMnO₂. Translated from Acta Scientiae Circumstantiae, 2005, 25(3): 351–355 [译自: 环境科学学报]     

玻璃载体TiO2薄层光催化降解久效磷农药

研究了利用TiO₂薄层光催化降解久效磷农药的可行性。结果表明,0.65×10-4mol/L的久效磷经375W中压汞灯照射60min,被完全光催化降解至PO₄3-;加入微量的Fe3++或H2O2可提高久效磷农药的光解率;另外还研究了TiO₂薄层的附着量、反应液初始pH值、空气流量等因素对光催化降解的影响。光照80 h,TiO₂的光催化活性没有减弱,可连续使用。      

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.     

腐殖酸对NH+4-N在饱和含水层中迁移的影响

通过等温吸附实验,研究了有和无腐殖酸2种情况下,NH 4＋-N在石英砂上的等温吸附过程,并运用Langmuir方程和Freundlich方程进行了拟合,计算了不同条件下NH 4＋-N在石英砂上的最大吸附量;通过室内土柱模拟实验,测定了不同时间内土柱出水中的NH 4＋-N、NO 3--N和NO 2--N的含量,分析了腐殖酸在饱和含水层中对水中NH 4＋-N迁移转化的影响,并运用伪二级动力学方程和二阶段吸附速率方程对动力学过程进行了拟合.结果表明,Langmuir方程和Freundlich方程均能很好地描述NH 4＋-N的等温吸附过程;腐殖酸的存在增加了石英砂对NH 4＋-N的吸附量,无腐殖酸时NH 4＋-N最大吸附量为0.205mg.g-1,有腐殖酸时NH 4＋-N最大吸附量为0.354 mg.g-1.室内土柱实验结果表明,在实验前期,腐殖酸通过增加吸附空间而增大了NH 4＋-N吸附量;当吸附饱和后,腐殖酸可能为硝化细菌等微生物提供碳源和能量,参与NH 4＋-N转化为NO 3--N和NO 2--N的化学反应,使有腐殖酸条件下的NH 4＋-N出水浓度始终低于无腐殖酸条件.伪二级动力学方程和二阶段吸附速率方程均能很好地描述NH 4＋-N的吸附过程（无腐殖酸条件下R2=0.992 3,R2=0.994 4;有腐殖酸条件下R2=0.997 7,R2=0.998 1）,推测石英砂对NH 4＋-N的吸附属于化学吸附过程;通过比较二阶段吸附速率常数k3（有、无腐殖酸时分别为0.247和0.143）和k4（有、无腐殖酸时分别为0.006 27和0.001 7）,发现NH 4＋-N的吸附主要表现为第一阶段吸附,不定向地吸附在石英砂表面的活性点位上,且腐殖酸的存在使NH 4＋-N的平衡吸附量qe增大.     

丙酮活化过一硫酸盐性能及非自由基机制

利用丙酮活化过一硫酸盐(Peroxymonosulfate,PMS)氧化降解酸性橙7(AO7),考察了丙酮投加量、PMS浓度、初始pH值及共存阴离子等反应条件对AO7氧化降解的影响,探讨了丙酮/PMS反应体系中的反应机制.结果表明,当初始p H为9.0、n(PMS)/n(AO7)为17.5∶1、丙酮投加量为10 mmol·L-1时,反应30 min可使AO7的降解率达到99.8%.在丙酮/PMS的活化体系中,随着丙酮投加量、PMS浓度和p H的升高,AO7的降解率也逐渐增大,碱性条件下最有利于AO7的降解.自由基淬灭实验分析表明,单线态氧(1O2)是氧化降解AO7的主要活性物种.Cl-、CO2-3对丙酮/PMS体系中AO7的降解有促进作用,离子浓度越高,AO7降解速率越快,腐殖酸(HA)的加入对AO7的降解有轻微的抑制作用.紫外可见光谱分析表明,AO7分子中的偶氮键及萘环结构被破坏,从而得到降解.     

UVA/Fe3O4活化过硫酸盐降解阿特拉津

为了解SO₄-·（硫酸根自由基）对阿特拉津的降解能力,以Fe₃O₄为K₂S₂O₈活化试剂,以阿特拉津为研究目标污染物,运用UVA/Fe₃O₄/K₂S₂O₈体系系统探讨阿特拉津在不同环境因素下的降解过程,并对催化剂的稳定性和重复利用进行了考察.结果表明:UVA/Fe₃O₄可以有效活化K₂S₂O₈来降解阿特拉津,最佳c（K₂S₂O₈）为1 mmol/L,反应6 h阿特拉津降解率可达到90%.淬灭试验表明,SO₄-·是该体系中的主要活性物种,贡献率约为96%;HO·的作用比较弱.初始pH为3时,阿特拉津6 h的降解率为98%,总铁的溶出量达到0.9 mg/L;而初始pH为7时,体系对阿特拉津的降解率达到85%,基本没有总铁的溶出,表现出了一定的稳定性.在腐殖酸存在的条件下,UVA/Fe₃O₄/K₂S₂O₈体系对阿特拉津的降解效果优于UVA/Fe₃O₄/H₂O₂体系.对Fe₃O₄催化剂进行3次循环测试,阿特拉津的降解率分别为90%、89%和86%.研究显示,UVA/Fe₃O₄能用于活化K₂S₂O₈的高级氧化体系中,可有效降解除草剂阿特拉津.      

利用热活化过硫酸盐技术去除阿特拉津

利用热活化过硫酸盐(S2O2-8)技术去除水中的阿特拉津(ATZ).结果表明,增加溶液中S2O2-8浓度或提高溶液反应温度,可加速ATZ的降解.ATZ的降解是一个二级反应,其速率和溶液中ATZ和S2O2-8的浓度都成正比.初始pH为3.0~10.0时,S2O2-8对ATZ都有很好的降解效果,在酸性和中性时,降解效率高于碱性条件.利用自由基探针发现,在酸性和中性条件下,起降解作用的主要是SO·-4,而碱性条件下OH·占主导.ATZ的降解受到Cl-、CO2-3和腐殖质(HA)的影响.其中,Cl-对反应的影响比较复杂,低浓度时Cl-会生成具有高氧化还原电位的Cl·促进ATZ的降解,而高浓度时Cl·会继续反应生成氧化能力相对较弱的Cl2·-,从而抑制反应的进行.HA和CO2-3都对反应有明显的抑制作用.     

Photocatalytic degradation of organochlorine compounds using TiO2 supported on fiberglass cloth

The feasibility of photocatalytic degradation of organochlorine compounds using TiO₂ supported on fiberglass cloth as a photocatalyst was studied. The results showed that 2.0×10^-4 mol/dm³ of dichloroethylene, trichloroethylene and tetrachloroethylene can be completely photocatalytically degraded within a short time under illumination with a 375W medium pressure mercury lamp. The effects of parameters such as illumination time, initial concentration of organochlorine compounds, amount of air flow and concentration of H₂O₂ on the photocatalytic degradation were investigated. The TiO₂ supported on the fiberglass was not easily detached and after 500h illumination there was no significant loss of photocatalytic activity of TiO₂. The passible mechanisms of photocatalytic degradation were discussed.     

光催化降解有机磷农药的研究

研究以ＴｉＯ２粉末作为光催化剂,光降解３种不同结构的有机磷农药的可行性。结果表明,有机磷农药结构不同其光降解率不同;浓度１．０×１０－４ｍｏｌ／Ｌ的４种有机磷农药,３７５Ｗ中压汞灯照射４０ｍｉｎ有机磷将完全转变为无机磷,并检测出人效磷农药催化降解的部分中间产物。研究光催化剂ＴｉＯ２的用量、空气流量、外加Ｆｅ３＋浓度对光催化降解的影响,并初步探讨了机理。     

真空紫外-亚硫酸盐法降解PFOS影响因素

通过试验,考察了亚硫酸盐浓度、pH值、全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)初始质量浓度及共存物质对真空紫外-亚硫酸盐法降解PFOS的影响.结果表明,亚硫酸盐浓度的增加有利于提高活性物种水合电子的量,PFOS降解率及脱氟率均随之提高,亚硫酸盐浓度从1 mmol·L~(-1)增加至20 mmol·L~(-1)时,PFOS降解率及脱氟率分别从45%及40%提高至97%及63%;随着原水pH值的升高,水合电子的生成量也随之增加,PFOS的降解率及脱氟率均提高,且脱氟率对pH值的变化更敏感;PFOS初始质量浓度的提高降低了PFOS的降解率及脱氟率,但PFOS的绝对降解量却大幅提高,当PFOS初始质量浓度从1 mg·L~(-1)提高至50 mg·L~(-1)时,PFOS在4 h内的降解量提高了约50倍,这主要是由于高污染物浓度条件下水合电子的利用率较高;Cl~-或HCO_3~-的存在对PFOS降解率影响较小,但对脱氟的影响较为明显,在试验研究的浓度范围内,PFOS脱氟率随Cl~-浓度的增加而提高,随HCO_3~-浓度的增加呈现先升高后降低的规律;腐殖酸的存在屏蔽了部分用于光化学反应的光,而且可以捕获体系的活性物种,从而降低了降解率及脱氟率.