聚乙烯醇固定化的微球菌AD3对除草剂阿特拉津的生物降解

从农药厂的工业废水和污泥的混合物中分离到高效降解除草剂阿特拉津的藤黄微球菌(Micrococcusluteus)AD3菌株。以聚乙烯醇(PVA)为包埋材料进行AD3菌株的固定化,对影响固定化细胞降解阿特拉津的因素(如阿特拉津浓度、温度、pH)和操作稳定性进行了研究。结果表明,在最适条件下(30℃、pH7.2、阿特拉津浓度500mg/L)固定化细胞的阿特拉津降解速度明显高于游离细胞。固定化细胞在低温、低pH和高阿特拉津浓度条件下的阿特拉津降解率,以及贮存和操作稳定性,也明显好于游离细胞。固定化细胞在15℃、pH7.2、阿特拉津浓度为500mg/L的条件下培养72h以后,阿特拉津降解率为90%,在相同条件下游离细胞的降解率仅为35%。固定化细胞在pH5.0、30℃、阿特拉津浓度为500mg/L的条件下培养72h以后,降解率为96%,在相同条件下游离细胞的降解率仅为40%。固定化细胞能够快速降解1000mg/L的阿特拉津,而游离细胞则不能。稳定性实验表明,固定化细胞重复使用30次以后其降解活力没有明显降低。     

UV/Fe(Ⅲ)-富马酸盐体系降解对硝基苯酚

研究了在紫外光(UV)照射下,Fe(Ⅲ)-富马酸盐体系对p-硝基苯酚(PNP)的光降解反应,考察了溶液pH、Fe(Ⅲ)、富马酸盐和PNP的初始浓度对PNP降解率的影响。结果表明,UV/Fe(Ⅲ)-富马酸盐体系对PNP有光降解作用,相比于只含Fe(Ⅲ)或者富马酸盐体系,同时加入Fe(Ⅲ)与富马酸盐构成的体系在降解PNP方面有协同作用。在pH 3.0~6.0范围内,PNP的降解率随着pH和PNP初始浓度的增大而降低,而随着Fe(Ⅲ)和富马酸盐的初始浓度的增大而增大。氯仿猝灭法证实,该体系在降解PNP反应过程中产生了超氧负离子自由基;采用荧光法和异丙醇猝灭法证实了该体系在反应过程中产生了羟基自由基,同时证实了羟基自由基为PNP光降解反应的主要反应物质。     

UV,LaFeO3共活化PDS氧化降解活性黑五EI北大核心CSCD

铁酸镧(La Fe O3)属钙钛矿型氧化物,具有良好的光催化活性、磁性和化学稳定性。采用超声辅助溶剂热法,通过调节水/丙三醇混合溶剂配比合成结晶度良好、表观粒径介于200 nm～1μm的La Fe O3多孔微球,在紫外光(UV)下共激发过二硫酸盐(PDS),构建UV/La Fe O3/PDS复合体系用以降活性黑五(RB5)。结果表明：La Fe O3投加量0.5 g·L-1,PDS浓度为0.5 mmol·L-1,RB5初始浓度为20 mg·L-1,p H为初始值(p H=5.6)时,在25 W紫外灯照射下体系50 min对RB5的降解率可达98.19%。p H变化对RB5的去除率影响不大,但溶液偏酸时反应速率常数最大,碱性次之,中性最小。PDS对光生电子的捕获促进了光生电子-空穴对的分离,是光催化和PDS高级氧化产生协同作用的主要原因。1O2,SO4-·和·OH 3种活性物质共存于UV/La Fe O3/PDS体系使得RB5快速、高效降解。     

辉光放电等离子体处理阳离子染料结晶紫废水

用辉光放电等离子体技术对结晶紫进行了降解脱色处理,考察了多种因素对结晶紫降解效果的影响。实验发现,提高电解质浓度和增加电压均可提高结晶紫的脱色效果,考虑到电极损耗,辉光放电最佳条件为:电解质浓度为2 g/L Na2SO4,电压为600 V。当改变溶液的初始pH值时,结晶紫的脱色率随溶液的初始pH值升高而增加,加入一定量H2O2能明显地提高结晶紫的脱色效率;若加入0.4 mmol/L Fe2 ,5 min时结晶紫的脱色率由原来的13.64%增加到91.36%。结果表明,辉光放电产生的.OH对结晶紫的降解起重要作用。最佳条件下,40 min内的脱色率达到93%,降解率为74%。     

亚微米级Cu0/Fe3O4复合物多相催化过一硫酸盐降解有机污染物

过一硫酸盐催化活化技术因其可产生强氧化性活性氧化物种,可快速氧化降解并矿化有机污染物的优异性能而备受关注.本文成功制备了亚微米级Cu0/Fe3O4复合物,发现其能多相催化过一硫酸盐产生单线态氧降解有机污染物.首先,以CuCl2·2H2O,FeCl2·4H2O和FeCl3·6H2O为铜源和铁源,水合肼为还原剂,采用水热法在180oC反应24 h制备了亚微米级磁性Cu0/Fe3O4复合物.表征结果显示,所制材料为Cu0和Fe3O4的复合物,颗粒大小约为220 nm;单一相Cu0和Fe3O4晶体粒径分别为33.8和106.2 nm,而Cu0/Fe3O4复合物中Cu0和Fe3O4晶体粒径分别减为20.8和31.9 nm.这表明Cu0和Fe3O4复合降低了Cu0和Fe3O4晶体粒径,有利于Cu0和Fe3O4的分散.BET测试结果表明,Cu0/Fe3O4复合物比表面积为4.6 m2/g,与Cu0颗粒的(4.2 m2/g)相当,但远小于Fe3O4的(15.6 m2/g).制备的Cu0/Fe3O4复合物可有效催化过一硫酸盐产生单线态氧降解罗丹明B、亚甲基蓝、金橙II、苯酚和对氯酚.当Cu0/Fe3O4复合物的用量为0.1 g/L,过一硫酸盐浓度为0.5 mmol/L和初始pH为7时,Cu0/Fe3O4复合物可在30 min内完全降解20μmol/L的罗丹明B、亚甲基蓝、金橙II以及0.1 mmol/L的苯酚和对氯酚.对比试验显示,在相同条件下,Cu0和Fe3O4颗粒分别可以降解28%和20%的罗丹明B.这表明Cu0/Fe3O4复合物中的Cu0和Fe3O4晶体在催化过一硫酸盐降解污染物的反应中具有协同作用,这主要来源于Cu0/Fe3O4复合物中Cu0和Fe3O4的晶体粒径变小和更好的分散.采用分光光度法测定了降解反应液中铜和铁离子的溶出量.当Cu0/Fe3O4复合物的用量为0.1 g/L,过一硫酸盐浓度为0.5 mmol/L和初始pH为7时,反应60 min后,降解液中铜和铁离子的浓度分别为0.22和0.1 mg/L,仅占复合物中总铜和总铁量的1.1%和0.2%,表明Cu0/Fe3O4复合物具有较强的化学稳定性.所制Cu0/Fe3O4复合物具有超顺磁性,借助磁场实现快速分离回收,可循环利用五次,表明其优越的催化稳定性.通过加入乙醇和叠氮化钠,考察了Cu0/Fe3O4复合物催化活化过一硫酸盐体系中的活性氧化物种.发现100 mmol/L乙醇的加入对污染物的降解无明显影响,而加入同等量的叠氮化钠可完全抑制污染物的降解,表明Cu0/Fe3O4复合物催化活化过一硫酸盐产生的主要活性氧物种为单线态氧.采用电子顺磁共振谱进一步证实了单线态氧的生成.基于以上研究,Cu0/Fe3O4复合物催化活化过一硫酸盐的机理为Cu0/Fe3O4作为一个电子媒介加速过一硫酸盐和污染物之间的电子转移,从而导致污染物被快速降解.该反应机理不同于常见的金属催化过一硫酸盐产生硫酸根和羟自由基的反应机理.我们推测,电导性优良的Cu0在此催化反应中起着关键性作用.本催化方法可作为一种绿色的氧化技术用于环境污染物的氧化降解处理.     

磁性光催化剂BiVO_4/Fe_3O_4降解亚甲基蓝的研究

本文用超声法将磁基体Fe3O4与BiVO4复合,制备了易于固液分离的磁性可见光催化剂BiVO4/Fe3O4,采用X射线衍射(XRD)、透射电子显微镜(TEM)等手段对样品的结构和形貌进行表征。以亚甲基蓝为降解对象,考察了BiVO4/Fe3O4的可见光催化活性,并研究了光催化体系中光催化剂用量、亚甲基蓝初始浓度、溶液的pH值、电子受体的存在对光催化过程的影响。结果表明,催化剂的最佳用量为2.0g/L,亚甲基蓝最佳初始浓度为10mg/L,溶液的最佳pH值为11,加入电子受体K2S2O8时,亚甲基蓝几乎完全降解。催化剂回收后连续使用3次,降解率仍然大于80%。     

Fe3O4@MIL-101(Fe)类芬顿降解盐酸四环素性能研究

通过水热合成法制备了Fe₃O₄@MIL-101(Fe)复合材料。采用扫描电子显微镜、傅里叶红外光谱仪和X射线衍射仪对其表面形貌和结构进行表征;以盐酸四环素(TC)为目标污染物,考察了反应温度、H₂O₂浓度、Fe₃O₄@MIL-101(Fe)投加量和pH对TC降解的影响和在不同离子存在条件下对TC降解性能的影响进行了探讨。结果表明:Fe₃O₄@MIL-101(Fe)晶体结构完整、结晶度良好、并呈现典型的八面体结构;当TC初始浓度100 mg/L,反应温度40℃,H₂O₂浓度20 mmol/L,Fe₃O₄@MIL-101(Fe)投加量0.15 g/L,TC溶液初始pH5时,TC的降解率达到89.50%;5次循环实验后,Fe₃O₄@MIL-101(Fe)对TC的降解率仍达56.51%,具有...     

Fe~(2+)活化过硫酸钠降解日落黄的研究

通过Fe~(2+)活化Na_2S_2O_8产生强氧化性的硫酸根自由基,利用硫酸根自由基氧化降解有机污染物。以日落黄为降解目标物,通过研究有无Fe~(2+)、Na_2S_2O_8对日落黄降解率的影响,来探讨Fe~(2+)活化Na_2S_2O_8降解日落黄的可行性,并采用叔丁醇和甲醇抑制剂的方法探究了降解日落黄的作用机理。重点考察了Fe~(2+)初始浓度、Na_2S_2O_8初始浓度、柠檬酸浓度以及pH值对Fe~(2+)活化Na_2S_2O_8降解日落黄的影响。实验结果表明:在Fe~(2+)-Na_2S_2O_8体系中,日落黄初始质量浓度为30 mg/L、Fe~(2+)摩尔浓度为1.0 mmol/L、Na_2S_2O_8摩尔浓度为2.0 mmol/L、柠檬酸摩尔浓度为1.0 mmol/L、pH值为3.0的条件下,反应时间为60 min时日落黄降解率可达95.37%。     

超声波诱导紫外光协同法降解苯酚

采用功率350W、40kHz超声波器和紫外光同时对水中的苯酚进行降解,考察了样品苯酚溶液的pH及浓度、加入6%H2O2和0.001mol/LFe2 (FeSO4)的量、超声波超声功率、紫外光照射的时间、紫外-超声联用降解的时间等条件的影响。结果表明,在苯酚的最佳降解条件(紫外-超声联用下作用60min,pH3～4,加入6%的H2O24mL和0.001mol/L的Fe2 (FeSO4)1.6mL)下,苯酚的降解率达91.8%,证明超声波诱导紫外光协同法是一种降解苯酚的有效方法。     

Meso-四-（4-磺基苯基）卟啉钴/过硫酸钠-过氧化氢催化氧化降解农药敌敌畏

研究了CoTPPS4/Na2S2O8-H2O2体系(CoTPPS4:meso-四-（4-磺基苯基）卟啉钴)对农药敌敌畏(DDVP)催化氧化降解效果,探讨了氧化剂种类及比例、催化剂用量、农药初始浓度、pH值及反应温度等因素对催化降解速度的影响,并在优化条件下对降解反应的动力学进行了考察。结果表明,随着催化剂用量增加、初始农药浓度的降低、pH值升高(pH值为5～9)和温度的上升,DDVP降解速率增加。室温时,在pH=9缓冲溶液中,农药初始浓度为1.015×10-4 mol/L、CoTPPS4加入量为2.4×10-3 g时,5 mL 0.050 mol/L Na2S2O8-H2O2（体积比4∶1）混合氧化剂存在条件下,7 h后DDVP农药降解率可达72.8%,反应速率常数为0.190 h-1。降解反应动力学研究表明,CoTPPS4催化混合氧化剂降解DDVP农药为表观一级反应,反应表观活化能Ea为5.052 kJ/mol。     

Highly active nanoscale zero-valent iron (nZVI)-Fe3O4 nanocomposites for the removal of chromium(VI) from aqueous solutions

For the first time, nanoscale zero-valent iron (nZVI)-Fe(3)O(4) nanocomposites, prepared by an in situ reduction method, are employed for chromium(VI) removal in aqueous environment. 96.4% Cr(VI) could be removed by these novel materials within 2h under pH of 8.0 and initial Cr concentration of 20 mg L(-1), compared with 48.8% by bare nFe(3)O(4) and 18.8% by bare nZVI. Effects of several factors, including mass composition of nZVI-Fe(3)O(4) nanocomposites, initial pH and Cr(VI) concentration, were evaluated. The optimal ratio of nFe(3)O(4) to nZVI mass lies at 12:1 with a fixed nZVI concentration of 0.05 g L(-1). Low pH and initial Cr(VI) concentration could increase both the Cr(VI) removal efficiency and reaction rate. Corresponding reaction kinetics fitted well with the pseudo second-order adsorption model. Free energy change (ΔG) of this reaction was calculated to be -4.6 kJ mol(-1) by thermodynamic study, which confirmed its spontaneous and endothermic characteristic. The experimental data could be well described by the Langmuir and Freundlich model, and the maximum capacity (q(max)) obtained from the Langmuir model was 100 and 29.43 mg g(-1) at pH 3.0 and 8.0, respectively. The reaction mechanism was discussed in terms of the mutual benefit brought by the electron transfer from Fe(0) to Fe(3)O(4).     

Determination of surface properties of iron hydroxide-coated alumina adsorbent prepared for removal of arsenic from drinking water

A novel type adsorbent was prepared by in situ precipitation of Fe(OH)3 on the surface of activated Al2O3 as a support material. The iron content of the adsorbent was 0.31+/-0.003% m/m (56.1 mmol/g); its mechanical and chemical stability proved to be appropriate in solutions. The total capacity of the adsorbent was 0.12 mmol/g, and the pH of zero point of charge, pH(zpc) = 6.9+/-0.3. Depending on the pH of solutions, the adsorbent can be used for binding of both anions and cations, if pH(eq) < pH(zpc) anions are sorbed on the surface of adsorbent (S) through [SOH2+] and [SOH] groups. A graphical method was used for the determination of pH(iep) (isoelectric points) of the adsorbent and values of pH(iep) = 6.1+/-0.3 for As(III) and pH(iep) = 8.0+/-0.3 for As(V) ions were found. The amount of surface charged groups (Q) was about zero within the a pH range of 6.5-8.6, due to the practically neutral surface formed on the adsorption of As(V) ions. At acidic pH (pH 4.7), Q = 0.19 mol/kg was obtained. The adsorption of arsenate and arsenite ions from solutions of 0.1-0.4 mmol/L was represented by Langmuir-type isotherms. A great advantage of the adsorbent is that it can be used in adsorption columns, and low waste technology for removal of arsenic from drinking water can be developed.     

Reduction of an azo dye acid black 24 solution using synthesized nanoscale zerovalent iron particles

The strong color and high total organic carbon (TOC) of laboratory-synthesized azo dye, C.I. Acid Black 24 (AB24), solution was substantially reduced with particles of chemically synthesized nanoscale zerovalent iron (NZVI) under varied conditions of experimental variables such as NZVI dosage, initial dye concentration, and pH. From the results, the synthesized NZVI particles can effectively remove color and TOC of AB24 dye solution under certain conditions. The best removal efficiencies for color and TOC were obtained as 98.9 and 53.8%, respectively, with an initial dye concentration of 100 mg L(-1) and an NZVI dosage of 0.3348 g L(-1). Additionally, the removal rates followed an empirical rate equation with respect to the initial dye concentration as well as the NZVI dosage. The NZVI dosage addition exponentially increments the removal efficiency, with observed empirical reaction rate constants (k) of 0.046-0.603 min(-1) for added NZVI of 0.0335-0.3348 g L(-1). Moreover, the largest unit removal capacity was 609.4 mg of AB24 uptake for each gram of NZVI (i.e., 609.4 mg AB24/g NZVI). Ultimately, the ideal operation conditions were 0.1674-0.3348 g L(-1) of NZVI dosage, 15-30 min of reaction time, and pH 4-9 for 25-100 mg L(-1) of initial dye concentration.     

Keggin型杂多阴离子PW11O39Fe(III)(H2O)4-电催化降解硝基苯

以Keggin型铁取代杂多阴离子PW11O39Fe(III)(H2O)4－ (PW11Fe)代替传统电芬顿(electro-Fenton)方法中的Fe3＋作为电催化剂, 构成一个新颖的电催化体系并用于中性水溶液中硝基苯的降解. 结果表明, 含有1.0 mmol•L－1硝基苯和1.0 mmol•L－1 PW11Fe的混合磷酸盐溶液(pH 6.86), 在－0.5 V电位和60 mL•min－1 O2流速下反应100 min, 硝基苯便完全降解. 降解的准一级表观速率常数与硝基苯的初始浓度有关, 当硝基苯的初始浓度为1.0, 2.0和5.0 mmol•L－1时, kobs分别为7.18×10－2, 3.57×10－2和1.47×10－2 min－1. 降解反应100 min的TOC(有机碳总量)去除率约为35%, 表明硝基苯的降解过程伴随着矿化.     

Removal of methyl orange from aqueous solution using bentonite-supported nanoscale zero-valent iron

Zero-valent iron (ZVI) nanoparticles tend to agglomerate, resulting in a significant loss in reactivity. To address this issue, synthesized bentonite-supported nanoscale zero-valent iron (B-nZVI) was used to remove azo dye methyl orange (MO) in aqueous solution. Batch experiments show that various parameters, such as pH, initial concentration of MO, dosage, and temperature, were affected by the removal of MO. Scanning electron microscopy (SEM) confirmed that B-nZVI increased their reactivity and a decrease occurred in the aggregation of iron nanoparticles for the presence of bentonite (B). Using B-nZVI, 79.46% of MO was removed, whereas only 40.03% when using nZVI after reacting for 10 min with an initial MO concentration of 100 mg/L (pH=6.5). Furthermore, after B-nZVI reacted to MO, XRD indicated that iron oxides were formed. FTIR showed that no new bands appeared, and UV-vis demonstrated that the absorption peak of MO was degraded. Kinetics studies showed that the degradation of MO fitted well to the pseudo first-order model. A degradation mechanism is proposed, including the following: oxidation of iron, adsorption of MO to B-nZVI, formation of Fe(II)-dye complex, and cleavage of azo bond. Finally, the removal rate of MO from actual wastewater was 99.75% when utilizing B-nZVI.     

Activation of sulfite by ferric ion for the degradation of 2,4,6-tribromophenol with the addition of sulfite in batches

In this work, the removal of 2,4,6-tribromophenol (TBP) by ferric ion-activated sulfite [Fe(III)/S(IV)] process was systematically investigated with determining the intermediate products and evaluating the influences of some operational conditions and water matrices. Our results show that batching addition of S(IV) benefits the S(IV) utilization efficiency and TBP removal, with SO₄^?? being the primary reactive radical accounting for TBA degradation. The maximum TBP removal in the Fe(III)/S(IV) process was observed at pH 4.0 and oxygen is essential in this process. With increasing Fe(III) and S(IV) dosages from 0.05 and 0.1 mmol/L to 0.2 and 2.0 mmol/L, respectively, TBP removal followed trends of first increase then decrease. As the acute toxicity of the TBP solution was significantly reduced, the Fe(III)/S(IV) process was believed to be a good choice in the treatment of TBP.     

新颖的PW11O39Fe(Ⅲ)(H2O)4-/H2O2类光-Fenton体系光催化降解苯胺

将Keggin型铁取代杂多阴离子PW11O39Fe(Ⅲ)(H2O)4-[PW11Fe(Ⅲ)(H2O)]构成的类光-芬顿体系用于水体生物难降解有机污染物苯胺(ArNH2)的降解。 研究了在紫外光照射和H2O2存在下,PW11Fe(Ⅲ)(H2O)对ArNH2降解的均相光催化作用。 考察了ArNH2、H2O2和PW11Fe(Ⅲ)(H2O)浓度对光催化降解反应速率的影响。 实验结果表明,0.1 mmol/L PW11Fe(Ⅲ)(H2O)+0.2 mmol/L H2O2+0.1 mmol/L ArNH2的中性溶液在300 W汞灯照射下反应60 min,ArNH2的降解率达100%,总有机碳(TOC)去除约52%。 同时讨论了PW11Fe(Ⅲ)(H2O)光催化H2O2产生羟基自由基的分子机制,并比较了酸性和中性条件下苯胺的光催化降解效果。     

乙酰丙酮基聚苯乙烯在萃取金属离子上的应用

大孔的苯乙烯-二乙烯苯共聚物经氯甲基化后,分别与乙酰丙酮镍、乙酰丙酮钠和四正丁基乙酰丙酮铵三种不同的乙酰丙酮盐反应,可制得聚3-(p-乙烯苄基)戊二酮-[2,4]。其中以由乙酰丙酮镍制得的聚合物最好,除二乙烯苯外,78%左右的苯环乙酰丙酮化了。该聚合物螯合Fe~(3 )和Ni~(2 )的能力与β-二酮基高聚物相仿或稍优。还比较了此类高聚物的物理机械性能。     

紫外/TiO2/芬顿复合工艺增强在近中性pH值下对布洛芬的降解能力

药品及个人护理品(PPCPs)造成的潜在环境污染已引起广泛关注. 布洛芬(IBP, 2-(4-异丁基苯基)丙酸)作为苯丙酸类非甾体抗炎药物, 是一种在水环境中广泛检测到的PPCPs类物质. 水环境中的IBP主要来自制药企业排放和人体代谢物, 因IBP具有不易挥发、物理性质稳定、半衰期较长和不易被生物吸收等特点, 其在环境的残留浓度较高且污染风险大. 目前,传统的水处理工艺并不能有效治理水中的IBP, 比如: 混凝剂和絮凝剂对IBP的去除效率低, 吸附和膜处理运行成本过高且不能矿化IBP. 近年兴起的光催化技术利用·OH和O2·-等强氧化性活性物种降解水中有机污染物, 将其彻底矿化, 实现污染物的无害处理. 光催化技术适用于常温、常压和中性pH环境, 该环境特点与污水环境十分匹配, 适合应用. 但异质光催化通常发生在催化剂表面, 有效反应活性位少, 反应速率不够高. 相比而言, 同质芬顿反应能够均匀、快速地在整个溶液中发生反应, 但芬顿反应必须在酸性条件下才可以进行.本文整合了异相光催化和均相光-芬顿反应的优点, 设计了紫外/TiO2/芬顿(PCF)复合工艺, 评估了在中性pH下对典型的PPCPs布洛芬的降解效果. 对比实验结果表明, PCF复合工艺对IBP的降解速率比传统的UV, UV/H2O2, Fenton, 光-Fenton和光催化快得多. 动力学分析发现, IBP的降解遵循两阶段的一级反应动力学, 且速率常数k1> k2. 本研究进一步优化了运行参数, 确定IBP降解的最佳条件为: pH = 4.2, [Fe2+]0= 0.20 mmol/L, [Fe2+]0/[H2O2]0= 1/40, [TiO2]0= 1.0 g/L. pH值的增加造成IBP降解速率略微降低, 但在30 min反应时间内, 中性pH (6.0-8.0)与最佳pH条件下的降解效率完全相同, 证明PCF在中性pH下进行水处理切实可行. 数据分析发现, lnk1和lnk2均与1/pH0, [IBP]0, [H2O2]0, [H2O2]0/[Fe2+]0和ln[TiO2]0线性相关, 据此建立了IBP去除效率的数学预测模型, 通过验证发现, 动力学模型曲线与实验数据高度契合, 表明模型的有效性高.