Replacement of H2O2 by O2 in Fenton and photo-Fenton reactions

The consumption of oxygen during the degradation of aniline by Fenton and photo-Fenton reactions is studied. The effect that parameters like aniline, Fe(II) and H2O2 initial concentration, pH, temperature and O2 flow rate have on the ratio O2 consumed/H2O2 consumed is examined. The determination of those combinations of experimental conditions for which an effective partial replacement of H2O2 by O2 as electron acceptor takes place is investigated. The results show that this replacement takes place in a variable extent, but the presence of H2O2 is necessary along the reaction, and the maximum consumption of O2 only takes place when the ratio amount of aniline mineralized vs. initial aniline concentration is minimal.     

臭氧-二氧化钛光催化技术脱除硫化氢

在连续性反应器内以臭氧-光催化技术氧化硫化氢,证实了臭氧对光催化脱除硫化氢有促进作用,探讨了可能存在的主要基元反应和二氧化钛失活的原因,考察了反应温度、臭氧含量、硫化氢初始体积分数等因素对臭氧-光催化技术脱除硫化氢的影响。结果表明,臭氧在光催化作用下快速分解为活性氧离子或自由基,硫化氢在臭氧和光催化联合作用下快速氧化为二氧化硫,最终转化为硫酸;硫酸在二氧化钛表面的沉积使其催化活性降低,导致硫化氢和二氧化硫的转化率逐渐下降。研究还发现,当硫化氢的初始体积分数为100×10-6时,臭氧和硫化氢的最佳摩尔比约为2:1;臭氧-光催化脱除硫化氢的最佳温度为70℃左右;降低硫化氢的初始体积分数可大幅度降低二氧化硫的选择性。     

Fe3O4/ZrO2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解

以浸渍法制备的新型纳米Fe3O4/ZrO2为催化剂,3,4-二氯三氟甲苯(3,4-DCBTE)为目标污染物,用Fe3O4/ZrO2-H2O2非均相类Fenton体系对目标污染物进行降解,考察催化剂的催化效果和温度、pH、H2O2投加量和掺杂比等因素对催化剂催化效果的影响。结果表明,以纳米Fe3O4/ZrO2作为催化剂的非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;随着温度的升高,纳米Fe3O4/ZrO2的催化效果不断提高;当pH降低时,催化剂的催化效果有明显提升,原始pH(pH=5.7)时反应去除效果最佳,去除率可达88.6%;催化剂用量的增加同样可以提高3,4-二氯三氟甲苯的降解效率;催化剂中Fe3O4:ZrO2的物质的量比为1:2时效果较其他掺杂比的催化剂效果更好,去除率最终可以达到96.82%;当H2O2投加量增加时,3,4-二氯三氟甲苯的降解效率先提高后降低,投加量为0.3 mL时去除效果最好,几乎可以完全去除目标有机物。以Fe3O4/ZrO2-H2O2非均相类Fenton体系处理3,4-二氯三氟甲苯时,目标污染物的降解符合一级反应动力学。     

Efficient use of Fe metal as an electron transfer agent in a heterogeneous Fenton system based on Fe0/Fe3O4 composites

In this work a novel heterogeneous Fenton system based on Fe(0)/Fe3O4 composites is described. The composites with several Fe(0)/Fe3O4 ratios were prepared by two different methods, i.e. mechanical alloying of Fe(0) and Fe3O4 powders and controlled reduction of Fe3O4 with H2. Reaction studies and detailed Conversion Electron M?ssbauer surface characterization of the composites Fe(0)/Fe3O4, Fe(0), Fe3O4, alpha-Fe2O3 and gamma-Fe2O3 suggested that Fe2+surf species are essential to produce an active Fenton system. Kinetic studies for the oxidation of the dye methylene blue, used as an organic model molecule, and for the peroxide decomposition suggest that the reactions proceed via HO* radicals generated from Fe2+surf species and H2O2 in a Fenton like mechanism. The increase in activity caused by the addition of Fe(0) is discussed in terms of a creation of Fe2+surf species during the preparation of the composite and by an electron transfer mechanism from Fe(0) to Fe3+surf during the Fenton reaction to regenerate the Fe2+surf active species.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

Kinetics of quinoline degradation by O3/UV in aqueous phase

The kinetics of quinoline degradation by O3/UV in aqueous phase was studied in this paper. It was found that the stoichiometric factor for the number of ozone molecule consumed by per quinoline molecule was 1. The second-order rate constants at 15 degrees C for the direct reaction of quinoline with ozone and that for the reaction of quinoline with *OH were determined to be 51.0 and 7.24 x 10(9) M(-1)s(-1), respectively. In O3/UV reaction system, *OH was the more important oxidant to degrade quinoline than ozone. For a comparison, in O3 reaction system, the relative importance of the two oxidants depended on the pH value greatly. To make the degradation of quinoline more practical, improvement of the concentration of *OH is more feasible.     

Modification of photocatalytic property of BaTiO3 perovskite structure by Fe2O3 nanoparticles for CO2 reduction in gas phase

In this work, perovskite structure of BaTiO₃ was coupled with Fe₂O₃ in different molar ratios achieving the best photocatalytic performance of CO₂ reduction in the presence of CH₄ as reducing agent; both of them are main greenhouse gases. The photocatalysts were synthesized by facile hydrothermal method. The samples were characterized by XRD, FTIR, FESEM, EDX, UV–Vis DRS, and photoluminescence (PL) analyses. The BaTiO₃ synthesized in this research showed a weak PL signal which is due to the intrinsic ferroelectric property as has been observed in previous reports. Compared to the pure BaTiO₃ and Fe₂O₃, the heterojunctions exhibited enhanced photocatalytic activity. The maximum CO₂ reduction under visible light irradiation was obtained to be 22% during 60 min process time. The enhanced photocatalytic activity could be attributed to the increased optical absorption, the good separation, and immigration of photogenerated charge carriers that decreased the recombination rate of charge carriers in the n–n heterojunction.

     

Fe3O4／Ag磁性纳米颗粒去除水中的铅离子

采用水相共沉淀法制备小尺寸磁性Fe3O4纳米颗粒,以没食子酸作为还原剂和表面修饰剂,还原Ag[（NH3）2]’制备出Fe3O4／Ag磁性纳米颗粒。研究该磁性纳米颗粒对水溶液中铅离子的吸附行为,研究结果表明,pH为7．0,吸附温度30℃时可得到最好的处理效果,铅的去除率可达99．7％以上,Fe3O4／Ag颗粒吸附行为符合二级动力学模型（R2〉0．99）。该磁性纳米颗粒经过多次再生处理后,仍具有很好的吸附效果,表明Fe3O4／Ag在水处理方面拥有良好的应用前景。     

聚乙烯亚胺/Fe3O4杂化磁性纳米吸附剂去除甲基橙

采用戊二醛共价交联法制备出了聚乙烯亚胺/Fe3O4杂化磁性纳米吸附剂(PEI-Fe3O4)。通过TEM、XRD、FT-IR、VSM和TGA等手段表征了材料的结构和性质。以甲基橙(MO)为吸附质,系统考察了pH值、吸附时间和染料初始浓度等因素对吸附材料性能的影响。结果表明,MO在PEI-Fe3O4上的吸附具有强烈的pH依赖性,pH为3时吸附量最大;吸附平衡仅需20 min,吸附过程符合准二级动力学模型;等温吸附过程更符合Langmuir模型,MO的最大吸附量为242.4 mg/g。重复实验表明,吸附剂经过15次吸附/解吸附循环后仍可维持最初的吸附性能,显示出良好的机械和化学稳定性。因此,该杂化吸附剂在染料废水中MO的去除方面具有良好的应用前景。     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

H2O2/Fe0、H2O2/Fe2+、H2O2/Fe3+3种体系处理印染废水

采用H2O2/Fe0、H2O2/Fe2+、H2O2/Fe3+3种体系分别对印染废水进行处理,研究pH 值、H2O2投加量、不同价态铁元素的投加量及反应时间对印染废水的COD和色度处理效果的影响。实验最佳的处理条件:H2O2/Fe0体系在pH 为3.0,Fe0投加量为3.0 mmol/L,H2O2投加量为9.0 mL/L,反应时间为40 min时,COD去除率达到95.99%,色度去除率达到100%;H2O2/Fe3+体系在pH 为3.0,Fe3+投加量为5.0 mmol/L,H2O2投加量为12.5 mL/L,反应时间为100 min时,COD去除率达到95.89%,色度去除率达到100%;H2O2/Fe2+体系在pH 为3.0,Fe2+投加量为6.0 mmol/L,H2O2投加量为12.0 mL/L,反应时间为100 min时,COD去除率达到95.85%,色度去除率达到100%。对比分析3种体系在各因素下的处理结果,H2O2/Fe0体系和H2O2/Fe3+体系都要优于H2O2/Fe2+体系,其中H2O2/Fe0体系的处理效果最好。     

铝铁电极联用电絮凝法处理Cu-EDTA络合废水

采用电絮凝法处理Cu-EDTA模拟废水,研究电极组合方式、初始pH值和氯化钠浓度3个因素对化学需氧量(COD)和Cu去除效果的影响。实验研究发现,当电极组合方式为2个铝阳极和2个铁阴极,起始pH值为3,氯化钠浓度为0.5 g/L,换极周期为40 min,反应时间为80 min时,COD去除率达到78.7%,Cu离子去除率达到99.9%。通过实验研究确定EDTA的去除机制主要是:酸性条件下的次氯酸氧化作用,碱性条件下的氢氧化物絮凝沉淀作用及单核态铝/铁与多核态铝/铁电荷中和作用,Cu的去除机制主要是氢氧化物的絮凝沉淀作用和铁电极的电沉积作用。     

Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

Temperature dependence of hydroxyl radical formation in the hv/Fe3+/H2O2 and Fe3+/H2O2 systems

The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.     

Degradation of polychlorinated dibenzo-p-dioxins in aqueous solution by Fe(II)/H2O2/UV system

The photodegradation of polychlorinated dibenzo-p-dioxins (PCDDs), which include tetra- to octa-CDDs (TeCDD, PeCDD, HxCDD, HpCDD and OCDD), was carried out in the presence of Fe(II) and H2O2 mixed reagent. The degradation efficiency was strongly influenced by UV irradiation, and the initial concentrations of H2O2 and Fe(II). An initial TeCDD concentration of 10 ng l(-1) was completely degraded within 20 min under the optimum conditions. All PCDDs tested were successfully degraded by Fe(II)/H2O2/UV treatment and complete degradation of TeCDD, PeCDD and HxCDD was achieved within 120 min. PCDD photodegradation rates decreased with the number of chlorine atoms. The degradation process of TeCDD by this system seems to be initiated by an oxidative reaction (OH* radical attack) because less chlorinated DDs as intermediate products were not detected. From the Frontier electron density calculation, the first OH* radical attack positions on TeCDD were found to be four C atoms neighboring two O atoms. The decomposition of TeCDD gave 4,5-dichlorocatechol as an intermediate product. A TeCDD degradation scheme was proposed based on the identified intermediate and the values of Frontier electron density. Based on these results, Fe(II)/H2O2/UV system could be useful technology for the treatment of wastewater containing persistent pollutants such as dioxins and polychlorinated biphenyls.     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

O3/ H2O2法对生化出水中不同种类有机物的去除效果研究

采用XAD-8/XAD-4吸附树脂联用技术将城市污水生化出水中有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,研究了O3/H2O2法对这4类有机物的去除效果.结果表明:(1)O3/H2O2法对生化出水中有机物的去除效果明显好于O3法、H2O2法.反应60 min时,O3/H2O2法对溶解有机碳(DOC)和254 nm波长处的单位比色皿光程下的紫外吸光度(UV254)的去除率分别达到49%和82%.(2)生化出水经O3/H2O2处理后,一部分疏水性有机物(疏水酸和非酸疏水物质)在反应过程中转化为亲水性有机物(弱疏水物质和亲水物质).(3)生化出水中71%的三卤甲烷生成势(THMFP)由疏水酸和亲水物质产生,特别是疏水酸,其产生的THMFP占总量的48%.反应60 min时,O3/H2O2法对疏水酸、非酸疏水物质、弱疏水物质和亲水物质产生的THMFP的去除率分别为64%、100%、88%和18%.     

EDTAD-modified cassava stalks loaded with Fe3O4: highly efficient removal of Pb2+ and Zn2+ from aqueous solution

Environmental Science and Pollution Research - In this study, a novel magnetic cassava stalk composite (M-EMCS) was prepared through modification with ethylenediamine tetraacetic anhydride (EDTAD)...