Catalytic degradation of methylene blue by Fenton like system: model to the environmental reaction

To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.

Photo-Fenton和Photo-Fenton-like试剂对萘羟基化反应的影响

实验以H_2O_2,乙腈、Fe(NO_3)_3·9H_2O、FeSO_4·7H_2O,为试剂,以自制光催化反应器制备了萘酚。研究了Photo-Fenton和Photo-Fenton-like反应体系中萘的羟基化反应,考察了Fe^(2+)、Fe^(3+)浓度、H_2O_2浓度、反应时间等因素对两种反应体系的影响。对于Photo-Fenton反应体系中,在[Fe^(2+)]=1.5mmol/L、[H_2O_2]=0.8 mol/L条件下,萘的转化率达43%,1-萘酚的收率为2.8%。对于Photo-Fenton-like反应体系,在[Fe^(3+)]=4.5 mmol/L,[H_2O_2]=0.2 mol/L条件下,萘的转化率为17%,1-萘酚的收率达4.6%;同条件下[H_2O_2]提高至1.0 mol/L时,萘的转化率可达90%,但1-萘酚的收率却有所下降。

Removal of benzotriazole by heterogeneous photoelectro-Fenton like process using ZnFe_2O_4 nanoparticles as catalyst

ZnFe2O4 nanoparticles （ZFNPs） were developed as catalyst for the degradation of benzotriazole （BTA） by heterogeneous photoelectro- Fenton （PE-Fenton） like process. ZFNPs were prepared by a co-precipitation process and then characterized with transmission electron microscopy （TEM）, X-ray fluorescence （XRF）, X-ray diffraction （XRD） and BET surface area. Using such ZFNPs as catalyst, the degradation of BTA was investigated. Due to the high catalytic activity of ZFNPs, PE-Fenton like process showed efficient degradation of BTA. The influencing factors such as pH, dosage of ZFNPs, applied potential and initial concentration of BTA were systematically investigated. Under the optimum conditions, 91.2% of BTA was removed after 180 rain treatment.

Efficient decomposition of sulfamethoxazole in a novel neutral Fered-Fenton like/oxalate system based on effective heterogeneous-homogeneous iron cycle

In this study,efficient sulfamethoxazole(SMX) degradation was demonstrated in a novel neutral FeredFenton like/oxalate(electro-Fe^2+/PDS/Ox,Fered-FL/Ox) system adopting pre-anodized Ti@Ti02 cathode.Optimization of operational parameters was conducted and the whole reaction mechanism based on the critical solid-liquid interfacial reactions was explored.An efficient neutral heterogeneous-homogenous iron cyclewould exist in the Fered-FL/Ox system,depending on the formation of specific C-O-Ti bonds through the inner sphere surface complex(ISSC) of Fe(C2 O4)3^3-.It would induce ultrafast electron transfer from the cathode to the FeⅢ core,effectively accelerating the neutral Fenton-like reactions and complete mineralization of SMX with relative low dosage of ferrous catalyst and applied voltage.The result of this study is expected to supply a good alternative in treating complex neutral industrial wastewaters.

Amplification effects of magnetic field on hydroxylamine-promoted ZVI/H_(2)O_(2) near-neutral Fenton like system

This study has demonstrated an interesting amplification effect of magnetic field (MF) on the hydroxylamine (HA)-promoted zero valent iron (ZVI)/H_(2)O_(2) Fenton-like system. Sulfamethoxazole (SMX) could be efficiently degraded at near neutral pH. Conditional parameters affecting the SMX degradation in the ZVI/H_(2)O_(2)/HA/MF system, e.g., pH and the dosages of ZVI, HA and H_(2)O_(2), were investigated. Unlike the acid-favorable ZVI/H_(2)O_(2) and ZVI/H_(2)O_(2)/HA systems, the MF-assisted system exhibited good performances even at pH up to 6.0 and highest degradation rate at pH of 5.0. ^(·)OH was still identified as the responsible oxidant. A mechanism involving the MF-enhanced heterogeneous-homogeneous iron cycle was proposed in the near-neutral ZVI/H_(2)O_(2)/HA system. Without MF, HA-induced reductive dissolution of the surface iron oxides occurred and thus leaded to homogeneous Fenton reactions. After the introduction of MF, the gradient magnetic field formed on the ZVI particles would induce the generation of concentration cells of Fe(II) and local corrosion of iron. Large amounts of aqueous and bounded Fe(II) catalyzed H_(2)O_(2) to efficiently produce ^(·)OH, while HA maintained the surface and bulk cycles of Fe(II)/Fe(III). The result of study is expected to provide a green, energy-free method in improving the effectiveness of ZVI-based Fenton-like technologies at weak-acidic circumstances.

负载型三维电极-电Fenton法处理活性艳橙X-GN废水

三维电极-电Fenton法是一种在电Fenton的基础上引入三维电极电催化技术的新型高级氧化法,在水处理中得到了广泛的应用。用过量浸渍煅烧法制备负载型三维电极,以采用该电极的三维电极-Fenton法处理活性艳橙X-GN废水。通过试验研究了pH、电压、Na_(2)SO_(4)投加量、Fe^(2+)投加量对处理效果的影响,并采用响应曲面法最优化实验条件。结果表明,当试验pH=4.7,电压为20.39 V,Na_(2)SO_(4)投加量为2.13 g/L,Fe^(2+)投加量为2.5 mmol/L时,COD和色度去除率可以达到85.41%和92.18%。负载型三维电极-电Fenton法对活性艳橙X-GN废水的色度和COD均具有较理想的处理效果。

Iron-glutamate-silicotungstate ternary complex as highly active heterogeneous Fenton-like catalyst for 4-chlorophenol degradation

A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst for 4-chlorophenol（4-CP） degradation at neutral pH value. The prepared FeШGluS iW was characterized using inductively coupled plasma atomic emission spectroscopy,thermogravimetry,Fourier-transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,X-ray diffraction,and field-emission scanning electron microscopy. The results showed that FeШGluS iW has the formula [Fe（C5H8NO4）（H2O）]2SiW 12O40？13H2O,with glutamate moiety and Keggin-structured SiW 12O404- heteropolyanion. The catalyst showed high catalytic activity in 4-CP degradation in the dark and under irradiation. Under the conditions of 4-CP 100 mg/L,FeШGluS iW 1.0 g/L,H2O2 20 mmol/L,and pH = 6.5,4-CP was completely decomposed in 40 min in the dark and in 15 min under irradiation. When the reaction time was prolonged to 2 h,the corresponding total organic carbon removals under dark and irradiated conditions were ca. 27% and 72%,respectively. The high catalytic activity of FeI IIGluS iW is resulted from hydrogen bonding of H2O2 on the FeI IIGluS iW surface. The enhanced degradation of 4-CP under irradiation arises from simultaneous oxidation of 4-CP through Fenton-like and photocatalytic processes respectively catalyzed by ferric iron and the SiW 12O404- hetropolyanion in FeШGluS iW.

铜半胱胺配合物类Fenton催化降解土霉素的研究

为有效去除污染水体中的土霉素,采用水浴升温合成法制备了铜半胱胺配合物(Copper-Cysteamine-Iodine,Cu-Cy-I),并通过扫描电子显微镜(Scanning Electron Microscope,SEM)、X射线衍射(X-ray Diffraction,XRD)、X射线光电子能谱(X-ray Photoelectron Spectroscopy,XPS)等方法对其形貌、结构、化学成分进行表征。为了研究Cu-Cy-I对土霉素的降解效果,考察了光照时间、H_(2)O_(2)浓度、溶液pH值、催化剂质量、溶液的初始质量浓度以及光源等因素的影响。结果显示,在100 m L质量浓度为100 mg/L的土霉素中加入20 mg Cu-Cy-I催化剂、0.025 mol/L H_(2)O_(2),置于高压汞灯下,照射100 min后对土霉素的降解率可达99.0%。采用自由基捕获试验探究了Cu-Cy-I/H_(2)O_(2)体系中的活性自由基,发现羟基自由基(Hydroxyl radical,·OH)、超氧自由基(Superoxide radical,·O_(2)^(-))和光生空穴(Photogenerated electrons,h^(+))三者共同作用并促进土霉素的降解。Cu-Cy-I对土霉素具有较高的降解效果,为抗生素废水的治理提供了一种新方法。

多孔MnO_(2)-Fe_(3)O_(4)壳聚糖微球用于增强类Fenton降解染料废水的研究

将壳聚糖与金属盐混合溶液滴入碱性溶液中,采用一步法制备了金属壳聚糖微球(MnO_(2)-Fe_(3)O_(4)/CS),并用于刚果红(CR)的类Fenton降解。结果表明,与单金属壳聚糖微球(MnO_(2)/CS、Fe_(3)O_(4)/CS)相比,MnO_(2)-Fe_(3)O_(4)/CS具有更好的催化活性;在最佳条件下(50 mg/L CR,pH=7,0.9 mol/L H_(2)O_(2),2.0 g/L催化剂,60 min),CR的去除率达到100%。MnO_(2)-Fe_(3)O_(4)/CS的高活性归因于其较大的比表面积和孔体积,特殊多孔结构有利于反应物的吸附/扩散和活性位点的暴露;Mn-Fe双金属之间的协同作用促进了电子传递,有效提高了催化活性。金属壳聚糖微球可以很容易地从反应体系中收集,重复使用5次后仍然保持较高催化活性(88.2%)。

磺胺嘧啶和磺胺二甲基嘧啶在纳米Fe_(3)O_(4)-nZVI类Fenton体系中的降解效果

用Fe_(3)O_(4)负载纳米零价铁(Fe_(3)O_(4)-nZVI)作为非均相催化剂,与H2O_(2)耦合构建类Fenton体系,以降解水中磺胺嘧啶(SDZ)和磺胺二甲基嘧啶(SMT).通过SEM、EDS、XRD和XPS对Fe_(3)O_(4)-nZVI材料进行了表征,并考察了Fe_(3)O_(4)-nZVI类Fenton体系中H2O_(2)浓度、Fe_(3)O_(4)-nZVI投加量、初始pH及Fe_(3)O_(4)-nZVI循环使用次数对SDZ和SMT降解效果的影响.结果表明,在25℃,SDZ和SMT初始浓度均为10 mg·L^(-1),H2O_(2)浓度分别为10 mmol·L^(-1)(SDZ)和15 mmol·L^(-1)(SMT),Fe_(3)O_(4)-nZVI投加量为0.8 g·L^(-1),初始pH为3的优化条件下,在180 min时,Fe_(3)O_(4)-nZVI类Fenton体系对水中SDZ和SMT的降解率分别为97.45%和95.51%,Fe_(3)O_(4)-nZVI重复利用4次后,对SDZ和SMT的降解率仍保持在87%以上,表明该材料具有良好的磁回收利用性能.拟一级动力学拟合参数R2均在0.93以上,表明Fe_(3)O_(4)-nZVI类Fenton法对SDZ和SMT的降解过程均符合拟一级动力学方程.且在各因素最优条件下,SDZ的反应速率常数均大于SMT的反应速率常数,这可能与二者的理化性质及分子结构有关,即磺胺类抗生素(SAs)的pKa值和水溶解度越小,疏水性越强,杂环基团上的甲基取代基数目越少,SAs越容易被降解.

高炉渣非均相类Fenton降解亚甲基蓝废水

本文以高炉渣为催化剂,通过非均相类Fenton的方法降解模拟亚甲基蓝废水,在有无光照的条件下,考察了高炉渣用量、H_(2)O_(2)用量、pH、反应时间等因素对模拟废水的色度及COD去除率的影响。实验证明:有光照条件下的去除效果均优于无光照,光照条件下该体系最佳条件为:pH=3,高炉渣用量为0.1 g/100 mL,H_(2)O_(2)(质量分数30%)为0.2 mL/100 mL,反应时间2 h,亚甲基蓝废水脱色率及COD去除率均达到100%。动力学研究表明:有光照条件下反应速率大于无光照条件,二者反应都更符合二级动力学模型。

以柚子皮为基底碳负载型多相Fenton-like催化剂制备及性能研究

以柚子皮为基底,采用浸渍法将合成与负载一步完成,制备出碳负载型高效多相Fenton-like催化剂,并将其应用于酸性橙Ⅱ溶液的脱色降解反应中。实验结果表明:催化剂中铁以Fe OOH形式存在,在催化剂用量为1 g/L、溶液p H为4条件下,反应30 min后酸性橙Ⅱ的脱色率达到78.5%,反应60 min后酸性橙Ⅱ的脱色率达到97.5%。加入可见光可以明显增强Fenton的反应效果,反应30 min后酸性橙Ⅱ的脱色率就达到98.5%。催化剂重复使用,酸性橙Ⅱ的脱色率差别不大,证明制备的催化剂具有良好的稳定性。

Exploitation of Fenton and Fenton-like reagents as alternative conditioners for alum sludge conditioning

The use of Fenton＇s reagent （Fe^2＋/H2O2） and Fenton-like reagents containing transition metals of Cu（Ⅱ）, Zn（Ⅱ）, Co（Ⅱ）, and Mn（Ⅱ） for an alum sludge conditioning to improve its dewaterability was investigated. The results obtained were compared with those obtained from conditioning the same alum sludge using cationic and anionic polymers. Experimental results show that Fenton＇s reagent was the best among the Fenton and Fenton-like reagents for the alum sludge conditioning. A considerable effectiveness of capillary suction time （CST） reduction efficiency of 47% can be achieved under test conditions of Fe^2＋/H2O2 = 20/125 mg/g DS （dry solid） and pH 6.0. The observation of floc-like particles after Fenton＇s reagent conditioning of alum sludge suggested that the mechanism of Fenton＇s reagent conditioning was different from that of polymer conditioning. In spite of the lower efficiency in the CST reduction of Fenton＇s reagent in alum sludge conditioning compared to that of polymer conditioning, Fenton＇s reagent offers a more environmentally safe option. Tiffs study provided an example of proactive treatment engineering, which is aimed at seeking a safe alternative to the use of polymers in sludge conditioning towards achieving a more sustainable sludge management strategy.

Enhanced Fenton,photo-Fenton and peroxidase-like activity and stability over Fe_3O_4/g-C_3N_4 nanocomposites

We prepared the Fe3O4/g‐C3N4nanoparticles(NPs)through a simple electrostatic self‐assembly method with a3:97weight ratio to investigate their Fenton,photo‐Fenton and oxidative functionalities besides photocatalytic functionality.We observed an improvement of the Fenton and photo‐Fenton activities of the Fe3O4/g‐C3N4nanocomposites.This improvement was attributed to efficient charge transfer between Fe3O4and g‐C3N4at the heterojunctions,inhibition of electron‐hole recombination,a high surface area,and stabilization of Fe3O4against leaching by the hydrophobic g‐C3N4.The obtained NPs showed a higher degradation potential for rhodamine B(RhB)dye than those of Fe3O4and g‐C3N4.As compared to photocatalysis,the efficiency of RhB degradation in the Fenton and photo‐Fenton reactions was increased by20%and90%,respectively.Additionally,the horseradish peroxidase(HRP)activity of the prepared nanomaterials was studied with3,3,5,5‐tetramethylbenzidinedihydrochloride(TMB)as a substrate.Dopamine oxidation was also examined.Results indicate that Fe3O4/g‐C3N4nanocomposites offers more efficient degradation of RhB dye in a photo‐Fenton system compared with regular photocatalytic degradation,which requires a long time.Our study also confirmed that Fe3O4/g‐C3N4nanocomposites can be used as a potential material for mimicking HRP owing to its high affinity for TMB.These findings suggest good potential for applications in biosensing and as a catalyst in oxidation reactions.

Fenton-like/生物滤池一体化反应器的构建及其特性研究

针对典型印染废水,文章以蔗糖和四氧化三铁自制的催化剂颗粒作为生物滤床中填料的一部分,构建Fenton-like/生物滤池一体化反应器。通过比较Fenton-like/生物滤池一体化反应器与分离式反应器在高级氧化预氧化阶段以及反应器出水阶段的溶解氧浓度、AO7及COD去除效率,并对Fenton-like/生物滤池一体化反应器的运行条件进行优化。研究结果表明与分离式反应器相比,一体化反应器最终出水DO浓度高出69.9%;AO7的平均去除率为96.38%,无显著差别;COD的去除率达到59.38%,高出分离式反应器19.64%。实践表明,采用一体化反应器处理印染废水,可以克服分离式反应器的缺点,能有效利用液体双氧水沿着污水的升流方向渗透到生物滤池基质的每个区域进而分解为氧气,提高DO浓度及COD去除率。

Fenton-like oxidation of azo dye in aqueous solution using magnetic Fe3O4-MnO2 nanocomposites as catalysts

In order to overcome the drawback of the low degree of separation from an aqueous solution of MnO_2, Fe_3 O_4-MnO_2 core-shell nanocomposites were used as heterogeneous Fenton-like catalysts for the removal of acid orange 7. On the basis of the catalyst characterization, the catalytic ability of the as-synthesized nanocomposites was examined. The results showed that Fe304-Mn02 core-shell nanocomposites had greater catalytic ability than Fe_3 O_4 or MnO_2 used alone. Meanwhile, the catalyst dosage, H_2 O_2 dosage, temperature, and initial pH had significant effects on the removal of acid orange 7. A high degree of stability and reusability were exhibited by Fe_3 O_4-MnO_2 core-shell nanocomposites. Both HO· and HO_2· were generated in the reaction and HO· was the main radical for the removal of acid orange 7. A mechanism for H_2 O_2 catalytic decomposition using Fe_3 O_4-MnO_2 core-shell nanocomposites to produce HO·is proposed.

三维电极电Fenton处理阿奇霉素制药废水研究

以钛涂钌铱电极(RuO_(2)-IrO_(2)/Ti)为阳极,石墨为阴极,活性炭为粒子电极构建三维电极电Fenton体系,研究三维电极电Fenton处理阿奇霉素制药废水的影响因素,系统性考察活性炭粒子电极类型及投加量对处理效果的影响,并通过改变极板间距、pH、曝气强度、电解电压、反应时间等因素,确定最佳反应条件。进一步通过正交实验比较各因素影响程度大小,优化三维电极电Fenton处理阿奇霉素制药废水实验条件。结果表明,以3 mm柱碳作为粒子电极,当其投加质量浓度为100 g/L时,最佳工艺条件为pH=3、电解电压15 V、曝气强度1.0 L/min、极板间距7 cm、反应时间2 h。此条件下,废水COD平均去除率为72.28%,B/C由初始的0.086上升至0.312,处理效果达最优。此外,各因素对于三维电极电Fenton处理阿奇霉素制药废水效果的影响程度为pH>曝气强度>电解电压>反应时间>极板间距。

Reactive species in resin supported heterogeneous Fenton-like oxidation of Malachite green solution

During the oxidative degradation of nonbiodegradable Malachite green (MG) by means of H2O2 /FeIIIR (iron supported on ion-exchage resin) in a dynamic column,the binding energy of the Fe(2p3/2) region for XPS spectra was found to be different between the top layer and the bottom layer in this column. Based on the data from XPS spectra and DMPO-OH·signal by EPR spectra,it is shown that the formation of ferryl (IV) is the key step for the oxidation of MG. The ferryl (IV) species can oxidize MG,and its redox potential is about 0. 739 - 0. 803 V measured by cyclic voltammograms (CV) . The catalytic capability of ferryl (IV) species was also evaluated,and it is found that it can promote the decomposition of H2O2 more efficiently than ferric iron. The removal rate of MG mainly depends on the adsorption of catalyst. Both ferryl (IV) and HO·radicals are the reactive species in the system. The oxidation of HO·is only a small part of the overall removal rate. Based on the obtained results,a possible mechanism for a resin-supported Fenton-like oxidation reaction is proposed.

紫外光引发Fenton氧化技术协同去除造纸中段废水COD_(Cr)的性能研究

对紫外光引发Fenton氧化技术协同处理造纸中段废水COD_(Cr)进行了研究,探究反应时间、FeSO_(4)·7H_(2)O浓度、H_(2)O_(2)浓度、pH值、紫外光强度等因素对COD_(Cr)去除效率的影响。实验结果表明,在反应时间80min,FeSO_(4)·7H_(2)O浓度0.6 mol/L,H_(2)O_(2)浓度0.3 mol/L,pH值为4,以及紫外光强度为14 mW/cm^(2)的最优条件下,该技术能够实现造纸中段废水74%的COD_(Cr)去除率。紫外光引发Fenton氧化技术能够有效促进Fenton氧化反应中·OH自由基的生成,提高造纸中段废水的COD_(Cr)去除效率。

原位生长孤立铁4A-Fe/聚醚砜复合膜的制备及其类Fenton降解苯酚性能

将膜分离与Fenton氧化技术结合,旨在实现有机废水的高效降解和催化剂的连续再利用.采用非溶剂致相分离法制备4A沸石/PES混合基质膜,通过浸渍法在4A沸石表面原位生长孤立铁物种,制备了4A-Fe/PES复合膜.利用SEM、FTIR、XPS等手段对膜形貌和结构进行详细表征.探究该膜在静态和动态条件下对苯酚的降解性能,并比较4A-Fe催化剂在粉末和膜形态下对H_(2)O_(2)分解的影响.结果表明,孤立铁的原位生长使沸石表面粗糙.动态条件下的降解效率显著高于静态,在pH值为2、H_(2)O_(2)添加量为31.6mmol/L、苯酚浓度为200mg/L条件下,仅1min内降解率可达96.1%.催化动力学显示,在pH值为2时,膜态降解速率是粉末态的56倍.经过5次循环,该膜对苯酚的降解率仍保持在90%以上.