Synthesis of nitrogen-doped carbon nanotubes-FePO4 composite from phosphate residue and its application as effective Fenton-like catalyst for dye degradation

Phosphate residue is regarded as a hazardous waste, which could potentially create significant environmental and health problems if it is not properly treated and disposed of. In this study, nitrogen-doped carbon nanotubes-FePO_4(NCNTs-FePO_4) composite was successfully synthesized from phosphate residue, and its application as an effective catalyst was explored. Firstly, an effective method was developed to recover FePO_4 from phosphate residue, achieving an impressive FePO_4 mass recovery rate of 98.14%. Then, the NCNTsFePO_4 catalyst was synthesized from the recovered FePO_4 by two main reactions, including surface modification and chemical vapor deposition. Finally, the synthesized NCNTs-FePO_4 was applied to photo-degrade 15 mg/L Rhodamine B(RhB) in a Fenton-like system. The results showed that 98.9% of RhB could be degraded in 60 min, closely following the pseudofirst-order kinetics model. It was found that even after six consecutive cycles, NCNTs-FePO_4 still retained a high catalytic capacity(50%). Moreover, ·OH radicals participating in the RhB degradation process were evidenced using quenching experiments and electron paramagnetic resonance analysis, and a rational mechanism was proposed. It was demonstrated that the materials synthesized from hazardous phosphate residue can be used as an effective catalyst for dye removal.     

纳米过氧化钙对地下水中硝基苯的类-Fenton降解效果

为了探究基于纳米过氧化钙（CaO₂）的类芬顿氧化技术（Modified Fenton,MF）修复污染地下水的可行性,本研究先对纳米CaO₂制备方法进行改进,制备出有效含量高达88.35%的纳米CaO₂粉末;其次,通过分析静态试验中反应体系的pH值、DO以及硝基苯浓度变化,探究纳米CaO₂降解硝基苯的过程和影响因素,确定了硝基苯的降解动力学和最佳反应条件;通过掩蔽实验探究不同自由基的作用效力;最后进行一维模拟柱动态模拟,综合分析评估纳米CaO₂去除硝基苯的机理和效果.结果表明：CaO₂投加量、EDTA-Fe²⁺浓度与硝基苯初始物质的量浓度满足48：8：1时降解效果最佳,其降解曲线符合一级动力学曲线,且反应过程中起主要降解作用的自由基是·OH,但降解效果会受到HCO₃^-、SO₄^2-、Ca²⁺、Mg²⁺等离子的影响;一维模拟柱的模拟结果表明,在存在适量铁的条件下,纳米CaO₂可以作为过氧化氢缓释剂,通过类芬顿催化产生自由基降解污染物,这说明纳米CaO₂在场地修复中具有较好的应用前景.     

Fe3O4-nZVI类Fenton法降解水中磺胺甲恶唑

采用共沉淀和液相还原两步法制得四氧化三铁负载纳米零价铁(Fe₃O₄-nZVI),将其作为类Fenton反应的催化剂用于水中磺胺甲恶唑(SMX)的降解.通过批实验法研究了H₂O₂浓度、Fe₃O₄-nZVI投加量、pH值、SMX初始浓度、反应温度等因素对SMX降解的影响.SEM、EDS、XRD和XPS表征结果表明,制备的Fe₃O₄-nZVI为纳米级磁性复合材料.批实验结果表明,在一定实验条件范围内,提高H₂O₂浓度、Fe₃O₄-nZVI投加量和反应温度,以及降低体系pH值,均可提高SMX的降解率.动力学拟合参数表明,SMX的类Fenton催化降解符合拟一级动力学模型.在25℃时,当H₂O₂浓度为10mmol/L、Fe₃O₄-nZVI投加量为0.8g/L、pH=3、SMX初始浓度为10mg/L,SMX在180min时的降解率为99.61%.用VSM测得Fe₃O₄-nZVI的饱和磁化强度为105.52emu/g,表明其易于磁回收.重复利用实验表明,Fe₃O₄-nZVI具有较好的反应活性和稳定性.自由基淬灭实验表明,·OH的氧化作用是SMX降解的主要机理.     

类芬顿试剂吸收去除气态元素汞

实验初步研究了类芬顿试剂为吸收剂对气态元素汞的脱除性能,考察了铁盐种类、pH、初始汞浓度、反应温度、卤素离子、甲酸添加量等因素对类芬顿试剂脱除气态元素汞性能的影响.结果表明,在pH 3.5条件下,以氯化铁为催化剂时,气态元素汞的脱除效率为76.4%;添加250μg.mL-1Cl-、150μg.mL-1Br-或5.0μg.mL-1甲酸均可以显著提高类芬顿反应体系对气态元素汞的脱除效果,最高脱除效率可达95%以上.     

Naval derusting wastewater containing high concentration of iron, treated in UV photo-Fenton-like oxidation

The UV photooxidation with Fe(III) and H2O2 was employed to treat a naval derusting wastewater, which contains the high COD (chemical oxygen demand) and various metal concentrations exceptionally with high concentrations of citric acid and iron. Because of its iron containment, the Fenton-like reaction automatically took place with the added amount of H2O2. The decomposition rate was found in a sequence of: UV/H2O2/Fe(III) > UV/H2O2 > Fe(II)/H2O2. Two H2O2 injection methods, single and multiple points, were evaluated. The multiple-point H2O2 injection was more e cient to decompose the citric acid. The decomposition of the synthetic citric acid and the real derusting citric acid wastewater was also compared. The 93% COD reduction of the derusting wastewater was achieved using the UV/H2O2/Fe(III) treatment.     

树脂负载FeⅢ F催化过氧化氢降解染料孔雀石绿

为强化多相类芬顿反应的速率,以氟为配体的三价铁氟化合物（FeⅢF/R）为催化剂,进行催化过氧化氢降解孔雀石绿实验.同时,探讨了初始pH值、温度、过氧化氢初始浓度和孔雀石绿初始浓度等对反应速率的影响.结果表明,与FeⅢ/R相比,催化剂FeⅢF/R具有更强的催化活性,能强化羟基自由基（OH· ）的产生.反应的最佳pH值为6.0;反应速率常数与过氧化氢和孔雀石绿（MG）的初始浓度呈正相关;温度越高,反应速率越快,反应遵循假一级反应动力学,反应活化能为89.30 kJ· mol-1.催化剂重复使用表明,铁在树脂表面负载比较牢固,具有较好的稳定性和耐用性.     

掺氮Ta2O5诱发可见光-类Fenton体系降解阿特拉津研究

通过制备具有强可见光吸收和活性的半导体掺氮Ta2O5,利用其可见光Fe3+还原活性,实现了可见光-类Fenton体系有效地降解阿特拉津.结果表明,氨气流量0.3 L.min-1、700℃氮化时间6 h制备出的掺氮Ta2O5在可见光下还原Fe3+的能力最佳;阿特拉津降解效果与各种操作条件———光强、催化剂投加量、Fe3+、H2O2、阿特拉津初始浓度及pH值有关,并通过H2O2的分解揭示影响的原因.在pH为2.6、[atrazine]0=18 mg.L-1、[H2O2]0=2.5 mmol.L-1、[Fe3+]0=0.5 mmol.L-1、掺氮Ta2O5投加量为0.6 g.L-1、500 W氙灯照射下,反应60 min时,阿特拉津的降解率为97%.该研究为可见光-类Fenton体系降解有机污染物的实际应用提供了基础数据和理论指导.     

Magnetically recoverable Fe3O4@polydopamine nanocomposite as an excellent co-catalyst for Fe3+ reduction in advanced oxidation processes

Advanced oxidation processes are widely applied to removal of persistent toxic substances from wastewater by hydroxyl radicals(·OH),which is generated from hydrogen peroxide(H_2O_2) decomposition.However,their practical applications have been hampered by many strict conditions,such as iron sludge,rigid pH condition,large doses of hydrogen peroxide and Fe~(2+),etc.Herein,a magnetically recyclable Fe_3O_4@polydopamine(Fe_3O_4@PDA) coreshell nanocomposite was fabricated.As an excellent reducing agent,it can convert Fe~(3+)to Fe~(2+).Combined with the coordination of polydopamine and ferric ions,the production of iron sludge is inhibited.The minimum concentration of hydrogen peroxide(0.2 mmol/L and Fe~(2+)(0.18 mmol/L)) is 150-fold and 100-fold lower than that of previous reports,respectively.It also exhibits excellent degradation performance over a wide pH range from 3.0 to 9.0.Even after the tenth recycling,it still achieves over 99% degradation efficiency with the total organic carbon degradation rate of 80%,which is environmentally benign and has a large economic advantage.This discovery paves a way for extensive practical application of advanced oxidation processes,especially in environmental remediation.     

Fe3O4/CeO2-H2O2非均相类Fenton体系下降解TCE的研究

采用浸渍法成功合成了新型催化剂纳米Fe3O4/CeO_2,并且用Fe3O4/CeO_2-H_2O_2非均相Fenton体系对TCE进行降解研究,考察了初始pH、H_2O_2浓度、温度及催化剂投加量等因素对于TCE降解效率的影响.实验结果表明,Fe3O4/CeO_2-H_2O_2非均相Fenton体系对TCE具有较好的去除效果:在初始pH=3,温度50℃,H_2O_2浓度30 mmol·L-1和Fe3O4/CeO_2投加量0.5 mg·L-1时,TCE去除率高达97.29%.同时实验结果表明pH在2~7范围内对TCE均有降解效果,所以相对于传统Fenton体系,该体系拥有更宽pH应用范围.目标污染物的降解符合一级动力学,反应活化能为30.77 k J·mol-1,表明反应易于进行.     

New Fe-immobilized natural bentonite plate used as photo-Fenton catalyst for organic pollutant degradation

Novel photo-Fenton catalysts were prepared by immobilizing iron species on commercial bentonite plates via two methods: (1) ion exchange reaction (Fe³⁺ vs. Na⁺) by aqueous suspension powder-clay/FeCl₃ followed by plate preparation, and (2) forced hydrolysis of Fe(NO₃)₃ onto a prefabricated clay plate. The last method led to a more photo-active Fe-oxide/bentonite plate. This material allowed, at a non-adjusted initial pH of 5.5 and in the presence of H₂O₂, the total degradation of resorcinol and 55% mineralization in 80 and 100 min of irradiation, respectively. The reached degradation percentages were correlated to the presence of dissolved iron, demonstrating that in these processes, the homogeneous photo-Fenton reactions were mainly responsible for the resorcinol elimination.Likewise, in slurry system, where clay has normally an increased surface area, there was no increase in activity because of a reduced leached iron probably due to the diminished light penetration in the suspension. Despite the lower surface area, in comparison to that of the slurry, the clay plates have the advantage, as heterogeneous photo-catalysts, that separation of the reaction media after treatment is not needed, and thus, a potential use for batch and continuous reaction systems is proposed.