2,4,6-三氯酚的UV/H2O2光化学降解

采用UV/H2O2工艺降解水中2,4,6-三氯酚(2,4,6-TCP),研究H2O2投加量、pH、阴离子、阳离子、叔丁醇和腐殖酸对降解效果的影响,并利用LC-HESI-MS-MS探讨UV/H2O2降解2,4,6-TCP的降解机理.研究结果表明:UV/H2O2降解2,4,6-TCP的过程符合拟一级反应动力学.随着H2O2投加量的增加,2,4,6-TCP的去除率和反应速率增加,当H2O2投加量为10 mmol/L时,反应速率常数K达到0.109 4 min-1.酸性条件更利于UV/H2O2降解2,4,6-TCP.水中各种离子的存在对2,4,6-TCP的光解速率有较大的影响,其中阴离子CO32-对反应均存在明显的抑制作用,阳离子Fe3+促进效果显著.2,4,6-TCP的UV/H2O2反应速率随叔丁醇浓度的增加而下降,腐殖酸在低浓度时促进反应进行,在高浓度时,2,4,6-TCP的降解受到抑制.水中2,4,6-三氯酚在UV/H2O2作用下主要发生脱氯反应,生成二氯邻二苯酚或二氯对二苯酚,未得到彻底矿化.     

氯代有机物的结构对光降解脱氯速率的影响

针对氯代有机化合物不易分解或被生物降解,而会在自然界中长时间滞留,使很多地表水和地下水受到污染的现状,研究了在紫外光/H2O2/草酸铁体系中,氯代有机物结构为光降解脱氯的规律,以及pH值对脱氯速度的影响,并探讨了光降解脱氯机理。     

Fe(Ⅲ)-草酸配合物光分解降解苯酚的研究

文章研究了Fe( )-草酸配合物在可见光及太阳光照射下,对苯酚的光解降解作用。结果表明,在pH=5.0、cFe( )=0.040mmol/L、cH2C2O4=1.44mmol/L(草酸分3次加入)及光照3h的条件下,20mg/L的苯酚的降解率为91%。溶液pH值、铁与草酸浓度比和苯酚浓度均对降解效果产生影响。     

UV/H_2O_2作用下冰中苯酚的光转化及其与羟基自由基的关系

在UV和H2O2作用下考察pH值、光强、H2O2初始浓度和无机离子等对冰中苯酚光解的影响,并利用二甲基亚砜(DMSO)捕获体系中生成的羟基自由基(·OH)研究·OH对冰中苯酚光解的影响.实验结果表明:H2O2可显著促进冰中产生·OH及苯酚光解;改变光强、pH值和H2O2的初始浓度,苯酚的光解率随体系中·OH浓度的增加而增大;加入NO-2和NO-3可抑制体系中产生·OH及苯酚光解;加入SO2-4不影响体系中·OH的产生及苯酚光解;加入CO2-3和HCO-3可抑制体系中产生·OH,但对苯酚光解影响较小,这是由于体系中产生了其他自由基所致.     

苯酚废水的光氧化降解研究

研究了UV/Fenton、日光/Fenton、UV/TiO_2和UV/Fe~(2+)等几种光氧化体系对模拟苯酚废水的氧化降解。结果表明,在上述几种光氧化体系中,UV/Fenton体系对苯酚的氧化降解能力最强,可很快地使苯酚矿化,日光/Fenton体系的降解能力次之;而UV/TiO_2与UV/Fe~(2+)体系对苯酚的降解效果较差。反应初始pH值与催化剂Fe~(2+)用量等因素对苯酚的降解均有很大影响,光Fenton反应体系中,pH值在3～4范围内,苯酚的矿化效果较佳,pH值超过此范围,矿化率则急剧下降;苯酚的矿化率随着Fe~(2+)用量的增加而逐渐增大,但当Fe~(2+)达到一定量时,再增加Fe~(2+)用量,苯酚的矿化率反而有所下降。     

Ti/α-PbO2/β-PbO2电极电催化氧化处理苯酚废水

采用电催化氧化法,以自制Ti/α-PbO2/β-PbO2电极为阳极,在室温条件下对苯酚模拟废水进行降解研究,探讨电流密度、电极间距、pH值及苯酚初始质量浓度对苯酚降解效率的影响规律.结果表明,在电流密度为600 A·m-2,电极间距为1.0 cm,pH值为3,苯酚初始质量浓度为100 mg·L-1的条件下,苯酚降解效率达92%以上.紫外光谱等实验结果表明,苯酚在氧化降解过程中会产生苯醌等中间产物,苯酚及其中间产物最终被矿化为CO2和H2O.     

UV/H2O2降解酚类物质动力学研究

利用UV／H2O2系统对苯酚进行氧化降解,不同的苯酚初始浓度,浓度自然对数与时间呈良好线性关系,表明苯酚与UV／H2O2系统中羟自由基反应可以按假一级动力学进行处理,其表现反应速率为0．00219s^-1;pH值由3．2升高至10．95时,苯酚的反应速率由0．00241s^-1下降至0．00110s^-1,说明pH对反应的速率有一定的影响．当反应体系温度由20℃上升至40℃时,间甲酚、苯酚和4-氯酚的反应速率常数分别为0．00419s^-1和0．00582s^-1、0．00219s^-1和0．00473s^-1、0．00160s^-1和0．00459s^-1,表明反应速率均有较大提高,反应自由能分别为29．341、12．521和40．158kJ／mol,说明在常规水处理过程中,羟自由基与酚类物质之间的反应在室温下就可以很快完成．     

UV/H2O2降解酚类物质动力学研究

利用UV/H2O2系统对苯酚进行氧化降解,不同的苯酚初始浓度,浓度自然对数与时间呈良好线性关系,表明苯酚与UV/H2O2系统中羟自由基反应可以按假一级动力学进行处理,其表观反应速率为0.00219s-1;pH值由3.2升高至10.95时,苯酚的反应速率由0.002 41 s-1下降至0.00110s-1,说明pH对反应的速率有一定的影响.当反应体系温度由20℃上升至40℃时,间甲酚、苯酚和4-氯酚的反应速率常数分别为0.004 19 s-1和0.005 82 s、0.002 19 s-1和0.004 73 s-1、0.00160s-1和0.004 59 s-1,表明反应速率均有较大提高,反应自由能分别为29.341、12.521和40.158 kJ/mol,说明在常规水处理过程中,羟自由基与酚类物质之间的反应在室温下就可以很快完成.     

纳米Fe/Ni催化降解2,4-二氯酚的机理及过程中参数变化

采用液相还原法制备了纳米Fe/Ni双金属材料,分析了其催化降解2,4-二氯酚的机理、降解过程中Ni的作用及相关参数变化。结果表明,2,4-二氯酚被纳米Fe/Ni降解的主要途径是2,4-二氯酚直接被脱去2个氯原子生成苯酚,此外也可先脱去一个氯原子生成2-氯酚或4-氯酚,然后继续脱氯生成苯酚;纳米Ni可将纳米Fe腐蚀产生的氢气转化为活性氢原子,活性氢原子再对2,4-二氯酚进行脱氯降解。在反应初期,溶液氧化还原电位及溶解氧浓度快速降低,pH及溶解铁浓度急剧升高,随着反应的进行,上述各参数值趋于稳定。     

零价铁还原降解2,4-二氯苯酚的实验研究

讨论了振荡时间、酸洗预处理、反应温度、pH值等因素对零价铁降解2 ,4 -二氯苯酚效果的影响,确定了最佳实验条件。结果表明,零价铁对2 ,4 -二氯苯酚的降解效果较好,实验条件下降解率在6 0 %以上。     

Photodegradation of Reactive Dyes by UV／Ferrioxalate／H2O2 System

Three types of simulated commercial reactive dye wastewater, separately prepared with FN-2BL red, C-R blue and C-2R yellow, were oxidized with UV/ferrioxalate/H2O2 system, especially by the introduction of Fe^2 ion. The experimental results show that the optimized experimental conditions are pH = 3.5, [Fe2 ] = 1mM, H2O2 782mg/L for FN-2BL red and C-R blue and H2O2 646mg/L for C-2R yellow, t=4h and T=80℃ when the concentration of dye is 400mg/L. Under such conditions, the observed COD and color removal efficiencies are above 94% and 99%, respectively for all the cases. This investigation has provided fundamental information for the treatment of wastewater containing reactive dyes using UV/ferrioxalate/H2O2 .     

超声／H2O2／CuO联合作用降解硝基苯

研究了在超声波/H2O2/金属氧化物体系中,金属氧化物(CuO,ZnO,Al2O3)对硝基苯降解的影响。结果表明:采用超声波/H2O2/CuO体系效果较好。对超声/H2O2/CuO联合作用的效果进行了研究,讨论了反应液的pH值、硝基苯的初始浓度等因素对硝基苯降解的影响。实验结果表明:pH值的变化对其降解效果没有明显影响;硝基苯的降解效果与其初始浓度有关,其降解过程符合一级反应动力学模型。     

超声波/H2O2协同降解亚甲基蓝

比较了不同处理方法对亚甲基蓝染料溶液的声化学降解作用,发现超声并加入H2O2时可加快反应速率,且反应在前4 h符合假一级动力学.研究了H2O2协同声化学对亚甲基蓝的降解作用,考察了H2O2用量、溶液初始pH值、曝气、反应温度和外加无机盐等因素对降解效率的影响.研究表明,溶液初始pH值为3.5时降解效果较好,有曝气时的声化学降解速率常数是无曝气时的2.7倍,升高温度能加快降解速率,不同离子对亚甲基蓝降解有不同的影响.UV-VIS扫描图谱显示,染料在紫外及可见区的吸收明显降低,初步探讨了亚甲基蓝的降解机理.     

漆酶催化降解氯酚类有机污染物

采用漆酶为催化剂,研究2,4－二氯酚、4－氯酚和2－氯酚的催化降解机理,探讨了反应时间、pH值、反应温度、氯酚浓度以及漆酶浓度对其降解效果的影响和最适降解条件。结果表明,漆酶催化氧化2,4－二氯酚的能力最强,其降解率10h内达到94%,4－氯酚为75%,2－氯酚为69%。2,4－二氯酚发生反应的最适pH值在5.2～6.0之间,4－氯酚在5.5附近,2－氯酚在4.5～5.5之间。漆酶对氯酚的降解率随着漆酶浓度、反应温度的升高而增大,但随着氯酚浓度的升高,不同氯酚的变化趋势并不相同。漆酶降解2,4－二氯酚的反应属于一级反应,反应活化能约为44.8 kJ·mol^-1。另外,利用戊二醛交联壳聚糖制成载体来固定化漆酶,固定化漆酶的活性虽低于自由漆酶,但稳定性明显增强,连续6d用其降解2,4－二氯酚,6h降解率始终在60%以上。     

Degradation of organic pollutants by a Co3O4-graphite composite electrode in an electro-Fenton-like system

A novel composite electrode was constructed by pressing together Co3O4 and graphite and it was used as the cathode in an electro-Fenton-like (EFL) system. The poor electron transport characteristic of Co3O4 was overcome by incorporating graphite. In situ electro-catalytic generation of hydroxyl radicals (·OH) occurred at high current efficiencies from pH 2-10, extending the traditional Fenton reaction pH range. Cyclic voltammetry and AC impedance spectrometry were used to characterize the composite electrode. The ability of the EFL system to degrade organic compounds was investigated using sulforhodamine B (SRB) and 2,4-dichlorophenol (2,4-DCP) as probes. Decoloration of SRB (1.0×10-5 mol/L) was complete (100%) in 150 min and SRB was effectively degraded from pH 2-10. The decomposition of SRB was studied using Fourier transform infrared spectroscopy (FT-IR) and total organic carbon (TOC) analysis and results indicated that the final degradation products were carbon dioxide, carboxylic acids and amines. The EFL system also decomposed 2,4-DCP and the degradation was 98.6% in 240 min. Electro-catalytic degradation of SRB occurs by a ·OH mechanism. After 5 times reused, the degradation rate of SRB did not significantly slow down. The electrode shows excellent potential for use in advanced oxidation processes (AOPs) used to treat persistent organic pollutants (POPs) in wastewater.     

固定化漆酶催化去除水中2,4-二氯苯酚

采用壳聚糖固定化漆酶催化去除水中的2,4－二氯苯酚,探讨了影响反应的不同因素,并与自由漆酶催化反应的条件进行了对比。结果表明,固定酶催化降解反应的最佳pH值在5.5左右,相对于自由漆酶,其最适pH 值向酸性偏移;降解反应的最适温度范围在30～45 ℃之间,较自由漆酶的反应温度范围增大;载体壳聚糖的吸附作用对降解反应和氯酚的去除率影响不大,氯酚的去除主要是漆酶催化氧化反应的结果;连续重复使用固定化漆酶去除模拟废水中的2,4-DCP,在重复操作6次之后,其降解效率仍能保持60%以上。     

Degradation of 2,4-dichlorophenol catalyzed by the immobilized laccase with the carrier of Fe3O4@MSS–NH2

With the Fe₃O₄@MSS (magnetic mesoporous silica spheres)–NH₂ as the carrier and the glutaraldehyde as crosslinking agent, the immobilized laccase has been prepared and characterized by XRD, IR, SEM and BET etc. Under the optimal conditions, the removal efficiency of 2,4-DCP reached 88 % and the removal efficiency still remained 61.5 % after five cycles of operations. In virtue of GC–MS analysis, 2,5-dimethoxyl-1,4-quinone, 2-chlorine-1,4-dimethoxyl benzene, 3,3′-dichlorine-4,4′-dimethoxyl biphenyl, maleic acid phenol ester, and three kinds of maleic acid, alcohol ester, and para-hydroxyl phenol ester compounds have been identified as intermediate and final degradation products of 2,4-DCP, respectively. Besides, the degradation products of 2,4-DCP have been confirmed by performing the ¹H-NMR and ¹³C-NMR experiments, further demonstrating the degradation mechanism of 2,4-DCP by the immobilized laccase.     

Characterization of nanoscale iron and its degradation of 2,4-dichlorophenol

Nanoscale iron was detected by TEM, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that the size of the nanoscale iron particles is in the range of 30–40 nm according to TEM image, and it contains abundant Fe₃O₄ as passivating layers on the surface of the core-shell structure. To improve its performance, dilute HCl was used for the removal of the passivating layers, and the degradation of 2,4-dichlorophenol (2,4-DCP) was measured for the nanoscale iron samples treated and untreated. Experimental results demonstrated that the removal of 2,4-DCP by untreated nanoscale iron is mainly due to the adsorption of 2, 4-DCP by nanoscale iron, and there are no degradation products detected by HPLC in the process. However, excellent dechlorination of 2,4-DCP was gained by HCl-treated nanoscale iron, and 2-chlorophenol, 4-chlorophenol and phenol were detected during the process. It was concluded that dechlorination is the key reaction pathway for the degradation of 2,4-DCP by activated nanoscale iron, and phenol is found to be the main product.     

H2O2敏化H3PW12O40／SiO2光催化降解甲基紫

采用溶胶一凝胶技术将Keggin型H3PW12O40负载在SiO2上,并用H2O2溶液对其进行敏化,制得HsPW12O40／SiO2／H2O2光催化剂．考察在模拟自然光条件下,甲基紫的初始浓度、溶液pH以及催化剂用量对甲基紫可见光催化降解率的影响．实验发现,在甲基紫初始浓度为30mg／L,溶液pH为2．5,催化剂的用量为0．6g／L的优化情况下,光降解2．5h,甲基紫的降解率达到92％．     

In_2S_3-Ag/TiO_2三元纳米体系光催化降解2,4-D的实验研究

采用两步沉积法首次合成出新三元纳米材料-In2S3-Ag/TiO2纳米管阵列,并用电子扫描显微镜(SEM)、光致发光光谱仪(PL)等仪器对该三元催化剂进行形貌、元素、晶体结构的表征与光电性能的测试,并将该三元催化体系应用于2,4-二氯苯氧乙酸(2,4-D)的光降解实验.结果表明,In2S3-Ag/TiO2三元纳米材料所特有的两步光激发体系使它的催化降解能力显著提高,在溶液pH为4.23时,140min内可实现对2,4-D 100%的去除;强酸和强碱的环境都不利于三元催化剂In2S3-Ag/TiO2对2,4-D的催化降解.最后对三元催化剂的光催化降解机理进行了探讨.