Direct and indirect photolysis of cyhalofop in aqueous systems

The photodegradation of the aryloxyphenoxy propionic herbicide cyhalofop-butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), and of its primary metabolite (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA) was studied in water at different irradiation wavelengths. The sunlight irradiation was investigated also in the presence of humic acid (HA), Fe oxide, titanium dioxide (TiO₂) and zinc oxide (ZnO) as photocatalysts.CyB and CyA were rapidly degraded by UV irradiation. CyB afforded the butyl ester of 2-[3-(4-cyano-2-fluorophenyl)-4-hydroxy-phenoxy]propanoic acid (CyI), a metabolite arising from a photo-Fries rearrangement. Instead, CyA yielded (R)-2-4-(4-carboxyl-2-fluorophenoxy)phenoxypropanoic acid (CyD), a dicarboxylic acid arising from the photo-hydrolysis of cyano group via amide. CyB was stable in simulated sunlight also in the presence of the catalysts tested.The irradiation of a CyA solution, in the presence of HA or Fe oxide, with simulated sunlight did not produce any significant degradation. In the same experimental conditions, CyA was totally mineralized in the presence of TiO₂ and ZnO.     

Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems

The photodegradation of two quinolinecarboxylic herbicides, 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and 3,7-dichloroquinoline-8-carboxylic acid (QCl), was studied in aqueous solution at different irradiation wavelengths. The effect of sunlight irradiation was investigated also in the presence of titanium dioxide (TiO₂). UV irradiation degraded rapidly QMe affording 7-chloro-3-methylquinoline (MeQ) through a decarboxylation reaction. The reaction rate was lower in the presence of dissolved organic carbon (DOC) because of the adsorption of the herbicide on the organic components. Instead, QCl was stable under both UV light and sunlight irradiation. The irradiation of QMe or QCl solutions with simulated sunlight in the presence of TiO₂ produced the complete mineralization of the two herbicides.     

Photocatalytic debromination of preloaded decabromodiphenyl ether on the TiO(2) surface in aqueous system

There have been serious concerns about polybromodiphenyl ethers (PBDEs) in the environment because of their global distribution and bioaccumulation. Owing to strong hydrophobicity of PBDEs, the regular photocatalytic system, in which the substrate is solvated in the bulk solution, is not applicable to the removal of the PBDEs in water. In this work, the photocatalytic reduction degradation of decabromodiphenyl ether (BDE209), the most-used PBDEs, was investigated in aqueous system, by pre-adsorbing it on the surface of photocatalyst. It was found that the preloaded BDE209 underwent efficient reductive debromination in aqueous system under irradiation with wavelength larger than 360 nm in the presence of electron donors such as methanol. Our experiments further show that such a preloaded system exhibits different characteristics from that in the organic solution. The meta-debrominated intermediate is predominant in the present system, while the ortho-debrominated one is the main nona-BDE products in the organic solution. In addition, different from other photocatalytic system, the pH has little effect on the photocatalytic reaction. We propose that these differences are originated from the formation of overlayer of hydrophobic BDE209 to limit the motion of BDE209 and the access of water and H⁺/OH⁻ to the TiO₂ surface.     

颜料红254-TiO_2光催化降解罗丹明B废水

以工业有机颜料C.I.颜料红254(DPP254)为敏化剂,通过溶剂热法对纯TiO2进行改性,得到复合光催化剂DPP254-TiO2。并通过XRD、SEM、UV-Vis DRS和N2吸附-脱附(BET和BJH)等测试手段对DPP254-TiO2进行了表征。以罗丹明B(RhB)为目标降解物,研究了DPP254-TiO2在可见光下对有机污染物的光催化降解性能。同时考察了DPP254含量、反应时间、RhB初始浓度和催化剂浓度等因素对RhB降解速率的影响。结果表明,改性后的催化剂光响应范围由紫外光区拓宽到可见光区。对其光催化反应机理进行了探讨。催化剂重复使用4次,活性没有明显降低,说明催化剂具有很好的稳定性。     

TiO2光催化氧化降解乳酸的工艺及机理研究

以TiO2为催化剂、紫外灯为光源对乳酸进行光催化降解实验,考察了乳酸初始浓度、TiO2用量、反应时间、曝气方式等因素对乳酸降解率的影响,并在此基础上应用正交实验对降解条件进行优化,同时对乳酸的降解机理进行了探索研究.实验结果表明:以300 W紫外汞灯为光源,在乳酸初始浓度为O.5 g/L、TiO2量为0.20 g/L、...     

碘掺杂TiO2可见光光催化性能研究

在低于100℃温度条件下,采用溶胶-凝胶法以钛酸正丁酯为钛源,碘酸钾为碘源,制备了I掺杂纳米TiO2催化剂(I-TiO2),运用X-射线衍射(XRD)、透射电镜(TEM)及X-射线光电子能谱(XPS)等对催化剂进行表征,结果表明,TiO2及I-TiO2催化剂均为锐钛矿,I吸附并包裹在TiO2表面或以间隙进入的形式存在,并未进入TiO2晶格。通过在可见光照射下(λ>420 nm)以罗丹明B(Rhodamine B,RhB)的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能,结果表明,掺杂比为nI:nTi=0.05∶1,焙烧温度为400℃,降解介质条件pH=7时,I-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱(IR),总有机碳(TOC)跟踪测定,比较了TiO2掺杂前后降解RhB和对氯苯酚(4-CP)的光催化特性差异;同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种,表明在可见光下,I-TiO2光催化体系中产生.OH高活性氧化物种从而氧化降解目标化合物。     

CdS-TiO_2/MWCNTs结构表征及其光催化性能

采用溶胶-凝胶法,制备了多壁碳纳米管(MWCNTs)负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜(TEM)、比表面分析(BET)、X射线衍射(XRD)和紫外-可见吸收光谱(UV-vis)等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明:纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。     

氮掺杂二氧化钛可见光催化降解曙红Y溶液

采用溶胶凝胶法制备了氮掺杂二氧化钛光催化剂,用XRD、SEM、FTIR和粒度分析仪对催化剂进行了表征,并且在可见光作用下对曙红Y溶液进行了光催化降解实验。研究了催化剂的投加量、曙红Y的初始浓度、光照时间和pH对曙红Y溶液的光降解效果。结果表明,以可见光作光源,催化剂的投入量为0.4 g,曙红Y溶液的初始浓度为20 mg/L,光照时间为50 min,pH=4条件下,曙红Y溶液的降解率达98.87%。     

碳纳米管/二氧化钛/壳聚糖催化薄膜光催化活性及苯降解机理

通过X-射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和紫外可见光漫反射谱(UV-vis)对碳纳米管/二氧化钛/壳聚糖复合薄膜的晶体结构和形貌进行表征,以室内空气典型污染物气相苯为模型反应物,研究碳纳米管/二氧化钛/壳聚糖催化薄膜的光催化活性及其对苯的光降解机理。结果表明,制备的碳纳米管/二氧化钛/壳聚糖催化薄膜所具有的良好催化活性归功于碳纳米管、二氧化钛和壳聚糖三者的协调效应;气相苯光降解产生的主要中间产物是乙酸乙酯和十一烷,以及少量的丙烯醛、4-羰基-甲基-苯乙酮、十二烷烃、2,4,-二叔丁基苯酚、二十一烷烃。根据红外光谱分析与GC/MS分析结果,进一步提出了气相苯的降解机理过程。     

Photolysis of the herbicide bispyribac sodium in aqueous medium under the influence of UV and sunlight in presence or absence of sensitizers

The photolysis of a rice herbicide Bispyribac sodium (Sodium 2, 6-bis [(4, 6-dimethoxypyrimidin-2-yl) oxy] benzoate) has been studied in different aqueous medium (distilled water, pond water and Irrigation water) under the influence of UV (λ max ≥ 250 nm) and sunlight in presence or absence of sensitizers (TiO₂ and KNO₃). The study was conducted under laboratory simulated condition which made it possible to evaluate the contribution of different factors viz. source of irradiation, solvent and sensitizers towards the photolysis of bispyribac sodium. The photodegradation proceeds via first order reaction Kinetics in all the cases. Five photo metabolites (M₁-M₅) were isolated in pure form by column chromatographic method from the irradiation system under UV influenced and TiO₂ as sensitizer. From the different spectral data (IR, NMR, UV-VIS, Mass) the structure of these five metabolites were assigned as M₁ (Phenol), M₂ [2, 6-Dihydroxy benzoic acid], M₃ [2, 6-bis [(4, 6 dimethoxypyrimidin-2yl) oxy] benzoic acid], M₄ [2-(3-Hydroxy-phenoxy)-pyrimidine-4, 6-diol] and M₅ as [2,4-Dihydroxy-3, 5-dimethoxy-6-(4-methoxy pyrimidine-2-yloxy)-benzoic acid]. Moreover, another six photometabolites (M₆-M₁₁) were identified from the different irradiation system on the basis of Micromass analysis. On the basis of MS/MS data analysis, the structure of these six photometabolites were assigned as M₆ [2-(4, 6-Dimethoxy-pyrimidin-2-yloxy)-6-hydroxy-benzoic acid], M₇ [2-Hydroxy-6-(4-hydroxy-6-methoxy-pyrimidin-2-yloxy)-benzoic acid], M₈ [4, 6-Dimethoxy-pyrimidin-2-ol], M₉ [6-Methoxy-pyrimidine-2, 4-diol], M₁₀ [2-Hydroxy-6-(pyrimidin-2-yloxy)-benzoic acid] and M₁₁ [2, 4, 6-Trimethoxy-pyrimidine]. The plausible Photodegradation pathways of bispyribac sodium in the present investigation were portrayed which proceeds via hydrolysis, hydrolytic cleavage, O-dealkylation, decarboxylation, dehydroxylation, O-alkylation and hydroxylation.     

模拟可见光下掺杂TiO2对甲醛溶液光催化降解

模拟自然条件下的可见光,以甲醛的光催化降解为探针反应,评价了通过溶胶凝胶法分别制备的8种（银Ag、铜Cu、铁Fe、钨W、铈Ce、镧La、硫S、氯Cl）掺杂TiO₂纳米晶体的光催化活性及对甲醛水溶液的去除效果。用X射线衍射、激光粒度分析和紫外-可见分光光谱表征了掺杂纳米TiO₂的微晶尺寸、晶体结构与光学性能。结果表明：Ce离子尽管有较大的半径但是主要还是掺杂到晶格中,Ce掺杂可以促进TiO₂由非正分锐钛矿相向锐钛矿相和金红石相的转变,抑制载流子复合,使TiO₂的光吸收带边发生红移且有利于对可见光的吸收,从而使Ce掺杂TiO₂在模拟可见光下光催化甲醛水溶液的能力得到明显提高。     

TiO2/Ti及其改性处理聚乙二醇模拟废水

采用溶胶-凝胶法制备TiO2/Ti负载体系,并以聚乙二醇2000（PEG-2000）为模拟废水对其光催化性能进行研究。实验表明,TiO2/Ti的最佳负载条件为镀膜层数8层、pH值为3、焙烧温度700℃、焙烧时间2 h,掺杂Fe3＋、Ag＋、La3＋、Pt4＋4种金属离子均可有效提高TiO2/Ti对PEG-2000模拟废水的处理效果,在Ag＋掺杂量为0.3%、焙烧温度800℃时,2.5h反应后的COD去除率达到了79.5%。XRD分析表明,金属离子的加入抑制了TiO2由锐钛矿相向金红石相转化。GC-MS分析表明,PEG-2000的光催化是大分子分解为小分子然后被矿化的过程。     

溶胶凝胶法制备磷钨酸掺杂TiO2薄膜及其光催化性能

以钛酸四丁酯为前驱物,采用溶胶凝胶法制备了磷钨酸掺杂的二氧化钛薄膜。通过XRD、FT-TR对该薄膜进行了表征,研究了薄膜在对氯苯酚光降解中的催化活性。结果表明,当磷钨酸与二氧化钛摩尔比为0.01∶1、薄膜烧结温度600℃、对氯苯酚溶液浓度30 mg/L（pH＝5）、光催化8 h的条件下,对氯苯酚的降解率超过90%,且薄膜可以重复使用。磷钨酸对二氧化钛的光催化活性具有明显的促进作用。     

负载TiO2浮石对污水处理厂二沉池出水的矿化与灭菌研究

城市污水处理厂第二沉淀池出水的污染物浓度较低,经过矿化及灭菌等深度处理后可以回用,从而减轻对淡水资源的需求。本实验采用溶胶凝胶法制备了负载TiO₂的浮石光催化剂,对城市污水处理厂第二沉淀池出水进行了矿化及灭菌处理研究。采用低压汞灯对处理水样照射2 h,有机物降解率可以达到50%,灭菌效率达到100%。处理后的水可以作为农作物灌溉、城市绿化和娱乐用水。负载在浮石表面的TiO2薄膜经过10次的光催化循环实验后,没有明显破损,可以再次循环使用。TiO₂浮石具有质轻、机械性能好和价格低等优点,该方法处理废水的适用浓度低,可以广泛应用于微污染水和城市污水处理厂出水的深度处理。     

TiO_2/EP光催化降解水体中微污染磺胺嘧啶的研究

制备了膨胀珍珠岩(EP)为载体的TiO2催化剂(TiO2/EP),对使用较为广泛的抗生素磺胺嘧啶(SDZ)进行了光催化降解研究,探讨了TiO2的负载量、溶液的初始浓度、初始pH、无机离子(HCO3-、SO42-和Cl-)和腐殖酸(HA)对SDZ降解效果的影响。结果表明:SDZ的光催化降解符合一级反应动力学方程;当TiO2最佳负载量为20 wt%,SDZ浓度为5 mg/L,pH=6.7,紫外光照射强度为1 000μW/cm2,反应时间为45 min时,SDZ的降解率达到96%;HCO3-在低浓度时能促进SDZ的光催化降解,高浓度时促进作用不明显;SO42-和Cl-对SDZ的光催化降解有轻微的抑制作用;HA对SDZ光催化降解有显著的抑制作用,浓度越高,抑制作用越强。UV-TiO2/EP是一种去除水体中微污染SDZ的有效方法。     

纳米TiO2-xNx催化剂的制备及其活性研究

以钛酸丁酯为前驱物、无水乙醇作溶剂、二乙醇胺作为抑制剂,采用溶胶凝胶法制备TiO₂溶胶,在NN₃气流中直接进行热处理,制备一系列不同焙烧温度的淡黄色的掺氮纳米TiO₂粉体。经XRD、UV-Vis和FTIR分析表明,实验制得的TiO_2-xN_x在350、400、450、500和550℃热处理3 h后仍为锐钛型;450℃保温3 h掺氮样品具有最佳的紫外-可见光响应,其吸收边红移至720 nm左右。罗丹明B的可见光降解实验及产物分析表明,掺氮样品具有良好的可见光催化活性。     

CuO/TiO2-H2O2可见光催化亚甲基蓝脱色效果及影响因素研究

以水解法制备的锐钛矿型TiO2为载体,制备了CuO/TiO2型光催化剂.以亚甲基蓝为对象,在可见光照射下研究了H2O3加入量、pH值和催化剂投加量对脱色效果的影响,同时与改性前的TiO2催化剂进行了脱色效果的对比.结果表明亚甲基蓝在碱性条件下能较好脱色,H2O2用量和CuO/TiO2催化剂投加量分别为每1 000 mL反应液各加入10 mL和0.1 g时脱色最好;另外,TiO2催化剂也在碱性条件下能较好脱色,H2O2用量和催化剂投加量分别为每1 000 mL反应液各加入12.5 mL和0.1 g时脱色最好.最优条件下对比实验表明,CuO/TiO2型催化剂在可见光照射下具有很高的催化活性,亚甲基蓝2 h脱色率达到88%,远好于改性前的TiO2和Degussa P25催化剂.     

Carbofuran removal in continuous-photocatalytic reactor: Reactor optimization,rate-constant determination and carbofuran degradation pathway analysis

Carbofuran (CBF) removal in a continuous-flow photocatalytic reactor with granular activated carbon supported titanium dioxide (GAC-TiO₂) catalyst was investigated. The effects of feed flow rate, TiO₂ concentration and addition of supplementary oxidants on CBF removal were investigated. The central composite design (CCD) was used to design the experiments and to estimate the effects of feed flow rate and TiO₂ concentration on CBF removal. The outcome of CCD experiments demonstrated that reactor performance was influenced mainly by feed flow rate compared to TiO₂ concentration. A second-order polynomial model developed based on CCD experiments fitted the experimental data with good correlation (R² ～ 0.964). The addition of 1 mL min^?1 hydrogen peroxide has shown complete CBF degradation and 76% chemical oxygen demand removal under the following operating conditions of CBF ～50 mg L^?1, TiO₂ ～5 mg L^?1 and feed flow rate ～82.5 mL min^?1. Rate constant of the photodegradation process was also calculated by applying the kinetic data in pseudo-first-order kinetics. Four major degradation intermediates of CBF were identified using GC-MS analysis. As a whole, the reactor system and GAC-TiO₂ catalyst used could be constructive in cost-effective CBF removal with no impact to receiving environment through getaway of photocatalyst.     

微乳液法合成掺硫纳米TiO2及其光催化性能研究

以钛酸四丁酯为钛源,硫脲为掺硫前驱物,采用聚乙二醇辛基苯基醚(Triton X-100)/正己醇/环己烷/氨水的微乳液体系合成了掺硫的纳米TiO2粉体;对其结构进行了表征,以甲基橙为目标降解物考察了其光催化性能.烧结温度通过影响TiO2的晶型转变和颗粒尺寸来影响其光催化性能,随着烧结温度的升高,TiO2的光催化性能先是...     

Vis/Co-TiO_2/KHSO_5体系Fenton-光催化协同降解苯酚

通过溶胶-凝胶法制备了同时具有可见光(Vis)光催化和Fenton催化双重活性的Co-TiO2催化剂。通过对比Vis/Co-TiO2/KHSO5、Co-TiO2/KHSO5和Vis/Co-TiO23种体系对苯酚的降解效果,Vis/Co-TiO2/KHSO5表现出明显的Fenton-光催化协同作用。进一步研究pH值、KHSO5与苯酚摩尔比(nKHSO5∶nC6H6O)和Co-TiO2投加量(mCo-TiO2)对Fenton-光催化协同降解苯酚效果的影响。结果表明,pH=6.9、nKHSO5∶nC6H6O=10∶1、mCo-TiO2=1.0 g/L时,降解率达100%。最后,结合XRD、XPS和UV-DRS等手段和催化活性实验数据分析了Vis/Co-TiO2/KHSO5体系的催化机理。