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.     

Degradation of Carbofuran in Water by Solar Photocatalysis in Presence of Photosensitizers

The effect of the presence of photosensitizers, methylene blue (MB) and rose Bengal (RB), on the degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) in water in a solar photocatalytic system was investigated. It was found that as compared to MB, RB generally showed a stronger effect on the decomposition of carbofuran under comparable conditions. Among the conditions studied, adding 2 × 10^?6 M of RB, that corresponding to 2% of the initial concentration of carbofuran solution in the system, rendered the most effective degradation of carbofuran. As a result, a carbofuran removal percentage of 69.9%, a mineralization efficiency of 28.0%, and a microtoxicity reduction of 65.0% could be achieved. The degradation and mineralization of carbofuran was found to follow the pseudo-first order reaction kinetics. The decomposition mechanism of carbofuran was further investigated through identification of the intermediates to elaborate the influence of dye photosensitizer on the solar photocatalysis of carbofuran in water. On the basis of the intermediates identified, including carbofuran phenol, 3-hydroxy carbofuran phenol, and substituted alcohols (3-phenoxy 1-propanol, 2-ethyl 1-hexanol, 2-butoxyl ethanol), it appears that hydrolysis and hydroxylation were the two key mechanisms for decomposing carbofuran during the process of solar photocatalysis with the aid of dye photosensitizer.     

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。     

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。     

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、...     

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%。     

Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

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%。     

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.     

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。     

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。     

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。     

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。     

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。     

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...     

CuCoOx/TiO2催化氧化NO性能研究

采用浸渍法制备了CuCoOx/TiO₂催化剂,考察了焙烧温度、反应温度、氧含量、NO浓度和空间速度对催化剂催化氧化NO性能的影响,并考察了催化剂的抗硫抗水性能。XRD、TPR和BET分析表明,350℃焙烧的催化剂具有CuCo₂O₄尖晶石结构,比表面积大,对NO的氧化效果好。在空速为5 000 h^-1,NO进口浓度500 mg/m³,含氧量10%的条件下,反应温度300℃时NO转化率可达79.5%,250℃时NO转化率接近50%。该催化剂具有良好的单独抗SO₂、抗H₂O毒化性能,H₂O和SO₂同时存在时很快失活。该催化剂可用于不同时含H₂O和SO₂的含NO气体催化氧化后再吸收处理。     

粉煤灰沸石负载Ce3+/TiO2光催化降解水中的菲和荧蒽

以钛酸四丁酯为前驱体,粉煤灰合成沸石为载体,采用溶胶-凝胶方法,在低温条件下制备了稀土铈掺杂的TiO₂光催化剂。利用SEM-EDS、XRD、FTIR对催化剂进行了分析和表征。以高压汞灯为灯源,对多环芳烃菲、荧蒽的降解进行了研究。实验考查了稀土铈掺杂质量分数、催化剂用量、溶液pH、目标物初始质量浓度等因素对光催化降解的影响,研究了其光降解动力学。结果表明,当稀土铈含量为0.5%,催化剂用量为3 g/L,pH偏碱性时,催化效果最佳。光催化反应符合Langmuir-Hinshelwood 动力学规律,菲、荧蒽的降解过程符合一级反应动力学,反应速率常数分别为0.0126 min^-1,0.0099 min^-1。     

Relationship between Pd oxidation states on TiO2 and the photocatalytic oxidation behaviors of nitric oxide

This study has been undertaken to investigate the relationship between Pd oxidation states on TiO₂ photocatalysts and their photocatalytic oxidation behaviors of NO. Three types of Pd-modified TiO₂ with different Pd oxidation states were prepared by wet impregnation method, neutralization method and photodeposition method, respectively. And these Pd-modified photocatalysts were characterized by X-ray diffraction analysis, X-ray photoelectron spectrum analysis (XPS), UV–Vis diffuse reflectance spectra and temperature programmed desorption (TPD). It was found from XPS results that the dominant oxidation states of Pd on these Pd-modified TiO₂ catalysts were Pd²⁺, PdO, and Pd⁰, respectively. NO-TPD results showed that the NO adsorption capacity was improved greatly by the modification of Pd²⁺ ions. The activity tests showed that Pd-modified TiO₂ by a wet impregnation method increased photocatalytic activity compared to pure TiO₂ (Degussa P25). It was concluded that Pd²⁺ ions on as-prepared TiO₂ catalysts provided key contributions to the improvement of photocatalytic activity. However, Pd⁰ and PdO deposits on TiO₂ almost had no positive effect on NO oxidation. The mechanism of photocatalytic oxidation of NO in gas phase over Pd-modified TiO₂ was also proposed.