负载型TiO2膜太阳光光催化降解活性深蓝K-R的研究

采用抛物线槽型反应装置,研究了玻璃弹簧和微珠负载型TiO2膜太阳光催化降解活性深蓝K-R,结果表明,由于玻璃弹簧具有良好的光透距离,脱色性能显著优于玻璃微珠,玻璃弹簧为载体,水溶液浓度为15mg/L,pH为3,流速为20mL/s,太阳光强度在1200 μW/cm2以上,光降解6h时,脱色率达到96%; 该降解反应可用一级反应动力学方程进行描述,反应速率常数（K）与光强I的关系为：K∝I1.92。     

Bacterial assisted phytoremediation for enhanced degradation of highly sulfonated diazo reactive dye

Purpose

Phytoremediation is the exploitation of plants and their rhizospheric microorganisms for pollutants treatment like textile dyes, which are toxic, carcinogenic and mutagenic from the effluent. The purpose of this work was to explore a naturally found plant and bacterial synergism to achieve an enhanced degradation of Remazol Black B dye (RBB).

Methods

In vitro cultures of Zinnia angustifolia were obtained by seed culture method. Enzymatic analysis of the plant roots and Exiguobacterium aestuarii strain ZaK cells was performed before and after decolorization of RBB. Metabolites of RBB formed after its degradation were analyzed using UV?CVis spectroscopy, high-performance liquid chromatography (HPLC), Fourier transform infrared (FTIR) and gas chromatography?Cmass spectrometry (GC-MS). Phytotoxicity studies were performed.

Results

The consortium ZE was found to be more efficient than individual plant and bacteria. Z. angustifolia roots showed significant induction in the activities of lignin peroxidase, laccase, DCIP reductase and tyrosinase during dye decolorization. E. aestuarii showed significant induction in the activities of veratryl alcohol oxidase, azo reductase and DCIP reductase. Analysis of metabolites revealed differential metabolism of RBB by plant, bacteria and consortium ZE. E. aestuarii and Z. angustifolia led to the formation of 3,6-diamino-4-hydroxynaphthalene-2-sulfonic acid, (ethylsulfonyl)benzene, and 3,4,6-trihydroxynaphthalene-2-sulfonic acid and propane-1-sulfonic acid, respectively, whereas consortium ZE produced 4-hydroxynaphthalene-2-sulfonic acid, naphthalene-2-sulfonic acid and 4-(methylsulfonyl)phenol. The phytotoxicity study revealed the nontoxic nature of the metabolites formed after dye degradation.

Conclusion

Consortium ZE was found to be more efficient and faster in the degradation of RBB when compared to degradation by Z. angustifoila and E. aestuarii individually.     

负载型TiO2膜太阳光光催化降解活性深蓝K-R的研究

采用抛物线槽型反应装置，研究了玻璃弹簧和微珠负载型TiO₂膜太阳光催化降解活性深蓝K-R，结果表明,由于玻璃弹簧具有良好的光透距离，脱色性能显著优于玻璃微珠，玻璃弹簧为载体，水溶液浓度为15mg/L,pH为3,流速为20mL/s,太阳光强度在1200 μW/cm₂以上，光降解6h时，脱色率达到96%； 该降解反应可用一级反应动力学方程进行描述，反应速率常数（K）与光强I的关系为：K∝I1.92。     

亚甲基蓝溶液的光催化脱色及降解

以高压汞灯为光源,在自ＴｉＯ２纳米粉末悬浮体系内,以在蓝溶液光催化降解脱色反应为模型,研究了其脱色降解动力学及其影响因素。研究表明,亚甲基蓝光催化反应动力学常数为４．５３μｍｏｌ／Ｌ．ｍｉｎ．吸附常数为３３．５５Ｌ／ｍｍｏｌ;随着ｐＨ值的上升以及Ｈ２Ｏ２的加入,其脱色降解速率加快。     

介孔TiO2的制备及光催化降解有机染料的研究

以十六烷基三甲基溴化胺为模板剂,用溶胶-凝胶法制备了介孔TiO2,用x射线衍射、透射电子显微镜、热重/差热分析及氮气吸附等方法对其进行了分析表征,并用偶氮染料阳离子红X-GRL为目标污染物分析了它的光催化活性.实验结果表明,450℃热处理后的介孔TiO2是锐钛矿型的,平均孔径为18 nm.氮气吸附曲线呈典型的介孔材料Ⅳ型吸附等温线特征.由于介孔TiO2具有较大的比表面积,因此表现出比非介孔TiO2高的光催化活性.     

镧负载改性TiO2太阳光催化降解微囊藻毒素的研究

考察了镧负载改性TiO2催化剂在太阳光下降解微囊藻毒素LR (MCLR)的效果及其影响因素。结果表明,镧负载改性的TiO2可显著增加MCLR在TiO2表面的吸附量,同时提高MCLR在太阳光下的降解率。随着镧负载量的增加,太阳光下MCLR降解率可从65%提高到95%,pH降低可促进MCLR的降解。改性TiO2对藻毒素的降解存在最佳投加量,实验结果表明,在pH=6,MCLR初始浓度为2 mg/L,0.001-La-TiO2的最佳投量为0.5 g/L,在3 600 μW/cm2太阳光下照射30 min,降解率可达97%。     

TiO_2胶体光催化降解罗丹明B染料

TiO2胶体从钛氧有机物水解制备,表征的方法有：X射线衍射光谱（XRD）、激光散射粒径分布、傅立叶变换红外光谱（FT-IR）、X射线光电子谱（XPS）和透射电子显微镜（TEM）。利用罗丹明B染料分子作为探针分子研究TiO2胶体的光催化活性,分析了pH、催化剂用量、外加氧化剂（H2O2）用量及罗丹明B初始浓度对TiO2胶体光催化活性的影响。结果表明：制备的TiO2胶体粒子平均粒径为13.8 nm（激光散法测定）,光催化降解罗丹明B染料的反应属于一级动力学反应,可以用Langmuir-Hinshewood模型加以描述,反应速率常数k1为0.08413 mg/（L.min）,平衡吸附常数k2为1.5305 L/mg;在pH为6,TiO2胶体用量为0.04%,H2O2（含量30%）用量为0.2%（V/V）,光照度为69.6μW/cm2时,5 h后罗丹明B染料的降解率可达到99%以上;相似的条件,0.2%的P25 TiO2粉体光催化处理染料水时,罗丹明B的降解率为90%。纳米TiO2胶体不仅可以提高罗丹明B的光催化降解率,还具有用量少,可有效降低水处理成本的特点。     

改进Fenton体系处理蒽醌染料的研究

以活性艳蓝KN-R作为研究对象,用UV/Fenton和solar/Fenton/草酸(H2C O4)体系对其进行处理,对反应体系的影响因素作综合的评价.得到处理蒽醌染料废水的最佳条件:dye(活性艳蓝KN-R):Fe2 :H2O2:H2C2O4为5:1:15:1.5,pH为3.0,反应时间为40 min.在最佳条件下,solar/Fenton/H2C2O4体系脱色率达到100%,COD和TOC去除率分别达到87%和66%以上.改进的Fenton方法能使难降解有机染料迅速脱色,矿化程度较高.并对此体系处理活性艳蓝KN-R废水的脱色过程进行动力学模拟,得到此反应为拟一级反应.     

Performance of photocatalytic reactors using immobilized TiO2 film for the degradation of phenol and methylene blue dye present in water stream

TiO2 thin film photocatalyst was successfully synthesized and immobilized on glass reactor tube using sol-gel method. The synthesized TiO2 coating was transparent, which enabled the penetration of ultra-violet (UV) light to the catalyst surface. Two photocatalytic reactors with different operating modes were tested: (a) tubular photocatalytic reactor with re-circulation mode and (b) batch photocatalytic reactor. A new proposed TiO2 synthesized film formulation of 1 titanium isopropoxide: 8 isopropanol: 3 acetyl acetone: 1.1 H2O: 0.05 acetic acid (in molar ratio) gave excellent photocatalytic activity for degradation of phenol and methylene blue dye present in the water. The half-life time, t1/2 of photocatalytic degradation of phenol was 56 min at the initial phenol concentration of 1000 microM in the batch reactor. In the tubular photocatalytic reactor, 5 re-circulation passes with residence time of 2.2 min (single pass) degraded 50% of 40-microM methylene blue dye. Initial phenol concentration, presence of hydrogen peroxide, presence of air bubbling and stirring speed as the process variables were studied in the batch reactor. Initial methylene blue concentration, pH value, light intensity and reaction temperature were studied as the process variables in the tubular reactor. The synthesized TiO2 thin film was characterized using SEM, XRD and EDX analysis. A comparative performance between the synthesized TiO2 thin film and commercial TiO2 particles (99% anatase) was evaluated under the same experimental conditions. The TiO2 film was equally active as the TiO2 powder catalyst.     

Two stage biological treatment of a diazo reactive textile dye and the fate of the dye metabolites

A two stage anaerobic/aerobic bacterial process was used to decolorize and partially mineralize a reactive vinyl sulfone diazo dye C.I. Reactive Black 5 (RB5) in a synthetic wastewater. Since the anchor group of reactive dyes reacts during the dyeing process, the effect the degree of hydrolysis of the vinyl sulfone dye had on decolorization, mineralization and toxicity in each stage was investigated. An overall color removal of approximately 65% was found for both the fully and partially hydrolyzed dye. Partial mineralization of the fully hydrolyzed RB5 was achieved in the two stage rotating disc reactors. While the anchor group metabolite p-aminobenzene-2-hydroxyethylsulfonic acid (p-ABHES) was mineralized, an oxidized form of the center metabolite (1,2-ketimino-7-amino-8-hydroxynaphthalene-3,6-disulfonic acid) remained in the aerobic stage effluent, causing the effluent to be colored although no RB5 was present. Partially hydrolyzed dye in the influent with vinyl forms of the anchor group caused cessation of biogas production and a reduction in decolorization efficiency in the anaerobic stage. No evidence for mineralization of the partially hydrolyzed dye or its metabolites was found. A method for evaluating dye mineralization using lumped parameters is presented.     

TiO2-rGO制备及其对亚甲基蓝溶液的降解

本实验用改进的Hummers法制备氧化石墨烯(GO),通过溶胶-凝胶法制备得到TiO2-石墨烯复合材料(TiO2-rGO),研究了不同制备条件对复合材料光催化性能的影响。采用X射线衍射(XRD),拉曼光谱(Raman),比表面积(BET),扫描电镜(SEM),透射电镜(TEM)、紫外-可见(UV-Vis)吸收光谱和荧光光谱(PL)等测试手段对复合材料进行表征。结果表明,TiO2-rGO复合材料中的TiO2为锐钛相,且能均匀附着在石墨烯片层上,呈现层状堆积结构;与纯TiO2相比,复合材料具有较大的比表面积和更高的可见光响应。研究了该复合催化剂在紫外光下对亚甲基蓝以降解效果。当焙烧温度为450℃、TiO2/GO质量比为125:1时,制备得到的TiO2-rGO具有最优的光催化效果。     

Photocatalytic degradation of textile dye X3B by heteropolyoxometalate acids

Reactive brilliant red X3B, one recalcitrant textile dye, was decolorized in water by (Photo)-Fenton reactions and TiO(2) photocatalysis [Chemosphere 43 (2001) 1103]. Complementary to this study, the present work has shown the effectiveness of several Keggin-type heteropolyoxomatalates (POM) as a photocatalyst for X3B degradation in water at pH 1.0 under UV light (lambda>/=320 nm) irradiation. Among four POMs, the relative activity was observed to be H(3)PW(12)O(40)z.Gt;H(4)SiW(12)O(40)>H(4)GeW(12)O(40)>H(3)PMo(12)O(40). The reaction was dependent of pH, light intensity and the catalyst loading, but not obviously of the molecular oxygen dissolved in water. Compared to the photocatalyst of TiO(2) (Degussa p25), H(3)PW(12)O(40) was less efficient for the dye bleaching and mineralization. The mechanism study reveals that hydroxyl radicals are involved in the degradation of X3B (and Rhodamine B) by POM photocatalysis.     

H4SiW12O40/TiO2/beads光催化降解亚甲基蓝的研究

以钛酸四丁酯为原料,空心微珠为载体,采用溶胶-凝胶法制备TiO2/beads光催化剂载体,然后浸渍法制备出H4SiW12O40/TiO2/beads表面负载修饰型复合光催化剂,并运用SEM、XRD、FT-IR和DRS对催化剂进行表征和分析。研究了H4SiW12O40/TiO2/beads对亚甲基蓝降解的光催化活性,考察了光强度、pH值、曝气量、底物浓度和催化剂用量等对催化效率的影响。实验结果表明,在中性条件下,H4SiW12O40/TiO2/beads催化剂的投加量为0.25 g/L,浓度为7.5 mg/L的亚甲基蓝溶液在250 W的紫外灯和600 W的可见光灯下光照60 min降解率分别可达到94.5%和55%。     

超声波-零价铁协同降解废水中活性深蓝M-2GE的研究

研究了超声波-零价铁对废水中活性深蓝M-2GE的协同降解,探讨了铁粉添加量、超声波功率、介质pH和染料的浓度等对活性深蓝M-2GE降解效率的影响。结果表明,零价铁的存在可显著提高废水中活性深蓝M-2GE的超声降解效率,其降解率随着铁粉添加量的增多而升高。介质pH对活性深蓝M-2GE的降解有显著影响,pH=3时降解率最高。另外增大超声功率有利于有机污染物的降解,有机染料的浓度越低,降解率越高。     

Fenton-like/TiO2催化介质阻挡放电体系对活性艳蓝的降解

为了提高等离子放电对染料的降解效率,研究了Fenton-like/TiO2耦合催化介质阻挡放电体系对活性艳蓝(X-BR)的脱色效果及降解机理。结果表明,投加Fe2+ 或Fe3+与TiO2组成的耦合催化体系可以显著提高X-BR的脱色率。反应10 min后,紫外可见扫描光谱和阴离子(Cl-、NO3-、SO42-)产量分析表明,介质阻挡放电体系可以有效破环蒽醌发色基团,耦合催化体系不仅强化了蒽醌结构的破坏,同时更加有效地破坏了苯环和萘环结构从而提高了TOC降解率。最后,比较研究了投加Mn2+ 和Cu2+对X-BR的脱色效果,在投加浓度均为0.5 mmol/L条件下,两者对X-BR的脱色起到抑制作用,因此,两者不适合作为耦合催化介质阻挡放电体系的添加离子。     

Solar TiO2-assisted photocatalytic degradation of IGCC power station effluents using a Fresnel lens

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.     

粉煤灰负载铁离子催化氧化活性黄染料废水

以粉煤灰为载体,制备铁/粉煤灰负载型催化剂,并利用该催化剂催化H2O2氧化降解活性黄染料废水,探讨了H2O2投加量、催化剂投加量、染料初始浓度和初始pH值等因素对染料废水COD去除率和脱色率的影响。结果表明,当染料废水COD初始浓度为200 mg/L,初始pH值为1.7,投加0.5 g/100 mL催化剂及加入1.0 mL浓度为1.13 mol/L的H2O2溶液时,处理效果最好,此时染料废水的COD去除率和脱色率分别达到63%和99%,并且废水的可生化性得到很大的提高。利用该负载催化剂能够有效地减少活性黄染料废水中Fe3+的残留量。     

Solar photocatalytic degradation of mono azo methyl orange and diazo reactive green 19 in single and binary dye solutions: adsorbability vs photodegradation rate

The objective of this study was to examine the effects of adsorbability and number of sulfonate group on solar photocatalytic degradation of mono azo methyl orange (MO) and diazo Reactive Green 19 (RG19) in single and binary dye solutions. The adsorption capacity of MO and RG19 onto the TiO₂ was 16.9 and 26.8 mg/g, respectively, in single dye solution, and reduced to 5.0 and 23.1 mg/g, respectively, in the binary dye solution. The data obtained for photocatalytic degradation of MO and RG19 in single and binary dye solution were well fitted with the Langmuir–Hinshelwood kinetic model. The pseudo-first-order rate constants of diazo RG19 were significant higher than the mono azo MO either in single or binary dye solutions. The higher number of sulfonate group in RG19 contributed to better adsorption capacity onto the surface of TiO₂ than MO indicating greater photocatalytic degradation rate.     

La2O3/ZnO/TiO2光催化降解活性艳红K-2BP的研究

采用溶胶-凝胶法制备了La2O3/ZnO/TiO2复合光催化剂,以紫外灯为光源,活性艳红K-2BP为模型降解物,研究了La2O3/ZnO/TiO2的光催化性能。结果表明：当锌和镧的掺杂量w(ZnO)=20%, w(La2O3)=0.5%, 煅烧温度为500℃时,La2O3/ZnO/TiO2复合光催化剂的光催化活性最高;当催化剂投加量4 g/L,通气量800 mL/min,初始pH值3.12时,La2O3/ZnO/TiO2对活性艳红K-2BP的降解效果最好。实验证明,La2O3/ZnO/TiO2对活性艳红K-2BP的降解遵从Langmuir-Hinshelwood动力学模型,测得其反应速率常数k＝11.5 mg/(L·min);吸附常数K＝2.88×10-2 L/mg。     

Photocatalysis enhancement by electric field: TiO2 thin film for degradation of dye X-3B

According to the theory of photocatalysis, the efficiency of photocatalysis decreases mostly due to the recombination of photo-generated electron-hole pairs. An electric field across a photocatalyst can promote the separation of photo-generated electrons and holes and prevent them from recombination so as to enhance the efficiency of photocatalysis. And the synergetic decomposition efficiency of photocatalysis and an electric field is greater than that of the simple combine of their single efficiency. The performance of photocatalysis enhanced by electric field (PEEF) and operating conditions such as the direction of the electric field, the voltages between the two electrodes, the material of the electrodes, which may affect the efficiency of PEEF, were investigated in this paper. The results indicate that the system of PEEF abides the established theory of photocatalysis.