Simulated-sunlight-activated photocatalysis of Methylene Blue using cerium-doped SiO2/TiO2 nanostructured fibers

Cerium-doped SiO₂/TiO₂ nanostructured fibers were fabricated by electrospinning technology. The prepared fibers were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Using the fibers as catalysts, photocatalytic degradation of Methylene Blue (MB) aqueous solution was carried out under simulated sunlight. The 0.2% Ce doping proved to be the optimal concentration for the doping of TiO₂/SiO₂, compared to other Ce-doped molar concentrations. The 0.2% Ce-doped SiO₂/TiO₂ fibers exhibited higher photocatalytic activity than industrial Degussa P25 and the samples doped with only Ce or SiO₂. The reasons for improving the photocatalytic activity were also discussed. Several operational parameters were studied, which showed that the photocatalytic efficiency of MB was influenced by parameters such as the initial dye concentration, the initial pH, inorganic anions, and so on. In addition, the influences of an electron acceptor and a radical scavenger suggested that OH was the dominant photooxidant during the photocatalytic process. The reuse evaluation of the fibers indicated that their photocatalytic activity had good stability.     

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2

Three types of TiO₂ nanostructures were synthesized via a facile hydrolysis method at 195 °C. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO₂ were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller porosimetry, ultraviolet–visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO₂ had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO₂. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N–F-TiO₂ nanomaterial shows considerable potential for water treatment under sunlight irradiation.     

Rubber sheet strewn with TiO2 particles:Photocatalytic activity and recyclability

A new method for the preparation of rubber sheet strewn with titanium dioxide particles (TiO₂-strewn sheet) is presented. This simple and low cost method is based on the use of TiO₂ powder (Degussa P25) being strewn onto the sheet made from rubber latex (60% HA) through a steel sieve. The characteristic of the TiO₂-strewn sheet was studied by using scanning electron microscopy/energy dispersive X-ray spectrometer (SEM/EDS) and X-ray diffractometer (XRD) techniques. The photocatalytic activity of TiO₂-strewn rubber sheet was evaluated using Indigo Carmine (IC) dye as a model for organic dye pollutant in water. The results showed that the TiO₂-strewn sheet could degrade IC dye solution under UV light irradiation. The effects of pH, initial concentration, and the intensity of UV light on the photodegradation were also investigated. Kinetics of the photocatalytic degradation was of the first-order reaction. The used TiO₂-strewn sheet can be recovered and reused. The recycling uses did not require any cleaning between successive uses and no decline in the photodegradation efficiency was observed compared with freshly prepared TiO₂-strewn sheet.     

Synthesis of TiO2 visible light catalysts with controllable crystalline phase and morphology from Ti-bearing electric arc furnace molten slag

TiO₂ visible light catalysts with different crystalline phases and morphologies were synthesized from titanium-bearing electric arc furnace molten slag (Ti-bearing EAF slag) by using a simple acidolysis process. The effects of the pH of the HCl solution, liquid to solid ratio (R_L/S, HCl solution to the residue ratio, mL/g) and acidolysis time on the micro-morphology and crystalline phase of as-prepared TiO₂ photocatalysts were systematically investigated. The results indicated that with decreasing pH in the HCl solution and increasing R_L/S, the crystalline phase and micro-morphology of the obtained TiO₂ nanostructures tended to transform from anatase type TiO₂ with spherical nanoparticle structures to rutile type TiO₂ with needle-like nanorod structures. The acidolysis time had little influence on the crystalline phase but great impact on the size of the obtained TiO₂. The growth mechanism of TiO₂ from Ti-bearing EAF slag during the acidolysis process was also discussed. In addition, the influence of R_L/S on the photocatalytic properties of the synthesized nanostructured TiO₂ was studied. The results showed that the photodegradation efficiency for Rhodamine B solution could reach 91.00% in 120 min when the R_L/S was controlled at 50:1.     

酸性红3B的杂多酸光催化降解动力学

以杂多酸Pw₁₂O^3-₄₀为催化剂,研究了酸性红3B的光催化降解动力学.光强、催化剂浓度、酸性红3B初始浓度对光催化的速率均有正效应其中,光解速率与光强、酸性红3B初始浓度成正比;在催化剂浓度不大(吸光值<2)时,光解速率与催化剂投加量成正比体系中的溶解氧对催化剂起到氧化再生作用;驱氧条件下,由于催化剂再生受到抑制,光解速率减慢Pw₁₂O^3-₄₀光催化降解酸性红3B的动力学符合Langmuir-Hinshelwood模型,溶液中催化剂和酸性红3B之间存在预络合作用,达到平衡后发生光氧化.与UV/TiO₂法相比,uV/PW₁₂O^3-₄₀法降解有机物的速率更快.     

Acid-assisted hydrothermal synthesis of nanocrystalline TiO2 from titanate nanotubes: Influence of acids on the photodegradation of gaseous toluene

In order to efficiently remove volatile organic compounds (VOCs) from indoor air, onedimensional titanate nanotubes (TiNTs) were hydrothermally treated to prepare TiO₂ nanocrystals with different crystalline phases, shapes and sizes. The influences of various acids such as CH₃COOH, HNO₃, HCl, HF and H₂SO₄ used in the treatment were separately compared to optimize the performance of the TiO₂ nanocrystals. Comparedwith the strong and corrosive inorganic acids, CH₃COOH was not only safer andmore environmentally friendly, but also more efficient in promoting the photocatalytic activity of the obtained TiO₂. Itwasobserved that the anatase TiO₂ synthesized in 15 mol/L CH₃COOH solution exhibited the highest photodegradation rate of gaseous toluene (94%), exceeding that of P25 (44%) by a factor ofmore than two. The improved photocatalytic activity was attributed to the small crystallite size and surface modification by CH₃COOH. The influence of relative humidity (20%-80%) on the performance of TiO₂ nanocrystals was also studied. The anatase TiO₂ synthesized in 15 mol/L CH₃COOH solution was more tolerant tomoisture than the other TiO₂ nanocrystals and P25.     

Efficient dechlorination of chlorinated solvent pollutants under UV irradiation by using the synthesized TiO2 nano-sheets in aqueous phase

Titanium dioxide(TiO2), which is the widely used photo-catalyst, has been synthesized by simple hydrothermal solution containing tetrabutyl titanate and hydrofluoric acid. The synthesized product has been applied to photo-degradation in aqueous phase of chlorinated solvents, namely tetrachloroethene(PCE), trichloroethene(TCE) and 1,1,1-trichloroethane(TCA). The photo-degradation results revealed that the degradation of these harmful chemicals was better in UV/synthesized TiO2 system compared to UV/commercial P25 system and UV only system. The photo-catalytic efficiency of the synthesized TiO2 was 1.4, 1.8 and 3.0 folds higher compared to the commercial P25 for TCA, TCE and PCE degradation, respectively. Moreover, using nitrobenzene(NB) as a probe of hydroxyl radical(.OH), the degradation rate was better over UV/synthesized TiO2, suggesting the high concentration of.OH generated in UV/synthesized TiO2system. In addition,.OH concentration was confirmed by the strong peak displayed in EPR analysis over UV/synthesized TiO2system. The characterization result using XRD and TEM showed that the synthesized TiO2 was in anatase form and consisted of well-defined sheet-shaped structures having a rectangular outline with a thickness of 4 nm, side length of 50 nm and width of 33 nm and a surface 90.3 m2/g. XPS analysis revealed that ≡Ti-F bond was formed on the surface of the synthesized TiO2. The above results on both photocatalytic activity and the surface analysis demonstrated the good applicability of the synthesized TiO2 nano-sheets for the remediation of chlorinated solvent contaminated groundwater.     

磷钨酸光催化降解染料废水研究

以253.7m紫外灯和太阳光为光源,研究了磷钨酸对几种模拟染料废水的光催化脱色性能,实验结果表明,深溶初始pH值及调节溶液pH值所用酸的类型对磷钨酸光催化活性有影响;催化剂投加量及溶液初始浓度是影响溶液脱色率的重要因素,当溶液中磷钨酸的浓度为0.03g/L,初始pH值为2,初始浓度为10mg/L的甲基橙,甲基红、酸性大红及墨水蓝溶液,阳光辐照3h,除墨水蓝外,其它各溶液脱色率均可达到90%以上。     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

Evaluating the effectiveness of marine actinobacterial extract and its mediated titanium dioxide nanoparticles in the degradation of azo dyes

Aim of the present study was to synthesize titanium dioxide nanoparticles （YiO2 NPs） from marine actinobacteria and to develop an eco-friendly azo-dye degradation method. A total of five actinobacterial isolates were isolated from Chennai marine sediments, Tamilnadu, India and analyzed for the synthesis of TiO2 NPs using titanium hydroxide. Among these, the isolate PSV 3 showed positive results for the synthesis of TiO2 NPs, which was confirmed by UV analysis. Further characterization of the synthesized TiO2 NPs was done using XRD, AFM and FI＇-IR analysis. Actinobacterial crude extract and synthesized TiO2 NPs was found efficient in degrading azo dye such as Acid Red 79 （AR-79） and Acid Red 80 （AR-80）. Degradation percentage was found to be 81% for AR-79, 83% for AR-80 using actinobacterial crude extract and 84% for AR-79, 85% for AR-80 using TiO2 NPs. Immobilized actinobacterial ceils showed 88% for AR-79 and 81% for AR- 80, dye degrading capacity. Degraded components were characterized by FT-IR and GC-MS analysis. The phytotoxicity test with 500 μg/mL of untreated dye showed remarkable phenotypic as well as cellular damage to Tagetes erecta plant. Comparatively no such damage was observed on plants by degraded dye components. In biotoxicity assay, treated dyes showed less toxic effect as compared to the untreated dyes.     

Decolorization of dye solutions with Ruditapes philippinarum conglutination mud and the isolated bacteria

Application of Ruditapes Philippinarum conglutination mud (RPM) for decolorizing synthetic dye solutions was studied. RPM showed good activity for decolorization of Methylene Blue, Crystal Violet, Malachite Green, and Ink Blue. The amount of the RPM had great effect on the decoloration rate of the dye solutions. However, the decoloration rate did not continue to increase when the amount of mud exceeded the optimum dose. The temperature of the dye solution had a remarkable effect on the decolorization rate of Ink Blue solution, but had little effect on the other three dye solutions. The initial pH of the dye solutions evidently affected the decolorization rate of Malachite Green solution, but had less effect on the other three. The decolorization rate of the dye solutions increased significantly with treatment time within 8 hr, but tended to be steady after 8 hr for Methylene Blue, Crystal Violet and Malachite Green solutions, and after 12 hr for Ink Blue solution. The decolorization efficiencies for the four dye solutions under the optimum conditions were all above 90%. Seventeen strains screened from RPM showed flocculation ability for kaolin clay suspension. Out of them, the flocculation rate of strain ZHT3-9 and strain ZHT4-13 were up to 88.14% and 86.01%, respectively. ZHT3-9 was studied, and its decolorization rate for Methylene Blue, Crystal Violet, and Malachite Green reached 90.02%, 89.21%, and 80.29%, respectively. By morphological, physiological and biochemical characteristics analysis and 16S rRNA sequencing, the strain ZHT3-9 was identified as Arthrobacter sp.     

Surface modification of polypropylene non-woven fibers with TiO2 nanoparticles via layer-by-layer self assembly method: Preparation and photocatalytic activity

Polypropylene (PP) meltblown fibers were coated with titanium dioxide (TiO₂) nanoparticles using layer-by-layer (LbL) deposition technique. The fibers were first modified with 3 layers of poly(4-styrenesulfonic acid) (PSS) and poly(diallyl-dimethylammonium chloride) (PDADMAC) to improve the anchoring of the TiO₂ nanoparticle clusters. PDADMAC, which is positively charged, was then used as counter polyelectrolyte in tandem with anionic TiO₂ nanoparticles to construct TiO₂/PDADMAC bilayer in the LbL fashion. The number of deposited TiO₂/PDADMAC layers was varied from 1 to 7 bilayer, and could be used to adjust TiO₂ loading. The LbL technique showed higher TiO₂ loading efficiency than the impregnation approach. The modified fibers were tested for their photocatalytic activity against a model dye, Methylene Blue (MB). Results showed that the TiO₂ modified fibers exhibited excellent photocatalytic activity efficiency similar to that of TiO₂ powder dispersed in solution. The deposition of TiO₂ 3 bilayer on the PP substrate was sufficient to produce nanocomposite fibers that could bleach the MB solution in less than 4 hr. TiO₂-LbL constructions also preserved TiO₂ adhesion on substrate surface after 1 cycle of photocatalytic test. Successive photocatalytic test showed decline in MB reduction rate with loss of TiO₂ particles from the substrate outer surface. However, even in the third cycle, the TiO₂ modified fibers are still moderately effective as it could remove more than 95% of MB after 8 hr of treatment.     

TiO2/膨润土复合材料对Hg2+的吸附性能研究

利用纳米TiO_2对膨润土进行复合改性,制备TiO_2/膨润土复合材料.采用电镜扫描、X-射线衍射表征改性前后膨润土的结构和形貌.通过室内模拟实验,以膨润土为对照,研究不同添加量、pH、吸附时间及初始Hg~(2+)浓度等条件下,TiO_2/膨润土复合材料对Hg~(2+)的吸附特性与性能,同时通过正交试验,探究TiO_2/膨润土复合材料吸附Hg~(2+)的最优条件.结果表明,改性后的膨润土颗粒明显变小,且颗粒疏松多空孔,层间距增大.相比于膨润土,TiO_2/膨润土复合材料吸附性能得到极大提高.TiO_2/膨润土复合材料对Hg~(2+)的吸附率均随着添加量、pH、吸附时间的增大而增大,添加量为1.5 g·L~(-1)、pH为7.0、吸附时间为120 min时,吸附率达98.0%以上.但TiO_2/膨润土复合材料对Hg~(2+)的吸附率随着初始Hg~(2+)浓度的增大而减小.通过4种动力学模型拟合发现,吸附过程符合假二级动力学方程,吸附以化学吸附为主.吸附等温线更符合Langmuir等温方程,属于典型的单分子层吸附,最大吸附量为20.66 mg·g-1.吸附Hg~(2+)的最优实验条件:添加量为2.0 g·L~(-1),pH为8.0,初始Hg~(2+)浓度为45 mg·L~(-1),吸附时间为16 h,此时吸附率99.9%,平衡浓度为0.034 mg·L~(-1).     

光催化氧化法处理染料中间体H酸水溶液

为了去除水中难氧化的有害染料中间体Ｈ酸,研究以ＴＩＯ２、ＺｎＯ、ＣｄＳ和Ｆｅ２Ｏ３为催化剂,采用低压汞灯为光源,对Ｈ酸水溶液进行光催化氧化实验．结果表明：ＴｉＯ２和ＣｄＳ的催化效果最好．采用ＴｉＯ２作催化剂,光催化氧化５ｈ后,Ｈ酸分解率可达９０％,反应速率遵从Ｌａｎｇｍｕｉｒ－Ｈｉｎｓｈｅｌｗｏｏｄ方程,Ｋ＝１２．３Ｌ／ｍｍｏｌ,ｋ＝２５．２×１０－６ｍｏｌ／ｈ．溶液中投加１０ｍｇ／Ｌ的Ｆｅ３＋或Ａｇ＋,可使反应时间缩短２—３ｈ．研究探讨了ｐＨ、ＴｉＯ２投加量和Ｈ酸浓度对催化氧化过程的影响．     

羧基稻草阳离子吸附剂的制备及其去除水溶液中亚甲蓝的研究

为促进工业废水处理并降低废水处理费用,研究了柠檬酸热化学酯化法改性稻草制备可生物降解阳离子吸附剂的方法.实验比较了天然和改性稻草去除溶液中阳离子染料(亚甲蓝)的能力,研究了不同实验参数(pH值、吸附剂量、染料浓度、离子强度、吸附时间)对亚甲蓝吸附效果的影响在pH为2～10范围内,天然稻草去除亚甲蓝的能力随pH值的增加而增加,而改性稻草在pH≥3时对染料的去除率达到最大.改性稻草用量大于1.5g·L-1时几乎能完全去除浓度为250mg·L-1亚甲蓝溶液中的染料.改性稻草用量为2.0g·L-1对浓度为50～450mg·L-1的亚甲蓝溶液去除率保持在98%以上.增加溶液的离子强度会导致亚甲蓝去除率降低.染料吸附等温线符合Langmuir模式.吸附过程符合准一级反应动力学方程.酯化改性使染料的吸附剂粒子内扩散速率常数(kid)大大增加.研究结果表明,改性稻草是良好的亚甲蓝吸附剂.     

RGO/TiO2光催化降解2,4-二氯苯氧乙酸研究

通过Hummers法及紫外光/热还原工艺制得还原氧化石墨烯(RGO),采用溶胶-凝胶-煅烧法,以RGO和钛酸酊脂为前驱体制备出RGO/TiO2光催化复合材料,并利用XRD、FT-IR等对其进行了表征.对RGO/TiO2光催化降解性能的研究发现,复合光催化剂RGO/TiO2对2,4-二氯苯氧乙酸(2,4-D)的光催化降解活性显著优于纯TiO2,并且发现负载量和pH值对光催化降解性能有较大的影响:RGO/TiO2投加量为1.2g·L~(-1)、RGO负载量2%、pH为3、初始浓度为50 mg·L~(-1)反应12 h,2,4-D去除率达到98.75%;2,4-D降解率随着RGO/TiO2投加量的增大先增大后减小;RGO/TiO2对2,4-D的降解为脱氯还原和催化氧化过程,产生氯酚、苯酚等中间产物.     

TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应

以内分泌干扰物阿特拉津为模型污染物,研究了TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应.结果表明,在H2O2存在条件下,金红石TiO2经可见光激发可持续稳定地产生.OH自由基,在Fe3+协同作用下,.OH自由基生成量急剧增加;TiO2能可见光催化H2O2降解阿特拉津,金红石TiO2显示出较锐钛矿TiO2及混晶TiO2(TiO2P25)更高的催化活性,反应60 min,阿特拉津的降解率可达40%;以Fe3+协同TiO2可见光催化H2O2降解阿特拉津时,反应效率显著加快,反应5 min即对阿特拉津的降解率达到100%,而金红石TiO2显示出更为明显的协同效应.     

酸度对染料臭氧化脱色效果及溶液毒性的影响

研究了20种染料溶液在臭氧氧化过程中吸光度的变化以及pH对氧化速率的影响,应用发光菌毒性检测法测定了活性翠兰KN-G,直接混纺大红D-GLN和酸性橙Ⅱ三种染料溶液在臭氧氧化过程中的急性毒性. 结果表明:臭氧氧化20种染料的脱色过程符合一级反应动力学,其相关系数(R2)均大于0.950 0,反应溶液的初始pH对染料的脱色率有一定的影响. 染料溶液初始浓度相同时,pH为2的酸性条件更有利于染料的降解,在前45 s,酸性溶液脱色率比中性溶液高出了6%～25%. 在臭氧氧化染料溶液的过程中,溶液接近无色时,毒性较大,但随着氧化的进行其毒性逐渐降低.      

TiO2诱导下左旋氧氟沙星的可见光降解及其机制

左旋氧氟沙星是一种新型污染物.单一的左旋氧氟沙星(LFV)和Ti O2无可见光响应,但二者共存下左旋氧氟沙星能发生显著的可见光降解.为此研究Ti O2用量、溶液p H以及左旋氧氟沙星浓度对Ti O2/Vis(可见光)降解左旋氧氟沙星的影响及机制.结果表明,左旋氧氟沙星能吸附在Ti O2表面,吸附服从准二级吸附动力学和Langmuir吸附等温线.吸附左旋氧氟沙星的Ti O2漫反射UV-Vis光谱进一步表明二者形成表面复合物.左旋氧氟沙星的Ti O2/Vis降解动力学符合LangmuirHinshelwood方程.合适的Ti O2浓度和中性p H有利于光解过程的进行.自由抑制实验、N2保护下左旋氧氟沙星的Ti O2/Vis降解实验揭示·O-2是该过程中的主要活性物种.同时,无氧左旋氧氟沙星-Ti O2悬浮液光照不同时间的UV-Vis光谱证明体系中存在电子向Ti O2导带的注入.依据实验结果提出吸附在Ti O2表面的左旋氧氟沙星与Ti O2形成表面复合物,在可见光照下发生电子迁移,从而引发左旋氧氟沙星降解.本研究表明利用污染与Ti O2形成表面复合物诱导其可见光降解可用来去除水中某些有机污染物.     

Adsorption of Disperse Blue SBL dye by synthesized poorly crystalline hydroxyapatite

The present study has been undertaken to evaluate the adsorption in batch mode of a disperse dye (Disperse Blue SBL) by poorly crystalline hydroxyapatite synthesized by coprecipitation between Ca(NO_3)_2 and (NH_4)_2HPO4 reagents in aqueous solution at room temperature. The adsorption experiments were carried out to investigate the factors that influence the dye uptake by the adsorbent, such as the contact time under agitation, adsorbent dosage, initial dye concentration, solution temperature, and pH. The e...