Photocatalytic degradation of methyl orange by TiO2-coated activated carbon and kinetic study

TiO2-coated activated carbon (AC) grain (TiO2/AC) was prepared through hydrolytic precipitation of TiO2 from Tetrabutylorthotitanate and following heat treatment. The TiO2/AC was characterized by BET, SEM, XRD and optical absorption spectroscopy. The samples were employed as catalysts for methyl orange photocatalytic oxidation degradation in aqueous suspension, used as probe reaction. The kinetics of methyl orange photodegradation was analyzed. The results indicate that BET surface area of TiO2-coated ACs decreased drastically in comparison with the original AC with increasing TiO2 coatings by more than 1 doped cycle. Nano-TiO2 particles were dispersed on the AC with the size of 20-40 nm. Crystalline TiO2 doped onto AC was from anatase to rutile with increase of heat-treatment temperature. The TiO2/AC was shown high photoactivity for the photodegradation of methyl orange (MO) dyestuff in aqueous solution under UV irradiation. The kinetics of photocatalytic MO dyestuff degradation was found to follow a pseudo-first-order rate law. It was observed that the presence of the AC enhanced the photoefficiency of the titanium dioxide catalyst. Different amount of TiO2 coatings induced different increases in the apparent first-order rate constant of the process. The kinetic behavior could be described in terms of a modified Langmuir-Hinshelwood model. The values of the adsorption equilibrium constants for the organic molecules, KC, and for the rate constants, kc, were certainly dependent on TiO2 content. At 47wt% TiO2 coatings with the highest rate constant, the KC and kc was 0.1116l mmol(-1) and 0.1872 mmol l(-1) min(-1), respectively. The mechanism of methyl orange degradation was discussed in terms of the titanium dioxide photosensitization by the AC.     

Treatment of textile dyehouse wastewater by TiO2 photocatalysis

The oxidative degradation of an actual textile dyehouse wastewater was investigated by means of photocatalysis in the presence of TiO2. The UV-A-induced photocatalytic oxidation over TiO2 suspensions was capable of decolorizing the effluent completely, as well as reducing chemical oxygen demand (COD) sufficiently (COD reduction generally varied between about 40% and 90% depending on the operating conditions) after 4 h of treatment. Two crystalline forms of TiO2, viz. anatase and rutile, were tested for their photocatalytic activity and anatase was found to be more active than rutile. The extent of photocatalytic degradation was found to increase with increasing TiO2 concentration up to 0.5 g/L TiO2, above which degradation remained practically constant, reaching a plateau. Furthermore, textile effluent degradation was enhanced at acidic conditions (i.e. pH = 3) and in the presence of hydrogen peroxide. To assess catalyst activity on repeated use, experiments were performed where the catalyst was recovered and reused; after three successive uses, TiO2 had sufficiently retained its photocatalytic activity. Finally, the luminescent marine bacteria Vibrio fischeri was used to assess the acute ecotoxicity of samples prior to and after the photocatalytic treatment and it was found that ecotoxicity was fully eliminated following photocatalytic oxidation.     

Visible-light-induced photocatalysis of low-level methyl-tertiary butyl ether (MTBE) and trichloroethylene (TCE) using element-doped titanium dioxide

While the photocatalytic degradation of various volatile organic compounds in conjunction with UV light has been widely reported, visible-light-induced photocatalytic degradation of low-levels of the pollutants MTBE and TCE, which have been linked to potential adverse health effects, is rarely reported. The present study examined whether visible-light-activated S- or N-doped TiO₂ photocatalytic technology can be used to control indoor concentrations of MTBE and TCE. This study consists of the characterization of the doped TiO₂ powders, as well as an investigation of their photocatalytic activities. In regards to both powders, a shift of the absorbance spectrum towards the visible light region was observed. An activity test suggested that these photocatalysts exhibited reasonably high degradation efficiencies towards MTBE and TCE under visible light irradiation. The degradation efficiencies of MTBE and TCE by S- and N-doped photocatalysts exceeded 75 and 80%, respectively, at input concentrations (IC) of 0.1 ppm. Degradation efficiency was dependent on both IC and relative humidity. TCE could enhance the degradation efficiency of MTBE even under visible-light irradiation. The estimated mineralization efficiencies (MEs) were comparable to those of previous studies conducted with UV/TiO₂ systems. Similar to the relative degradation efficiencies, the ME of TCE was higher in comparison to that of MTBE. The CO production measured during the photocatalytic processes represented a negligible addition to indoor CO levels. These results suggest that visible-light-activated S- and N-doped TiO₂ photocatalysts may prove a useful tool in the effort to improve indoor air quality.     

Surface modification of TiO2 by a ruthenium(II) polypyridyl complex via silyl-linkage for the sensitized photocatalytic degradation of carbon tetrachloride by visible irradiation

A new ruthenium(II) photosensitizer, [Ru(II)(py-pzH)(3)](2+) (where py-pzH=3-(2'-pyridyl)pyrazole), has been synthesized. The complex displayed outstanding excited state redox properties (estimated Ru(III)/Ru(II)* approximately -1.24 V vs. NHE) and was expected to sensitize the injection of electrons into the conduction band of anatase TiO(2) upon visible irradiation. The photosensitizer was anchored onto the surface of anatase TiO(2) particles via in situ silylation. The silyl-linkage displayed excellent stability in both aqueous media, over a wide pH range, and in common organic solvents. The resultant material, TiO(2)-[Ru(II)(py-pz-Si identical with )(3)], was found to be able to mediate degradation of CCl(4) in neutral aqueous medium under broad band visible irradiation (lambda>450 nm). The relation between the rate of degradation and concentration of substrate was explored and the mechanism of the photodegradation of the perhalogenated organic was discussed.     

Preliminary trial on degradation of waste activated sludge and simultaneous hydrogen production in a newly-developed solar photocatalytic reactor with AgX/TiO2-coated glass tubes

A solar fluidized tubular photocatalytic reactor (SFTPR) with simple and efficient light collector was developed to degrade waste activated sludge (WAS) and simultaneously produce hydrogen. The photocatalyst was a TiO₂ film doped by silver and silver compounds (AgX). The synthesized photocatalyst, AgX/TiO₂, exhibited higher photocatalytic activity than TiO₂ (99.5% and 30.6% of methyl orange removal, respectively). The installation of light collector could increase light intensity by 26%. For WAS treatment using the SFTPR, 69.1% of chemical oxygen demand (COD) removal and 7866.7 μmol H₂/l-sludge of hydrogen production were achieved after solar photocatalysis for 72 h. The SFTPR could be a promising photocatalysis reactor to effectively degrade WAS with simultaneous hydrogen production. The results can also provide a useful base and reference for the application of photocatalysis on WAS degradation in practice.     

Degradation of paracetamol in aqueous solutions by TiO2 photocatalysis

In this study, photo/photocatalytic oxidation of common analgesic and antipyretic drug, paracetamol (acetaminophen), was investigated to determine the optimal operating conditions for degradation in water. UVA (365 nm) radiation alone degraded negligible amount of paracetamol, whereas paracetamol concentration decreased substantially under an irradiation of UVC (254 nm) with marginal changes in total organic carbon (TOC). In the presence of TiO2, much faster photodegradation of paracetamol and effective mineralization occurred; more than 95% of 2.0mM paracetamol was degraded within 80 min. The degradation rate constant decreased with an increase in the initial concentration of paracetamol, while it increased with light intensity and oxygen concentration. The degradation rate also increased with TiO2 loading until a concentration of 0.8 g L(-1). The degradation rate slowly increased between pH 3.5 and 9.5, but significantly decreased with increasing pH between 9.5 and 11.0. Based on the experimental data, a kinetic equation describing paracetamol photocatalytic degradation with various process parameters is obtained.     

Effects of water parameters on the degradation of microcystin-LR under visible light-activated TiO2 photocatalyst

A study was performed to determine the effect of pH, alkalinity, natural organic matter (NOM) and dissolved oxygen in the performance of nitrogen and fluorine doped TiO₂ (NF-TiO₂) for the degradation of hepatotoxin microcystin-LR (MC-LR) in synthetic and natural water under visible light irradiation. The initial degradation rate of MC-LR was fastest under acidic conditions (3.50 ± 0.02 × 10⁻³ μM min⁻¹ at pH 3.0) and decreased to 2.29 ± 0.07 × 10⁻³ and 0.54 ± 0.02 × 10⁻³ μM min⁻¹ at pH 5.7 and 7.1, respectively. Attractive forces between the opposite charged MC-LR and NF-TiO₂ are likely responsible for the enhancement in the photocatalytic decomposition of MC-LR resulting from increased interfacial adsorption. For carbonate buffered solutions, the photocatalytic activity of NF-TiO₂ was reduced when increasing the carbonate concentration up to 150 mg CaCO₃ L⁻¹. The scavenging of radical species by the bicarbonate ion at pH 7.1 is discussed. In the presence of NOM, the degradation rates decreased as pH and initial concentration of the NOM increased. The inhibition was higher with fulvic acid than humic acid under alkaline conditions. Oxygenated solution yields higher NF-TiO₂ photocatalytic degradation of MC-LR compared to nitrogen sparged solution at pH 5.7. The involvement of specific reactive oxygen species implicated in the photodegradation is proposed. Finally, no significant degradation is observed with various natural waters spiked with MC-LR under visible light (λ > 420 nm) but high removal was achieved with simulated solar light. This study provides a better understanding of the interactions and photocatalytic processes initiated by NF-TiO₂ under visible and solar light. The results indicate solar photocatalytic oxidation is a promising technology for the treatment of water contaminated with cyanotoxins.     

共掺杂Cu-Ce/TiO2光催化降解室内甲醛气体的研究

采用溶胶-凝胶法制备Cu-Ce/TiO2纳米颗粒,在环境测试仓内进行甲醛的可见光催化降解实验,评估其光催化活性.正交实验结果表明:3个因素对其光催化效果影响的程度是Cu-Ce掺杂负载量＞Cu-Ce摩尔比＞烧结温度;在可见光条件下对甲醛气体光催化效果的优化方案为:Cu-Ce掺杂负载量3%,Cu-Ce掺杂摩尔比1:1,烧结温度500℃.     

Photocatalytic degradation of trichloroethylene in water using TiO2 pellets

A recirculating system of aqueous trichloroethylene (TCE) solutions through the packed bed reactor with TiO2 pellets has been developed in order to mineralize TCE without difficulties for filtration and recovery of catalyst. The TiO2 pellets prepared by sol gel method have photocatalytic activity similar to commercially available PC-101 and PC-102 in the powder form and to ST-B11 pellets. In batch experiments with TiO2 powders, Degussa P-25 is the most active photocatalyst, which indicates that specific surface area is not an important factor controlling the photocatalytic activity in aqueous solutions. The degradation rates of TCE in the recirculating system with TiO2 pellets decreased in the presence of H2O2, while were remarkably accelerated by adding S2O8(2-). The presence of S2O8(2-) ions more than 0.01 mol dm(-3) completely suppressed hole-electron recombination and mineralized 50 ppm TCE with the 2 h irradiation. In a reactor without TiO2 photocatalysts, TCE was photodegraded by SO4- radicals which produced by photodissociation of S2O8(2-). The degradation rates increased with increase of the initial S2O8(2-) concentration. However, TCE was not mineralized but converted to intermediates which were slowly degraded to Cl- by continuing the irradiation.     

Effect of Pt/TiO2 characteristics on temporal behavior of o-cresol decomposition by visible light-induced photocatalysis

Platinum deposited TiO(2) films were prepared on quartz substrates by dip-coating process for the photodecomposition of o-cresol. The characteristics of Pt/TiO(2) and the temporal behavior of o-cresol decomposition by Pt/TiO(2) photocatalysis under visible light irradiation were investigated. Platinum deposited on TiO(2) photocatalysts was characterized by Brunauer-Emmett-Teller (BET) surface area measurement, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), diffuse reflectance UV-Vis spectra (DRS) and photoluminescence (PL) emission spectra. The results indicated that the deposition of platinum on TiO(2) promoted the optical absorption in the visible region and made it possible to be excited by visible light. The decomposition rate of o-cresol under visible light irradiation from a fluorescent lamp was enhanced to noticeably extents for experiments conducted with Pt/TiO(2) containing platinum up to 0.50wt% platinum because of the presence of Ti(3+) resulted from the platinum deposited on the TiO(2) surface; and the formation of Schottky Barrier between platinum and TiO(2) preventing the recombination of electric holes and electrons. Specifically, the reaction rate of o-cresol photodegradation at pH 9 using the 0.50wt% Pt/TiO(2) was 4.8 times than that of using pure TiO(2). The intermediates identified by GC/MS spectroscopy during the photocatalytic oxidation of o-cresol. The proposed kinetic model could be adequately applied to describe the temporal behavior of the o-cresol decomposition with and without the dosage of Pt on TiO(2) in aqueous solution by UV/TiO(2) process.     

The preparation of TiO2 nanometer photocatalyst film by a hydrothermal method and its sterilization performance for Giardia lamblia

The photocatalytic property of TiO(2) is utilized to sterilize the Giardia lamblia in an aqueous solution in this study. The TiO(2) colloidal solution used for the film was prepared by the modified hydrothermal method and it was directly coated on a UV-lamp, which was set up using a photoreactor manufactured in our laboratory. The TiO(2) film was very stably attached to the UV-lamp, and it was transparent until 5-time coating. The size of the TiO(2) particle in the film was distributed around 20-30 nm and the film thickness was about 200 nm per 1-time coating.The G. lamblia cell was just partially damaged under UV-irradiation without a TiO(2) photocatalyst, but the dead cell became very small and the dead body finally disappeared with an increase in the intensity of UV-irradiation after 2 h. In addition, under the TiO(2)/UV-irradiation system, the sterilized (dead) rate of G. lamblia was very fast. The sterilizing power increased at lower pH in the initial step, but it rather increased at a higher pH in the final step. And the sterilization of G. lamblia was very sensitive to the temperature, and resulted in an increase in the sterilized rate at higher temperatures. On the basis of these experimental observations, it can be concluded that TiO(2) photocatalyst under UV-irradiation could be adopted as one of the sterilization modalities for the G. lamblia.     

CdS/TiO2改性混凝土光催化性能研究

利用高能球磨法将纳米TiO2和CdS进行复合,制备能够响应可见光的纳米复合光催化剂CdS/TiO2。采用掺入法将复合CdS/TiO2等量替换水泥制备光催化混凝土试块,本实验研究了不同掺量(0、2%、5%、8%)对混凝土的光催化性能的影响。通过降解甲基橙的实验发现,在紫外光下,同掺量的纯TiO2混凝土与复合CdS/TiO2混凝土的催化性能相差不大;在可见光下,CdS/TiO2改性混凝土与纯TiO2混凝土相比,催化性能有所提高,5%掺量的CdS/TiO2(400r/min)混凝土光催化效果最佳,催化效率最高达到纯TiO2混凝土的1.4倍。     

Photocatalytic degradation of Reactive Red 22 in aqueous solution by UV-LED radiation

Photocatalytic processes using TiO(2) as a catalyst have attracted extensive attention for decomposition of organic contaminants. The determination of optimum reactor design and operational conditions are the major concerns for the development and potential application of the photocatalytic process. Various photoreactor types, photocatalyst arrangements, light sources, and operation conditions were reported. This study was focused on the application of the ultraviolet light emitting diode (UV-LED) as the UV light source for the photocatalytic decomposition of Reactive Red 22 (RR 22). The temporal behavior of the photocatalytic decomposition of RR 22 in aqueous solution by the UV-LED/TiO(2) with a rectangular planar fixed-film reactor operated in a recirculation mode was studied under various conditions including initial dye concentration, periodic illumination, light intensity, and arrangements of TiO(2) coating. The decomposition of RR 22 in aqueous solution by TiO(2) photocatalytic processes with the UV-LED was found to be technically feasible with a high TiO(2) coated weight (1.135g) and low pH value (pH 2). A Langmuir-Hinshelwood-type kinetic equation was adequate for modeling the photocatalytic decomposition of RR 22 by the UV-LED/TiO(2) photocatalytic processes. The experimental results indicated that the photonic efficiency with periodic illumination was much higher than those with continuous illumination. The photonic efficiencies with the quartz-liquid-catalyst (QLC) arrangement were higher than those with the quartz-catalyst-liquid (QCL) arrangement for experiments conducted at lower applied light intensity; however, the photonic efficiencies for these two arrangements were nearly identical for experiments conducted at higher light intensities.     

H2O2/TiO2 photocatalytic oxidation of metol. Identification of intermediates and reaction pathways

The applicability of H2O2 to increase the efficiency of TiO2 photocatalytic degradations was investigated. The photographic developer metol [N-methyl-p-aminophenol] that does not adsorb on the surface of TiO2 particulates was used as a model for this purpose. It was proved that metol was mineralised under oxidation with H2O2/TiO2/UV through different thermal and photochemical reactions. Identification of intermediates by both HPLC-electron impact-MS and HPLC-electrospray ionisation-MS helped to elucidate the role of H2O2 and TiO2 in the degradation process and to establish degradation pathways. Intermediates yielded were partially oxygenated aromatic species and dimers, which were amenable to oxidation. The optimal degradation conditions found for mineralisation were 0.4 M H2O2, 5 mg/ml TiO2, pH 9 and irradiation centred at 360 nm (4.9 mW/cm2). The use of oxidants opens an interesting medium to the treatment of effluents containing a diversity of organics since they increase substantially the efficiency of TiO2 photocatalytic degradations.     

Enhancement of photocatalytic activity by metal deposition: characterisation and photonic efficiency of Pt, Au and Pd deposited on TiO2 catalyst

Pt, Au and Pd deposited TiO2 have been prepared and characterised by surface analytical methods such as surface area, XRD, and scanning electron micrograph and photophysical characterisation by diffuse reflectance spectroscopy. The photocatalytic activity of the doped catalysts was ascertained by the photo-oxidation of leather dye, acid green 16 in aqueous solution illuminated with low-pressure mercury lamp ( approximately 254 nm). The effect of metal contents on the photocatalytic activity was investigated. The highest photonic efficiency was observed with metal deposition level of less than 1 wt%.     

纳米TiO_2对水中对羟基苯甲酸吸附及光催化降解

以BDH粉末TiO2为光催化剂,研究了水体中对羟基苯甲酸在纳米Ti02颗粒上的吸附行为,并研究了时羟基苯甲酸的二氧化钛光催化降解效果.结果表明:TiO2对羟基苯甲酸的吸附作用明显依赖于水溶液的pH,对羟基苯甲酸的光催化降解效果与其在催化剂表面的吸附行为密切相关,提高吸附速率,对羟基苯甲酸的去除率也随之提高.     

Photocatalytic degradation of non-steroidal anti-inflammatory drugs with TiO2 and simulated solar irradiation

The aim of this work is to evaluate and compare the degradation achieved for three non-steroidal anti-inflammatory drugs (NSAIDs) by heterogeneous TiO2 photocatalytic means in aqueous solution at laboratory scale. The selected pharmaceutical compounds were diclofenac (DCF), naproxen (NPX) and ibuprofen (IBP). These compounds were used in their sodium salt chemical form. Previous experiments (adsorption, photolysis and thermodegradation) were developed to evaluate non-catalytic degradation for each NSAID. Photocatalytic experiments were carried out in a Xe-lamp reactor in order to study the influences of different operational conditions (catalyst load, temperature and dissolved oxygen concentration). These results showed that the optimum amount of TiO2, to achieve maximum degradation, of IBP was 1g/L. In contrast, the maximum degradation for DCF or NPX was observed at a TiO2 loading of 0.1g/L. Temperature had a significant effect only for NPX degradation, achieving almost 99% phototransformation. No significant differences were observed for DCF and IBP at 20, 30 and 40 degrees C. Dissolved oxygen concentration was an important parameter to increase the degradation for NPX and IBP. However, it was observed that its rate of mineralization did not increase. Intermediate metabolites were detected in all cases. Hydroxyl metabolites were the most important residual compounds after the photocatalytic treatment of IBP. The inhibition percentage of bioluminescence from Vibro fischeri--as a toxicity parameter--increased during the irradiation time due to the residual concentration of the hydroxyl metabolites generated. However, after 120 min, in experiments with 40 mg/L of dissolved oxygen, a decrease of the % inhibition was observed. Only photocatalytic treatment of IBP drives to a satisfactory biodegradability index BOD5/COD (between 0.16 and 0.42) and, only in this case, a post-biological treatment could be suggested.     

Preparation and photocatalytic performance of Fe (III)-amidoximated PAN fiber complex for oxidative degradation of azo dye under visible light irradiation

Polyacrylonitrile (PAN) fiber was modified with hydroxylamine hydrochloride to introduce amidoxime groups onto the fiber surface. These amidoxime groups were used to react with Fe (III) ions to prepare Fe (III)-amidoximated PAN fiber complex, which was characterized using SEM, XRD, FTIR, XPS, DMA, and DRS respectively. Then the photocatalytic activity of Fe-AO-PAN was evaluated in the degradation of a typical azo dye, C. I. Reactive Red 195 in the presence of H₂O₂ under visible light irradiation. Moreover, the effect of the Fe content of Fe-AO-PAN on dye degradation was also investigated. The results indicated that Fe (III) ions can crosslink between the modified PAN fiber chains by the coordination of Fe (III) ions with the amino nitrogen atoms and hydroxyl oxygen atoms of the amidoximation groups to form Fe (III)-amidoximated PAN fiber complex, and the Fe content of which is mainly determined by Fe (III) ions and amidoximation groups. Fe (III)-amidoximated PAN fiber complex is found to be activated in the visible light region. Moreover, Fe (III)-amidoximated PAN fiber complex shows the catalytic activity for dye degradation by H₂O₂ at pH = 6.0 in the dark, and can be significantly enhanced by increasing light irradiation and Fe content, therefore, it can be used as a new heterogeneous Fenton photocatalyst for the effective decomposition of the dye in water. In addition, ESR spectra confirm that Fe (III)-amidoximated PAN fiber complex can generate more OH radicals from H₂O₂ under visible light irradiation, leading to dye degradation. A possible mechanism of photocatalysis is proposed.     

Antifungal capability of TiO2 coated film on moist wood

Photocatalytic oxidation by TiO₂ has been shown to deactivate biological pollutants. Most previous studies evaluated TiO₂'s antimicrobial performance using bacteria, with Escherichia coli most commonly applied as the test microbe. There have not been concentrated studies focusing on the photocatalytic disinfection of fungi which widely exist in buildings and cause health problems. In this study, the antifungal activity of TiO₂ photocatalytic reaction against Aspergillus niger was investigated for moist wood boards during periods of several weeks. TiO₂ coated film in the presence of UVA (365 nm) irradiation exhibited antifungal capability. No visible growth was observed on specimens during the photo-process. Re-growth appeared in subsequent dark, indicating that the photocatalytic reaction was not sufficient for total disinfection against mold fungi but did suppress fungi growth. The study sheds light on conditions and potential applications of photocatalytic deactivation of fungi.     

Cross-flow microfiltration with periodical back-washing for photocatalytic degradation of pharmaceutical and diagnostic residues-evaluation of the long-term stability of the photocatalytic activity of TiO2

The combination of semiconductor photocatalysis with cross-flow microfiltration accompanied by periodical back-washing was investigated in a pilot plant. The investigation included the testing of membrane materials because the membrane must resist the abrasion and the periodical back-washing. Another objective of this investigation was to assess the potential of two different TiO(2) materials (Hombikat UV100 and P25) for continuous photocatalytic degradation of persistent organic pollutants. The study focused on the long-term stability of the photocatalytic activity of TiO(2) during its continuous application. The combination of photocatalysis and cross-flow microfiltration allowed the separation and reuse of TiO(2) after the photocatalytic degradation of clofibric acid, carbamazepine and iomeprol. The investigations showed that the photocatalytic activity of P25 and Hombikat UV100 was constant during continuous usage over several days. This study indicates the high potential of the combination of heterogeneous photocatalytic oxidation processes with cross-flow microfiltration accompanied by periodical back-washing of the membrane. Thus environmentally relevant pharmaceuticals and X-ray contrast media can be transformed and mineralized in a continuous water treatment process.