Photocatalytic degradation of aqueous pollutants using silica-modified TiO(2)

Photocatalytic degradation (PCD) of several aqueous pollutants was investigated using a porous silica-coated titanium dioxide (SiO(2)-TiO(2)) photocatalyst. Several cationic, neutral and anionic pollutants were tested. The results indicate that modifying the surface properties of TiO(2) using silica significantly enhances the PCD rate of the cationic pollutants. The rate enhancement decreased with an increase in substrate concentration, especially for the quaternary amines, and was attributed to the decrease in initial adsorption. However, no significant rate-increase resulted for acetate and phenol. Results suggest that the increased presence of cationic pollutants at the catalyst surface caused the rate enhancement.     

Photocatalytic degradation of reactive black 5 in aqueous solutions: Effect of operating conditions and coupling with ultrasound irradiation

The degradation of reactive black 5 (RB 5), a representative diazo dye found in textile effluents, by means of ultraviolet irradiation (9W UVA) over TiO(2) suspensions, ultrasound irradiation (80kHz, 135W) and their combined application was investigated. Several commercial TiO(2) catalysts were screened and an anatase Hombicat UV 100 sample exhibited considerable activity in terms of solution decoloration, COD and ecotoxicity reduction. Photocatalytic degradation increased with increasing TiO(2) loading (in the range 0.05-1g/L) and decreasing dye concentration (in the range 120-20mg/L) and solution pH (in the range 9-2.6). At the typical conditions employed in this study (60mg/L dye, 0.25mg/L catalyst, ambient pH=5.8, oxygen sparging), complete decoloration was achieved after 60min of reaction. Addition of H(2)O(2) up to 0.01M hindered degradation, scavenging the photogenerated holes and hydroxyl radicals. Ultrasound irradiation resulted in low decoloration, e.g. less than 10% after 60min at 60mg/L dye and oxygen sparging and slightly improved under an argon atmosphere. The simultaneous application of ultraviolet and ultrasound irradiation resulted in increased decoloration compared to that achieved by photocatalysis and sonolysis operating separately; moreover, the overall sonophotocatalytic effect was greater than the additive effect of the two processes, implying possible synergy.     

Photocatalytic degradation of 2,4-dinitrophenol (DNP) by multi-walled carbon nanotubes (MWCNTs)/TiO2 composite in aqueous solution under solar irradiation

Nanosized multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite and neat TiO₂ photocatalysts were synthesized by sol-gel technique using tetrabutyl titanate as a precursor. The as prepared photocatalysts were characterized using XRD, SEM, FTIR and UV-vis spectra. The samples were evaluated for their photocatalytic activity towards the degradation of 2,4-dinitrophenol (DNP) under solar irradiation. The results indicated that the addition of an appropriate amount of MWCNTs could remarkably improve the photocatalytic activity of TiO₂. An optimal MWCNTs:TiO₂ ratio of 0.05% (w/w) was found to achieve the maximum rate of DNP degradation. The effects of pH, irradiation time, catalyst concentration, DNP concentration, etc. on the photocatalytic activity were studied and the results obtained were fitted to the Langmuir-Hinshelwood model to study the degradation kinetics. The optimal conditions were an initial DNP concentration of 38.8 mg/L at pH 6.0 with catalyst concentration of 8 g/L under solar irradiation for 150 min with good recyclisation of catalyst. The degree of photocatalytic degradation of DNP increased with an increase in temperature. The MWCNTs/TiO₂ composite was found to be very effective in the decolorization and COD reduction of real wastewater from DNP manufacturing. Thus, this study showed the feasible and potential use of MWCNTs/TiO₂ composite in degradation of various toxic organic contaminants and industrial effluents.     

Photocatalytic degradation of nitrobenzene using titanium dioxide and concentrated solar radiation: chemical effects and scaleup

Photocatalytic degradation of nitrobenzene (NB) using titanium dioxide (Degussa P-25) as photocatalyst and concentrated solar radiation has been studied. The effects of various factors, such as the presence of anions common in the industrial wastewater, the initial pH and the addition of FeSO(4), were investigated. The intermediates detected were o, p,m-nitrophenols and dihhydroxy derivatives indicating that degradation proceeds via z.rad;OH radicals. Degradation of NB was studied in three reactors of different diameters to ascertain the effect of photon penetration depth on the degradation.     

Concurrent filtration and solar photocatalytic disinfection/degradation using high-performance Ag/TiO2 nanofiber membrane

A facile polyol synthesis was used for the deposition of Ag nanoparticles on electrospun TiO₂ nanofibers for the subsequent fabrication of Ag/TiO₂ nanofiber membrane. The permeate flux of the Ag/TiO₂ nanofiber membrane was remarkably high compared to commercial P25 deposited membrane. The Ag/TiO₂ nanofiber membrane achieved 99.9% bacteria inactivation and 80.0% dye degradation under solar irradiation within 30 min. The Ag/TiO₂ nanofiber membrane also showed excellent antibacterial capability without solar irradiation. Considering the excellent intrinsic antibacterial activity and high-performance photocatalytic disinfection/degradation under solar irradiation, this novel membrane proved to have promising applications in water purification industry.     

Electrochemically assisted photocatalytic degradation of Acid Orange 7 with beta-PbO2 electrodes modified by TiO2

Modification of beta-PbO(2) electrodes was carried out by TiO(2) co-deposition and characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The 2.0 g TiO(2) (the amount of TiO(2) used in 200 mL electrodeposition solution) modified beta-PbO(2) electrode was more compact and more uniform in comparison with the unmodified beta-PbO(2) electrode. TiO(2) particles were tightly attached on and between beta-PbO(2) crystals on modified beta-PbO(2) electrode. It was also used in electrochemically assisted photocatalytic degradation (EAPD) of Acid Orange 7. Compared with the total efficiency by a single application of ultraviolet irradiation and electrochemical procedure, application of a 1.5 V potential in EAPD improved the apparent first-order rate constant by 44.2% for 2.0 g TiO(2) modified beta-PbO(2) electrode even if it was not freshly used. A synergetic effect was significant. Within the amount of TiO(2) investigated, the more TiO(2) used in electro-deposition solution, the higher the degradation efficiencies were. Effects of initial dye concentration, initial pH values and applied potentials across the electrodes were investigated. Acidic condition and high potentials applied across the electrodes favored color or TOC removal of the dye. Decolorization rate decreased with an increase in the dye concentration in the range of 5-50mg/L. Experiments above demonstrate that TiO(2) modified beta-PbO(2) electrode, which realized TiO(2) immobilization successfully, performed well in EAPD of Acid Orange 7.     

Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: Evaluation of operational and kinetic parameters

Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe²⁺/H₂O₂) and heterogeneous photocatalysis with titanium dioxide (TiO₂) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe²⁺ and H₂O₂ were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe²⁺ and H₂O₂ concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO₂ process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment.     

Photocatalytic oxidation of DBP precursors using UV with suspended and fixed TiO2

French River water (Nova Scotia, Canada) was separated into six different natural organic matter (NOM) fractions, including hydrophobic acids, bases and neutrals and hydrophilic acids, bases and neutrals. The raw water, as well as each of the NOM fractions were analysed for disinfection by-product (DBP) formation potential before and after advanced oxidation with UV/TiO₂ to determine the efficacy of this treatment for the removal of DBP precursors. The UV/TiO₂ treatment was carried out with a nanostructured thin film (NSTF), coated with TiO₂ which is compared with the use of a TiO₂ suspension. For the raw river water, removals of total trihalomethane formation potential (TTHMFP) and total haloacetic acid formation potential (THAA₉FP) were found to be approximately 20% and 90%, respectively, with 50 mJ/cm² UV exposure and 1 mg/L TiO₂. For the fractionated samples, approximately 75% of both trihalomethane (THM) and haloacetic acid (HAA) precursors were found to be associated with the hydrophobic acid fraction. For this individual fraction the same UV/TiO₂ treatments exhibited approximately 20-25% removal of both TTHMFP and THAA₉FP, suggesting that the fractionation process may have affected the treatability of HAA precursors or may have altered the results of the oxidation processes.     

Inactivation and surface interactions of MS-2 bacteriophage in a TiO2 photoelectrocatalytic reactor

Inactivation of MS-2 bacteriophage in a TiO₂ photoelectrocatalytic system was evaluated, wherein TiO₂ particles were coated onto an indium tin oxide (ITO) electrode and an electrical potential was applied under black light blue (BLB) irradiation. MS-2 phage inactivation was greatly enhanced by anodic potential, whereas cathodic potential completely inhibited inactivation. Experiments performed with radical scavengers showed that inactivation was primarily caused by hydroxyl radicals, both in the bulk phase and on the TiO₂ surface. Application of positive potential to the electrode was found to result in two distinct beneficial effects: (i) electrostatic attraction between the negatively charged viral capsid and catalyst surface, causing improved usage of surface-bound hydroxyl radical, in comparison to conventional TiO₂ photocatalytic disinfection; and (ii) higher reactive oxygen species production. Results also suggest that inactivation of various microorganisms including Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Bacillus subtilis spores and Cryptosporidium parvum oocyst was enhanced via positive potential induction to TiO₂.     

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.     

Optical density and photonic efficiency of silica-supported TiO2 photocatalysts

Over the last years, many research groups have developed supported TiO2-based materials in order to improve the engineering applications of photocatalytic technologies. However, not many attempts have been made to evaluate the optical behavior of these materials. This work focuses on the study of the photonic efficiencies of silica-supported TiO2 photocatalysts following the photodegradation of dichloroacetic acid (DCA) as model compound. Catalysts with different types of silica support and titania loadings were tested and their activity was found to be in correlation with the results of the clusters size distribution of the TiO2 nanocrystals. The photonic efficiency of the supported photocatalysts depends extremely on the optical density of the solid suspensions. Influence of the textural properties of the support and the titania loading on the optical density as well as on the photonic efficiency of the materials are discussed. The dependence of the absorption of radiation by the suspension on the catalyst concentration is also analyzed.     

Field solar degradation of pesticides and emerging water contaminants mediated by polymer films containing titanium and iron oxide with synergistic heterogeneous photocatalytic activity at neutral pH

Photocatalytic degradation of phenol, nalidixic acid, mixture of pesticides, and another of emerging contaminants in water was mediated by TiO₂ and iron oxide immobilized on functionalized polyvinyl fluoride films (PVF^f-TiO₂-Fe oxide) in a compound parabolic collector (CPC) solar photoreactor. During degradation, little iron leaching (<0.2 mg L⁻¹) was observed. Phenol was efficiently degraded and mineralized at operational pH < 5 and nalidixic acid degradation was complete even at pH 7, but mineralization stopped at 35%. Pesticide mixture was slowly degraded (50%) after 150 min of irradiation. Degradation of the emergent contaminant mixture was successful for eight compounds and less efficient for six other compounds. The significant reactivity differences between tested compounds were assigned to the differences in structure namely that the presence of complexing or chelating groups enhanced the rates.PVF^f-TiO₂-Fe oxide photoactivity gradually increased during 20 days of experiments. X-ray photoelectron spectroscopy (XPS) measurements revealed significant changes on the catalyst surface. These analyses confirm that during photocatalysis mediated by PVF^f-TiO₂-Fe oxide, some iron leaching led to enlargement of the TiO₂ surface exposed to light, increasing its synergy with iron oxides and leading to enhanced pollutant degradation.     

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.     

Application of nano TiO(2) towards polluted water treatment combined with electro-photochemical method

A novel composite reactor was prepared and studied towards the degradation of organic pollutants in this work. In the reactor, a UV lamp was installed to provide energy to excite nano TiO(2), which served as photocatalyst, leading to the production of hole-electron pairs, and a three-electrode electrolysis system was used to accumulate H(2)O(2) which played an important role in the degradation process. The reactor was evaluated by the degradation process of rhodamine 6G (R-6G), and the data obtained in the experiments showed that the combination of the photochemical and electrochemical system raised the degradation rate of R-6G greatly; the working mechanism of the reactor was also discussed in the article. The prepared reactor was also utilized to treat polluted water from dyeing and printing process. After continuous treatment for 0.5h, chemical oxygen demand biochemical oxygen demand, quantity of bacteria and ammonia nitrogen of the polluted water were reduced by 93.9%, 87.6%, 99.9% and 67.5%, respectively, which indicated that the method used here could be used for effective organic dyes degradation.     

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%.     

Solar photocatalytic treatment of synthetic municipal wastewater

The photocatalytic organic content reduction of a selected synthetic municipal wastewater by the use of heterogeneous and homogeneous photocatalytic methods under solar irradiation has been studied at a pilot-plant scale at the Plataforma Solar de Almeria. In the case of heterogeneous photocatalysis the effect of catalysts and oxidants concentration on the decomposition degree of the wastewater was examined. By an accumulation energy of 50 kJL(-1) the synergetic effect of 0.2 gL(-1)TiO(2) P-25 with hydrogen peroxide (H(2)O(2)) and Na(2)S(2)O(8) leads to a 55% and 73% reduction of the initial organic carbon content, respectively. The photo-fenton process appears to be more efficient for this type of wastewater in comparison to the TiO(2)/oxidant system. An accumulation energy of 20 kJL(-1) leads to 80% reduction of the organic content. The presence of oxalate in the Fe(3+)/H(2)O(2) system leads to an additional improvement of the photocatalytic efficiency.     

Effect of sunlight irradiation on photocatalytic pyrene degradation in contaminated soils by micro-nano size TiO2

The enhanced catalytic pyrene degradation in quartz sand and alluvial and red soils by micro-nano size TiO₂ in the presence and absence of sunlight was investigated. The results showed that the synergistic effect of sunlight irradiation and TiO₂ was more efficient on pyrene degradation in quartz sand and red and alluvial soils than the corresponding reaction system without sunlight irradiation. In the presence of sunlight irradiation, the photooxidation (without TiO₂) of pyrene was very pronounced in alluvial and red soils and especially in quartz sand. However, in the absence of sunlight irradiation, the catalytic pyrene degradation by TiO₂ and the photooxidation (without TiO₂) of pyrene were almost nil. This implicates that ultra-violet (UV) wavelength range of sunlight plays an important role in TiO₂-enhanced photocatalytic pyrene degradation and in photooxidation (without TiO₂) of pyrene. The percentages of photocatalytic pyrene degradation by TiO₂ in quartz sand, alluvial and red soils under sunlight irradiation were 78.3, 23.4, and 31.8%, respectively, at 5 h reaction period with a 5% (w/w) dose of the amended catalyst. The sequence of TiO₂-enhanced catalytic pyrene degradation in quartz sand and alluvial and red soils was quartz sand > red soil > alluvial soil, due to different texture and total organic carbon (TOC) contents of the quartz sand and other two soils. The differential Fourier transform infrared (FT-IR) spectra of degraded pyrene in alluvial soil corroborate that TiO₂-enhanced photocatalytic degradation rate of degraded pyrene was much greater than photooxidation (without TiO₂) rate of degraded pyrene. Based on the data obtained, the importance for the application of TiO₂-enhanced photocatalytic pyrene degradation and associated organic contaminants in contaminated soils was elucidated.     

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.     

The effect of engine emission on canola biodiesel blends with TiO2

The role of nanoparticles and nanofluid additives for biodiesel has gained consistent position in the current trend as they contribute to increase the performance of the engine with lower emission. In addition, additives also help to increase the engine reliability and lifespan. In this work, the effects of canola biodiesel blends of 20% proportions with diesel were investigated at 100% of engine load. The fuel is tested in a multi-cylinder water-cooled direct ignition (DI) engine. There are numerous notable works on nanofluid; however, the addition of TiO₂ nanoparticle as additive to produce canola biodiesel fuel is very limited. With the addition of the TiO₂ nanoparticle on Canola biodiesel blend in the DI engine, the exhaust property of gases such as CO, HC and NO_X is reduced. Furthermore, the combustion characteristics of the engine are improved. The canola biodiesel blends also resulted in lower NO_x emission as well as low smoke.