Photocatalytic mineralization of a water pollutant,Sunset Yellow dye by an advanced oxidation process using a modified catalyst

ZnS-loaded TiO₂ (ZnS–TiO₂) was synthesized by a sol–gel method. The catalyst was characterized by using different techniques (XRD, HR-SEM, EDS, DRS, PL, XPS, and BET methods). The photocatalytic activity of ZnS–TiO₂ was investigated for the degradation of Sunset Yellow FCF (SY) dye in an aqueous solution using ultraviolet light. ZnS–TiO₂ is found to be more efficient than prepared TiO₂, TiO₂–P25, TiO₂ (Merck), and ZnS at pH 7 for the mineralization of SY. The effects of operational parameters such as the amount of photocatalyst, dye concentration, and initial pH on photo mineralization of SY have been analyzed. The mineralization of SY has been confirmed by chemical oxygen demand measurements. The catalyst is found to be reusable.     

Degradation of endocrine disruptor bisphenol A in drinking water by ozone oxidation

The ozone oxidation of endocrine disruptor bisphenol A in drinking water was investigated. A stainless completely mixed reactor was employed to carry out the degradation experiments by means of a batch model. With an initial concentration of 11.0 mg/L, the removal efficiencies of BPA (bisphenol A) could be measured up to 70%, 82%, and 90% when the dosages of ozone were 1, 1.5, and 2 mg/L, respectively. The impacts on BPA degradation under the conditions of different ozone dosages, water background values, BPA initial concentrations, and ozone adding time were analyzed. The results showed that ozone dosage plays a dominant role during the process of BPA degradation, while the impact of the contact time could be ignored. UV wavelength scanning was used to confirm that the by-products were produced, which could be absorbed at UV254. The value of UV254 was observed to have changed during the ozonation process. Based on the change of UV254, it could be concluded that BPA is not completely degraded at low ozone dosage, while shorter adding time of total ozone dosage, high ozone dosage, and improvement of dissolved ozone concentration greatly contribute to the extent of BPA degradation. The effects of applied H₂O₂ dose in ozone oxidation of BPA were also examined in this study. The O₃-H₂O₂ processes proved to have similar effects on the degradation of BPA by ozone oxidation.     

Degradation and reduction of acute toxicity of environmentally persistent perfluorooctanoic acid (PFOA) using VUV photolysis and TiO2 photocatalysis in acidic and basic aqueous solutions

Degradation and toxicity reduction of perfluorooctanoic acid (PFOA) were investigated using TiO₂ adsorption, vacuum ultraviolet (VUV) photolysis, and VUV/TiO₂ photocatalysis in acidic and basic aqueous solutions. Chemical analyses of PFOA and its selected by-products and an acute toxicity assessment using the luminescent bacteria Vibrio fischeri (Microtox®) were conducted during and after the various treatment methods. PFOA was found to be best treated by VUV/TiO₂ at pH 4 with HClO₄, as illustrated by the almost complete degradation of PFOA within 360?min and rapid removal of acute microbial toxicity within 60?min. This difference in the efficiency may be attributed to the strong oxidation effectiveness of the radical species generated in acidic media and the electron scavenger effect of the addition of HClO₄ in VUV/TiO₂ photocatalysis. In addition, the proposed method could effectively decompose other perfluorocarboxylic acid (PFCA) species (C₃–C₇ perfluoroalkyl groups) if the initial intermediates formed were longer-chain species that degraded stepwise into shorter-chain compounds by VUV photolysis and VUV/TiO₂ photocatalysis in acidic and basic aqueous solutions.     

Removal of methylene blue by coupling black carbon adsorption with TiO2 photodegradation

In this study, the removal of methylene blue (MB) by the coupling of black carbon (BC) and TiO₂ was investigated. The effects of different parameters such as catalyst dose, sorbent, initial concentrations of dye, pH of the solutions, recycles on discoloration, and chemical oxidation demand (COD) reduction of MB were monitored to optimize the reaction conditions. The discoloration and COD conversation rate of MB obtained by the coupling process were 100% after 90?min irradiation. The synergistic effect of MB-adsorption on BC followed by degradation through TiO₂ photocatalysis was proved by FT–IR spectrophotometer. The BC as by-product of natural materials is a promising adsorbent for waste water treatment.     

Titanium dioxide photocatalysis for pharmaceutical wastewater treatment

Heterogeneous photocatalysis using the semiconductor titanium dioxide (TiO₂) has proven to be a promising treatment technology for water purification. The effectiveness of this oxidation technology for the destruction of pharmaceuticals has also been demonstrated in numerous studies. This review highlights recent research on TiO₂ photocatalytic treatment applied to the removal of selected pharmaceuticals. The discussions are tailored based on the therapeutic drug classes as the kinetics and mechanistic aspects are compound dependent. These classes of pharmaceuticals were chosen because of their environmental prevalence and potential adverse effects. Optimal operational conditions and degradation pathways vary with different pharmaceutical compounds. The main conclusion is that the use of TiO₂ photocatalysis can be considered a state-of-the-art pharmaceutical wastewater treatment methodology. Further studies are, however, required to optimize the operating conditions for maximum degradation of multiple pharmaceuticals in wastewater under realistic conditions and on an industrial scale.     

Photocatalytic treatment of dimethoate by solar photocatalysis at pilot plant scale

Titanium dioxide photocatalysis, using 200 mgl⁻¹ of TiO₂, and photo-Fenton, using 20 mg l⁻¹ of iron, were applied to the treatment of dimethoate dissolved in water at 50 mg l⁻¹. A heterogeneous photocatalysis test was performed in a 35-l solar pilot plant with Compound Parabolic Collectors (CPCs) under natural illumination. A homogeneous photocatalysis test was performed in a different solar pilot plant with four CPC units and a total volume of 75 l. In this work total disappearance of dimethoate and 90% of mineralization were attained in both solar treatments. Treatment time, hydrogen peroxide consumption and ferric phosphate precipitation during photo-Fenton treatment were discussed. An erratum to this article can be found at     

Degradation of azo dye reactive violet 5 by TiO2 photocatalysis

The photocatalytic degradation of hydrolyzed reactive violet 5 (RV5) using titanium dioxide (TiO₂) was investigated in this study. The effects of various factors including the amount of photocatalyst, RV5 concentration, light intensity, and pH on photocatalytic degradation were evaluated. The photodegradation efficiency was 90% after 20 min of irradiation and reached nearly 100% after 80 min under the condition of pH 4 and temperature of 25°C. The decolorization rate typically followed first-order reaction, and increased markedly with increasing amount of photocatalyst, pH as well as light intensity. The total mineralization, based on total organic carbon (TOC) concentration was 53% after 20 min of UV light exposure and approached nearly 100% after 140 min. The final mineralization product was formylformamide. The photodegradation was faster than the mineralization, indicating that the intermediate products of decolorization were resistant to photodegradation. In this study, we found that toxicity of RV5 significantly decreased after decolorization. Our study suggests that the photocatalytic degradation treatment of RV5 with TiO₂ in wastewater is a simple and fast method.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO<Subscript>2</Subscript> 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.     

Dichlorvos degradation studied by 31P-NMR

We studied the hydrolysis and TiO₂ photocatalysis of the pesticide dichlorvos at pH 2.6–9 using phosphorus-31 nuclear magnetic resonance (³¹P NMR). We found that the hydrolysis of dichlorvos led to the formation of dimethyl phosphate at pH 5.6–9. On the other hand, TiO₂ photocatalysis decomposed dichlorvos into dimethyl phosphate, which further reacted to form monomethyl phosphate at pH 2.6 and 9. Monomethylphosphate was hydrolysed into phosphate at pH 2.6. ³¹P NMR is therefore a promising tool to study the degradation of organophosphorus pesticides.     

Pathway of the ozonation of 2,4,6-trichlorophenol in aqueous solution

The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H₂O₂, Cl^? formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H₂O₂. The maximal concentration of H₂O₂ detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H₂O₂ resulted in the generation of a lot of OH? radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH? radicals together. With the inhibition of OH? radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O₃/OH? were proposed in this study.     

Structural effect on photocatalytic degradation of metallised azo dyes in aqueous TiO2 suspension

Three metallised azo dyes were investigated under TiO₂‐photocatalytic and photosensitised conditions in aqueous buffering solutions. The degradation follows apparent first‐order kinetics. The size and strength of intramolecular conjugation determine the light‐fastness of the investigated dyes. Compared with ¹O₂ produced in photosensitised process, the more powerful *OH radicals in TiCO₂ photocatalytic process are highly reactive towards the investigated azo dyes. And as a result, the TiO₂‐photocatalysis makes little less distinction in the degradation kinetic data of the azo dyes compared with the photosensitised degradation of them.     

Remediation of Kraft E1 and black liquor effluents by biological and chemical processes

We sutdied the application of the bacteria Azotobacter vinellandi on the treatment of effluents from pulp and paper industry. Two types of treatment employing this microorganism were studied: biological treatment isolated and combined with stages of pre- or post-treatment using ozonation or photocatalysis processes. In the biological treatment, the siderophores production by A. vinellandi had a major effect on the efficiency of effluents degradation. Among the different combined treatments, the best results were obtained with the photocatalytic pre-treatment.     

Visible light photocatalytic degradation of microplastic residues with zinc oxide nanorods

Microplastics have recently become a major environmental issue due to their ubiquitous distribution, uncontrolled environmental occurrences, small sizes and long lifetimes. Actual remediation methods include filtration, incineration and advanced oxidation processes such as ozonation, but those methods require high energy or generate unwanted by-products. Here we tested the degradation of fragmented, low-density polyethylene (LDPE) microplastic residues, by visible light-induced heterogeneous photocatalysis activated by zinc oxide nanorods. The reaction was monitored using Fourier-transform infrared spectroscopy, dynamic mechanical analyser and optical imaging. Results show a 30% increase of the carbonyl index of residues, and an increase of brittleness accompanied by a large number of wrinkles, cracks and cavities on the surface. The degree of oxidation was directly proportional to the catalyst surface area. A mechanism for polyethylene degradation is proposed.

     

Photocatalytic removal of nitrogen oxides via titanium dioxide

We studied the removal of nitrogen oxides pollutants via TiO₂ Degussa P25 powder by photocatalysis. Parameters such as mass of catalyst, geometric irradiated surface, catalyst morphology, and thermal treatment were tested to explain the photocatalytic concentration decrease of nitrogen oxides. According to our working conditions, the conversion rates increased until an optimal value of the TiO₂ weight, 35% of NO concentration and around 20% of NOx, was decomposed by the photocatalysis. The NOx removal increased proportionally with the irradiated geometric surface. The structural transformation of anatase to rutile performed by thermal treatment involved the decrease of the photocatalytic activity.     

Degradation of bisphenol A by photo-fenton processes

The photo-Fenton reactions, which could yield hydroxyl radicals via the catalytic degradation of H₂O₂ by Fe(II), were focused as one of the abiotic degradation processes of bisphenol A (BPA) in surface waters. At pH 6, in the presence of H₂O₂ only, 32% of BPA was degraded after 120?min of irradiation. However, 97% of BPA was degraded in the presence of both H₂O₂ and Fe(II). Without light irradiation, no BPA degradation was observed even in the presence of Fe(II) and H₂O₂. These results show that photo-Fenton processes are effective in the natural attenuation of BPA in surface water. In addition, the presence of humic acids (HAs), which were of more aliphatic nature, resulted in enhancing BPA degradation via the photo-Fenton processes. Therefore, HAs can be one of the important factors in enhancing the degradation of BPA in surface water via the photo-Fenton processes.     

Efficient oxidation of bisphenol A with oxysulfur radicals generated by iron-catalyzed autoxidation of sulfite at circumneutral pH under UV irradiation

There is actually a need for efficient methods to clean waters and wastewaters from pollutants such as the bisphenol A endocrine disrupter. Advanced oxidation processes currently use persulfate or peroxymonosulfate to generate sulfate radicals. There are, however, few reports on the use of sulfite to generate sulfate radicals, instead of persulfate or peroxymonosulfate, except for dyes. Here we studied the degradation of the bisphenol A using iron(III) as catalyst and sulfite as precursor of oxysulfur radicals, at initial pH of 6, under UV irradiation at 395 nm. The occurrence of radicals was checked by quenching with tert-butyl alcohol and ethanol. Bisphenol A degradation products were analyzed by liquid chromatography coupled with mass spectrometry (LC–MS). Results reveal that iron(III) or iron(II) have a similar oxidation efficiency. Quenching experiments show that the oxidation rate of bisphenol A is 47.7 % for SO ₄ ^·? , 37.3 % for SO ₅ ^·? and 15 % for HO^·. Bisphenol A degradation products include catechol and quinone derivatives. Overall, our findings show that the photo-iron(III)–sulfite system is efficient for the oxidation of bisphenol A at circumneutral pH.     

Investigation of the effects of humic acid and H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s^?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Kinetic studies of the degradation of parabens in aqueous solution by ozone oxidation

Ozone degradation of a mixture containing methylparaben, ethylparaben, propylparaben, butylparaben and benzylparaben was carried out in aqueous solution. The degradation followed the pseudo-first-order kinetic model and occurs with two ozonation stages with the observed rate constants of second stage ozonation, k _obs2, being higher than the observed rate constants in first stage, k _obs1. The k _obs1 of parabens was found to increase exponentially whilst k _obs2 was found to maximize at 35°C. Both k _obs1 and k _obs2 were found to decrease exponentially with respect to the initial concentration of parabens. Both pH and ozone dose showed positive effects on the rate of degradation. It was also observed that an ozone dose of 0.67 g/h resulted in the removal of 99% of parabens in 12 min, and also the removal of 61 and 32% of chemical oxygen demand (COD) and total organic carbon (TOC), respectively, in 3 h of ozonation time for a 500 μM of solution of parabens.     

Modified titanium oxide (TiO2) nanocomposites and its array of applications: a review

Titania (TiO₂) has been the focus of attention of researchers since the first demonstration of its capability to generate the photocatalytic splitting of water into hydrogen and oxygen. However, there seems to be a recent surge in the research activity, involving modified TiO₂ nanoparticles (NP), which are considered to be more effective due to different physicochemical properties in comparison to unmodified fine particle analogs. Several strategies have been employed to modify TiO₂ to reduce recombination rates of photogenerated charge carriers to enhance the optimal functioning of TiO₂. Doping with cations and anions and coupling it with another semiconductor are the most well-known modification methods used. Titania nanocomposites are known to have a plethora of applications. Photoexcitation of these particles are seen to be extraordinarily effective in eliciting microbial death which makes it an attractive candidate for the manufacturing of antimicrobial coatings. On the other hand, TiO₂ induces the oxidation of various organic refractory compounds like tetracycline, sulfamethazine, and bisphenol. The photo-electrocatalytic oxidation technique which amalgamates the principle of photocatalysis and electrolysis serves as a newer, unswerving, and cost effective water treatment process. In the biomedical arena, use is now acknowledged for the photodynamic therapy of cancer, cell imaging, biological sensors, drug delivery system, and as endonucleases. In the commercial front, it is utilized in creams owing to its small particle size, which facilitates absorption through skin. It is also employed as ultraviolet blocking agents in sunscreen and commonly encountered as a brilliant white pigment in paint due to its brightness, high refractive index and resistance to discoloration. Its use in solar cells has also been reported. This review aims to encompass the new progress of modified TiO2 nanocomposites for efficient applications, emphasizing the future trends of TiO2 in arenas like healthcare, environment, biomedical, food, personal care, and pharmacy and also highlights the commercial implications of this promising nanomaterial.