Photocatalytic degradation of para-hydroxybenzoic acid: Relationship between substrate adsorption and photocatalytic degradation

 Dark adsorption and photocatalytic degradation of para-hydroxybenzoic acid (PHBA) was studied in the presence of Degussa P-25 titanium dioxide photocatalyst under concentrated solar radiation. This work includes the study of the effect of pH, and of the presence of different anions and cations on dark adsorption and photocatalytic degradation (PCD) of PHBA on titanium dioxide. The results obtained clearly indicate that there is a link between the extent of adsorption of PHBA and its PCD. Conditions that favor greater adsorption of PHBA also favor a greater PCD. This points to the possibility that the mechanism of PCD involves a surface reaction between adsorbed PHBA and OH ° radical. Anions were generally found to have a detrimental effect on the photocatalytic degradation of PHBA. Cl^– caused the greatest decrease in the PCD followed by NO₃ ^–, HCO₃ ^– and SO₄ ^2–. Cations Cu²⁺ and Fe²⁺ were not found to assist the degradation of PHBA, possibly due to the anions associated with them. Received: 15 May 2000 / Accepted: 15 July 2000     

Photocatalytic degradation of Remazol Red F3B using ZnO catalyst

The photocatalytic degradation of aqueous solution of a commercial azo-reactive textile dye, Remazol Red F3B, has been investigated in a batch slurry reactor, in the presence of ZnO catalyst using two different UV light sources emitting at 254 nm and 365 nm. The effects of various process variables on degradation performance of the process have been investigated. The results showed that decolourization and total organic carbon (TOC) removal are both affected in the same manner by the solution pH in the pH range 6-10, showing maxima at pH 7 and pH 10. They are inversely related to the dye concentration, they increase in power-law with the light intensity. Decolourization is faster with 365 nm UV. TOC removal is not affected by UV wavelength in the initial period up to 20 min, after which it progresses faster under 365 nm UV radiation. These results indicate that the UV wavelength influences especially the degradation rate of the intermediate products generated during the initial period of the photocatalytic process. Finally, catalyst loading affects both efficiencies in the same trend, which are maximized at about 2 g/l catalyst loading.     

Photolytic (UVC) and photocatalyic (UVC/TiO2) decomposition of pyridines

The degradation of 2-chloropyridine (2-CPY) and its degradation primary product 2-hydroxypyridine (2-HPY) was studied by means of ultraviolet (UV) irradiation at 254nm. Photolytic and photocatalytic experiments were conducted on 2-CPY and 2-HPY aqueous solutions in a batch reactor with internal recycle in laminar and turbulent conditions at 50 degrees C in a closed but not airtight system with and without additional aeration, at solution ambient pH and at controlled pH conditions, with use and in the absence of radical scavenger. The solution volume was 0.4L and initial substrate concentrations were approximately 2.6mmol/L (0.25-0.3g/L depending on the substrate). Where applicable 1g/L TiO(2) (P-25) was used, suspended in the liquid in a form of turbulent slurry or using a glass tube around the UV-lamp on which a fixed TiO(2) catalytic layer had been deposited. At the aforementioned conditions 2-CPY readily degrades photolytically, the catalytic path having very little influence. In all cases 2-CPY produces 2-HPY which further degrades to other products. Aeration, pH and the presence of catalyst and/or radical scavengers do not affect the rate of decomposition of 2-CPY, but have a strong influence on the further decomposition of the produced 2-HPY. 2-HPY decomposition proceeds both catalytically and photolytically following oxygen dependent and oxygen independent pathways.     

Photocatalytical degradation of 1,3-dichloro-2-propanol aqueous solutions by using an immobilized TiO2 photoreactor

The photocatalytic oxidation of 1,3-dichloro-2-propanol (1,3-DCP) was studied by following the target compound degradation, the total organic carbon removal rate and by identifying the oxidation products. The reaction was performed in a batch recycle reactor, at room temperature, using UV radiation, H2O2 as oxidant, and immobilized TiO2 as catalyst. 1,3-Dichloro-2-propanone, chloroacetyl-chloride, chloroacetic acid, formic and acetic acid were detected as reaction intermediates and a possible pathway for the oxidation of 1,3-dichloro-2-propanol is proposed. The effect of the oxidative agent's initial concentration was investigated and it was established that higher concentrations of H2O2 slow down the reaction rate. The investigation of the effect of the 1,3-DCP initial concentration showed no influence on the degradation process. The carbon and chloride ion mass balance calculations confirmed the fact that chlorinated intermediates are formed and that they degrade with a lower rate than 1,3-DCP.     

Studies on photodegradation of two commercial dyes in aqueous phase using different photocatalysts

The present study involves the photocatalytic degradation of Methyl Orange (MO) and Rhodamine 6G (R6G), employing heterogeneous photocatalytic process. Photocatalytic activity of various semiconductors such as titanium dioxide (TiO(2)), zinc oxide (ZnO), stannic oxide (SnO(2)), zinc sulphide (ZnS) and cadmium sulphide (CdS) has been investigated. An attempt has been made to study the effect of process parameters viz., amount of catalyst, concentration of dye and pH on photocatalytic degradation of MO and R6G. The experiments were carried out by irradiating the aqueous solutions of dyes containing photocatalysts with UV and solar light. The rate of decolorization was estimated from residual concentration spectrophotometrically. Similar experiments were carried out by varying pH (2-10), amount of catalyst (0.25-2.0g/l) and initial concentration of dye (5-200mg/l). The experimental results indicated that the maximum decolorization (more than 90%) of dyes occurred with ZnO catalyst and at basic pH and the maximum adsorption of MO was noticed at pH 4 and of R6G at pH 10. The percentage reduction of MO and R6G was estimated under UV/solar system and it was found that COD reduction takes place at a faster rate under solar light as compared to UV light. In case of R6G, highest decolorizing efficiency was achieved with lower dose of catalyst (0.5g/l) than MO (1g/l) under similar conditions. The performance of photocatalytic system employing ZnO/solar light was observed to be better than ZnO/UV system.     

Studies on TiO(2)/ZnO photocatalysed degradation of lignin

The photocatalytic degradation of lignin obtained from wheat straw kraft digestion has been investigated by using TiO(2) and ZnO semiconductors. ZnO has been found to be a better photocatalyst than TiO(2). The different variables studied, include catalyst dose, solution pH, oxidant concentration and initial concentration of the substrate. The degradation of lignin was favorable at pH 11. Optimum values of catalyst dose and oxidant concentration were found to be 1g/l and 12.2 x 10(-6) M, respectively. The degradation of the organic compound was also evaluated as COD removal and increase in the COD removal was observed with increase in degradation rate. An attempt has also been made to explore the applicability of ZnO in immobilized mode for the degradation of lignin under solar light for industrial scale application. Further the comparative evaluation of ZnO in slurry/immobilized mode has been carried out.     

Solar photocatalytic degradation of resorcinol a model endocrine disrupter in water using zinc oxide

Photocatalytic degradation (PCD) of resorcinol a potent endocrine disrupting chemical in aqueous medium was investigated by ZnO under sunlight irradiation in a batch photoreactor. The influence of various parameters such as photocatalyst amount, initial concentration of resorcinol and pH was examined for maximum PCD of resorcinol. A considerable influence of pH upon the chemical oxygen demand (COD) disappearance was observed. In general, neutral or basic pH is favorable for COD removal of resorcinol. PCD intermediates were identified using FTIR and GC/MS. Two of the initial oxidation intermediates detected were 1,2,4-trihydroxy-benzene and 1,2,3-trihydroxy-benzene. FTIR studies revealed 1,2,4-trihydroxy-benzene as the major PCD intermediate. A working photodegradation mechanism is also suggested for PCD of resorcinol. This work envisages the great potential that sunlight mediated photocatalysis has in the removal of resorcinol from waste water.     

Solar assisted photocatalytic and photochemical degradation of Reactive Black 5

The photocatalytic oxidative degradation of Reactive Black 5 (RB 5) has been investigated using TiO(2)-P25 as photocatalyst and sunlight as irradiation source in slurry form. The degradation was carried out at different experimental conditions to optimize the parameters such as amount of catalyst, concentration of dye and pH. A complete degradation of 3.85 x 10(-4) M dye solution under solar irradiation was observed in 3.5 h. The photochemical degradation using hydrogen peroxide results in the partial removal of the dye.     

Visible light active photocatalytic degradation of bisphenol-A using nitrogen doped TiO2

Nitrogen doped titania was prepared by low temperature sol-gel method using titanium precursor and nitrogen containing bases like triethylamine and tetramethyl ammonium hydroxide compounds. The materials were characterized by XRD, BET, SEM, XPS, DRS-UV, and FT-IR techniques. DRS-UV study substantially indicates shift of the absorption edge of TiO2 to lower energy region. The phase composition, crystallinity, specific surface area, and visible light activity of nitrogen doped titania depend upon the preparation conditions. Photocatalytic degradation of bisphenol-A in aqueous medium was investigated by TiO2 and nitrogen doped TiO2 under visible light irradiation in a batch photocatalytic reactor. The results indicate higher visible light activity for nitrogen doped TiO2 than commercial TiO2 (Degussa P25) for bisphenol-A degradation. The influence of various parameters such as initial concentration of bisphenol-A, catalyst loading and pH was examined for maximum degradation efficiency.     

Photocatalytic degradation of methylene blue in TiO2 aqueous suspensions using microwave powered electrodeless discharge lamps

Photocatalytic degradation of methylene blue (MB) in TiO(2) aqueous suspensions using microwave (MW) powered electrodeless discharge lamps (EDLs) was studied. MB of initial concentration 100 mg/l was mainly decomposed in the process of photocatalytic degradation using EDLs (PCD/EDLs) after 15 min of irradiation. The corresponding mineralization efficiency was 45%. The influence of factors as EDLs, solution volume and TiO(2) catalyst dosage on the decomposition of MB in the PCD/EDLs process was also investigated. The optimal decomposition efficiency was observed when EDLs-4 (four 10 mm x 50 mm EDLs), solution volume of 50 ml and TiO(2) catalyst dosage of 1-4 g/l were used in the study. The PCD/EDLs process was promising in treating MB polluted water.     

Application of visible-light photocatalysis with nitrogen-doped or unmodified titanium dioxide for control of indoor-level volatile organic compounds

The present study evaluated visible-light photocatalysis, applying an annular reactor coated with unmodified or nitrogen (N)-doped titanium dioxide (TiO(2)), to cleanse gaseous volatile organic compounds (VOCs) at indoor levels. The surface chemistry investigation of N-doped TiO(2) suggested that there was no significant residual of sulfate ions or urea species on the surface of the N-doped TiO(2). Under visible-light irradiation, the photocatalytic technique using N-doped TiO(2) was much superior to that for unmodified TiO(2) for the degradation of VOCs. Moreover, the degradation efficiency by a reactor coated with N-doped TiO(2) was well above 90% for four target compounds (ethyl benzene, o,m,p-xylenes), suggesting that this photocatalytic system can be effectively employed to cleanse these pollutants at indoor air quality (IAQ) levels. The degradation efficiency of all target compounds increased as the stream flow rate (SFR) decreased. For most target compounds, a reactor with a lower hydraulic diameter (HD) exhibited elevated degradation efficiency. The result on humidity effect suggested that the N-doped photocatalyst could be employed effectively to remove four target compounds (ethyl benzene, o,m,p-xylenes) under conditions of less humidified environments, including a typical indoor comfort range (50-60%). Consequently, it is suggested that with appropriate photocatalytic conditions, a visible-light-assisted N-doped photocatalytic system is clearly an important tool for improving IAQ.     

Photodegradation of acetaminophen in TiO(2) suspended solution

This study investigated the photocatalytic degradation of acetaminophen (APAP) in TiO(2) suspended solution under a 250 W metal halide lamp. The influence of some parameters on the degradation of acetaminophen was studied and described in details, such as initial APAP concentration, initial pH value and TiO(2) dosage. After 100 min irradiation, about 95% of APAP is decomposed in the 1.0 g L(-1) TiO(2) aqueous solution with an initial concentration of 100 micromol L(-1). The effect of adsorption at three different pH values has also been analyzed and it has been conducted that pH 3.5, at which APAP was readily adsorbed also degraded at a faster rate. Reaction rate at pH 6.9 and pH 9.5 was 2.84 and 2.96 microM min(-1), respectively. Direct hole (h(+)) oxidation and ipso-substitution was found to be the main initial step for APAP degradation. Main reaction intermediates and products were identified by GC/MS analysis. The mechanism of acetaminophen photocatalytic degradation in TiO(2) suspended solution was studied not only experimentally but also theoretically by calculating the frontier electron density of APAP. The results obtained indicated that TiO(2) photocatalytic degradation is a highly effective way to remove APAP from wastewater and drinking water without any generation of more toxic products.     

Degradation of sodium dodecyl sulphate in water using solar driven Fenton-like advanced oxidation processes

Synthetic wastewater samples containing a model surfactant were treated using two different Fenton-like advanced oxidation processes promoted by solar radiation; the photo-Fenton reaction and Co/PMS/UV processes. Comparison between the different experimental conditions was performed by means of the overall surfactant degradation achieved and by obtaining the initial rate in the first 15 min of reaction (IR15). It was found that, for dark Fenton reaction, the maximum surfactant degradation achieved was 14% under low iron and oxidant concentration. Increasing Fenton reagents by one magnitude order, surfactant degradation achieved 63% in 60 min. The use of solar radiation improved the reaction rate by 17% under same conditions and an additional increase of 12.5% was obtained by adjusting initial pH to 2. IR15 values for dark and irradiated Fenton reactions were 0.143 and 0.154 mmol/min, respectively, for similar reaction conditions and this value increased to 0.189 mmol/min when initial pH was adjusted. The use of the Co/PMS system allow us to determine an increase in the degradation rate, for low reaction conditions (1 mM of transition metal; 4 mM oxidant) similar to those used in dark Fenton reaction. Surfactant degradation increased from 3%, for Fenton reaction, to 44.5% in the case of Co/PMS. When solar irradiation was included in the experiments, under same reaction conditions described earlier, surfactant degradation up to 64% was achieved. By increasing Co/PMS reagent concentration by almost 9 times under irradiated conditions, almost complete (>99%) surfactant degradation was reached in 5 min. Comparing IR15 values for Co/PMS and Co/PMS/UV, it allow us to observe that the use of solar radiation increased the degradation rate in one magnitude order when compared with dark experiments and further increase of reagent concentration increased reaction rate twice.     

Electrochemical degradation and toxicity reduction of C.I. Basic Red 29 solution and textile wastewater by using diamond anode

Electrochemical oxidation of Basic Red 29 (BR29) was studied in a bipolar trickle tower (BTT) reactor by using Raschig ring shaped boron-doped diamond (BDD) electrodes, which were originally employed by the present researchers, in a recirculated batch mode. The model solution was prepared with BR29 using distilled water. The effects of initial dye concentration, Na(2)SO(4) concentration as supporting electrolyte, current density, flow rate and initial pH on the removal efficiency were investigated, and practically, complete BR29 removal (over 99%) was obtained in all the studies. After optimum experimental conditions were determined, textile wastewater has also studied by monitoring the destruction of color and COD. With the textile wastewater, 97.2% of color and 91% of COD removal were, respectively, achieved at the current density of 1mA/cm(2). Microtox toxicity tests were performed in both BR29 solution and textile wastewater under optimum experimental conditions, and relatively good toxicity reductions were obtained with respect to the initial values. According to the results, BDD anode was seen to be a unique material for the degradation of BR29 and COD and also the reduction of toxicity simultaneously.     

Photochemical degradation of 1,3-dichloro-2-propanol aqueous solutions

The photochemical oxidation of 1,3-dichloro-2-propanol (1,3-DCP) was studied by following the target compound degradation, the total carbon removal rate by a total organic carbon (TOC) analyzer and by identifying the oxidation products by gas chromatography-mass spectrometry (GC-MS). The reaction was performed in a batch recycle reactor, at room temperature, using UV radiation provided by a low pressure 12W Hg lamp and H(2)O(2) as oxidant. Chloride ions, formic, acetic and chloroacetic acid were measured by ion chromatography. Apart from the chloride ions and the organic acids, the presence of 1,3-dichloro-2-propanone and chloroacetyl chloride was also detected and a possible pathway is proposed for the degradation of the parent compound. Complete degradation of 1,3-dichloro-2-propanol was achieved and the TOC removal reached as much as 80% at the end of the reaction time. The effect of the initial concentration of hydrogen peroxide was investigated and it was established that higher concentrations of H(2)O(2) slow down the reaction rate. Finally, the effect of the initial concentration of 1,3-DCP was investigated.     

Bioremediation of anthracene contaminated soil in bio-slurry phase reactor operated in periodic discontinuous batch mode

Bioremediation of soil-bound anthracene was studied in a series of bio-slurry phase reactors operated in periodic discontinuous/sequencing batch mode under anoxic-aerobic-anoxic microenvironment using native soil microflora. Five reactors were operated for a total cycle period of 144 h (6 days) at soil loading rate of 16.66 kg soil/m(3)/day at 30 +/- 2 degrees C temperature. The performance of the bioreactors was studied at various substrate loading rates (volumetric substrate loading rate (SLR), 0.1, 0.2 and 0.3g anthracene/kg soil/day) with and without bioaugmentation (domestic sewage inoculum; 2 x 10(6) CFU/g of soil). Control reactor (without microflora) showed negligible degradation of anthracene due to the absence of biological activity. The performance of the bio-slurry system with respect to anthracene degradation was found to depend on both substrate loading rate and bioaugmentation. Application of bioaugmentation showed positive influence on the rate of degradation of anthracene. Anthracene degradation data was analysed using different kinetic models to understand the mechanism of bioremediation process in the bio-slurry phase system. Variation in pH/oxidation-reduction potential (ORP), soil microflora and oxygen consumption rate correlated well with the substrate degradation pattern observed during soil slurry phase anthracene degradation.     

Photocatalytic degradation of phenol in aqueous solutions by Pr-doped TiO2 nanoparticles

Photocatalytic degradation of phenol in water was examined using Pr-doped TiO₂ nanoparticles. These photocatalysts were synthesized by an acid-peptized sol–gel method from titanium tetra-isopropoxide with different concentrations of Pr(III) dopant and calcination temperatures. Several tools such as XRD, BET surface area, SEM, and EDX, were used to evaluate particle structure, size distribution, and composition. The optical absorption properties of the prepared particles were also measured. Photocatalytic activity of the particles was studied in a batch reactor containing phenol solution with 400 W UV irradiation. Parameters affecting photocatalytic process such as the catalyst crystallinity, light absorption efficiency, the dosage of catalyst, dopant and phenol concentrations were investigated. The Pr-doped TiO₂ showed high activity for photocatalytic degradation of phenol. The presence of Pr ions in the TiO₂ particles would cause a significant absorption shift towards the visible region. The degradation process was optimized using 1 g/L Pr-doped TiO₂ with a Pr(III) concentration of 0.072 mol% after 2 h irradiation. It was shown that photodegradation followed a pseudo-first-order kinetics and the rate constant changed with phenol concentration.     

Pilot scale annular plug flow photoreactor by UV/H2O2 for the decolorization of azo dye wastewater

A pilot scale annular plug flow photoreactor with thin gap size, which combines with UV irradiation and hydrogen peroxide, was employed to deal with colored dyeing wastewater treatment. In the experiment, a mono-azo dye acid orange 10 was the target compound. The experimental parameters such as flow rate, hydrogen peroxide dosage, UV input power, pH and dye initial concentrations in a pilot scale photoreactor with flow rate of 9.32 m3day(-1) were investigated. Ultimately, the degradation rates were calculated and compared with a 100-l batch reactor. In our plug flow photoreactor design, the degradation rate of acid orange 10 was 233 times higher than that of 100-l annular batch reactor with same UV light source. The residence time needed for 99% decolorizing of 100 l of 20 mgl(-1) acid orange 10 wastewater was 26.9 min for the thin gap plug flow reactor and was far shorter than that of batch reactor needed.     

Photocatalytic degradation of 2,4-dinitrophenol

Contamination of the food supply from agricultural waste is an increasing concern worldwide. Numerous hazardous chemicals enter the environment from various industrial sources daily. Many of these pollutants, including 2,4-dinitrophenol (2,4-DNP), are water soluble, toxic, and not easily biodegradable. The solar photocatalytic degradation of 2,4-DNP was investigated in a solution of titanium dioxide (TiO(2)) that was prepared to be an optically clear aqueous solution of nanosized particles of TiO(2). In order to achieve optimal efficiency of the photodegradation, the effects of light intensity and pH were conducted. All experiments were carried out in a batch mode. At a pH of 8, maximum removal of 70% of 2,4-DNP was achieved within 7h of irradiation time. The nearly homogeneous solution of 5.8nm TiO(2) particles, size determined by XDS, were very effective in the photocatalytic degradation of 2,4-DNP.     

Degradation of aqueous solutions of camphor by heterogeneous photocatalysis

In this study the photocatalytic degradation of aqueous solutions of camphor was investigated by using TiO2 and ZnO photocatalysts. In the presence of artificial UV-light the highly photosensitive camphor was almost totally degraded after reaction times of 60 min. However, under these conditions the mineralization degree was lower than 25%. In the presence of semiconductors the degradation was complete after a treatment time of about 30 min. Moreover, the mineralization was considerably greater, mainly with the use of TiO2 (> 80% at reaction time of 60 min). Heterogeneous photocatalytic processes applied in the presence of solar radiation show a promising degradation capability. TiO2-based processes afforded mineralization degrees of about 90% after a reaction time of 120 min, when the system was assisted by aeration.