Comparison of catalytic activity of two platinised TiO2 films towards the oxidation of organic pollutants

Two types of platinised TiO2 films, i.e., Pt-TiO2/ITO and Pt(TiO2)/ITO, were prepared by a procedure of dip-coating and subsequent photo-deposition, and photo-deposition and subsequent dip-coating, respectively. They were well characterized by DRS, XRD spectra, SEM microscopy and photoelectrochemical measurement. Their photocatalytic, dark catalytic and photoelectrocatalytic activities were investigated using formic acid as a model organic pollutants. Compared with pure TiO2/ITO film, the photocatalytic activity of the platinised TiO2 films were apparently improved. However, the improvement was considerably dependent on the preparation method of these films. Pt-TiO2/ITO not only possessed higher photocatalytic activity but also showed a dark catalytic activity towards HCOOH degradation. As a sequence, it was first emphasized that the dark catalytic effect of Pt-TiO2/ITO was partly responsible for degradation of formic acid in the photocatalytic oxidation process. Although the Pt(TiO2)/ITO film does not exhibit the dark catalytic activity, its photocatalytic degradation efficiencies towards HCOOH are higher than that of Pt-TiO2/ITO film. Therefore, in view of enhanced photocatalytic activity, the Pt(TiO2)/ITO was more favored than Pt-TiO2/ITO film.     

Photoelectrocatalytic degradation of pentachlorophenol in aqueous solution using a TiO2 nanotube film electrode

Titanium dioxide (TiO2) nanotube film electrodes are fabricated by the anodic oxidation method. Scanning electron microscopy (SEM) showed that these tubes were well aligned and organized into high-density uniform arrays. XRD analysis showed the TiO2 nanotubes to be in the anatase crystal form. The TiO2 nanotube film electrode exhibited increased photoelectrocatalytic (PEC) capability compared to a traditional TiO2 film electrode fabricated using the anodizing method for pentachlorophenol (PCP) degradation in aqueous solution. The bias potential, pH value, and electrolyte concentration were shown to be important factors influencing the degradation of PCP by the PEC method using the TiO2 nanotube film electrode as the working electrode.     

纳米复合ZnO-TiO2晶体的制备及其光电催化性能研究

采用溶胶-凝胶法制备了纳米复合半导体ZnO-TiO2薄膜,并进行了结构和光电催化性能的测试.TiO2薄膜对五氯酚溶液的光电催化降解结果表明当输入正向偏压后,其光催化性能有较大提高.由于ZnO的掺入,半导体薄膜电极的光吸收能力增强;同时,Zn2+可能作为光生载流子的浅俘获中心,导致表面界面电荷转移加速,从而延长光生电子/空穴对的寿命并抑制其复合,有效地提高了TiO2薄膜光电催化活性.     

Photoelectrocatalytic degradation of recalcitrant organic pollutants using TiO2 film electrodes: an overview

Photoelectrocatalytic (PEC) technology involved applying an electrical bias to a TiO₂ film electrode, has been widely applied to the degradation of refractory organic pollutants, owing to its high degradation efficiency. This paper reviews recent developments in the PEC degradation of recalcitrant organic contaminants using a TiO₂ film electrode. The preparation and application of various TiO₂ film electrodes have been investigated, as well as the parameters that influence PEC activity such as the crystal structure, the film thickness and substrate material, the applied electrical bias, the solution pH and conductivity. The improvement of PEC activity by doping the TiO₂ film electrode with metal and non-metal ions has been discussed. The mechanism and kinetics for the PEC degradation of organic pollutants have also been highlighted.     

Enhancement of photocatalytic oxidation of humic acid in TiO2 suspensions by increasing cation strength

This study aimed at improving the photocatalytic (PC) oxidation of humic acids (HA) in TiO2 suspensions by adding cationic ion such as calcium or magnesium. A set of tests was first conducted in the dark to study the adsorption of HA onto TiO2 in suspensions at different pH and calcium concentrations. The experiment demonstrated that the adsorption of HA onto the TiO2 particles was either pH-dependent or calcium strength-dependent due to electrostatic interaction and calcium ion bridging. The photodegradation of HA in the presence of UV irradiation was investigated as a function of pH and the concentration of calcium and magnesium ions. The results showed that the adsorption behavior between HA and TiO2 played a very important role during the PC oxidation process. The PC oxidation could be enhanced at neutral pH by increasing the cation strength. The kinetics of HA PC degradation in TiO2 suspensions with different initial concentrations was also studied using the Langmuir-Hinshelwood model.     

Photocatalytic activity of TiO2 films grown on different substrates

Titanium dioxide films were prepared on glass, indium-tin oxide (ITO) glass and p-type monocrystalline silicon and studied for the photocatalytic degradation of rhodamine B in an aqueous medium. Raman, AFM, and XPS spectroscopic investigations of these films indicated that microstructure of titanium oxide films were greatly affected by the substrate materials. Rutile was confirmed to be easily formed on the surface of ITO glass, and TiO2 tended to grow as closely packed particles that were elongated strips with an average size of 20 nm, and had lovely contrast with the perfectly round particles grown on p-type monocrystalline silicon. Charge transfer between the film and silicon substrate was verified by surface photovoltage spectra. This may be the real reason why the films grown on ITO glass and silicon substrates exhibit higher photocatalytic reactivity than the film on glass substrate. Moreover, the different surface properties also seem to be responsible for the different activity.     

Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

Photocatalytic oxidation of pesticide rinsate

Pesticide rinsate has been considered as one of the major threats for the environment. In this study, photocatalysts such as TiO2 and O3 were used to promote the efficiency of direct UV photolysis to prevent such wastewater pollution. Carbofuran (a carbamate pesticide) and mevinphos (an organophosphate pesticide) with a concentration of 100 mg/L were selected as the test pesticide rinsates. Parent pesticide compound, COD, and microtoxicity analysis were employed to investigate the effect of photocatalyst on the degradation efficiency of pesticide in rinsate. It was found that the photocatalytic oxidation process (UV/O3, UV/TiO2) showed much higher COD removal and microtoxicity reduction efficiency for pesticide rinsate than did direct UV photolysis under the imposed conditions, suggesting that photocatalytic oxidation processes such as UV/O3 and UV/TiO2 could be a better alternative to treat pesticide rinsate. In addition, it was noted that increasing the initial pH of mevinphos rinsate to a basic level was required to reach higher COD removal efficiency and positive microtoxicity reduction efficiency while it was not necessary for the treatment of carbofuran rinsate.     

Simultaneous oxidation of EDTA and reduction of metal ions in mixed Cu(II)/Fe(III)-EDTA system by TiO2 photocatalysis

Both the photooxidation of EDTA and the photoreduction of metal ions in metal-EDTA systems were investigated. EDTA oxidation by TiO(2) photocatalysis occurred sequentially as Cu(II)-EDTA>Cu(II)/Fe(III)-EDTA>Fe(III)-EDTA. For Cu(II)-EDTA, EDTA was completely decomposed after only 60min of irradiation. The rate of EDTA decomposition was directly correlated with the initial Cu(II) concentration in the case of a mixed Cu(II)/Fe(III)-EDTA system. The metal ions in a single metal-EDTA complex were removed following significant decomposition of EDTA. For a mixed Cu(II)/Fe(III)-EDTA system, however, no copper was removed whereas almost all of the iron was removed. The iron and copper species deposited on the TiO(2) surface were identified via EPR and XPS as mixed FeO/Fe(3)O(4) and Cu(0)/Cu(2)O, respectively.     

Removal of faecal indicator pathogens from waters and wastewaters by photoelectrocatalytic oxidation on TiO2/Ti films under simulated solar radiation

Purpose

The disinfection efficiency of water and secondary treated wastewater by means of photoelectrocatalytic oxidation (PEC) using reference strains of Enterococcus faecalis and Escherichia coli as faecal indicators was evaluated. Operating parameters such as applied potential (2?C10?V), initial bacterial concentration (10³?C10⁷?CFU/mL), treatment time (up to 90?min) and aqueous matrix (pure water and treated effluent) were assessed concerning their impact on disinfection.

Methods

PEC experiments were carried out using a TiO₂/Ti film anode and a zirconium cathode in the presence of simulated solar radiation. Bacterial inactivation was monitored by the culture method and real-time SYBR green PCR.

Results

A 6.2 log reduction in E. faecalis population was achieved after 15?min of PEC treatment in water at 10?V of applied potential and an initial concentration of 10⁷?CFU/mL; pure photocatalysis (PC) led to only about 4.3 log reduction, whilst negligible inactivation was recorded when the respective electrochemical oxidation process was applied (i.e. without radiation). PEC efficiency was generally improved increasing the applied potential and decreasing initial bacterial concentration. Regarding real wastewater, E. coli was more susceptible than E. faecalis during treatment at a potential of 5?V. Wastewater disinfection was affected by its complex composition and the contained mixed bacterial populations, yielding lower inactivation rates compared to water treatment. Screening the results obtained from both applied techniques (culture method and real-time PCR), there was a discrepancy regarding the recorded time periods of total bacterial inactivation, with qPCR revealing longer periods for complete bacterial reduction.

Conclusions

PEC is superior to PC in terms of E. faecalis inactivation presumably due to a more efficient separation and utilization of the photogenerated charge carriers, and it is mainly affected by the applied potential, initial bacterial concentration and the aqueous matrix.     

Decolorizing of lignin wastewater using the photochemical UV/TiO2 process

Studies on applying the photochemical UV/TiO2 oxidation process to treat the lignin-containing wastewater for dissolved organic carbon (DOC), color and reducing A254 (the absorption at the wavelength of 254 nm) have been carried out. The data obtained in this study demonstrate that the UV/TiO2 process is effective in oxidizing the lignin thus reducing the color and DOC of the wastewater treated. The combined UV/TiO2 treatment can achieve better removal of DOC and color than the UV treatment alone. Color removal, based on American Dye Manufacture Index (ADMI) measurement, is greater than 99% if the pH is maintained at 3.0 with the addition of 1 g l(-1) TiO2. When 10 g l(-1) TiO2 is applied, the oxidation reduction potential (ORP) value is reached to result in an 88% removal of both DOC and color. A model was developed based on the variation of ORP during the photochemical reaction to simulate the decoloring process. The proposed model can be used to predict the color removal efficiency of the UV/TiO2 process.     

Photocatalytic and photoelectrocatalytic humic acid removal and selectivity of TiO(2) coated photoanode

In this study, photocatalytic (PC) and photoelectrocatalytic (PEC) treatment methods were comparatively investigated as a possible means of removing humic acid (HA) following absorbance at 254nm (UV(254)) and total organic carbon (TOC) analysis. The enhanced HA degradation rates were obtained in the PEC system over the conventional PC process under acidic, neutral and alkaline conditions. Preliminary and binary experiments were performed to determine the selectivity of the photoanode in terms of HA and chloride oxidation. TOC, chlorine and photocurrent parameters proved that HA was selectively removed before chlorine generation. The inhibitory effect of carbonate ions on the performance of photoanode was also studied under different pH values.     

Bromate formation on the non-porous TiO2 photoanode in the photoelectrocatalytic system

The increasing use of ozone in water disinfection processes has been the focus of considerable concern in regards to inorganic disinfection by product formation of bromate in waters containing bromide. Due to the public health risk caused by the presence of bromate as a suspected carcinogen, attention had been addressed to the conditions under which bromate is formed. In this study, photoanodic bromine generation and bromate (BrO(3)(-)) formation were investigated using a TiO(2) electrode in a photoelectrocatalytic (PEC) treatment process. The separation of anodic and cathodic reactions in the PEC system resulted in a pH decrease from 9.3 to 3.0 in the photoanode compartment and an increase to 11.0 in the cathode compartment. Under a photo-illumination intensity of 5.7 m W cm(-2) UV, a biasing potential of +1.0V vs SCE, a pH of 6.0 and at a NaBr concentration of 1.0 x 10(-2) M, active bromine formation increased over time with 2.4 x 10(-6) M min(-6) rate and reached a steady-state concentration of 1.44 x 10(-4) M in 60 min. Bromate formation was detected after a lag-period of 15 min and exhibited a continuous increasing trend with respect to irradiation time. No bromate formation was observed below pH 6.5 whereas an increasing bromate concentrations and pH up to pH=8.5 were noted.     

Enhanced photocatalytic reduction reaction over Bi(3+)-TiO(2) nanoparticles in presence of formic acid as a hole scavenger

A series of Bi(3+)-doped TiO(2) (Bi(3+)-TiO(2)) catalysts with a doping concentration up to 2wt% were prepared by a sol-gel method. The prepared photocatalysts were characterized by different means to determine their chemical composition, surface structure and light absorption properties. The photocatalytic activity of different Bi(3+)-TiO(2) catalysts was evaluated in the photocatalytic reduction of nitrate in aqueous solution under UV illumination. In the experiments, formic acid was used as a hole scavenger to enhance the photocatalytic reduction reaction. The experiments demonstrated that nitrate was effectively degraded in aqueous Bi(3+)-TiO(2) suspension by more than 83% within 150min, while the pH of the solution increased from 3.19 to 5.83 due to the consumption of formic acid. The experimental results indicate that the presence of Bi(3+) in TiO(2) catalysts substantially enhances the photocatalytic reaction of nitrate reduction. It was found that the optimal dosage of 1.5wt% Bi(3+) in TiO(2) achieved the fastest reaction of nitrate reduction under the experimental condition. Bismuth ions deposit on the TiO(2) surface behaves as sites where electrons accumulate. Better separation of electrons and holes on the modified TiO(2) surface allows more efficient channeling of the charge carriers into useful reduction and oxidation reactions rather than recombination reactions. Two intermediate products of nitrite and ammonia during the reaction were also monitored to explore the possible mechanisms of photoluminescence quenching and photocatalytic reduction in the context of donor-acceptor interaction with electron trapping centers.     

Photocatalytic oxidation of gaseous DMF using thin film TiO2 photocatalyst

The heterogeneous photocatalytic oxidation of gaseous N,N'-dimethylformamide (DMF) widely used in the manufacture of synthetic leather and synthetic textile was investigated. The experiments were carried out in a plug flow annular photoreactor coated with Degussa P-25 TiO2. The oxidation rate was dependent on DMF concentration, reaction temperature, water vapor, and oxygen content. Photocatalytic deactivation was observed in these reactions. The Levenspiel deactivation kinetic model was used to describe the decay of catalyst activity. Fourier transform infrared (FTIR) was used to characterize the surface and the deactivation mechanism of the photocatalyst. Results revealed that carbonylic acids, aldehydes, amines, carbonate and nitrate were adsorbed on the TiO2 surface during the photocatalytic reaction. The ions, NH4+ and NO3-, causing the deactivation of catalysts were detected on the TiO2 surface. Several treatment processes were applied to find a suitable procedure for the regeneration of catalytic activity. Among these procedures, the best one was found to be the H2O2/UV process.     

Inactivation of bacteria under visible light and in the dark by Cu films. Advantages of Cu-HIPIMS-sputtered films

Introduction

The Cu polyester thin-sputtered layers on textile fabrics show an acceptable bacterial inactivation kinetics using sputtering methods.

Materials and methods

Direct current magnetron sputtering (DCMS) for 40?s of Cu on cotton inactivated Escherichia coli within 30?min under visible light and within 120?min in the dark. For a longer DCMS time of 180?s, the Cu content was 0.294% w/w, but the bacterial inactivation kinetics under light was observed within 30?min, as was the case for the 40-s sputtered sample.

Results and discussion

This observation suggests that Cu ionic species play a key role in the E. coli inactivation and these species were further identified by X-ray photoelectron spectroscopy (XPS). The 40-s sputtered samples present the highest amount of Cu sites held in exposed positions interacting on the cotton with E. coli. Cu DC magnetron sputtering leads to thin metallic semi-transparent gray?Cbrown Cu coating composed by Cu nanoparticulate in the nanometer range as found by electron microscopy (EM). Cu cotton fabrics were also functionalized by bipolar asymmetric DCMSP.

Conclusion

Sputtering by DCMS and DCMSP for longer times lead to darker and more compact Cu films as detected by diffuse reflectance spectroscopy and EM. Cu is deposited on the polyester in the form of Cu₂O and CuO as quantified by XPS. The redox interfacial reactions during bacterial inactivation involve changes in the Cu oxidation states and in the oxidation intermediates and were followed by XPS. High-power impulse magnetron sputtering (HIPIMS)-sputtered films show a low rugosity indicating that the texture of the Cu nanoparticulate films were smooth. The values of R _q and R _a were similar before and after the E. coli inactivation providing evidence for the stability of the HIPIMS-deposited Cu films. The Cu loading percentage required in the Cu films sputtered by HIPIMS to inactivate E. coli was about three times lower compared to DCMS films. This indicates a substantial Cu metal savings within the preparation of antibacterial films.     

Oxidation of diethylene glycol with ozone and modified Fenton processes

This paper describes a study of oxidation of diethylene glycol (DEG) by ozone and modified Fenton process (hydrogen peroxide and ferric salt mixture) in aqueous solution. Both oxidation processes were able to oxidize relatively high concentrations of DEG effectively. DEG reacted primarily through hydroxyl radical produced by decomposition of ozone, and about 3 mol of ozone were consumed per mole of DEG removed during the process. For modified Fenton oxidation, stepwise addition of hydrogen peroxide (H2O2) and ferric salt (Fe(III)) resulted in much higher removal of DEG than one-time pulse addition of the chemicals. The extent of DEG removal increased with increasing concentrations of both H2O2 and Fe(III). Oxidant consumption per mole of DEG oxidized was one order of magnitude higher for hydrogen peroxide than those observed for ozone. Overall, ozonation produced higher concentrations of aldehydes, and modified Fenton treatment produced higher concentrations of carboxylic acids for the same levels of DEG oxidation. The major products of ozonation were glycolaldehyde, glyoxal, formaldehyde, acetaldehyde, and acetic, formic, pyruvic, oxalic and glyoxalic acids. The major products of modified Fenton oxidation were formaldehyde, and formic and acetic acids.     

Photodegradation of alachlor with the TiO(2) film immobilised on the glass tube in aqueous solution

Alachlor photodegradation was performed using TiO(2), which was synthesized by a modified sol-gel method. The thickness of a TiO(2) film immobilised by a 5-time dip-coating was 174 nm and the average diameter of TiO(2) particles was about 10-15 nm in SEM images. The crystal structure of a TiO(2) film calcinated at 300 degrees C for 1 h was observed as a typical anatase type. The stability of a TiO(2) film by a modified sol-gel method was 4% better than TiO(2) by a typical sol-gel method.The removal rate of alachlor with both Fe(3+) and UV radiation in the absence of TiO(2) was 0.28 mg/l/h in 10 h and the removal rate of alachlor with Fe(3+)/UV in the presence of TiO(2) was 0.32 g/l/h, which was higher by 14% than that with Fe(3+)/UV system. TOC concentration during the alachlor degradation with both TiO(2) and UV radiation in the absence of added Fe(3+) decreased from 100%, through 81% and 51%, to 44% with time elapses of 4, 8, and 10 h, respectively, while TOC concentration with both added Fe(3+) and UV radiation in the absence of TiO(2) decreased from 100% to 70% in 10 h.     

Enhanced photocatalysis of pentachlorophenol by metal-modified titanium (IV) oxide

The effects of four metals (Ag, Au, Pt, and Cu) doped on TiO2 on the photocatalysis of pentachlorophenol (PCP) were investigated. The results of this study indicated that all four metals-doped TiO2 catalysts were able to enhance the efficiency of PCP photocatalysis with an optimum metallic content of 0.1 wt%. For the metal-doped TiO2 samples (Au, Pt, and Cu), the patterns of light absorption were significantly extended toward visible light spectra in the wavelengths between 400 and 800 nm. The photocatalysis of PCP was pH dependent with the maximum degradation rate achieved in the solution at pH 3. The formation of chloride ion corresponded with the concentration of PCP degraded which confirmed that dechlorination was the major pathway of PCP photocatalysis. The overall toxicities of PCP samples were reduced with the extension of light exposure using the microtox test. The results of PCP photocatalysis are also discussed based on the characteristics of metal/TiO2 including X-ray differential (XRD) patterns, Brunquer Emmett Teller (BET) specific area analysis, and Ultra Violet (UV)-Vis absorption spectra.     

Decomposition of benzene and toluene in air streams in fixed-film photoreactors coated with TiO2 catalyst

The decomposition of benzene and toluene in air streams by UV/TiO2 process was studied in different annular photoreactors under various operating conditions. The shells of reactors used in this research are made of stainless steel, Pyrex glass, or titanium. The TiO2 film was coated to the inner surface of the reactors by either rotating coating or sol-gel techniques. The TiO2 films coated by sol-gel technique were found to be smoother and more uniform than those coated by rotating coating. However, experimental results indicated that the photocatalysis of benzene or toluene in a glass reactor with rotating-coated TiO2 film delivered higher decompositions in air streams than that with sol-gel coated reactors. Benzene and toluene were decomposed more effectively in a coated glass reactor than in a coated stainless steel reactor under the same operating conditions. The presence of water vapor in air-stream plays an important role in the decomposition of benzene and toluene, and a relative humidity of approximately 5-6% was found to be adequate. The presence of excessive amounts of humidity retarded the decomposition to certain extents possibly results from the competitive adsorption of water molecules on the active sites of TiO2.