Oxidative degradation of pyrene in contaminated soils by δ-MnO2 with or without sunlight irradiation

The enhanced oxidative degradation of pyrene in quartz sand and alluvial and red soils by micro-nano size birnessite (δ-MnO₂) in the presence and absence of sunlight was investigated. The degradation of pyrene by δ-MnO₂ in quartz sand showed very little synergistic effect of sunlight irradiation on δ-MnO₂ oxidizing power. However, pyrene degradation by δ-MnO₂ in alluvial and red soils was greater under solar irradiation than the combination of photooxidation of pyrene and oxidation of pyrene by δ-MnO₂. The oxidative degradation percentages of pyrene by δ-MnO₂ under sunlight irradiation are 94.8, 97.7, and 100% for alluvial soil, red soil, and quartz sand, respectively. Oxidative degradation percentages of pyrene by δ-MnO₂ in alluvial and red soils with irradiation of sunlight almost attained a maximum at 1 h with a 5% (w/w) dose of the amended oxidant. Due to their different total organic carbon (TOC) contents, the sequence of enhanced oxidative degradation of pyrene by δ-MnO₂ in quartz sand and alluvial and red soils was quartz sand > red soil > alluvial soil. Further, this study revealed that δ-MnO₂-enhanced oxidative degradation of pyrene is very pronounced in contaminated soils in situ even at deep soil layers where irradiation by sunlight is very limited.     

Synergetic effect between photocatalytic degradation and adsorption processes on the removal of phenolic compounds from olive mill wastewater

The photocatalytic degradation of two phenolic compounds, p-coumaric acid and caffeic acid, was performed with a suspended mixture of TiO₂ and powdered activated carbon (PAC) (at pH = 3.4 and 8). Adsorption, direct photolysis and photocatalytic degradation were studied under different pH and UV light sources (sunlight vs. 365 nm UV lamps). The potential for reusing this catalyst mixture in sequential photocatalytic runs was examined as well. Quantum yields for the direct photolysis of caffeic acid under solar and artificial 365 nm light were calculated (for the first time) as 0.005 and 0.011, respectively.A higher removal rate of contaminants by either adsorption or photocatalysis was obtained at a low pH (pH 4). Furthermore, the addition of PAC increased the removal efficiency of the phenolic compounds. Fast removal of the pollutants from the solution over three sequential runs was achieved only when both TiO₂ and PAC were present. This suggests that at medium phenolic concentrations, the presence of PAC as a co-sorbent reduces surface poisoning of the TiO₂ catalyst and hence improves photocatalysis degradation of phenolic pollutants.The adsorption equilibrium of caffeic acid or p-coumaric acid on TiO₂, PAC and the combined mixture of TiO₂ and PAC follows the Langmuir isotherm model. Experiments with PAC TiO₂ mixture and olive mill wastewater (anaerobically treated and diluted by a factor of 10) showed higher removal of polyphenols than of chemical oxygen demand (COD). 87% removal of total polyphenols, compared to 58% of COD, was achieved after 24 h of exposure to 365 nm irradiation (7.6 W/m²) in the presence of a suspended mixture of TiO₂ and PAC, indicating “self-selectivity” of polyphenols.     

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

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

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.     

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.     

Photolytic and photocatalytic decomposition of aqueous ciprofloxacin: Transformation products and residual antibacterial activity

Previous work demonstrates that widely used fluoroquinolone antibacterial agents, including ciprofloxacin, are degraded by means of aqueous ultraviolet photolytic and titanium dioxide (TiO₂) photocatalytic (using both ultraviolet-A (UVA) and visible light (Vis) irradiation) treatment processes. In this study, we investigate the effects of photolytic and photocatalytic treatment processes on the antibacterial activity of ciprofloxacin solutions under controlled laboratory conditions. In agreement with earlier work, rates of ciprofloxacin degradation under comparable solution conditions (100 μM ciprofloxacin, 0 or 0.5 g/L TiO₂, pH 6, 25 °C) follow the trend UVA-TiO₂ > Vis-TiO₂ > UVA. Release of ammonia and fluoride ions is observed and a range of organic products have been identified with liquid chromatography-tandem mass spectrometry. However, the identified organic products all appear to retain the core quinolone structure, raising concerns about residual antibacterial potency of the treated solutions. Quantitative microbiological assays with a reference Escherichia coli strain indicate that the antimicrobial potency of ciprofloxacin solutions track closely with the undegraded ciprofloxacin concentration during photolytic or photocatalytic reactions. Quantitative analysis shows that for each mole of ciprofloxacin degraded, the antibacterial potency of irradiated solutions decreases by approximately one “mole” of activity relative to that of the untreated ciprofloxacin solution. This in turn indicates that the ciprofloxacin photo(cata)lytic transformation products retain negligible antibacterial activity relative to the parent compound. The energy demands for achieving one order of magnitude reduction in antibacterial activity within the experimental system are estimated to be 175 J/cm² (UVA-only), 29 J/cm² (Vis-TiO₂), and 20 J/cm² (UVA-TiO₂), which indicates that the UVA-TiO₂ photocatalysis is the most energy efficient process for achieving ciprofloxacin inactivation under laboratory conditions.     

Antifungal capability of TiO2 coated film on moist wood

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

Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20 mg L⁻¹ of antibiotic oxolinic acid (OA). The effects of catalyst load (0.2-1.5 g L⁻¹) and pH (7.5-11) were evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, low pH values and 1.0 g L⁻¹ of TiO₂ favoured the efficiency of the process. Under optimal conditions the evolution of the substrate, chemical oxygen demand, dissolved organic carbon, toxicity and antimicrobial activity on Escherichia coli cultures were evaluated. The results indicate that, under optimal conditions, after 30 min, the TiO₂ photocatalytic system is able to eliminate both the substrate and the antimicrobial activity, and to reduce the toxicity of the solution by 60%. However, at the same time, ∼53% of both initial DOC and COD remain in solution. Thus, the photocatalytical system is able to transform the target compound into more oxidized by-products without antimicrobial activity and with a low toxicity. The study of OA by-products using liquid chromatography coupled with mass spectrometry, as well as the evaluation of OA degradation in acetonitrile media as solvent or in the presence of isopropanol and iodide suggest that the reaction is initiated by the photo-Kolbe reaction. Adsorption isotherm experiments in the dark indicated that under pH 7.5, adsorption corresponded to the Langmuir adsorption model, indicating the dependence of the reaction on an initial adsorption step.     

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.     

Preparation of DNA-adsorbed TiO2 particles — Augmentation of performance for environmental purification by increasing DNA adsorption by external pH regulation

We have previously developed a novel photocatalyst, DNA-attached titanium dioxide (DNA-TiO₂), useful for the recovery and decomposition of chemicals [Suzuki et al. Environ. Sci. Technol. 42, 8076, 2008]. Chemicals accumulated in DNA near the surface of TiO₂ and were degraded under UV light. The efficiency of their removal was dependent on the amount of DNA adsorbed on TiO₂, indicating the attachment of larger amounts of DNA to result in higher efficiency. In this study, we succeeded in improving the performance of DNA-TiO₂ by increasing the amount of DNA adsorbed by regulating the external pH. The adsorption of DNA by TiO₂ dramatically increased at pH2, to about fourfold that at other pH values (pH4-10). Repeating the process of DNA addition increased the adsorption further. The attached DNA was stable on the surface of TiO₂ at pH2-10 and 4-56 °C, the same as DNA-TiO₂ prepared at pH7. As the DNA-TiO₂ prepared at pH2 retained much DNA on its surface, chemicals (methylene blue, ethidium bromide, etc.) which could intercalate or react with DNA were effectively removed from solutions. The photocatalytic degradation was slow at first, but the final degradation rate was higher than for non-adsorbed TiO₂ and DNA-TiO₂ prepared at pH7. These results indicated that preparation of DNA-TiO₂ at pH2 has advantages in that much DNA can be attached and large amounts of chemicals can be concentrated in the DNA, resulting in extensive decomposition under UV light.     

Photoassisted reduction of metal ions and organic dye by titanium dioxide nanoparticles in aqueous solution under anoxic conditions

The photoassisted reduction of metal ions and organic dye by metal-deposited Degussa P25 TiO₂ nanoparticles was investigated. Copper and silver ions were selected as the target metal ions to modify the surface properties of TiO₂ and to enhance the photocatalytic activity of TiO₂ towards methylene blue (MB) degradation. X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were used to characterize the crystallinity, chemical species and morphology of metal-deposited TiO₂, respectively. Results showed that the particle size of metal-deposited TiO₂ was larger than that of Degussa P25 TiO₂. Based on XRPD patterns and XPS spectra, it was observed that the addition of formate promoted the photoreduction of metal ion by lowering its oxidation number, and subsequently enhancing the photodegradation efficiency and rate of MB. The pseudo-first-order rate constant (k_obs) for MB photodegradation by Degussa P25 TiO₂ was 3.94 × 10^− 2 min^− 1 and increased by 1.4-1.7 times in k_obs with metal-deposited TiO₂ for MB photodegradation compared to simple Degussa P25 TiO₂. The increase in mass loading of metal ions significantly enhanced the photodegradation efficiency of MB; the k_obs for MB degradation increased from 3.94 × 10^− 2 min^− 1 in the absence of metal ion to 4.64-7.28 × 10^− 2 min^− 1 for Ag/TiO₂ and to 5.14-7.61 × 10^− 2 min^− 1 for Cu/TiO₂. In addition, the electrons generated from TiO₂ can effectively reduce metal ions and MB simultaneously under anoxic conditions. However, metal ions and organic dye would compete for electrons from the illuminated TiO₂.     

Membrane vis-LED photoreactor for simultaneous penicillin G degradation and TiO2 separation

The hybrid membrane photoreactor (MPR) combining a photoreactor irradiated with visible-light-emitting diode (vis-LED) and a cross-flow microfiltration (MF) membrane module was investigated in both closed-loop and continuous flow-through modes for the simultaneous degradation of penicillin G (PG) and separation of visible-light responsive TiO₂ particles, namely C-sensitized-N-doped TiO₂ (T300) and C-N-S tridoped TiO₂ (T0.05-450). The turbidity of permeate water was <0.2 NTU for both T300 and T0.05-450 suspensions in the MPR system operated at different transmembrane pressures (TMPs) and cross-flow velocities (CFVs), indicating effective separation of TiO₂ particles by the MF membrane. The operations at a higher TMP or lower CFV were more prone to induce TiO₂ deposition on the membrane surface without backwashing, which resulted in the membrane fouling, the loss of TiO₂ from the photoreactor and the decrease of PG photocatalytic degradation efficiency. 75% and 84% of PG were degraded in the closed-loop MPR without backwashing operated at 10 kPa and 0.15 m s⁻¹ after 4 h of vis-LED irradiation using 1.0 g L⁻¹ of T300 and T0.05-450, respectively. With backwashing of the membrane, the PG photocatalytic degradation efficiencies in the closed-loop MPR could be significantly enhanced to achieve 93% and 95% using 1.0 g L⁻¹ of T300 and T0.05-450, respectively, which were almost comparable to those achieved in the batch photoreactor. Due to its shorter hydraulic residence time in the photoreactor, the PG degradation efficiency in the continuous flow-through MPR with backwashing was lower than that achieved in the closed-loop MPR.     

Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment

Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO₂ semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO₂ based photoanode using an optic fiber support. The novel arrangement of a TiO₂ layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 μm thickness SnO₂:Sb films on which the photoactive TiO₂ layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO₂:Sb and TiO₂ showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H₂O₂ close to 50% as compared to different types of TiO₂ films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L⁻¹) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.     

Mineralization enhancement of a recalcitrant pharmaceutical pollutant in water by advanced oxidation hybrid processes

Degradation of the biorecalcitrant pharmaceutical micropollutant ibuprofen (IBP) was carried out by means of several advanced oxidation hybrid configurations. TiO₂ photocatalysis, photo-Fenton and sonolysis - all of them under solar simulated illumination - were tested in the hybrid systems: sonophoto-Fenton (FS), sonophotocatalysis (TS) and TiO₂/Fe²⁺/sonolysis (TFS). In the case of the sonophoto-Fenton process, the IBP degradation (95%) and mineralization (60%) were attained with photo-Fenton (FH). The presence of ultrasonic irradiation slightly improves the iron catalytic activity. On the other hand, total removal of IBP and elimination of more than 50% of dissolved organic carbon (DOC) were observed by photocatalysis with TiO₂ in the presence of ultrasound irradiation (TS). In contrast only 26% of mineralization was observed by photocatalysis with H₂O₂ (TH) in the absence of ultrasound irradiation. Additional results showed that, in the TFS system, 92% of DOC removal and complete degradation of IBP were obtained within 240 min of treatment. The advanced oxidation hybrid systems seems to be a promising alternative for full elimination/mineralization for the recalcitrant micro-contaminant IBP.     

Mechanism of phenol photodegradation in the presence of pure and modified-TiO(2): A review

In recent years, the application of heterogeneous photocatalytic water purification processes has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible-light spectrum. By far, titania has played a much larger role in this scenario compared to other semiconductor photocatalysts due to its costly effectiveness, inert nature and photostability. A substantial amount of research has focused on the enhancement of TiO₂ photocatalysis by modification with metal, non-metal and ion doping.This paper aims to review and summarize the recent works on the titanium dioxide (TiO₂) photocatalytic oxidation of phenol and discusses various mechanisms of phenol photodegradation (indicating the intermediates products) and formation of OH radicals. Phenol degradation pathway in both systems, TiO₂/UV and doped-TiO₂/Vis, are described.     

Effect of water-matrix composition on Trimethoprim solar photodegradation kinetics and pathways

Direct photolysis and solar TiO₂ photocatalysis of Trimethoprim (TMP) in different water matrices (demineralised and simulated seawater) have been studied. Direct photolysis yielded a similar, slow TMP degradation rate in both water matrices, and the formation of very stable photo-transformation products. Dissolved organic carbon decreased slightly after prolonged irradiation. The main intermediate identified was a ketone derivative (trimethoxybenzoylpyrimidine), which was proved to be a photosensitizer of TMP degradation. During TiO₂ photocatalysis, TMP was completely eliminated in both water matrices at a similar rate, however, the mineralization rate was appreciably reduced in seawater, which can be explained by the presence of inorganic species acting as hydroxyl radical scavengers, and directly affecting photocatalytic efficiency. Identification of intermediates showed differences between the two processes but hydroxylation, demethylation and cleavage of the original drug molecule were observed in both.     

Photocatalytic cement-based materials: Comparison of nitrogen oxides and toluene removal potentials and evaluation of self-cleaning performance

Using cement-based building materials as a matrix for nano-photocatalysts is an important development for the large scale application of photocatalytic technologies. Air pollution mitigation and self-cleaning surface are two major applications of photocatalytic building materials. In this study, a comparison was made to evaluate the performance of TiO₂ modified concrete surface layers for NO_x and VOC degradation. The self-cleaning performance of TiO₂ modified self-compacting mortars (SCM) developed for decorative applications was also evaluated. The results show that the photocatalytic conversion of toluene by the TiO₂ modified surface layer was not detected, although NO_x could be effectively removed under the same conditions. The presence of toluene did not influence the NO_x removal process. TiO₂ modified SCM were found to be effective in the discoloration of rhodamine B under UV and strong halogen light irradiation. The level of adsorption of the air contaminants onto the active sites of the cement-TiO₂ composite was identified to be the key factor determining the subsequent photocatalytic efficiency.     

Enhance the photocatalytic activity for the degradation of organic contaminants in water by incorporating TiO2 with zero-valent iron

Titanium dioxide (TiO₂) has become the most popular photocatalyst in treating persistent organic pollutants. The main disadvantage of TiO₂ is the diminishing photocatalytic activity over time due to the electron-hole pair recombination. Many studies have aimed to prolong the photocatalytic life of TiO₂. Among them, incorporation of zero-valent iron (ZVI) is one of the approaches. In this study, a novel nano TiO₂/Fe⁰ composite (NTFC) was synthesized from a nano neutral TiO₂ sol and a nano zero-valent iron (nZVI), both prepared in our laboratory. The structure, composition and physical property of the NTFC are characterized. The photocatalytic activity of the NTFC was evaluated by the reductive decolourization of an azo dye, Acid Black-24 (AB-24), and was found superior to those of nZVI and nano neutral TiO₂ sol. Evidence suggests that the enhanced activity of NTFC is highly correlated to the ratio of ferrous to ferric ion in the system. The quantities of ferrous and ferric ions in the nZVI and NTFC systems were monitored separately. In the nZVI system, the concentration of ferric ions decreased significantly with time while a high level of ferrous ions was maintained in the NTFC suspension. The ferrous/ferric ratio of the NTFC suspension was substantially increased after irradiation by UV. Evidence from EPR analysis suggests that the excited electrons in the conduction band of the TiO₂ can be trapped by the half reaction of Fe³⁺/Fe²⁺, reducing the probability of electron-electron hole pair recombination and sustaining the catalytic life of TiO₂. Corrosion tests further proved that by incorporating TiO₂ with zero-valent iron the surface oxidation of nZVI can be effectively prevented.     

Degradation of NO using photocatalytic coatings applied to different substrates

This article deals with the degradation of NO present in the air by means of a photocatalytic oxidation process based on TiO₂ nanoparticles incorporated in a polymer-matrix-based coating. The experimental set-up consisted of a flow type reactor adapted from the ISO 22197-1 standard. NO₂ in the gas phase, and nitrate ions adsorbed on the photocatalytic surface were detected as finals products. Various parameters influencing the NO degradation efficiency were studied: the coating composition, the substrate nature, the initial concentration of NO, the polluted air flow rate and the humidity. Compared to glass, the use of mortar as the substrate enhanced the photocatalytic performance of coatings by reducing the generation of gaseous NO₂ as a by-product.     

Carbon-sensitized and nitrogen-doped TiO2 for photocatalytic degradation of sulfanilamide under visible-light irradiation

A novel carbon-sensitized and nitrogen-doped TiO₂ (C/N-TiO₂) was synthesized by a facile sol-gel method using titanium butoxide as both titanium precursor and carbon source, and nitric acid as nitrogen source. The calcination temperature had a great effect on the crystal phase structure, nitrogen incorporation into the TiO₂ lattice and content of carbonaceous species. The incorporated carbonaceous species could serve as photosensitizer, while the nitrogen doping could lead to the remarkable red shift of absorption edge of C/N-TiO₂. The C/N-TiO₂ calcinated at 300 °C (T300) exhibited the highest photocatalytic activity for sulfanilamide (SNM) degradation under irradiation of visible-light-emitting diode (vis-LED). The SNM photocatalytic degradation and mineralization were more efficient in acidic conditions due to the carbon photosensitizing effect. Insignificant inhibitory effects were observed in the presence of chloride, nitrate and sulfate, while bicarbonate, phosphate and silica could inhibit the SNM mineralization to different degrees. Acetate, ammonium and sulfate were released during SNM mineralization. T300 exhibited good photochemical stability and could be reused for 5 times with less than 10% decrease in the SNM removal efficiency. The acute toxicity of SNM solution could be reduced over prolonged photocatalysis according to the Microtox assay.