Titania Nanotubes Grown on Carbon Fibers for Photocatalytic Decomposition of Gas-Phase Aromatic Pollutants.
ABSTRACT: This study aimed to prepare titania (TiO₂) nanotube (TNT) arrays grown on un-activated carbon fibers (UCFs), with the application of different TiO₂ loadings based on the coating-hydrothermal process, and to evaluate their photocatalytic activity for the degradation of sub-ppm levels of aromatic pollutants (benzene, toluene, ethyl benzene, and o-xylene (BTEX)) using a plug-flow photocatalytic reactor. The characteristics of the prepared photocatalysts were determined by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), transmission electron microscopy (TEM), UV-visible absorption spectroscopy (UV-Vis) and X-ray diffraction (XRD) analyses. Spectral analysis showed that the prepared photocatalysts were closely associated with the characteristics of one-dimensional nanostructured TiO₂ nanotubes for TNTUCFs and spherical shapes for TiO₂-coated UCF (TUCF). The photocatalytic activities of BTEX obtained from TNTUCFs were higher than those obtained from a reference photocatalyst, TUCF). Specifically, the average degradation efficiencies of BTEX observed for TNTUCF-10 were 81%, 97%, 99%, and 99%, respectively, while those observed for TUCF were 14%, 42%, 52%, and 79%, respectively. Moreover, the photocatalytic activities obtained for TNTUCFs suggested that the degradation efficiencies of BTEX varied with changes in TiO₂ loadings, allowing for the optimization of TiO₂ loading. Another important finding was that input concentrations and air flow rates could be important parameters for the treatment of BTEX, which should be considered for the optimization of TNTUCFs application. Taken together, TNTUCFs can be applied to effectively degrade sub-ppm levels of gas-phase aromatic pollutants through the optimization of operational conditions.
Project description:N-F-co-embedded titania (N-F-TiO₂) photocatalysts with varying N:F ratios were synthesized and tested for their ability to photocatalyze the degradation of pollutants present at indoor air levels using visible light. The synthesis was achieved using a solvothermal process with tetrabutyl titanate, urea and ammonium fluoride as sources of Ti, N and F, respectively. Three selected volatile organic compounds (toluene, ethyl benzene and o-xylene) were selected as the test pollutants. The prepared composites were characterized using X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Ultra-violet (UV)-visible spectroscopy. The photocatalytic degradation efficiencies of N-F-TiO₂ composites were higher than those obtained using pure TiO₂ and N-TiO₂. Moreover, these efficiencies increased as the N:F ratio decreased from sixteen to eight, then decreased as it dropped further to three, indicating the presence of an optimal N:F ratio. Meanwhile, as retention time decreased from 12.4 to 0.62 s, the average photocatalytic efficiencies decreased from 65.4% to 21.7%, 91.5% to 37.8% and 95.8% to 44.7% for toluene, ethyl benzene and o-xylene, respectively. In contrast, the photocatalytic reaction rates increased as retention time decreased. In consideration of all of these factors, under optimized operational conditions, the prepared N-F-TiO₂ composites could be utilized for the degradation of target pollutants at indoor air levels using visible light.
Project description:In order to develop original and efficient visible light response photocatalysts for degrading organic pollutants in wastewater, new photocatalysts Bi₂GaSbO₇ and Bi₂InSbO₇ were firstly synthesized by a solid-state reaction method and their chemical, physical and structural properties were characterized. Bi₂GaSbO₇ and Bi₂InSbO₇ were crystallized with a pyrochlore-type structure and the lattice parameter of Bi₂GaSbO₇ or Bi₂InSbO₇ was 10.356497 Å or 10.666031 Å. The band gap of Bi₂GaSbO₇ or Bi₂InSbO₇ was estimated to be 2.59 eV or 2.54 eV. Compared with nitrogen doped TiO₂, Bi₂GaSbO₇ and Bi₂InSbO₇, both showed excellent photocatalytic activities for degrading methylene blue during visible light irradiation due to their narrower band gaps and higher crystallization perfection. Bi₂GaSbO₇ showed higher catalytic activity compared with Bi₂InSbO₇. The photocatalytic degradation of methylene blue followed by the first-order reaction kinetics and the first-order rate constant was 0.01470 min-1, 0.00967 min-1 or 0.00259 min-1 with Bi₂GaSbO₇, Bi₂InSbO₇ or nitrogen doped TiO₂ as a catalyst. The evolution of CO₂ and the removal of total organic carbon were successfully measured and these results indicated continuous mineralization of methylene blue during the photocatalytic process. The possible degradation scheme and pathway of methylene blue was also analyzed. Bi₂GaSbO₇ and Bi₂InSbO₇ photocatalysts both had great potential to purify textile industry wastewater.
Project description:A well designed and accurate method of control of different shell thickness and electronic transmission in a Z-scheme core@shell system is conducive to obtaining an optimum photocatalytic performance. Herein, the Z-scheme heterojunction of egg-like core@shell CdS@TiO₂photocatalysts with controlled shell thickness (13 nm, 15 nm, 17 nm, 22 nm) were synthesized by a facile reflux method, and the CdS@TiO₂ structure was proved by a series of characterizations. The photodegradation ratio on methylene blue and tetracycline hydrochloride over the 0.10CdS@TiO₂ composites with TiO₂ shell thickness of 17 nm reached 90% in 250 min and 91% in 5 min, respectively, which was almost 9.8 times and 2.6 times than that of TiO₂ and CdS on rhodamine B respectively under visible light. Besides, the higher total organic carbon removal ratio indicated that most of the pollutants were degraded to CO₂ and H₂O. The Z-scheme electronic transfer pathway was studied through radical species trapping experiments and electron spin resonance spectroscopy. Moreover, the relationship between shell thickness and photocatalytic activity demonstrated that different shell thickness affects the separation of the electron and holes, and therefore affected the photocatalytic performance. In addition, the effects of pollutants concentration, pH, and inorganic anions on photocatalytic performance were also investigated. This work can provide a novel idea for a well designed Z-scheme heterojunction of core@shell photocatalysts, and the study of photocatalytic performance under different factors has guiding significance for the treatment of actual wastewater.
Project description:Benzene, toluene, ethylbenzene and xylenes (BTEX) are some of the common environmental pollutants originating mainly from oil and gas industries, which are toxic to human as well as other living organisms in the ecosystem. Here we investigate photocatalytic degradation of BTEX under visible light irradiation using supported zinc oxide (ZnO) nanorods grown on glass substrates using a microwave assisted hydrothermal method. ZnO nanorods were characterized by electron microscopy, X-ray diffraction (XRD), specific surface area, UV/visible absorption and photoluminescence spectroscopy. Visible light photocatalytic degradation products of BTEX are studied for individual components using gas chromatograph/mass spectrometer (GC/MS). ZnO nanorods with significant amount of electronic defect states, due to the fast crystallization of the nanorods under microwave irradiation, exhibited efficient degradation of BTEX under visible light, degrading more than 80% of the individual BTEX components in 180 minutes. Effect of initial concentration of BTEX as individual components is also probed and the photocatalytic activity of the ZnO nanorods in different conditions is explored. Formation of intermediate byproducts such as phenol, benzyl alcohol, benzaldehyde and benzoic acid were confirmed by our HPLC analysis which could be due to the photocatalytic degradation of BTEX. Carbon dioxide was evaluated and showed an increasing pattern over time indicating the mineralization process confirming the conversion of toxic organic compounds into benign products.
Project description:In this work, TiO? photocatalysts, co-doped with transition metal ions vanadium (V) and cobalt (Co) ((V,Co)?TiO?), were synthesized by the sol?gel method. The synthesized photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and desorption measurement, UV-Vis absorption and photoluminescence spectrum (PL) spectra. The results show that V and Co co-doping has significant effects on sample average crystalline grain size, absorption spectrum, recombination efficiency of photo-induced electron-hole pairs (EHPs), and photocatalytic degradation efficiency of methylene blue (MB). (V,Co)?TiO? photocatalyst exhibits an obvious red shift of the absorption edge to 475 nm. Photocatalytic degradation rate of (V,Co)?TiO? sample for MB in 60 min is 92.12% under a Xe lamp with a cut-off filter (? > 400 nm), which is significantly higher than 56.55% of P25 under the same conditions. The first principles calculation results show that V and Co ions doping introduces several impurity energy levels, which can modulate the location of the valence band and conduction band. An obvious lattice distortion is produced in the meantime, resulting in the decrease in photo-generated EHP recombination. Thus, (V,Co)?TiO? photocatalyst performance is significantly improved.
Project description:Hybrid materials of conjugated polymer and titanium(IV) oxide have attracted considerable attention concerning their potential benefits, including (i) efficient exploitation of visible light, (ii) a high adsorption capacity for organic contaminants, (iii) and effective charge carriers separation. The new class of the photocatalysts is promising for the removal of environmental pollutants in both aqueous and gaseous phases. For the first time, in this study, the polyaniline (PANI)-TiO<sub>2</sub> hybrid composite was used for the degradation of phenol in water and toluene in the gas phase. Polyaniline-TiO<sub>2</sub> was prepared by the in situ polymerization of aniline on the TiO<sub>2</sub> surface. The obtained hybrid material was characterized by diffuse reflectance spectroscopy (DR/UV-Vis), X-ray diffraction (XRD), fast-Fourier transformation spectroscopy (FTIR), photoluminescence (PL) spectroscopy, microscopy analysis (SEM/TEM), and thermogravimetric analysis (TGA). An insight into the mechanism was shown based on the photodegradation analysis of charge carrier scavengers. Polyaniline is an efficient TiO<sub>2</sub> photosensitizer for photodegradation in visible light (? > 420 nm). The trapping experiments revealed that mainly h+ and <b>?</b>OH were the reactive oxygen species that were responsible for phenol degradation. Furthermore, the PANI-TiO<sub>2</sub> hybrid nanocomposite was used in gypsum plaster to study the self-cleaning properties of the obtained building material. The effect of PANI-TiO<sub>2</sub> content on the hydrophilic/hydrophobic properties and crystallographic structure of gypsum was studied. The obtained PANI-TiO<sub>2</sub>-modified gypsum plaster had improved photocatalytic activity in the reaction of toluene degradation under Vis light.
Project description:A screening study on seven photocatalysts was performed to identify the best candidate for pharmaceutical products degradation in water. Photocatalysts were deposited as thin films through a sol-gel process and subsequent dip-coating on glass slides. The efficiency of each photocatalyst was assessed through the degradation of methylene blue first, and then, through the degradation of 15 different pharmaceutical products. Two main types of synthesis methods were considered: aqueous syntheses, where the reaction takes place in water, and organic syntheses, where reactions take place in an organic solvent and only a stoichiometric amount of water is added to the reaction medium. Photocatalysts synthesized via aqueous sol-gel routes showed relatively lower degradation efficiencies; however, the organic route required a calcination step at high temperature to form the photoactive crystalline phase, while the aqueous route did not. The best performances for the degradation of pharmaceuticals arose when Evonik P25 and silver nanoparticles were added to TiO?, which was synthesized using an organic solvent. In the case of methylene blue degradation, TiO? modified with Evonik P25 and TiO? doped with MnO? nanoparticles were the two best candidates.
Project description:In the present study, polymer supported nanocomposites, consisting of bio-based poly(ethylene furanoate) polyester and TiO₂ nanoparticles, were prepared and evaluated as effective photocatalysts for anti-inflammatory/analgesic drug removal. Nanocomposites were prepared by the solvent evaporation method containing 5, 10, 15, and 20 wt% TiO₂ and characterized using Fourier Transform Infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Thin films of them have been prepared by the melt press and optimization of the photocatalytic procedure was conducted for the most efficient synthesized photocatalyst. Finally, mineralization was evaluated by means of Total organic carbon (TOC) reduction and ion release, while the transformation products (TPs) generated during the photocatalytic procedure were identified by high-resolution mass spectrometry.
Project description:TiO?-SnS? composite semiconducting photocatalysts with different building component ratios were prepared by hydrothermal synthesis (TiO?-SnS?-HT) and by immobilization of commercial TiO? and SnS? particles (TiO?-SnS?-COMM). The band gap values, which determine the catalysts’ photoactivity, were examined by diffuse reflectance spectroscopy and Kubelka?Munk transformations. The catalysts’ surface properties: specific surface area, charge and adsorption capacitance at the solid?solution interface were characterized using BET analysis, potentiometric titration and electrochemical impedance spectroscopy, respectively. The electronic band structure of TiO?-SnS? photocatalyst, as the key property for the solar-driven photocatalysis, was deduced from the thermodynamic data and the semiconducting parameters (type of semiconductivity, concentration of the charge carriers, flat band potential) obtained by Mott?Schottky analysis. The photoactivity of both composites was studied in photocatalytic treatment of diclofenac (DCF) under simulated solar irradiation and was compared to the benchmark photocatalyst (TiO? P25) activity. The influence of process parameters, such as pH, H?O?, and composite formulation on the effectiveness of DCF removal and conversion was investigated and discussed by employing response surface modeling (RSM) approach. The photocatalytic efficiency of both composite materials was discussed on the basis of the hetereojunction formation that facilitated the photoelectron transfer, promoting more efficient photocatalytic degradation of DCF.
Project description:Advanced oxidation processes driven by renewable energy sources are gaining attention in degrading organic pollutants in waste waters in an efficient and sustainable way. The present work is focused on a study of TiO? nanotubes as photocatalysts for photoelectrocatalytic (PEC) degradation of acetaminophen (AMP) at different pH (3, 7, and 9). In particular, different TiO? photocatalysts were synthetized by stirring the electrode at different Reynolds numbers (Res) during electrochemical anodization. The morphology of the photocatalysts and their crystalline structure were evaluated by field emission scanning electron microscopy (FESEM) and Raman confocal laser microscopy (RCLM). These analyses revealed that anatase TiO? nanotubes were obtained after anodization. In addition, photocurrent densities versus potential curves were performed in order to characterize the electrochemical properties of the photocatalysts. These results showed that increasing the Re during anodization led to an enhancement in the obtained photocurrents, since under hydrodynamic conditions part of the initiation layer formed over the tubes was removed. PEC degradation of acetaminophen was followed by ultraviolet-visible absorbance measurements and chemical oxygen demand tests. As drug mineralization was the most important issue, total organic carbon measurements were also carried out. The statistical significance analysis established that acetaminophen PEC degradation improved as hydrodynamic conditions linearly increased in the studied range (Re from 0 to 600). Additionally, acetaminophen conversion had a quadratic behavior with respect to the reaction pH, where the maximum conversion value was reached at pH 3. However, in this case, the diversity of the byproducts increased due to a different PEC degradation mechanism.