Photodegradation of o‐Cresol with Ag Deposited on TiO2 under Visible and UV Light Irradiation

This study investigated the effect of dosage of Ag on the characteristics of TiO₂, quantum yield, and temporal decomposition behavior of o‐cresol in an annular reactor under ultraviolet (UV) and visible light irradiation. In order to extend light absorption and minimize the rapid recombination during photoreaction, the Ag deposited on TiO₂ photocatalysts was prepared by a photodeposition process. The results of diffuse reflectance spectra (DRS) indicated that Ag deposited on TiO₂ promoted the optical absorption in the visible region and made it possible for it to be excited by visible light. The degradation rate of o‐cresol with 0.50 wt % Ag/TiO₂ under visible light irradiation was 2.0 times that with pure TiO₂.     

Gasphasensynthese von Kern/Mantel‐Partikeln am Beispiel von TiO2‐Nanopartikeln mit elektrisch leitendem Mantel

An advanced process enables synthesis and coating of individual TiO₂‐core particles with a shell of transparent conducting oxide (TCO) from the gas phase in one reactor. TiO₂ particles were coated with fluorine‐doped tin oxide (SnO₂:F) or antimony‐doped tin oxide (SnO₂:Sb). Specific electrical conductivity of the core/shell particles was up to 8 · 10^–3 S cm^–1. Variation of process parameters allows modifying dopant level and conductivity in an easy way.     

Synthesis,physical properties,and characterization of starch‐based blend films by adding nano‐sized TiO2/poly(methyl metacrylate‐co‐acrylamide)

The purpose of this study was to improve the physical properties and to expand the application range of starch‐based blend films added nano‐sized TiO₂/poly(methyl methacrylate‐co‐acrylamide) (PMMA‐co‐AM). Starch‐based blend films were prepared by using corn starch, polyvinyl alcohol (PVA), nano‐sized PMMA‐co‐AM, nano‐sized TiO₂/PMMA‐co‐AM particles, and additives, i.e., glycerol (GL) and citric acid (CA). Nano‐sized PMMA‐co‐AM was synthesized by emulsion polymerization and TiO₂ nanoparticles were also prepared by using sol–gel method. Nano‐sized TiO₂/PMMA‐co‐AM particles were synthesized by wet milling for 48 h. The morphology and crystallinity of TiO₂, nano‐sized PMMA‐co‐AM and TiO₂/PMMA‐co‐AM particles were investigated by using the scanning electron microscope (SEM) and X‐ray diffractometer (XRD). In addition, the functional groups of the TiO₂/PMMA‐co‐AM particles were characterized by IR spectrophotometry (FTIR). The physical properties such as tensile strength (TS), elongation at break (%E), degree of swelling (DS), and solubility (S) of starch‐based films were evaluated. It was found that the adding of nano‐sized particles can greatly improve the physical properties of the prepared films. The photocatalytic degradability of starch/PVA/nano‐sized TiO₂/PMMA‐co‐AM composite films was evaluated using methylene blue (MB) and acetaldehyde (ATA) as photodegradation target under UV and visible light. The degree of decomposition (C/C₀) of MB and ATA for the films containing TiO₂ and CA was 0.506 and 0.088 under UV light irradiation and 0.586 (MB) and 0.631 (ATA) under visible light irradiation, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A Visible Light Photocatalyst of Carbonate‐Like Species Doped TiO2

Carbon‐doped TiO₂ nanomaterials have been successfully synthesized via an effective two‐step procedure involving hydrothermal method and followed by a low‐temperature calcination treatment process, through which a controllable amount of carbonate‐like species could be incorporated into TiO₂. First‐principles calculations suggest the TiO₂ doped with carbon in form of carbonate‐like species can effectively extend the adsorption of the material from ultraviolet region to visible light. And it is experimentally found that carbon‐doped TiO₂ nanomaterials exhibit much higher photocatalytic activity than reference P25 and TiO_2?xN_x catalysts toward the liquid‐phase degradation of organic pollutants under visible light (420 nm < λ < 800 nm) irradiation. The presence of synergic effect between carbonate‐like doping and anatase TiO₂ is believed to play an essential role in affecting the photocatalytic reactivity, and the response to the visible light is ascribed to the narrowed band gap energy controlled by carbon doping. Moreover, the roles of active species in the photocatalytic process are compared using different types of active species scavengers. Meanwhile, the degradation mechanism of the photocatalysis is proposed. It is hoped that our work could provide valuable information on the design of carbonate‐like doped semiconductor with more excellent properties and set the foundation for the further industrial application.     

Photocatalytic degradation of dyestuff wastewater under visible light irradiation using micron‐sized mixed crystal TiO2 powders

A phase transformation of micron‐sized TiO₂ powder from anatase to rutile was attempted by heat‐treatment in order to generate a new mixed crystal TiO₂ with high associated photocatalytic activity. Heat‐treated micron‐sized TiO₂ powders at different transition stages were characterized by X‐ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT‐IR) and transmission electron microscopy (TEM) methods. The tests of photocatalytic activity of the heat‐treated micron‐sized TiO₂ powders were conducted by the photocatalytic degradation of Rhodamine B and Acid Red B under visible light irradiation. The results indicate that mixed crystal TiO₂ photocatalyst heat‐treated at 400 °C for 60 min shows the highest photocatalytic activity. It can effectively decompose the Rhodamine B and Acid Red B in aqueous solution after 6 h visible light irradiation. A remarkable improvement in photocatalytic activity of TiO₂ is caused by the formation of combined rutile–anatase phases and separation of photogenerated electron–hole pairs. Copyright © 2007 Society of Chemical Industry     

Photocatalytic Degradation of Benzene in Air Streams in an Optical Fiber Photoreactor

Photocatalytic decomposition of gaseous benzene at room temperature was studied with a differential‐type optical fiber reactor using TiO₂ as the photocatalyst. The effects of humidity, UV light intensity and benzene concentration on the performance of the reactor for benzene decomposition were investigated. It was observed that both the apparent quantum yields of benzene decomposition and CO₂ production were superior to the traditional photoreactor, especially under limited UV light supply. In addition, deactivation of the TiO₂ catalyst heavily relied on the humidity contained in the airflow. Purging with ozone‐containing air rapidly decomposed the organic residues adhering to the TiO₂ surface and regenerated the deactivated catalyst within 30 minutes.     

Preparation and characterization of cerium‐doped titanium dioxide/ultrahigh‐molecular‐weight polyethylene porous composites with excellent photocatalytic activity

Porous ultrahigh‐molecular‐weight polyethylene (UHMWPE)‐based composites filled with surface‐modified Ce‐doped TiO₂ nanoparticles (Ce–TiO₂/UHMWPE) were prepared by template dissolution. The composites were characterized by Fourier transform infrared spectroscopy, ultraviolet (UV)–visible spectroscopy, diffuse reflectance spectra, and scanning electron microscopy); the photocatalytic activity was also evaluated by the decomposition of methyl orange under UV exposure. The results demonstrate that the severe aggregation of Ce–TiO₂ nanoparticles could be reduced by surface modification via a silane coupling agent (KH570). The Ce–TiO₂/UHMWPE porous composites exhibited a uniform pore size. Doping with Ce⁴⁺ effectively extended the spectral response from the UV to the visible region and enhanced the surface hydroxyl groups of the TiO₂ attached to the matrix. With a degradation rate of 85.3%, the 1.5 vol % Ce–TiO₂/UHMWPE sample showed the best photocatalytic activity. The excellent permeability of the porous composites is encouraging for their possible use in wastewater treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microwave photocatalysis III. Transition metal ion‐doped TiO2 thin films on mercury electrodeless discharge lamps: preparation,characterization and their effect on the photocatalytic degradation of mono‐chloroacetic acid and Rhodamine B

BACKGROUND: Mercury electrodeless discharge lamps (Hg‐EDLs) were used to generate UV radiation when exposed to a microwave field. EDLs were coated with doped TiO₂ in the form of thin films containing transition metal ions Mⁿ⁺ (M = Fe, Co, Ni, V, Cr, Mn, Zr, Ag). Photocatalytic degradation of mono‐chloroacetic acid (MCAA) to HCl, CO₂, and H₂O, and decomposition of Rhodamine B on the thin films were investigated in detail. RESULTS: Polycrystalline thin doped TiO₂ films were prepared by dip‐coating of EDL via a sol–gel method using titanium n‐butoxide, acetylacetone, and a transition metal acetylacetonate. The films were characterized by Raman spectroscopy, UV/Vis absorption spectroscopy, X‐ray photoelectron spectroscopy (XPS), electron microprobe analysis and by atomic force microscopy (AFM). The photocatalytic activity of doped TiO₂ films was monitored in the decomposition of Rhodamine B in water. Compared with the pure TiO₂ film, the UV/Vis spectra of V, Zr and Ag‐doped TiO₂ showed significant absorption in the visible region, and hence the photocatalytic degradation of MCAA had increased. The best apparent degradation rate constant (0.0125 min^?1), which was higher than that on the pure TiO₂ film by a factor of 1.7, was obtained with the Ag(3%)/TiO₂ photocatalyst. The effect of doping level of vanadium acetylacetonate on the photocatalytic efficiency of the V‐doped TiO₂ was determined. CONCLUSIONS: Transition metal ion‐doped TiO₂ thin films showed significant absorption in the visible region. The metal doped TiO₂ photocatalyst (with an appropriate amount of V, Zr and Ag) on the Hg‐EDLs increased the degradation efficiency of MCAA in a microwave field. Copyright © 2009 Society of Chemical Industry     

Synthesis and visible‐light‐derived photocatalysis of titania nanosphere stacking layers prepared by chemical vapor deposition

BACKGROUND: In this study, visible‐light‐derived photocatalytic activity of metal‐doped titanium dioxide nanosphere (TS) stacking layers, prepared by chemical vapor deposition (CVD), was investigated. The as‐grown TS spheres, having an average diameter of 100–300 nm, formed a layer‐by‐layer stacking layer on a glass substrate. The crystalline structures of the TS samples were of anatase‐type. RESULTS: Ultraviolet (UV) absorption confirmed that metallic doping (i.e. Co and Ni) shifted the light absorption of the spheres to the visible‐light region. With increasing dopant density, the optical band gap of the nanospheres became narrower, e.g. the smallest band gap of Co‐doped TS was 2.61 eV. Both Ni‐ and Co‐doped TS catalysts showed a photocatalytic capability in decomposing organic dyes under visible irradiation. In comparison, Co‐doped TiO₂ catalyst not only displays the adsorption capacity, but also the photocatalytic activity higher than the N‐doped TiO₂ catalyst. CONCLUSION: This result can be attributed to the fact that the narrower band gap easily generates electron–hole pairs over the TS catalysts under visible irradiation, thus, leading to the higher photocatalytic activity. Accordingly, this study shed some light on the one‐step efficient CVD approach to synthesize metal‐doped TS catalysts for decomposing dye compounds in aqueous solution. Copyright © 2010 Society of Chemical Industry     

Photoactive behavior of polyacrylonitrile fibers based on silver and zirconium co‐doped titania nanocomposites: Synthesis,characterization, and comparative study of solid‐phase photocatalytic self‐cleaning

Silver and zirconium co‐doped and mono‐doped titania nanocomposites were synthesized and deposited onto polyacrylonitrile fibers via sol–gel dip‐coating method. The resulted coated‐fibers were characterized by X‐ray diffraction (XRD), scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, thermogravimetric analysis, and BET surface area measurement. Photocatalytic activity of the TiO₂‐coated and TiO₂‐doped coated fibers were determined by photomineralization of methylene blue and Eosin Y under UV–vis light. The progress of photodegradation of dyes was monitored by diffuse reflectance spectroscopy. The XRD results of samples indicate that the TiO₂, Ag‐TiO₂, Zr‐TiO₂, and Ag‐Zr‐TiO₂ consist of anatase phase. All samples demonstrated photo‐assisted self‐cleaning properties when exposed to UV–vis irradiation. Evaluated by decomposing dyes, photocatalytic activity of Ag–Zr co‐doped TiO₂ coated fiber was obviously higher than that of pure TiO₂ and mono‐doped TiO₂. Our results showed that the synergistic action between the silver and zirconium species in the Ag‐Zr TiO₂ nanocomposite is due to both the structural and electronic properties of the photoactive anatase phase. These results clearly indicate that modification of semiconductor photocatalyst by co‐doping process is an effective method for increasing the photocatalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A Comparison on Physical,Structural, and Photocatalytical Properties of TiO2 Nanopowders Produced Using Sol‐Gel and Flame Spray Pyrolysis

In this study, nanoscale photocatalyst TiO₂ powders were synthesized via sol‐gel and flame spray pyrolysis (FSP). Phase structures and ratios were analyzed by X‐ray diffractometer (XRD). Size, specific surface area, and morphologies were determined using particle size analyzer, Brunauer‐Emmett‐Teller theory, and scanning electron microscope, respectively. Anatase phase with some rutile together was obtained in XRD analysis. The degradation rates of aqueous methylene blue (MB) by TiO₂ nanopowders were calculated using UV–vis spectrophotometer. It was found that MB decomposition was successfully achieved with significantly high efficiencies for both sol‐gel and FSP‐derived powders with small differences.     

Preparation and characterization of a novel activated carbon‐supported N‐doped visible light response photocatalyst (TiO2−xNy/AC)

A photocatalyst, TiO_2?xN_y/AC (activated carbon (AC) supported N‐doped TiO₂), highly active in both the Vis and UV range, was prepared by calcination of the TiO₂ precursor prepared by acid‐catalyzed hydrolysis in an ammonia atmosphere. The powders were characterized by diffuse reflectance spectroscopy, scanning electron microscopy, X‐ray diffraction, N₂ adsorption, Fourier transform infrared spectroscopy and phenol degradation. The doped N in the TiO₂ crystal lattice creates an electron‐occupied intra‐band gap allowing electron‐hole pair generation under Vis irradiation (500–560 nm). The TiO_2?xN_y/AC exhibited high levels of activity and the same activity trends for phenol degradation under both Vis and UV irradiation: TiO_2?xN_y/AC calcined at 500 °C for 4 h exhibited the highest activity. The band‐gap level newly formed by doped N can act as a center for the photo‐generated holes and is beneficial for the UV activity enhancement. The performance of the prepared TiO_2?xN_y/AC photocatalyst revealed its practical potential in the field of solar photocatalytic degradation of aqueous contaminants. Copyright © 2007 Society of Chemical Industry     

Niobium‐Doped Titania Photocatalyst Film Prepared via a Nonaqueous Sol‐Gel Method

Niobium‐doped Titanium dioxide (Nb:TiO₂) transparent films were successfully deposited on glass substrates using a non‐aqueous sol‐gel spin coating technique. The effect of Nb concentration on the structural and photocatalytic properties of Nb:TiO₂ films was studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV visible spectroscopy. The films with 12 at.% (atomic percent) Nb doped TiO₂ showed excellent photocatalytic activity through 97.3% degradation of methylene blue (MB) after 2 h of UV irradiation.     

The effect of Fe2+ state in electrical property variations of Sn‐doped hematite powders

The structural, electrical, and chemical properties of Sn‐doped Fe₂O₃ powders were investigated. Various quantities of Sn‐doped Fe₂O₃ powders were synthesized using solid‐state reactions. Rietveld analysis for the powders that were doped below 2% revealed a phase‐pure Sn‐doped Fe₂O₃ structure (i.e., identical to Fe₂O₃ structure). Alternatively, the analysis for the powders that were doped more than 3% exhibited secondary phase. The unit cell volume and electrical conductivity of the phase‐pure samples increased with an increase in the doping concentration. X‐ray photoelectron spectroscopy measurements showed an increased Fe²⁺ state with the increase in Sn doping concentration. Therefore, the improved electrical conductivity and unit cell volume with the increase in doping concentration of the phase‐pure powders might be related to the increased Fe²⁺ state.     

Visible light photocatalytic activity of TiO2/heat‐treated PVC film

BACKGROUND: Semiconductor TiO₂ has been investigated extensively due to its chemical stability, nontoxicity and inexpensiveness. However, the wide band gap of anatase TiO₂ (about 3.2 eV) only allows it to absorb UV light. TiO₂ nanoparticles modified by conditional conjugated polymers show excellent photocatalytic activity under visible light. However, these conjugated polymers are not only expensive, but also difficult to process. Polyvinyl chloride (PVC) was heat‐treated at high temperature to remove HCl and a C?C conjugated chain structure was obtained. When TiO₂ nanoparticles were dispersed into the conjugated polymer film derived from PVC, this composites film exhibited high visible light photocatalytic activity. RESULTS: The photocatalytic activity of TiO₂/heat‐treated PVC (HTPVC) film was investigated by degrading Rhodamine B (RhB) under visible light irradiation. The photodegradation of RhB follows apparent first‐order kinetics. The rate constants of RhB photodegradation in the presence of the TiO₂/HTPVC films with different mass content of TiO₂ are 16–56 and 4–14 times that obtained in the presence of the pure HTPVC and TiO₂/polymethyl methacrylate (PMMA) composite film, respectively. The TiO₂/HTPVC film showed excellent photocatalytic activity and stability after 10 cycles under visible light irradiation. CONCLUSION: TiO₂/HTPVC film exhibits high visible light photocatalytic activity and stability. Copyright © 2012 Society of Chemical Industry     

Visible Photocurrent in Chemically Doped TiO2‐Based Schottky Diodes

The delicate tuning of TiO₂ electronic structure is essential to achieve the maximized photoresponse of light harvesting energy devices such as photocatalysis and photovoltaic cells. In this study, the photocurrent response of TiO₂‐based diodes with and without Fluorine doping method was investigated. The differences in electronic structure between undoped and F‐doped TiO₂ thin films are associated to the Fermi energy level which determines the available empty state energy against the valence band maximum. The incident photoconversion efficiency results indicate that the visible photoabsorption process and charge transport can be enhanced by energy matching between subgap states in TiO₂ and the interference light and provides an effective strategy for light harvesting using TiO₂.     

Facile Ion‐Exchange Synthesis and Visible Light Photocatalytic Studies of Cu2+, Sn2+, and Ag+‐Substituted LiMg0.5Ti0.5O2

A novel series of visible light‐sensitive Cu²⁺, Sn²⁺, and Ag⁺‐substituted LiMg_0.5Ti_0.5O₂ photocatalysts were synthesized by a facile ion‐exchange method and characterized by XRD, UV‐Vis diffuse reflectance spectra, scanning electron microscopy equipped with an X‐ray energy‐dispersive spectroscopy, Brunauer‐Emmett‐Teller surface area, inductively coupled plasma mass spectrometry, and thermal gravimetric analysis. The characterization results showed that morphology, crystallite size, and surface areas of the ion‐exchange products were almost similar to the parent compound. Absorption edges of Ag⁺‐doped (AMT), Cu²⁺‐doped (CMT), and Sn²⁺‐doped (SMT) samples were red shifted remarkably into the visible light region while parent LiMg_0.5Ti_0.5O₂ (LMT) was UV active. Photocatalytic activity of these samples was evaluated by studying the degradation of methylene blue and nitro benzene under visible light irradiation and the stability of all samples during photocatalytic experiment was also investigated. The activity of all photocatalysts was ranked accordingly as SMT ≥ AMT > CMT > LMT. The correlation between photocatalytic properties, band gap energy, rate of recombination of the charge carriers, and amount of ^●OH radicals generated during photocatalysis and the underlying reasons were discussed.     

Adsorption backup following light-emitting diode-irradiated photocatalytic unit for control of low-degraded toxic gaseous compounds

Although several visible light-emitting diode (LED)-irradiated photocatalysts exhibited low photocatalytic decomposition efficiencies for toxic gaseous pollutants, activated carbon fiber (ACF) has rarely been used as a backup adsorption device for photocatalytic systems. Accordingly, this study accessed the applicability of a supplemental ACF following a visible LED-irradiated S-TiO₂ unit for the control of low-degraded benzene and toluene. The characteristics of the S-TiO₂ and ACF were determined using an XRD, a UV-Vis-NIR, and an FTIR spectrophotometer. For an LED/S-TiO₂ system, low degradation efficiencies regarding benzene and toluene (close to zero-7.2% and 7.1–64.4%, respectively) were found. In contrast, the mean degradation efficiencies of both compounds obtained from the photocatalytic-ACF hybrid system were all close to 100%. In addition, no peaks were observed in the gas chromatogram of air samples taken at the outlet of the hybrid system, whereas several trace peaks were observed in the standalone photocatalytic reactor results. The breakthrough of the ACF occurred at approximately 14 and 28 hours for benzene and toluene, respectively, and saturation occurred at approximately 28 and 42 hours, respectively. Consequently, this study newly found that the supplemental activated carbon fiber following a visible LED-irradiated S-TiO₂ unit could be applied effectively for the control of low-degraded toxic benzene and toluene.     

Photocatalytic degradation of benzene,toluene, ethylbenzene,and xylene (BTEX) using transition metal-doped titanium dioxide immobilized on fiberglass cloth

Transition metal (Fe, V and W)-doped TiO₂ was synthesized via the solvothermal technique and immobilized onto fiberglass cloth (FGC) for uses in photocatalytic decomposition of gaseous volatile organic compounds—benzene, toluene, ethylbenzene and xylene (BTEX)—under visible light. Results were compared to that of the standard commercial pure TiO₂ (P25) coated FGC. All doped samples exhibit higher visible light catalytic activity than the pure TiO₂. The V-doped sample shows the highest photocatalytic activity followed by the W- and Fe-doped samples. The UV-Vis diffuse reflectance spectra reveal that the V-doped sample has the highest visible light absorption followed by the W- and Fe-doped samples. The X-ray diffraction (XRD) patterns indicate that all doped samples contain both anatase and rutile phases with the majority (>80%) being anatase. No new peaks associated with dopant oxides can be observed, suggesting that the transition metal (TM) dopants are well mixed into the TiO₂ lattice, or are below the detection limit of the XRD. The X-ray absorption near-edge structure spectra of the Ti K-edge transition indicate that most Ti ions are in a tetravalent state with octahedral coordination, but with increased lattice distortion from Fe- to V- and W-doped samples. Our results show that the TM-doped TiO₂ were successfully synthesized and immobilized onto flexible fiberglass cloth suitable for treatment of gaseous organic pollutants under visible light.     

Experimental analysis and optimization of the synthesizing property of nitrogen‐modified TiO2 visible‐light photocatalysts

BACKGROUND: The aim of this study was to investigate improvement of the photocatalytic activity of visible‐light driven nitrogen‐modified TiO₂ (N‐TiO₂) powder toward methyl blue (MB) and direct blue‐86 (DB‐86) dyes. The Taguchi method with an L₉ orthogonal array was applied to plan the synthesis parameters, i.e. nitrogen sources, nitrogen source concentrations, stirring time and calcined temperatures. 95% confirmation experiments were undertaken to verify the effectiveness of the Taguchi method. RESULTS: All N‐TiO₂ photocatalysts were shifted toward the visible light region with the optical band gap (Eg). Nitrogen source concentrations were significant parameters for the photocatalytic decolorization rate constants (k values). In comparison with pure TiO₂, the photodecolorization behavior of N‐TiO₂ toward DB‐86 was superior with a reaction rate constant of 1.68 × 10^?3 min^?1, and a 4 h photodecolorization efficiency of 34%. CONCLUSION: The Taguchi method was reported to alter the surface properties of commercial Degussa P25 TiO₂, which could then be used as a visible‐light driven photocatalyst. The visible‐light‐driven photocatalyst was investigated to determine material characteristics. Greater photodecolorization of MB and DB‐86 dye pollutants using optimally‐prepared N‐TiO₂ under visible light irradiation was successfully obtained. Copyright © 2011 Society of Chemical Industry