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     

Microwave photochemistry V: Low‐pressure batch and continuous‐flow microwave photoreactors with quartz mercury electrodeless discharge lamps. Photohydrolysis of mono‐chloroacetic acid

BACKGROUND: Low‐pressure batch and continuous‐flow microwave photoreactors were equipped with microwave powered quartz mercury electrodeless discharge lamps (Hg‐EDLs). Photohydrolysis of aqueous mono‐chloroacetic acid (MCAA) into hydroxyacetic acid and HCl was chosen as the model reaction to evaluate these photoreactors. The effects of operational parameters on the MCAA photolysis through a UV/MW process were investigated. RESULTS: Studies were carried out at relatively high MCAA concentration (0.1 mol L^?1). The photoreaction course was monitored by the pH change in the solution. The MCAA conversion was optimized as a result of a trade‐off between the thermal dependence of the photochemical quantum yield (which increases with increasing temperature) and the thermal dependence of the EDL light intensity of 254 nm line (which increases with decreasing temperature). The microwave photoreactors made it possible to study the temperature dependence of MCAA photohydrolysis. CONCLUSION: It was found that operational parameters (i.e. reaction temperature, quantum yield) had important effects on photoefficiency. Photohydrolysis of MCAA in the microwave photoreactors can be enhanced by the UV/MW system. The results of conversions (in 120 min) for the particular photoreactor set‐ups show that the best reaction conditions for MCAA photolysis were obtained in the low‐pressure batch microwave photoreactor (the conversion was 46% at 80 °C). Copyright © 2009 Society of Chemical Industry     

Influence of TiO2‐Layer Thickness of Spray‐Coated Glass Beads on Their Photocatalytic Performance

TiO₂ is a suitable catalyst for potential photocatalytic processes, e.g., in wastewater treatment. For a technical realization of such processes, the application of immobilized TiO₂ in a continuous process would be desirable. However, since UV radiation has a limited penetration depth into a packed bed of pure TiO₂, supporting it on UV‐transparent glass beads offers the possibility to implement continuous photocatalytic processes in a fixed‐bed reactor. Considering this fact, glass beads were coated with TiO₂ powder in a fluidized‐bed reactor. The coated glass beads with varying TiO₂ layer thickness were tested in the photocatalytic degradation of methylene blue, and the influence of an addition of methyl cellulose during the coating process on the photocatalytic performance was investigated.     

Decomposition of gas‐phase aromatic hydrocarbons by applying an annular‐type reactor coated with sulfur‐doped photocatalyst under visible‐light irradiation

BACKGROUND: Unlike many water pollution applications, visible‐light‐driven photocatalysis of gas‐phase pollutants has been reported only rarely. The present study was performed to investigate the feasibility of applying S‐doped visible‐light‐induced TiO₂ to treat gas‐phase aromatic hydrocarbons, using a continuous air‐flow annular‐type reactor. RESULTS: The prepared S‐enhanced TiO₂ powders, along with a commercially available TiO₂ powder (Degussa P‐25), were characterized using diffuse reflectance UV‐VIS‐NIR spectrophotometry, Fourier transform infrared (FTIR) spectrophotometry, X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermogravimetry (TG) analyses. A photocatalytic activity test exhibited an increasing trend in degradation reaction rates with increase in flow rate but a decreasing trend in terms of degradation efficiencies. Several experimental conditions induced reasonably high decomposition efficiencies with respect to toluene, ethyl benzene and o,m,p‐xylenes (close to or above 90%), although benzene exhibited a somewhat lower decomposition efficiency. CONCLUSIONS: The S‐doped TiO₂ and undoped P25 TiO₂ powders exhibited different catalyst characteristics. The results demonstrate that an annular‐type reactor coated with visible‐light‐activated S‐doped TiO₂ can serve as an effective tool to treat gas‐phase aromatic hydrocarbon streams. Copyright © 2009 Society of Chemical Industry     

Radiation model of a TiO2‐coated,quartz wool,packed‐bed photocatalytic reactor

The radiation field of a packed‐bed photocatalytic reactor filled with quartz wool coated with titanium dioxide was modeled using the Monte Carlo technique and the following information: the radiation flux emitted by the lamps, the diameter size distribution of the quartz fiber cloth, the mass of quartz fibers and of TiO₂ that was immobilized on the fiber surface as well as the refractive index, and the spectral absorption coefficient of the materials of the system. Modeling predictions were validated with radiometer measurements of the transmitted radiation through the reactor, the root mean square error being <9.7%. Finally, by means of a parametric study, the validated model was used to analyze the effect of the design variables, such as the radii of the quartz fibers, thickness of the TiO₂ coatings, and amount of TiO₂‐coated quartz wool, on the distribution and nonuniformity of the radiative energy distribution inside the reactor. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

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     

The comparative study of photocatalytic self‐cleaning properties of synthesized nanoscale titania and zirconia onto polyacrylonitrile fibers

The photocatalytic activity of TiO₂ and ZrO₂‐coated polyacrylonitrile (PAN) fibers was compared through the self‐cleaning of methylene blue and eosin yellowish. TiO₂ and ZrO₂ nanocrystals were successfully synthesized and deposited onto PAN fibers with photocatalytic self‐cleaning activity using the sol‐gel process at low temperature. The pristine and treated samples have been characterized by several techniques, such as scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, diffuse reflectance spectroscopy, X‐ray diffraction, and thermogravimetric analysis. The TiO₂ nanoparticles with 10–20 nm in size, and ZrO₂ with 20–40 nm have been synthesized to form dispersed particles on the fiber surface, which shows photocatalytic properties when exposed to UV–Vis light. The photocatalytic activity, tested by measuring the degradation of adsorbed methylene blue and Eosin Y. Photocatalytic activity of TiO₂‐coated fibers toward dyes degradation was higher than that of ZrO₂‐coated fibers. This preparation technique can be also applied to new fabrics to create self‐cleaning and UV irradiation protection properties in them. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation into Photocatalytic Degradation of Gaseous Benzene in a Circulated Photocatalytic Reactor (CPCR)

Due to the fact that suspended TiO₂ powder enjoys free contact with gaseous pollutant molecules in photocatalytic reactors, it can generally achieve better efficiency than immobilized TiO₂ catalysts. However, difficulties with the separation of this catalyst powder from treated pollutants and its re‐use often limit its application. Therefore, a circulated photocatalytic reactor (CPCR) was designed to enhance the performance of the photocatalytic degradation of gaseous benzene. TiO₂ film photocatalysts were prepared by the sol‐gel method at low temperatures and coated onto the inner wall of this reactor by a bonding agent composed of poly‐(2, 2‐dimethyl)‐acrylic ethylene ester emulsion in which TiO₂ powder was characterized by FTIR, TEM and SEM. In particular, the influences of initial concentration and gas flow rate of benzene on the degradation conversion, D_p, apparent reaction rate constants, k_r, initial degradation rate, r, and the deactivation and regeneration of catalyst in the CPCR, were investigated. The results indicated that the degradation conversion, apparent reaction rate constants and initial degradation rate were closely correlated to the initial concentration of benzene. To elucidate the factors governing the observations, the adsorption characteristics and kinetics of the photocatalytic degradation of benzene were analyzed using the Langmuir adsorption isotherm and Langmuir‐Hinshelwood kinetic model. It was found that the reaction kinetics were best described by a fixed pseudo‐first‐order kinetic equation of photocatalytic degradation of gaseous benzene in the CPCR.     

Polyaniline modified mesoporous titanium dioxide that enhances oxo‐biodegradation of polyethylene films for agricultural plastic mulch application

Mesoporous titanium dioxide (M‐TiO₂) nanoparticles were successfully prepared followed by chemical modification with different contents of polyaniline (PANI/M‐TiO₂) and were used to accelerate the photo‐oxidation and biodegradation process of low‐density polyethylene (LDPE) film. The influence of these additives as a pro‐oxidant additive on the accelerated degradation of LDPE was investigated by photocatalytic oxidation under UV light irradiation and biodegradation with fungal strains. It was found that the as‐prepared PANI modified M‐TiO₂ particles exhibited an obvious light response from 400 to 800 nm which can improve the utilization of solar light. Compared with M‐TiO₂, PANI/M‐TiO₂ exhibited better photocatalytic performance when irradiated under UV light and the subsequent biodegradation efficiency was enhanced. Enhancement of the photocatalytic performance of PANI/M‐TiO₂ could be attributed to good dispersibility and compatibility of PANI/M‐TiO₂ in the LDPE matrix, a narrow band gap, effective separation of photogenerated electron–hole pairs and the chromophoric group of PANI which was used as a photosensitizer in the LDPE/PANI/M‐TiO₂ composite film. © 2019 Society of Chemical Industry     

Novel thin‐film reactor for photocatalytic degradation of pesticides in an aqueous solution

A thin‐film reactor was fabricated with immobilised TiO₂ and this reactor was used for photocatalytic mineralisation of common pesticides, 2,4‐dichlorophenoxyacetic acid (DPA) and monocrotophos (MCP), and their commercially formulated products in an aqueous solution. Zeolites HY and Hβ with different physico‐chemical properties were chosen as support material. The supported TiO₂ was used for the degradation and mineralisation studies. TiO₂/zeolite‐supported photocatalyst showed enhanced degradation efficiency compared with bare TiO₂ for both DPA and MCP. Formulated pesticides were mineralised at shorter irradiation times than technical grade pesticides. The results clearly demonstrated that the good adsorption capacity of the support, and the effective light utilisation by TiO₂, improved the photocatalytic activity of supported TiO₂. Reusability studies have also shown the stability of supported photocatalysts. Copyright © 2004 Society of Chemical Industry     

Preparation of poly(methyl methacrylate‐co‐maleic anhydride)/SiO2?TiO2 hybrid materials and their thermo‐ and photodegradation behaviors

The optically transparent poly(methyl methacrylate‐co‐maleic anhydride) P(MMA‐co‐MA)/SiO₂? TiO₂ hybrid materials were prepared using 3‐aminopropyl triethoxysilane as a coupling agent for organic and inorganic components. Real‐time FTIR was used to monitor the curing process of hybrid sol, indicating that imide group formation decreased with increasing titania content. scanning electron microscopy, atomic force microscopy, and differential scanning calorimetry results confirmed their homogeneous inorganic/organic network structures. TGA analysis showed that incorporated titania greatly prohibits the thermodegradation of hybrid films, especially at the content of 5.3 wt %, showing an increase of about 32.6°C at 5% loss temperature in air. The UV degradation behavior of P(MMA‐co‐MA) studied by quasi‐real‐time FTIR showed that TiO₂ incorporated in the hybrid network provides a photocatalytic effect rather than a UV‐shielding effect. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1714–1724, 2005     

Enhanced Solid‐Phase Photocatalytic Degradation Activity of a Poly(vinyl chloride)‐TiO2 Nanocomposite Film with Bismuth Oxyiodide

A new type of photodegradable poly(vinyl chloride)‐bismuth oxyiodide/TiO₂ (PVC‐BiOI/TiO₂) nanocomposite film was prepared by embedding a nano‐TiO₂ photocatalyst modified by BiOI into the commercial PVC plastic. The solid‐phase photocatalytic degradation behavior of the as‐prepared film was investigated in ambient air at room temperature under UV light irradiation, with the aid of UV‐Vis spectroscopy, weight loss monitoring, scanning electron microscopy, and FT‐IR spectroscopy. Compared to the PVC‐TiO₂ nanocomposite film, the PVC‐BiOI nanocomposite film and the pure PVC film, the PVC‐BiOI/TiO₂ nanocomposite film exhibited a higher photocatalytic degradation activity. The optimal mass ratio of BiOI to TiO₂ was found to be 0.75 %. The weight loss rate of the PVC‐BiOI/TiO₂ nanocomposite film reached 30.8 % after 336 h of irradiation, which is 1.5 times higher than that of the PVC‐TiO₂ nanocomposite film under identical conditions. The solid‐phase photocatalytic degradation mechanism of the nanocomposite films was briefly discussed.     

Modeling and experimental verification of radiative transfer of a flat‐plate photoreactor with immobilized photocatalyst

A cost‐effective design of photocatalytic reactor needs efficient contact of the polluted substance with the solid catalyst while uniformly irradiating the solid catalyst with light. In the present paper, an immobilized photocatalyst comprising TiO₂ coated on Pyrex‐glass‐coils (abbreviated hereafter as TGC) was developed, and a flat‐plate photocatalytic reactor packed with TGC was designed. The reactor has some advantages such as low pressure drop, intensification of mass transfer; relatively uniform distribution of light radiation; high ratio of illuminated catalyst surface area to volume, and is flexible enough for large‐scale application. The radiation intensity distribution and the two‐flux model parameters were measured, and the two‐flux model was solved numerically. The experimental values were compared with the theoretical predictions. Good agreement was obtained with a maximum deviation about 10%. Finally, the two‐flux model described the radiation intensity distribution and local volumetric rate of energy absorption in the flat‐plate reactor packed with TGC. © 2002 Society of Chemical Industry     

TiO2‐Modified Flower‐Like Bi2WO6 Nanostructures with Enhanced UV‐Vis Photocatalytic Activity

Anatase TiO₂‐modified flower‐like Bi₂WO₆ nanostructures were prepared by a simple hydrothermal reaction followed by layer‐by‐layer deposition and calcination. The photocatalytic activity was evaluated using Brilliant Red X3B, an anionic azo dye, as the target organic pollutant under UV‐Vis light irradiation. The experiment results showed that the photocatalytic activity of the hybrid increases first and then decreases with increasing loading amount of TiO₂. The hybrid coated with four layers of TiO₂ (containing 20 wt‐% TiO₂) showed the highest photocatalytic activity, which is 10.45 and 3.20 times higher than that of pure Bi₂WO₆ and TiO₂, respectively. The improved photocatalytic performance of TiO₂‐modified Bi₂WO₆ nanostructures could be ascribed to the improved light‐harvesting ability, efficient photo‐generated electron‐hole separation, and enhanced adsorption of the dye. This work may shed light on the design of complex architectures and the exploitation of their potential applications.     

Effects of carbon‐coated titanium dioxide nanoparticles as a photostabilizer on the photodegradation of rigid poly(vinyl chloride)

In this study, nanocomposites of rigid poly(vinyl chloride) (UPVC) using the synthesized carbon‐coated titanium dioxide (TiO₂) nanoparticles and commercial powder of titanium dioxide (with rutile structure) were prepared by melt blending. The presence of carbon‐coated TiO₂ nanoparticles with rutile structure in UPVC matrix led to an improvement in photo stability of UPVC nanocomposites in comparison with commercial UPVC. The photocatalytic degradation behavior of nanocomposites was investigated by measuring their structural changes, surface tension, and mechanical and morphological properties before and after UV exposure for 700 h. It was found that mechanical and physical properties of UPVC nanocomposites are not considerably reduced after UV exposure in the presence of carbon‐coated TiO₂ nanoparticles even in small percentage of nanoparticles in comparison with the presence of commercial TiO₂ particles. Therefore, it can be concluded that UPVC/TiO₂ nanocomposite with low content of carbon‐coated TiO₂ nanoparticles(0.25 wt %) illustrated high stability under light exposure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40228.     

Synthesis of a montmorillonite‐supported titania nanocomposite with grafted cellulose as a template and its application in photocatalytic degradation

We report a study on the synthesis of anatase titania (TiO₂) particles with the sol–gel method at room temperature. We immobilized the particles on a grafted‐cellulose intercalated montmorillonite (MMT). This nanocomposite, cellulose‐g‐poly(4‐vinyl pyridine)/MMT/TiO₂, could be applied in the photocatalytic degradation of organic pollutants efficiently because of the addition of a sorbent, the grafted cellulose. The synthesized nanocomposite was characterized with Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. Methyl orange was used as a model molecule to study photocatalytic degradation. The nanocomposite exhibited a better photocatalytic activity than in the absence of the grafted cellulose. The kinetics of the photocatalytic degradation could be described by pseudo‐first‐order rate law. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42627.     

Hydrothermal synthesis of titanium dioxide using acidic peptizing agents and their photocatalytic activity

We have prepared TiO₂ nanoparticles by the hydrolysis of titanium tetraisopropoxide (TTIP) using HNO₃ as a peptizing agent in the hydrothermal method. The physical properties of nanosized TiO₂ have been investigated by TEM, XRD and FT-IR. The photocatalytic degradation of orange II has been studied by using a batch reactor in the presence of UV light. When the molar ratio of HNO₃/TTIP was 1.0, the rutile phase appeared on the titania and the photocatalytic activity decreased with an increase of HNO₃ concentration. The crystallite size of the anatase phase increased from 6.6 to 24.2 nm as the calcination temperature increased from 300 °C to 600 °C. The highest activity on the photocatalytic decomposition of orange II was obtained with titania particles dried at 105 °C without a calcination and the photocatalytic activity decreased with increasing the calcination temperature. In addition, the titania particles prepared at 180 °C showed the highest activity on the photocatalytic decomposition of orange II. This paper was prepared at the 2004 Korea/Japan/Taiwan Chemical Engineering Conference held at Busan, Korea between November 3 and 4, 2004.     

Design of gas‐phase synthesis of core‐shell particles by computational fluid–aerosol dynamics

Core‐shell particles preserve the bulk properties (e.g., magnetic and optical) of the core while its surface is modified by a shell material. Continuous aerosol coating of core TiO₂ nanoparticles with nanothin silicon dioxide shells by jet injection of hexamethyldisiloxane precursor vapor downstream of titania particle formation is elucidated by combining computational fluid and aerosol dynamics. The effect of inlet coating vapor concentration and mixing intensity on product shell thickness distribution is presented. Rapid mixing of the core aerosol with the shell precursor vapor facilitates efficient synthesis of hermetically coated core‐shell nanoparticles. The predicted extent of hermetic coating shells is compared with the measured photocatalytic oxidation of isopropanol by such particles as hermetic SiO₂ shells prevent the photocatalytic activity of titania. Finally, the performance of a simpler, plug‐flow coating model is assessed by comparisons with the present detailed computational fluid dynamics (CFD) model in terms of coating efficiency and silica average shell thickness and texture. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Synthesis of High‐Temperature‐Stable TiO2 and its Application on Ag+‐Activated Ceramic Tile

The main purpose of study was to provide a common synergy using Ag⁺‐doped calcium phosphate powder and high‐temperature‐stable TiO₂ for antibacterial and photocatalytic tile applications. Thermally stable SiO₂‐modified TiO₂ active layer was deposited on Ag⁺‐activated ceramic tiles by spray coating. The results showed that a nearly 100% cleanability degree was detected for SiO₂‐modified TiO₂ (TS)‐coated antibacterial tiles when compared uncoated and unmodified TiO₂‐coated tiles. Antibacterial tests and colorimetric analyses indicated that ceramic tiles provide both antibacterial and photocatalytic properties simultaneously.