Microwave photocatalysis II: novel continuous‐flow microwave photocatalytic experimental set‐up with titania‐coated mercury electrodeless discharge lamps

BACKGROUND: A continuous‐flow microwave photocatalytic reactor was set up consisting of a glass tube equipped with microwave powered mercury electrodeless discharge lamps (EDLs) coated with thin films of nanoporous titanium(IV) oxide. The effect of operational parameters on photocatalytic degradation of aqueous mono‐chloroacetic acid (MCAA) by a TiO₂/UV/MW process was investigated. RESULTS: Studies were carried out at a relatively high concentration of MCAA (0.1 mol L^?1), and revealed that reaction temperature and light intensity of the EDLs depend inversely on the flow rate, but that the 366 nm line intensity of EDL is directly proportional to the reaction temperature. The photodegradation of MCAA was enhanced by heating and significantly enhanced by air bubbling of the reaction mixture in the glass reservoir at laboratory temperature. The photocatalytic efficiency increased with the number of titania‐coated EDLs inserted in the glass tube reactor. CONCLUSIONS: It was found that the operational parameters (i.e. flow rate, reaction temperature, number of titania‐coated EDLs, and air bubbling) had important effects on degradation efficiency. The photocatalytic degradation of MCAA on thin films of titanium(IV) oxide in the continuous‐flow microwave photoreactor can be enhanced in the TiO₂/UV/MW system. Copyright © 2009 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     

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.     

Enhanced photoresponse and photocatalytic activities of graphene quantum dots sensitized Ag/TiO2 thin film

TiO₂ thin films were fabricated through hydrothermal method. Silver nanoparticles were loaded on TiO₂ thin films via photoreduction technique. Subsequently, the graphene quantum dots (GQDs) were spin‐coated on the Ag/TiO₂ nanocomposites thin films. The crystal structure, surface morphology and UV‐vis absorbance were tested by XRD, SEM and ultraviolet‐visible spectrophotometer. These results indicated that Ag nanoparticles and GQDs are anchored on the TiO₂ nanorods. Absorbance of Ag/TiO₂ and GQDs/Ag/TiO₂ nanocomposite thin films have been extended into the visible region. Visible‐light response of the samples were investigated by electrochemical workstation. The photoresponse of the sample can be enhanced by sensitization of the Ag nanoparticles and GQDs. The enhanced visible‐light response may be due to the surface plasmon resonance of silver nanoparticles and visible absorbance of GQDs. The highest photocatalytic activity has been observed in the 9‐GQDs/Ag/TiO₂ composite thin film. The efficient charge separation and transportation can be achieved by introducing the Ag nanoparticles and GQDs in the TiO₂ thin film.     

Enhanced photocatalytic activity of highly transparent superhydrophilic doped TiO2 thin films for improving the self-cleaning property of solar panel covers

Undoped and metal doped nanocrystalline TiO₂ transparent thin films were synthesized on glass substrates via sol-gel/dip-coating method. TiO₂ thin film coatings can be applied to the surfaces of solar panels to impart self-cleaning properties to them. The structural and optical properties of few nanometer-thick films were characterized by XRD, SEM, CA, AFM, XPS, and UV–Vis spectrophotometry techniques. The stoichiometric TiO₂ films crystallized in anatase phase, with a particle size of ～100 nm, which were uniformly distributed on the surface. The prepared films with a roughness of ～1–5 nm, increased the hydrophilicity of the glass surface. Reducing the amount of Ti precursor (X) favored the improvement of film quality. To improve the photocatalytic activity of the TiO₂ thin film, it was doped with Ni, Cd, Mo, Bi and Sr metal ions. The effect of metal doping on the photocatalytic activity of the films was investigated using the degradation process of methylene blue (MB) dye as the model contaminant. Among the prepared coatings, the Sr–TiO₂ film showed the highest efficiency for MB degradation. It increased the dye degradation efficiency of the films under both UV and Vis lights. The kinetic investigations also showed that the degradation of MB by TiO₂ and M ? TiO₂ films obeyed the pseudo-first order kinetics.     

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.     

Photocatalysis of Ag Doped TiO x Films Prepared at Room Temperature

The aim of this paper is an investigation of the photocatalytic efficiency of TiO _x thin films deposited by DC reactive magnetron sputtering at low temperature and doped by Ag noble metal. Crystallographic structure and chemical composition of as-deposited films were examined by XRD and RBS, respectively. Ag/TiO _x films morphology was studied by SEM analysis. The photocatalytic activity was evaluated from the decomposition speed of an aqueous solution of the Acid Orange 7, exposed to UV/VIS light. A systematic change of Ag concentration in TiO _x films led to a maximum activity. Such a maximum is discussed taking into account composition, morphology and structure of the films.     

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     

Preparation and characterisation of silver‐ or copper‐doped TiO2 catalysts and their catalytic activity in dye degradation

In this study, silver‐ or copper‐doped TiO₂–Ce‐, TiO₂–La‐, and commercial TiO₂ (P25)‐supported catalysts were prepared. The catalysts and supports were characterised by powder X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption studies. UV‐light‐assisted heterogeneous Fenton‐like oxidation of two different‐structure dyes (anionic azo dye Orange II, CI Acid Orange 7 and cationic triphenylmethane dye Crystal Violet, CI Basic Violet 3) was investigated over the catalysts. Higher catalytic activity was observed in the oxidation of Orange II than in the oxidation of Crystal Violet. For both dyes, the TiO₂–Ce and TiO₂–La‐supported catalysts, which were in the form of anatase only, gave higher photocatalytic activity than the P25‐supported catalysts, which were in the form of anatase and rutile. Complete colour removal was observed during oxidation of Orange II over Cu/TiO₂–Ce and Cu/TiO₂–La catalysts, whereas the highest degree of decolorisation, 89.3%, was achieved by oxidation of Crystal Violet over Ag/TiO₂–Ce. The pH of the solution affected the surface state of the TiO₂, thus affecting the photocatalytic degradation of the dyes. The surface area of the catalysts is also a key parameter that influences their photocatalytic activity. It was observed that catalysts having higher surface areas brought about greater dye degradation.     

Template‐free synthesis of single‐/double‐walled TiO2 nanovesicles: Potential photocatalysts for engineering application

Single‐ and double‐walled anatase TiO₂ nanovesicles have been, respectively, prepared by a template‐free hydrothermal treatment of Ti(SO₄)₂ with H₂O₂ and urea. Photocatalytic degradation of Rhodamine B indicates that double‐walled TiO₂ nanovesicles have an initial lower but a final higher photocatalytic efficiency than single‐walled ones. All nanovesicles have significantly lower performance than commercially available P25 TiO₂. The enhanced capacity for UV light absorption and· OH radicals production, large specific surface area, and unique hierarchical hollow architectures contribute to the enhanced photocatalytic activity and improved feasibility of anatase TiO₂ nanovesicles for engineering applications. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1478–1482, 2015     

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.     

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     

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     

Effects of V and Zn codoping on the microstructures and photocatalytic activities of nanocrystalline TiO2 films

To enhance the photocatalytic activity of TiO₂, V and Zn co-doped TiO₂ films were synthesized by the sol–gel method. The experimental results indicated that the films were composed of round-like nano-particles or aggregates. V and Zn codoping could not only obviously increase the specific surface area of TiO₂ but also result in the narrowed band gap of TiO₂ sample. The photocatalytic activities of the TiO₂ films were evaluated by the photocatalytic decomposition of organic dyes in aqueous solution. Compared with un-doped TiO₂ film or single doped TiO₂ film, V and Zn co-doped TiO₂ film exhibited excellent photocatalytic activities under both UV light and visible light. The improvement mechanism by V and Zn codoping was also discussed.     

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     

Electrospun polyamide‐6 membranes containing titanium dioxide as photocatalyst

Electrospun polyamide‐6 membranes containing titanium dioxide (TiO₂) photocatalyst were prepared and characterized. By tailoring the electrospinning parameters it was possible to obtain membranes having two different thicknesses, namely 5 and 20 µm, in which TiO₂ particles were homogeneously dispersed. As a comparison, hybrid films made with polyamide‐6 matrix and TiO₂ filler were successfully produced, with inorganic/organic ratios of 10 and 20 wt%. The photocatalytic activity of both hybrid systems was evaluated by following the degradation of methylene blue as a target molecule as a function of UV irradiation time. A smoother degradation was recorded for the electrospun membranes with respect to the hybrid films probably due to a less exposed surface because of the highly porous structure. Even if a longer photodegradation time was necessary, the degradation of the dye was successfully achieved. Copyright © 2010 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     

Effect of nano‐TiO2 dispersion on PEO polymer electrolyte property

Polymer electrolyte membranes based on poly(ethylene oxide) (PEO) doped with TiO₂ nanoparticles were synthesized by simple solution cast technique. Mesoporous TiO₂ film was prepared by doctor‐blade method. The modified polymer membranes and the mesoporous films were characterized by SEM, TEM, AFM, ionic conductivity, and J‐V measurements. Dye‐sensitized solar cells (DSSC) have been fabricated in which PEO‐polymer electrolyte doped with and without nano‐TiO₂ were sandwiched between porous TiO₂ and counter electrodes. The DSSC with nano‐TiO₂ doped polymer electrolyte shows better performance (1.68%) in comparison with pristine polymer electrolyte (1.07%), which is due to improved ionic conductivity value in polymer electrolyte system by nano‐TiO₂ doping. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

UV-curable polyurethane acrylate–Ag/TiO2 nanocomposites with superior UV light antibacterial activity

Polyurethane acrylate (PUA)–Ag/TiO₂ nanocomposites were synthesized through in situ polymerization. The well-dispersed Ag/TiO₂ nanorods serve as photoinitiator. Meanwhile, the PUA–Ag/TiO₂ nanocomposite films exhibit superior activity toward the photocatalytic degradation of Escherichia coli under UV light. The excellent UV curing and antibacterial activities can be ascribed to the synergistic effect of Ag and TiO₂, which promotes the effective electron/hole separation and thus generates various reactive species. Thin films with these nanoparticles are more hydrophilic after UV illumination. And the antibacterial mechanism of the UV-curable PUA–Ag/TiO₂ nanocomposites was proposed.     

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