A novel TiO2 − xNx/BN composite photocatalyst: Synthesis,characterization and enhanced photocatalytic activity for Rhodamine B degradation under visible light

A novel TiO_2 − xN_x/BN composite photocatalyst was prepared via a facile method using melamine–boron acid adducts (M·2B) and tetrabutyl titanate as reactants. The morphological results confirmed that nitrogen-doped TiO₂ nanoparticles were uniformly coated on the surface of porous BN fibers. A red shift of absorption edge from 400 nm (pure TiO₂) to 520 nm (TiO_2 − xN_x/BN composites) was observed in their UV–Vis light absorption spectra. The TiO_2 − xN_x/BN photocatalysts exhibited enhanced photocatalytic activity for the degradation of Rhodamine B (RhB) and the highest photocatalytic degradation efficiency reached 97.8% under visible light irradiation for 40 min. The mechanism of enhanced photocatalytic activity was finally proposed.     

Preparation of novel nanometer TiO2 catalyst doped with upconversion luminescence agent and investigation on degradation of acid red B dye using visible light

An unreported nanometer TiO₂ photocatalyst doped with upconversion luminescence agent (40CdF₂ · 60BaF₂ · 0.8Er₂O₃) utilizing visible light was prepared. Its photocatalytic activity was checked through the photocatalytic degradation of acid red B as a model compound under visible light irradiation. Results show that the upconversion luminescence agent prepared as dopant can effectively turn visible lights to ultraviolet lights, which can be absorbed by nanometer TiO₂ particles to produce the electron-cavity pairs. Therefore, the photocatalytic ability of this novel TiO₂ photocatalyst has greatly been enhanced compared with undoped and common TiO₂ photocatalyst.     

Inactivation of pathogenic Klebsiella pneumoniae by CuO/TiO2 nanofibers: A multifunctional nanomaterial via one-step electrospinning

The fabrication and characterization of one-dimensional CuO/TiO₂ nanofibers with high photocatalytic and antibacterial activities are presented. The CuO/TiO₂ nanofibers were prepared by electrospinning of colloid composed of titanium isopropoxide, poly(vinylpyrroliodine) (PVP) and copper nanoparticles and calcination at 700 °C in air for 1 h. The antibacterial activity was tested using Klebsiella pneumoniae as model organism by calculation of the minimum inhibitory concentration (MIC). The obtained CuO/TiO₂ nanofibers showed prominent photocatalytic activity under visible light to degrade reactive black5 and reactive orange16 dyes in aqueous solutions and effectively catalyze K. pneumoniae inactivation. The decomposition process of the cell wall and cell membrane was directly observed by TEM analysis after the exposure of the K. pneumoniae to the nanofibers. Interestingly, the introduced photocatalyst can be reused with the same photocatalytic activity. Overall, the combination of CuO and TiO₂ can be synergistic and resulted in CuO/TiO₂ composite nanofibers having superior photocatalytic and antimicrobial potential to impede K. pneumoniae growth which causes bacterium to die ultimately.     

Suspension high velocity oxy-fuel spraying of a rutile TiO2 feedstock: Microstructure,phase evolution and photocatalytic behaviour

Nano-structured TiO₂ coatings were produced by suspension high velocity oxy fuel (SHVOF) thermal spraying using water-based suspensions containing 30 wt% of submicron rutile powders (~180 nm). By changing the flame heat powers from 40 kW to 101 kW, TiO₂ coatings were obtained with distinctive microstructures, phases and photocatalytic behaviour. Spraying with low power (40 kW) resulted in a more porous microstructure with the presence of un-melted nano-particles and a lower content of the anatase phase; meanwhile, high powers (72/101 kW) resulted in denser coatings and rougher surfaces with distinctive humps but not necessarily with a higher content of anatase. Linear sweep voltammetry (LSV) was used to evaluate the photocatalytic performance. Surprisingly, coatings with the lowest anatase content (~20%) using 40 kW showed the best photocatalytic behaviour with the highest photo-conversion efficiency. It was suggested that this was partially owing to the increased specific surface area of the un-melted nano-particles. More importantly, the structural arrangement of the similarly sized TiO₂ nano-crystallites between rutile and antase phases also created catalytic “hot spots” at the rutile−anatase interface and greatly improved the photo-activity.     

TiO2 photocatalysis in cementitious systems: Insights into self-cleaning and depollution chemistry

The present work offers a general overview about application of titanium dioxide (or titania), TiO₂, photocatalysis to concrete technology in relation to enhanced aesthetic durability and depollution properties achieved by implementing TiO₂ into cement. Chemistry of degradation of Rhodamine B (RhB), a red dye used to assess self-cleaning performances of concretes containing TiO₂, as well as oxidation of nitrogen oxides (NOx), gaseous atmospheric pollutants responsible for acid rains and photochemical smog, is investigated using two commercial titania samples in cement and mortar specimens: a microsized, m-TiO₂ (average particle size 153.7 nm ± 48.1 nm) and a nanosized, n-TiO₂ (average particle size 18.4 nm ± 5.0 nm). Experimental data on photocatalytic performances measured for the two samples are discussed in relation to photocatalyst properties and influence of the chemical environment of cement on titania particles. Impacts on applications in construction concrete are also discussed.     

Functionalizing slag wool fibers with photocatalytic activity by anatase TiO2 and CTAB modification

Anatase TiO₂ coatings prepared by solvothermal process in a neutral ethanol solution of isopropyl titanate at 160 °C have been grown on slag wool fibers (SWF) which were modified by hexadecyltrimethylammonium bromide (CTAB) in advance. X-ray diffraction patterns confirmed the coatings are of a nanocrystalline anatase structure, and scanning electron microscopy observations and energy-dispersive X-ray spectrum revealed a continuous coverage of TiO₂ formed on the fiber surfaces. The photocatalytic activity of the samples was tested by the photocatalytic degradation of methylene blue (MB) solution. The results show that CTAB modified slag wool fibers (CMSWF) are not a suitable adsorbent for MB due to their weaker negative surface charges. Anatase TiO₂ coated CMSWF display higher photocatalyst activity than anatase TiO₂ coated SWF without CTAB modification, and Anatase TiO₂ coated CMSWF are relatively stable under UV-light irradiation.     

Effect of Pt loading and calcination temperature on the photocatalytic hydrogen production activity of TiO2 microspheres

TiO₂ microspheres were synthesized by hydrothermal reaction using Ti(OBu)₄ as the precursor. In order to enhance the efficiency of water splitting by the TiO₂ microspheres, Pt-modified TiO₂ microspheres were prepared by the impregnation-reduction method. The diameter of TiO₂ microspheres is around 5–10 μm. The photocatalytic performances of the catalysts were measured by hydrogen generation from a mixture of water and methanol under UV light irradiation. The photocatalytic activity of the TiO₂ microspheres was remarkably enhanced by loading Pt. The optimal Pt loading is 1.2 wt%. Pt/TiO₂ microspheres exhibit about 125 times greater H₂ production rate than the unmodified TiO₂ microspheres. The effect of calcination temperature on photocatalytic activity of the TiO₂ microspheres was also investigated.     

Visible light-active sub-5 nm anatase TiO2 for photocatalytic organic pollutant degradation in water and air,and for bacterial disinfection

Visible-light-sensitive sub-5 nm anatase titanium dioxide (TiO₂) nanoparticles (NPs) were fabricated without any doping and calcination treatments. The energy band gap was effectively narrowed to ~ 2.98 eV. The surface and subsurface hydroxyl defects were ascertained as the origin for the band gap narrowing and for the efficient azo-based dye degradation in water and formaldehyde decomposition in air, as well as disinfection of Staphylococcus aureus bacteria, under visible light irradiation.     

Preparation of graphene film decorated TiO2 nano-tube array photoelectrode and its enhanced visible light photocatalytic mechanism

Graphene film decorated TiO₂ nano-tube array (GF/TiO₂ NTA) photoelectrodes were prepared through anodization, followed by electrodeposition strategy. Morphologies and structures of the resulting GF/TiO₂ NTA samples were characterized by scanning electrons microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. In addition, the optical and photoelectrochemical properties were investigated through UV–visible light diffuse reflection spectroscopy, photocurrent response and Mott–Schottky analysis. Furthermore, the photodecomposition performances were investigated through yield of hydroxyl radicals and photocatalytic (PC) degradation of methyl blue (MB) under visible light irradiation. It was found that GF/TiO₂ NTA photoelectrode exhibited intense light absorption both in UV light and visible region, higher transient photoinduced current of 0.107 mA cm⁻² and charge carrier concentration of 0.84 × 10¹⁹ cm⁻³, as well as effective PC performance of 65.9% for the degradation of MB. Furthermore, contribution of several reactive species to the PC efficiency of GF/TiO₂ NTA photoelectrode was distinguished. Moreover, the enhanced visible light PC mechanism was proposed and confirmed in detail.     

Enhanced photocatalytic activity of electrospun TiO2/ZnO nanofibers with optimal anatase/rutile ratio

The photocatalytic characteristics of the TiO₂/ZnO nanofibers synthesized by electrospinning followed by calcinating at different temperatures to alter the anatase-to-rutile ratio are investigated. The results demonstrate that the photocatalytic activity of TiO₂/ZnO nanofibers is enhanced by optimizing the anatase/rutile ratio among the trade-off effects of the band-gap energy, the electron/hole recombination rate, and the surface area. When calcined at 650 °C, the TiO₂/ZnO nanofibers with optimal anatase/rutile ratio (48:52) balancing these trade-off effects have the highest photocatalytic efficiency both in the degradation of RhB in liquid and conversion of NO gas.     

Preparation and photocatalytic properties of macroporous honeycomb alumina ceramics used for water purification

In this work, porous alumina ceramics with highly ordered capillaries were successfully fabricated by ionotropic gelation process of alginate/alumina suspensions. By varying the initial solid loading (10–30 wt%) of slurries, the porosity of alumina ceramics ranged from 60.4% to 79.5% with controlled pore size (180–315 μm). Due to the well-crosslinked macroporous structure and large specific surface areas, the porous ceramics were utilized as the photocatalyst supports of TiO₂ catalysts whose photocatalytic activity was characterized by degrading methyl blue under UV irradiation. TiO₂ coatings prepared by sol–gel method demonstrated excellent adhesion to the substrates. When the solid loading of supports reached 15 wt%, the TiO₂ coatings showed the highest photocatalytic efficiency of 79.52%. Besides, TiO₂ films possessed nearly the same photocatalytic activity as titania/water suspension. Thus, the honeycomb ceramic prepared by self-organization process holds promise for use as photocatalyst supports in water purification without recycling process of powders.     

Hydrothermal preparation of Ag-TiO2 nanostructures with exposed {001}/{101} facets for enhancing visible light photocatalytic activity

Nano-composite materials of Ag nanoparticles dispersed TiO₂ nanocubes with exposed {001}/{101} crystal faces were fabricated mainly via a flexible one-step method of hydrothermal treatment with different content of Ag from 1 up to 3 mol%. Prepared photocatalysts were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy, UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. These analysis was carried out for understanding the contribution of different content of silver for enhancing the photocatalytic activity of TiO₂ nanocubes. Prepared silver nanoparticles had small particle size and grafted to the {101} crystal face of TiO₂ with the role of template control agent and linking agent. The photocatalytic performance of Ag-TiO₂ nanocubes were researched via Rhodamine B dye removal under visible light irradiation ( ≧420 nm). Ag-TiO₂ composite materials with the content of 2 mol% Ag showed the best photocatalytic activity for degradation of Rhodamine B, which was five times more than bare TiO₂ and associated with the localized surface plasmon resonance (LSPR) propelled effect. The mechanism by which silver enhanced the photocatalytic activity of TiO₂ was also demonstrated.     

Solar photocatalytic decolorization of dyes in solution with TiO2 film

Application of TiO₂ film to solar photocatalysis of organic dyes, including Methylene Blue (MB) (λ_max, 660 nm), RR195 (λ_max, 540 nm) and RY145 (λ_max, 420 nm), was investigated. It was found that after 6-h solar irradiation, the extent of color degradation of dyes using solar photocatalytic system without TiO₂ film was quite limited. The color removal percentage for MB, RR195, and RY145 was found to be 23.3, −9.3, and −20.7%, respectively, resulting from competitions between the photosensitizing reaction and formation of colored intermediates during solar irradiation. However, as TiO₂ film was applied, the color degradation capability of solar photocatalytic system was significantly improved, in spite of the fact that only approximately 7% of solar irradiation belongs to the UV region. The color removal percentage for MB, RR195, and RY145 was up to 93.6%, 85.3%, and 71.1%, respectively, after 6-h irradiation. We believed that in such a solar photocatalytic system immobilized with TiO₂ film, both the maximum absorbance wavelength of the dye and the adsorbability of the dye on TiO₂ film played significant roles on the rate and efficiency of color removal of the dye solutions. Moreover, the possible reaction mechanism was proposed. The solar photocatalytic process with immobilized TiO₂ film was found to follow the pseudo-first order reaction kinetics. Color removal rate of MB was almost twice of that of RY145. Accordingly, the photocatalytic degradation process using solar light as an irradiation source, and immobilized TiO₂ as a photocatalyst, showed potential application for the decolorization of wastewater.     

Effect of carbon doping on WO3/TiO2 coupled oxide and its photocatalytic activity on diclofenac degradation

The improved photocatalyst carbon-doped WO₃/TiO₂ mixed oxide was synthesized in this study using the sol–gel method. The catalyst was thoroughly characterized by X-ray diffraction (XRD), diffuse reflectance UV–vis spectroscopy, N₂ adsorption desorption analysis, scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM/EDX), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic efficiency of the prepared materials was evaluated with respect to the degradation of sodium diclofenac (DCF) in a batch reactor irradiated under simulated solar light. The progress of the degradation process of the drug was evaluated by high-performance liquid chromatography (HPLC), whereas mineralization was monitored by total organic carbon analysis (TOC) and ion chromatography (IC). The results of the photocatalytic evaluation indicated that the modified catalyst with tungsten and carbon (TWC) exhibited higher photocatalytic activity than TiO₂ (T) and WO₃/TiO₂ (TW) in the degradation and mineralization of diclofenac (TWC>TW>T). Complete degradation of diclofenac occurred at 250 kJ m⁻² of accumulated energy, whereas 82.4% mineralization at 400 kJ m⁻² was achieved using the photocatalytic system WO₃/TiO₂-C. The improvement in the photocatalytic activity was attributed to the synergistic effect between carbon and WO₃ incorporated into the TiO₂ structure.     

Photocatalytic performance of plasma sprayed Pt-modified TiO2 coatings under visible light irradiation

Plasma sprayed Pt/TiO₂ coatings were prepared by Atmospheric Plasma Spraying process. As-sprayed coatings were characterized by TEM, XRD and XPS. The photocatalytic performance was evaluated through the photo mineralization of methylene blue. All the Pt modified titanium dioxide coatings show significant absorption in the visible light range, while the pure titania coating reflects almost all the visible light. The photocatalytic efficiencies of as-sprayed pure TiO₂ coating and Pt/TiO₂ coatings are almost same under the irradiation of visible light. However, the efficiencies of all Pt/TiO₂ coating are greatly improved comparing with that of pure TiO₂ coating by applying 15 V external bias under the irradiation of visible light.     

Visible-light-induced photocatalytic activity of TiO2−xNy prepared by solvothermal process in urea–alcohol system

Nitrogen-doped anatase, rutile and brookite titania photocatalyst TiO_2−xN_y which can be excited by visible light were prepared by mixing aqueous TiCl₃ solutions with urea ((NH₂)₂CO) and various type of alcohols followed by solvothermal treatment at 190 °C. The phase composition, crystallinity, microstructure and specific surface area of titania powders greatly changed depending on the pH and type of solvents. Violet, yellowish and grayish TiO_2−xN_y with excellent visible light absorption and photocatalytic activity were prepared. The TiO_2−xN_y powders prepared in urea–methanol solution showed excellent photocatalytic ability for the oxidative destruction of nitrogen monoxide under irradiation of visible light λ > 510 nm.     

AgBr@Ag/TiO2 core–shell composite with excellent visible light photocatalytic activity and hydrothermal stability

AgBr@Ag/TiO₂ core–shell photocatalysts were fabricated by a facile green route. TiO₂ was uniformly coated on the surface of cubic AgBr, making AgBr@Ag/TiO₂ core–shell photocatalyst show excellent hydrothermal stability. Beneficial from that Ag nanoparticles and AgBr can respond to visible light and core–shell structure can effectively separate the photogenerated electrons and holes, AgBr@Ag/TiO₂ core–shell composites exhibited outstanding visible light photocatalytic activity for the degradation of acid orange 7. The activity of AgBr@Ag/TiO₂ is related to the thickness of TiO₂ shell, and the optimal shell thickness for obtaining the highest activity is 10 nm.     

Hydrothermal processing and in situ surface modification of metal oxide nanomaterials

In situ surface modification of TiO₂ and ZnO metal oxide particles has been carried out under hydrothermal conditions within a wide range of temperature and pressure (T = 150–400 °C; P = up to 20 MPa). The influence of the surfactant and selective doping with active metal ions on the crystal size, morphology, and photocatalytic activity of TiO₂ and ZnO particles has been carried out. A systematic characterization of the product has been carried out using powder XRD, FTIR, TGA, SEM/TEM, and UV–vis spectroscopy. Similarly the photocatalytic activity in these metal oxides varies with the size, shape and dopant metals.     

Channelled optical fibre photoreactor for improved air quality control

An optical fibre reactor with 30 hexagonal-shaped channels distributed within the optical fibre structure was investigated as a gas-phase photocatalytic reactor. TiO₂ photocatalyst, with SiO₂ sol acting as a binder, was coated on the channel walls at a thickness of 1.5 μm. Effective light propagation lengths of 3.4 and 4.9 cm were observed for incidental angles of 81.5° and 87.1°, respectively. The TiO₂-coated channelled optical fibre reactor (COFR) was assessed for the photocatalytic degradation of gas-phase ethylene. The photocatalytic reaction rate of ethylene degradation was linear with respect to the incident photons. The reaction rate order for the incident photons was determined to be 0.93. Despite a longer effective light propagation length for an incidental angle of 87.1°, the quantum yield was independent of the incidental angle. The independence of the quantum yield on the incident photons and the angle of light incidence was attributed to the COFR design, where the propagating light was wholly confined within the reactor and, in turn, more effectively utilised by the TiO₂.     

TiO2 nanofibers assembled on graphene-silver platform as a visible-light photo and bio-active nanostructure

The heterogeneous titanium oxide-reduced graphene oxide-silver (TiO₂/RGO/Ag) nanocomposites were successfully prepared by incorporation of two dimensional (2D) RGO nanosheets and spherical silver nanoparticles (NPs) into the 1D TiO₂ nanofibers. The novel TiO₂/RGO/Ag nanocomposites were synthesized by loading TiO₂ nanofibers, prepared via electrospinning technique, on the RGO/Ag platform. The resulting nanocomposites have been characterized using various techniques containing transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultra-violet-visible (UV–vis) spectroscopy. Microscopic studies clearly verified the existence of TiO₂ nanofibers with Ag NPs on the surface of RGO sheet and formation of TiO₂/RGO/Ag nanocomposites. Moreover, the results of UV–vis spectroscopy demonstrated that TiO₂/RGO/Ag nanocomposites extended the light absorption spectrum toward the visible region and significantly enhanced the visible-light photocatalytic performance of the prepared samples on degradation of rhodamine B (Rh. B) as a model dye. It was found that, incorporation of 50 µl RGO/Ag into the TiO₂ nanofibers lead to a maximum photocatalytic performance. Also, the improvement of the inactivation of Escherichia coli (E. coli) bacteria under visible-light irradiation was revealed by introduction of RGO/Ag into the TiO₂ matrix. The significant enhancement in the photo and bio-activity of TiO₂/RGO/Ag nanocomposites under visible-light irradiation can be ascribed to the RGO/Ag content by acting as electron traps in TiO₂ band gap.