Photocatalytic and adsorptive treatment of 2,4-dinitrophenol using a TiO2 film covering activated carbon surface

Anatase titanium dioxide (TiO₂) in particle sizes of roughly 0.5–20 μm was prepared from amorphous TiO₂ in an aqueous H₂O₂ solution by heating at 90 °C for 9 h and directly deposited on a PET film. On the other hand, granular activated carbon (AC) particles in sizes of 1–2 mm in diameter were adhesively deposited on a PET film, and their surfaces were also coated with TiO₂. The resulting three preparations (TiO₂-, AC-, and TiO₂/AC-PET films) were set up in an annular-flow reactor to treat aqueous solutions of 2,4-dinitrophenol (DNP) in a batch-recirculation mode. The rate of DNP adsorption onto the TiO₂/AC-PET film without UV irradiation was almost the same as that onto the AC-PET film, indicating that the attraction of DNP to AC was not lowered in the presence of TiO₂ film. Observation of SEM photographs suggests that this result is attributed to the porous structure of the thin TiO₂ film covering AC particles. The rate of DNP removal by the TiO₂-AC PET film under UV irradiation was 2.9 times higher than that by the TiO₂-PET film under UV irradiation, and was 1.1 times higher than the rate of DNP adsorption onto the AC-PET film. The rate of DNP removal by the AC-PET film decreased by 40% after six runs, while that by the TiO₂/AC-PET film decreased by 22%. Durable experiments using the TiO₂/AC-PET and AC-PET films clarified that the lifetime of the TiO₂/AC-PET film is at least two times longer than that of the AC-PET film. This result suggests that DNP molecules are photocatalytically decomposed when passing through the porous TiO₂-PET film, which lessens a burden of DNP adsorption on AC. Moreover, the DNP treatments in the batch-recirculation flow system suggested that the TiO₂/AC-PET film saturated with DNP can be successfully regenerated at 60 °C.     

Plant mediated green synthesis and antibacterial activity of silver nanoparticles using Crataegus douglasii fruit extract

In this study, silver nanoparticles were synthesized using the Crataegus douglasii fruit extract as a reducing agent. The reaction process was monitored by UV–vis spectroscopy. Further characterization was carried out using scanning electron microscopy (SEM). To optimize the biosynthesis of silver nanoparticles, the effect of process variables such as extract concentrations, mixing ratio of the reactants, time and pH were also investigated. The SEM images showed silver nanoparticles with 29.28 nm size and nearly spherical shape at 24 h interaction time. The antibacterial activity of the synthesized silver nanoparticles was confirmed against Staphylococcus aureus and Escherichia coli.     

Thin-film nanocomposites of diamond-like carbon and titanium oxide; Osteoblast adhesion and surface properties

Thin films of a novel, nanocomposite material consisting of diamond-like carbon and polycrystalline/amorphous TiO_x (DLC-TiO_x, x ≤ 2) were prepared using pulsed direct-current plasma enhanced chemical vapour deposition (PECVD). Results from Raman spectroscopy indicate that the DLC and TiO_x deposit primarily as segregated phases. Amorphous TiO₂ is found to be present on the surface region of the film and there is evidence for the presence of crystalline TiO in the bulk of the film. The hydrophilicity of the DLC-TiO_x films increased with increasing titanium content. Culture studies with human osteoblasts revealed that the differences in three-day cell adhesion properties (count, morphology and area) between DLC and DLC-TiO_x films containing up to 13 at.% Ti were not statistically significant. However, the cell count was significantly greater for the films containing 3 at.% of Ti in comparison to those containing 13 at.% of Ti. A post-plasma treatment with Ar/O₂ was used to reduce the water contact angle, θ, by nearly 40° on the DLC-TiO_x films containing 3 at.% of Ti. A cell culture study found that the osteoblast count and morphology after three days on these more hydrophilic films did not differ significantly from those of the original DLC-TiO_x films. We compare these results with those for SiO_x-incorporated DLC films and evaluate the long-term osteoblast-like cell viability and proliferation on modified DLC surfaces with water contact angles ranging from 22° to 95°.     

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 dye sensitized solar cell by using supercritical carbon dioxide drying

Dye-sensitized solar cells (DSSC) derived from TiO₂ aerogel film electrodes were fabricated. TiO₂ aerogels were obtained by using sol–gel method and supercritical carbon dioxide (sc-CO₂) drying. First, TiO₂ wet gels were obtained by sol-gel method. Then, the solvents in the TiO₂ wet gels were replaced by acetone. The TiO₂ aerogels were obtained by using sc-CO₂ drying from the TiO₂ wet gels. The conditions of sc-CO₂ drying were at 313, 323 K and 7.8–15.5 MPa. The electrodes with TiO₂ aerogel films were obtained by deposition of the aerogels on glass substrates. The electrodes with TiO₂ aerogel films and a commercial particle film of various thickness were obtained by repetitive coatings and calcinations. The amount of dye adsorbed on the TiO₂ films with sc-CO₂ drying was higher than that of commercial particle film. The amount of dye adsorbed on the TiO₂ films increased with increasing surface area of the TiO₂ film. DSSCs were assembled by using the TiO₂ aerogel film electrodes and their current–voltage performance was measured. The power performance of DSSC made by supercritical drying was higher than that of commercial particles. The DSSC with the film electrode made at 313 K and 15.5 MPa showed the best power performance (J_sc = 7.30 mA/cm², V_oc = 772 mV, η = 3.28%).     

Preparation of oriented SiO32− doped TiO2 film and degradation of methylene blue under visible light irradiation

SiO₃^2? doped TiO₂ films with oriented nanoneedle and nanorectangle block structure has been firstly synthesized by hydrothermal synthesis method. The prepared samples are characterized, X-ray diffraction (XRD) results demonstrate that the SiO₃^2? doped TiO₂ films are rutile and brookite phases. The scanning electron microscope (SEM) analysis reveals that the quantity of O₂ affects the morphology of the SiO₃^2? doped TiO₂ films (SiTiA films prepared with unmodified substrate). The SiO₃^2? doped TiO₂ films (SiTiB films prepared with modified substrate) display two layers, one is porous structure, the other is nanoneedle structure. UV–vis, IR, transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) microscopy all prove that SiO₃^2? have been doped in the TiO₂ crystal structure. They have remarkable red shift and higher photocatalytic activity of degradation of methylene blue than P-25 under visible light (λ > 420 nm) irradiation. Besides, photocatalytic activity of the film is stable during 4 times recycling.     

Transparent and flexible films of new segmented polyurethane nanocomposites incorporated by NH2-functionalized TiO2 nanoparticles

In this work, TiO₂ nanoparticles are surface modified by NH₂-terminated organic moieties arised from 4,4′-methylene diphenyl diisocyanate (MDI). These nanoparticles are incorporated into ether-based segmented polyurethane (SPU) matrix. MDI is utilized as monomer together with poly(tetramethylene oxide) (PTMO) comonomer for preparing the final polymer as well. The NH₂-functionalized TiO₂ nanoparticles are covalently linked to the NCO terminals of the resulting SPU macromolecules during film preparation stage. Therefore, in addition to butylene glycol, these surface modified nanoparticles with enhanced organophilicity could play the role of the second chain extender of NCO-capped SPU macromolecules through formation of urea linkages. Optical and thermal behaviors of the transparent and flexible film (SPU/TiO₂–MDI) is compared with those of unmodified TiO₂ (SPU/TiO₂) and TiO₂-unloaded SPU films. Though the particle loading is only 5 wt.%, incorporation of TiO₂ and TiO₂–MDI nanoparticles into the SPU polymer enhances significantly the light absorption in UV region at 300–400 nm. SEM images of the prepared films clearly show a considerable decrease in particle aggregation for TiO₂–MDI into SPU matrix compared to that of unmodified TiO₂. TG analyses indicate a one-step decomposition pattern with onset temperatures of about 360 and 380 °C for neat SPU and SPU/TiO₂–MDI, respectively. Moreover, DTA thermograms of both nanocomposites show obviously two exothermic phase transitions in the thermal range of 330–440 °C.     

Synthesis of TiO2–Ag nanocomposite with sol–gel method and investigation of its antibacterial activity against E. coli

TiO₂–Ag nanocomposite was prepared by the sol–gel method and an azeotropic distillation with benzene was used for dehydration of the gel. Because of gel dehydration by distillation method a nanopowder with a surface area of 230 m²/g was produced which decreased to 80 m²/g after calcination. TEM micrographs and XRD patterns showed that spherical nanosized Ag particles (≈ 10 nm) were deposited among TiO₂ particles. The antibacterial activity of calcined powder at 300 and 500 °C was studied in the presence and in the absence of UV irradiation against Escherichia coli as a model for Gram-negative bacteria. The antibacterial tests confirmed the powder calcined at 300 °C possessed more antibacterial activity than the pure TiO₂, amorphous powder and the powder calcined at 500 °C under UV irradiation. In the absence of UV, the reduction in viable cells was observed only with calcinated powder at 300 °C.     

Antibacterial activity of photocatalytic electrospun titania nanofiber mats and solution-blown soy protein nanofiber mats decorated with silver nanoparticles

Highly porous photocatalytic titania nanoparticle decorated nanofibers were fabricated by electrospinning nylon 6 nanofibers onto flexible substrates and electrospraying TiO₂ nanoparticles onto them. Film morphology and crystalline phase were measured by SEM and XRD. The titania films showed excellent photokilling capabilities against E. coli colonies and photodegradation of methylene blue under moderately weak UV exposure (≤ 0.6 mW/cm² on a 15-cm illumination distance). In addition, solution blowing was used to form soy protein-containing nanofibers which were decorated with silver nanoparticles. These nanofibers demonstrated significant antibacterial activity against E. coli colonies without exposure to UV light. The nano-textured materials developed in this work can find economically viable applications in water purification technology and in biotechnology. The two methods of nanofiber production employed in this work differ in their rate with electrospinning being much slower than the solution blowing. The electrospun nanofiber mats are denser than the solution-blown ones due to a smaller inter-fiber pore size. The antibacterial activity of the two materials produced (electrospun titania nanoparticle decorated nanofibers and silver-nanoparticle-decorated solution-blown nanofibers) are complimentary, as the materials can be effective with and without UV light, respectively.     

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.     

Absorption boost of TiO2 nanotubes by doping with N and sensitization with CdS quantum dots

A process of obtaining N-doped TiO₂ nanotubes sensitized by CdS nanoparticles is presented, including detailed characterizations performed along the synthesis. Transparent TiO₂ films consisting of nanotubes, 2.5 µm long and of ~60 nm inner diameter, were obtained after anodization of a titanium film deposited onto FTO glass substrate. N-doping was achieved by annealing of TiO₂ film in ammonia. X-ray Photoelectron Spectroscopy measurements showed that nitrogen was substitutionally incorporated in the TiO₂ matrix, with the N:Ti concentration ratio of 1:100. The doping changed the optical properties of the material in such a way that the absorption edge was shifted from 380 nm to 507 nm, as observed from diffuse reflectance spectra. The influence of the microwave (MW) irradiation on the synthesized CdS quantum dots and their optical properties was investigated. It was shown that the diameter of CdS nanoparticles was increased due to releasing of S^2- ions from dimethyl sulfoxide (DMSO) as a consequence of the MW treatment. The (N)TiO₂ films were then used as substrates for matrix assisted pulsed laser deposition of the CdS quantum dots with DMSO as a matrix. The laser parameters for the deposition were optimized in order to preserve the nanotubular structure open, the latter being an important feature of this type of photoanode. The structure obtained under optimized conditions has an additional absorption edge shift, reaching 603 nm.     

Effect of TiO2 on UV stability of polymeric binder films used in waterborne facade paints

The effect of two TiO₂ polymorphs with different optical activity (rutile and anatase) on UV-stability of four polymeric binders used in water-borne paints is described. The latexes employed in this study are based on acrylic, styrene–acrylic, vinyl acetate and vinyl acetate–butyl acrylate (co)polymers. Thin films obtained from the respective latexes doped with 1% TiO₂ were exposed to accelerated weathering by irradiation with UV light (λ ≥ 275 nm) and analysed using electrokinetic potential (ζ-potential), FTIR ATR spectroscopy, SEM microscopy and contact angle. The study shows that while rutile particles dispersed evenly in all the polymer matrices, the anatase remained partly aggregated. Despite markedly different optical properties, both titania polymorphs showed similar and minor effects on accelerated weathering of all the polymeric binders. The trends in surface charge and wettability remained the same as for the undoped films. More pronounced changes were observed in spectroscopic measurements, which probe the films deeper into the bulk. For the styrene-based films a photochemical interaction between TiO₂ and the styrene chromophore resulted in quenching the absorption band of the titania's photogenerated surface-trapped holes.     

Control of refractive index by annealing to achieve high figure of merit for TiO2/Ag/TiO2 multilayer films

We modified the refractive index (n) of TiO₂ by annealing at various temperatures to obtain a high figure of merit (FOM) for TiO₂/Ag/TiO₂ (45 nm/17 nm/45 nm) multilayer films deposited on glass substrates. Unlike the as-deposited and 300 °C-annealed TiO₂ films, the 600 °C-annealed sample was crystallized in the anatase phase. The as-deposited TiO₂/Ag/as-deposited TiO₂ multilayer film exhibited a transmittance of 94.6% at 550 nm, whereas that of the as-deposited TiO₂/Ag/600 °C-annealed TiO₂ (lower) multilayer film was 96.6%. At 550 nm, n increased from 2.293 to 2.336 with increasing temperature. The carrier concentration, mobility, and sheet resistance varied with increasing annealing temperature. The samples exhibited smooth surfaces with a root-mean-square roughness of 0.37–1.09 nm. The 600 °C-annealed multilayer yielded the highest Haacke's FOM of 193.9×10⁻³ Ω⁻¹.     

Effect of Si doping on the photocatalytic activity and photoelectrochemical property of TiO2 nanoparticles

Si-doped TiO₂ nanoparticles with anatase crystalline phase were prepared by a hydrothermal method using acetic acid as the solvent. Photoelectrochemical studies showed that the photocurrent value for the 15% Si-doped TiO₂ electrode (54.4 μA) was much higher than that of the pure TiO₂ electrode (16.7 μA). In addition, the 15% Si-doped TiO₂ nanoparticles displayed the highest photocatalytic activity under ultraviolet light irradiation. So doping suitable amount of Si in TiO₂ nanoparticles was profitable for transferring photogenerated electrons and inhibiting the recombination of photogenerated electrons and holes. As a result, the photocatalytic activity of TiO₂ nanoparticles was improved.     

Polyimide/nano-TiO2 hybrid films having benzoxazole pendent groups: In situ sol–gel preparation and evaluation of properties

Polyimide/titania (PI/TiO₂) nanocomposite films have been successfully fabricated through the in situ formation of TiO₂ within a PI matrix via sol–gel method. Poly(amic acid) (PAA), which is the precursor of PI, was successfully synthesized by mixing pyromellitic dianhydride (PMDA), with equimolar amount of a diamine monomer having a pendent benzoxazole unit and two flexible ether linkages in N,N-dimethylformamide (DMF) solvent. Tetraethyl orthotitanate [Ti(OEt)₄] and acetylacetone were then added to the resulted PAA. After imidization at high temperature, PI/TiO₂ hybrid films were formed. The structure and morphology of the hybrid nanocomposites with different titania contents (0 wt%, 5 wt%, 10 wt%, and 15 wt%) were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. The results indicate that the TiO₂ nanoparticles were homogeneously dispersed in the hybrid films. The thermogravimetric analysis of nanocomposites confirms the improvement in the thermal stability with the increase in the percentage of titania nanoparticle. Transmission electron microscopy showed that the nanoparticles with an average diameter of 25–40 nm were dispersed in the polymer matrix.     

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.     

Investigation of antibacterial activity and related mechanism of a ruthenium(II) polypyridyl complex

Metal based drug represents a novel group of antimicrobial agents with potential application for the control of bacterial and fungal infections. In this study, we fabricate ruthenium(II) complex containing the polypyridyl ligands, namely [Ru(phen)₂(tip)] (ClO₄)₂ (RuTh) and carefully investigate its antibacterial activities against both the Gram-negative (G −) bacteria Escherichia coli (E. coli) and the Gram-positive (G +) bacteria Staphylococcus aureus (S. aureus). The RuTh is more toxic to S. aureus than that to E. coli. The antibacterial effects of RuTh are further investigated, revealing specific mechanisms. The results demonstrate that RuTh functions as a bactericide against the E. coli and S. aureus through disrupting bacterial cell wall integrity and its cellular components.     

Direct multipulse laser processing of titanium oxide–graphene oxide nanocomposite thin films

Nanocomposite thin films consisting of titanium oxide (TiO₂) nanoparticles (NPs) and graphene oxide (GO) platelets were deposited by a spin-coating technique. The obtained films were submitted to direct laser irradiation using a frequency quadrupled Nd:YAG (λ=266 nm, τ_FWHM≅3 ns, ν=10 Hz) laser source. The effect of the laser processing conditions, as laser fluence value and number of subsequent laser pulses incident onto the same target location, on the surface morphology, crystalline structure, and chemical composition of the TiO₂/GO nanocomposite thin films was systematically investigated. The laser fluence values were maintained below the vaporization threshold of the irradiated composite material. With the increase of the laser fluence and number of incident laser pulses melting and coalescence of the TiO₂ NPs into inter-connected aggregates as well as rippling of the GO platelets take place. The gradual reduction of GO platelets and the onset of anatase to rutile phase transition were observed at high laser fluence values.     

The effects of deposition temperature on structure and dielectric properties of Ba0.6Sr0.4TiO3 thin films produced by pulsed laser deposition

The effects of deposition temperature on orientation, surface morphology and dielectric properties of the thin films for Ba_0.6Sr_0.4TiO₃ thin films deposited on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition were investigated. X-ray diffraction patterns revealed a (2 1 0) preferred orientation for all the films. With rising substrate temperature from 650 °C to 700 °C, the crystallinity and crystal grain size of the films increase, the relative dielectric constant increases, but the dielectric losses have not obvious difference. The film deposited at 350 °C and annealed at 700 °C has strongly improved roughness and dielectric permittivity compared with the film only deposited directly at 700 °C. Three distinct relaxation processes within tan(δ) were found for the Ba_xSr_1?xTiO₃ film: a broadened process of the film relaxation, an intermediate peak which originates from Maxwell–Wagner–Sillars polarization, and an extremely slow process ascribed to leak current. The complex dielectric permittivity and loss can be fitted by an improved Cole–Cole model corresponding to a stretched relaxation function.     

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.