TiO2 nanofibers doped with rare earth elements and their photocatalytic activity

In the present study rare earth doped (Ln³⁺–TiO₂, Ln = La, Ce and Nd) TiO₂ nanofibers were prepared by the sol–gel electrospinning method and characterized by XRD, SEM, EDX, TEM, and UV-DRS. The photocatalytic activity of the samples was evaluated by Rhodamine 6G (R6G) dye degradation under UV light irradiation. XRD analysis showed that all the synthesized pure and doped titania nanofibers contain pure anatase phase at 500 °C but at 700 °C it shows both anatase and rutile phase. XRD result also shows that Ln³⁺-doped titania probably inhibits the phase transformation. The diameter of nanofibers for all samples ranges from 200 to 700 nm. It was also observed that the presence of rare-earth oxides in the host TiO₂ could decrease the band gap and accelerate the separation of photogenerated electron–hole pairs, which eventually led to higher photocatalytic activity. To sum up, our study demonstrates that Ln³⁺-doped TiO₂ samples exhibit higher photocatalytic activity than pure TiO₂ whereas Nd³⁺-doped TiO₂ catalyst showed the highest photocatalytic activity among the rare earth doped samples.     

Preparation of Pt-loaded TiO2 nanofibers by electrospinning and their application for WGS reactions

Preparation of Pt-loaded TiO₂ nanofibers and their catalytic performance for water gas shift (WGS) reactions have been explained in this work. The Pt-loaded TiO₂ nanofibers were obtained by electrospinning poly-ethylene oxide (PEO) aqueous solutions containing Ti(OH)_n slurry and Pt nanoparticles at room temperature, followed by calcination at 773 K for 4 h. The calcined nanofibers were rougher than the nanofibers of PEO/Ti(OH)_n/Pt due to the PEO degradation and oxidation of Ti(OH)_n to TiO₂. Diameters of the Pt-loaded TiO₂ nanofibers ranged between 200 and 900 nm. Catalytic activity of the Pt-loaded TiO₂ nanofibers for water gas shift (WGS) reactions was evaluated and it was observed that their activity was 5–7 times higher than that of a bulk catalyst. Such improvement is attributed to the larger surface area of the nanofiber catalyst compared to that of the bulk catalyst. To the best of our knowledge, this is the first demonstration of a synthesis of Pt-loaded TiO₂ nanofibers from a Ti(OH)_n nanoparticle slurry using electrospinning and its application to WGS reactions.     

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.     

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.     

Iron-doped TiO2 nanotubes with high photocatalytic activity under visible light synthesized by an ultrasonic-assisted sol-hydrothermal method

A series of iron-doped anatase TiO₂ nanotubes (Fe/TiO₂ NTs) catalysts with iron concentrations ranging from 0.88 to 7.00 wt% were prepared by an ultrasonic-assisted sol-hydrothermal process. The structures and the properties of the fabricated Fe/TiO₂ NTs were characterized in detail and photocatalytic activity was examined using a reactive brilliant red X-3B aqueous solution as pollutant under visible light. The lengths of the NTs were determined to range from 20 nm to 100 nm. The incorporation of the iron ions (Fe³⁺) into the TiO₂ nanotubes shifted the photon absorbing zone from the ultraviolet (UV) to the visible wavelengths, reducing the band gap energy from 3.2 to 2.75 eV. The photocatalytic activity of the Fe/TiO₂ NTs was 2–4 times higher than the values measured for the pure TiO₂ nanotubes.     

Photocatalytic hydrogen production from methanol aqueous solution under visible-light using Cu/S–TiO2 prepared by electroless plating method

Cu was loaded on the S-doped TiO₂ by electroless plating method. The prepared Cu/S–TiO₂ exhibited high photocatalytic activity for hydrogen generation, and the yield is up to 7.5 mmol h^− 1 g^− 1cat in methanol solution. Their physical structure and chemical properties were characterized by UV–Vis, XRD, XPS and EXAFS. The copper species were CuO and Cu₂O, and the sample showed excellent visible light absorption ability. Comparing with the sample prepared by chemical reducing method, the electroless plated copper on S–TiO₂ was highly dispersed, which could facilitate photo-generated charges capture, transfer and separation.     

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.     

Bismuth titanates candidates for high permittivity LTCC

Bi₂O₃–TiO₂ composites are known to possess attractive microwave dielectric properties. However, producing LTCC analogues with equally promising dielectric properties is problematic. Here, we show that judicious choice of both TiO₂ starting powders and dopants can produce composites with excellent properties. Three TiO₂ powders were evaluated: 1 μm-anatase, 1 μm-rutile and a nanosized (30 nm) mixture of 75–25 anatase-rutile. The best dielectric properties were obtained by using uncalcined nanosized anatase/rutile with Bi₂O₃ powder. By doping this Bi₂O₃–TiO₂ powder mixture with 0.112 wt.% CuO dielectric properties of Q × f = 9000 GHz, ɛ_r = 80 and τ_f = 0 ppm/K (at 300 K) were obtained at a sintering temperature of 915 °C.     

Effect of TiO2 nanoparticles on the antibacterial and physical properties of polyethylene-based film

TiO₂ nanoparticles and their application in packaging systems have attracted a lot of attention because of its antimicrobial activity. In this work, effect of TiO₂ nanoparticles on the antibacterial and physical properties of polyethylene (PE)-based film was investigated. Results indicated that the antibacterial activity of TiO₂-incorporated PE films should be due to the killing effect property of TiO₂ nanoparticles against microorganisms. The TiO₂-incorporated PE film exhibited more effective antibacterial activity for Staphylococcus aureus. The antibacterial activity to inactivate Escherichia coli or S. aureus was improved by UV irradiation. The inhibition ratio of TiO₂-incorporated PE films sample irradiated for 60 min by UV light was improved significantly, which were 89.3% for E. coli and 95.2% for S. aureus, respectively, compared to that of TiO₂-PE film without UV irradiation. The analysis of physical properties revealed that TiO₂ nanoparticles increased the tensile strength and elongation at break of PE-based film. The climate resistance of nano-TiO₂ films is greatly enhanced, compared to that of the blank PE film. Water vapor transmission increased from 18.1 to 24.6 g/m²·24 h with the incorporation of TiO₂ nanoparticles. Results revealed that PE based film incorporating with TiO₂ nanoparticles have a good potential to be used as active food packaging system.     

Effect of CuO/MnO additives on microstructure and microwave dielectric properties of 3ZrO2-3TiO2-ZnNb2O6 ceramics

The effect of CuO/MnO additives on phase composition, microstructures, sintering behavior, and microwave dielectric properties of 3ZrO₂-3TiO₂-ZnNb₂O₆ (3Z-3T-ZN) ceramics prepared by conventional solid-state route were systematically investigated. CuO/MnO doped ceramics exhibited a main phase of α-PbO₂-structured ZrTi₂O₆ and a secondary phase of rutile TiO₂. SEM results showed that the grain size of MnO doped ceramics became larger with increasing amount of dopants. The presence of CuO/MnO additives effectively reduced the sintering temperature of 3Z-3T-ZN ceramics to 1220 °C. MnO doped into ceramics could enhance the Q×f values significantly. The 0.5 wt% CuO doped 3Z-3T-ZN ceramics with 0.5 wt% of MnO, sintered at 1220 °C for 4 h, was measured to show superior microwave dielectric properties, with an ε_r of 41.02, a Q×f value of 44,230 GHz (at 5.2 GHz), and τ_f value of +2.32 ppm/°C.     

5.1% Apparent quantum efficiency for stable hydrogen generation over eosin-sensitized CuO/TiO2 photocatalyst under visible light irradiation

A dye-sensitized CuO incorporated TiO₂ catalyst was found to be an active photocatalyst for the photocatalytic hydrogen production from water under visible light (> 420 nm) irradiation in the presence of electron donors such as triethanolamine, acetonitrile and triethylamine. The stronger adsorption of eosin Y on the CuO incorporated TiO₂ catalyst by multidentate complexation than on pure TiO₂ was proved by the method of spectrophotometry, namely, the addition of CuO strongly improved the adsorption capability of TiO₂ toward eosin dye and this effect led to a high quantum efficiency of eosin-sensitized CuO/TiO₂ for photocatalytic water splitting. The electrons excited from the sensitizer molecules which were strongly adsorbed both on TiO₂ and CuO by the visible light injected into the conduction band (CB) of both TiO₂ and CuO, the electrons in CB of TiO₂ subsequently transferred to CB of CuO, which resulted in a build-up of excess electrons in the conduction band of CuO. Consequently, the accumulation of excess electrons in CuO causes a negative shift in the Fermi level of CuO. As a result of that, the significant enhancement of apparent quantum yield (∼5.1%) and a good stability was obtained over the dye-sensitized 1.0 wt% CuO/TiO₂ photocatalyst.     

Promoting role of transition metal oxide on ZnTiO3–TiO2 nanocomposites for the photocatalytic activity under solar light irradiation

Transition metal oxide (Fe₂O₃, Co₃O₄ and CuO) loaded ZnTiO₃–TiO₂ nanocomposites were successfully prepared by solid state dispersion method. The structural, morphological and optical properties of samples were characterized by TGA/DTA, XRD, BET, FT-IR, DRS, PL, XPS and SEM techniques. The photocatalytic activity of samples was investigated by degradation of 4-chlorophenol in water under sunlight. The Fe₂O₃ loaded sample was found to exhibit much higher photocatalytic activity than the other composite powders. 7Fe₂O₃/ZnTi sample has the highest percentage of 4-chlorophenol degradation (100%) and highest reaction rate (1.27 mg L⁻¹ min⁻¹) was obtained in 45 min. The enhancement of photocatalytic activity for ZnTiO₃–TiO₂ sample with Fe₂O₃ addition may be attributed to its small particle size, the presence of more surface OH groups, lower band gap energy than other samples in this paper and the presence of more hexagonal ZnTiO₃ phase in the morphology.     

Mesoporous CuO/TixZr1 − xO2 catalysts for low-temperature CO oxidation

Mesoporous CuO/Ti_xZr_1 − xO₂ catalysts were prepared by a surfactant-assisted method, and characterized by N₂ adsorption/desorption, TEM, XPS, in-situ FTIR and H₂-TPR. The catalysts exhibited high specific surface area (S_BET = 241 m²/g) and uniform pore size distribution. XPS and in-situ FTIR displayed that Cu⁺ and Cu²⁺ species coexisted in the catalysts. The CuO/Ti_xZr_1 − xO₂ catalysts presented obviously higher activity in CO oxidation reaction than the CuO/TiO₂ and CuO/ZrO₂ catalysts. Effect of molar ratios of Ti to Zr and calcination temperature on catalytic activity was investigated. The CuO/Ti_0.6Zr_0.4O₂ catalyst calcined at 400 °C exhibited excellent activity with 100% CO conversion at 140 °C.     

Enhanced blue-light photocatalytic H2 production using CdS nanofiber

The photocatalytic activity of CdS nanosphere, nanorod or nanofiber was investigated for the hydrogen production from either methanol–water or sulfide/sulfite solution irradiated with blue light. The nanostructured CdS were obtained by the precipitation method at high ethylenediamine content solutions and at moderate temperature conditions. The synthesized CdS nanofiber using CS₂ as sulfur source presented the highest photocatalytic activity for the H₂ production (954 μmol h^− 1 g^− 1) in the reaction system with four blue LED lamps. This high photoactivity was attributed to the quantum confinement effect generated by the small particle size of the nanofibers (D = ~ 5 nm and L = 25 nm).     

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.     

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.     

Synergic effect of cation doping and phase composition on the photocatalytic performance of TiO2 under visible light

The synergic effect of cation doping and phase composition for the further improvement of the photocatalytic activity of TiO₂ under visible light is reported for the first time. Fe^3 + and Sn^4 + co-doped TiO₂ with optimized phase composition were synthesized through a simple soft-chemical solution method. The visible-light-driven photocatalytic activity of Fe^3 + and Sn^4 + co-doped TiO₂ was 5 times of that of Evonik P25 TiO₂ using degradation of methylene blue as model reaction. The synthesized photocatalysts were characterized by powder X-ray diffraction, UV–Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, ¹¹⁹Sn Mössbauer spectroscopy, and X-ray absorption fine structure spectroscopy. It is indicated that Sn^4 + doping can facilitate the phase transition from anatase to rutile. The different ratios of anatase and rutile can be achieved by tuning the amount of Sn^4 + doped into the lattice. Furthermore, the doping of Sn^4 + into TiO₂ lattice can stabilize the phase composition when Fe^3 + is co-doped. In the Fe^3 + and Sn^4 + co-doped TiO₂, Sn^4 + is mainly used to tune and stabilize the phase composition of TiO₂ and Fe^3 + acts as a doping cation to narrow the band gap of TiO₂. Both band gap and phase composition of TiO₂ can be tuned effectively by the simultaneous introduction of Fe^3 + and Sn^4 +. The synergic effect of optimized phase composition (anatase/rutile = 25/75) and narrowed band gap should be the two main reasons for the promoted photocatalytic activity of TiO₂ under visible light.     

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.     

Low temperature hydrothermal synthesis of monodispersed flower-like titanate nanosheets

Monodispersed flower-like titanate superstructure was successfully prepared by simple hydrothermal process without any surfactant or template. N₂-sorption analysis, scanning electron microscopy (SEM), and X-ray diffraction (XRD) observation of as-synthesized product revealed the formation of flower-like titanate with diameter of about 250–450 nm and BET surface area (S_BET) of 350.7 m² g^?1. Upon thermal treatment at 500 °C, the titanate nanosheets were converted into anatase TiO₂ with moderate deformation of their structures. The as-prepared flower-like titanate showed high photocatalytic activity for H₂ evolution from water splitting reaction. Moreover, the sample heat treated at 500 °C exhibited higher photocatalytic activity than that of commercial TiO₂ anatase powder (ST-01).     

Low temperature sintering of lead-free Bi0.5(Na0.82K0.18)0.5TiO3 piezoelectric ceramics by co-doping with CuO and Nb2O5

Effect of excess CuO additive on the sintering behavior and piezoelectric properties of Bi_0.5(Na₈₂K_0.18)_0.5TiO₃ ceramics was investigated. The addition of small amount of excess CuO as low as 1 mol% was quite effective to lower the sintering temperature (T_s) of BNKT ceramics down to 975 °C while their piezoelectric properties were degraded by Cu doping. However, the electric field-induced strain was markedly enhanced by further addition of Nb₂O₅ with CuO without elevating T_s. The normalized strain S_max/E_max of 427 pm/V was obtained with a specimen sintered with 0.02 mol CuO and 0.03 mol Nb₂O₅ in excess.