STM imaging of a model surface of Ru(4,4′-dicarboxy-2,2′-bipyridine)2(NCS)2 dye-sensitized TiO2 photoelectrodes

A TiO₂(1 1 0)-(1 × 1) surface was prepared in an ultra-high vacuum, transported in laboratory air, and observed with a scanning tunneling microscope (STM) operated in a vacuum of 10⁻⁴ Pa. Empty state images showed atomically flat terraces separated by single-height steps, on which 5-fold-coordinated surface Ti atoms were observed as spots arranged in a rectangular lattice. The Ru(4,4′-dicarboxy-2,2′-bipyridine)₂(NCS)₂ (N3) dye was adsorbed on the TiO₂ surface by immersing the TiO₂ wafer into an acetonitrile solution of the dye. In the empty state images, individual N3 molecules were observed as oval particles protruding by 0.6 nm from the TiO₂ surface. The oval shape elongated to the [1  0] directions was attributed to electron tunneling from tip to unoccupied states localized at the two carboxyl groups bound to the TiO₂ surface.     

Synthesis and characterization of hydroxyapatite/titania nanocomposites using in situ precipitation technique

Hydroxyapatite/titania nanocomposites were successfully synthesized by in situ precipitation of precursor matters from hydroxyapatite and titania at 70 °C with different hydroxyapatite/titania ratios. X-ray diffraction, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface, scanning and transmission electron microscopes were employed to characterize the prepared nanocomposite powders. X-ray diffraction results indicated that hydroxyapatite and anatase (TiO₂) were the major crystalline phases. By increasing the amount of titania nano-particles, Fourier transform infrared spectroscopy revealed that (PO₄)³⁻ bands at 567, 1033 cm⁻¹ decreased. Brunauer–Emmett–Teller surface results also showed a reduction in surface areas of nanocomposites. Transmission electron microscope observations revealed that the aspect ratio of hydroxyapatite/TiO₂ nanocrystals increased by increasing TiO₂ proportion in nanocomposites. The observed nanorod crystals tended to thin, elongated and plate-like in shape.     

Preparation of poly-o-phenylenediamine/TiO2/fly-ash cenospheres and its photo-degradation property on antibiotics

A series of poly-o-phenylenediamine/TiO₂/fly-ash cenospheres(POPD/TiO₂/fly-ash cenospheres) composites have been prepared from o-phenylenediamine and TiO₂/fly-ash cenospheres under various polymerization conditions. The properties of the samples were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), specific surface area (BET), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance spectrum (UV-vis DRS). Photocatalytic activity was studied by degradation of antibiotics waste water under visible light. The results indicate that the photo-induced method is viable for preparing modified photocatalysts, and the modified photocatalysts have good absorption in visible light range. The photocatalysts of POPD/TiO₂/fly-ash cenospheres which have good performance are prepared at pH 3 and 4, and the polymerized time around 40 min. When the photocatalysts are prepared under the conditions of pH 3 and polymerized time 40 min, the degradation rate of roxithromycin waste water could reach near 60%, and it indicates that the way of POPD modified TiO₂/fly-ash cenospheres to degrade the antibiotics waste water is viable.     

Preparation and electroactive properties of a PVDF/nano-TiO2 composite film

In the present study, poly(vinylidene fluoride) (PVDF)/nano-TiO₂ electroactive film was prepared by coating a substrate with an acetone/DMF solution, which was evaporated at a high temperature (110 °C). The crystallisation behaviour, dynamic mechanical properties and electroactive properties of this PVDF/nano-TiO₂ electroactive film were investigated. The cross-section and surface of the film were observed with a scanning electron microscope (SEM). X-ray diffraction (XRD) results showed that the film containing the PVDF β phase, the desired ferroelectric phase, was obtained by crystallising the mixed solution of nano-TiO₂ and PVDF at 110 °C, while the film containing the α phase was obtained from the crystallisation of the pure PVDF solution at the same temperature. It was found that the storage modulus, the room-temperature dielectric constant and the electric breakdown strength of the composite films were much higher than those of a pure PVDF film. TiO₂ improved the mechanical properties and electroactive properties of the film. The results indicate that PVDF/nano-TiO₂ composite films can be applied to the fabrication of self-sensing actuator devices.     

A simple and low temperature process for super-hydrophilic rutile TiO2 thin films growth

We investigate an environmentally friendly aqueous solution system for rutile TiO₂ violet color nanocrystalline thin films growth on ITO substrate at room temperature. Film shows considerable absorption in visible region with excitonic maxima at 434 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), UV-vis, water surface contact angle and energy dispersive X-ray analysis (EDX) techniques in addition to actual photo-image that shows purely rutile phase of TiO₂ with violet color, super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 3.15 ± 0.4 nm, characterize the films. Band gap energy of 4.61 eV for direct transition was obtained for the rutile TiO₂ films. Film surface shows super-hydrophilic behavior, as exhibited water contact angle was 7°. Strong visible absorption (not due to chlorine) leaves future challenge to use these films in extremely thin absorber (ETA) solar cells.     

Supercritical carbon dioxide-assisted preparation of palladium nanoparticles on cyclotriphosphazene-containing polymer nanospheres

Poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) nanospheres with average diameter of 410 nm were synthesized rapidly at room temperature and then homogeneously decorated with Pd nanoparticles through an inorganic reaction in supercritical carbon dioxide-ethanol solution using PdCl₂ as a metal precursor. The resultant Pd/PZS nanocomposites were morphologically and structurally characterized by means of scanning electron microscopy, transmission electron microscope equipped with energy-dispersive X-ray spectroscopy, and X-ray diffraction techniques. Characterization results showed that the Pd nanoparticles with good dispersibility could be well anchored onto the surfaces of the PZS nanospheres and the size of Pd nanoparticles could be controlled easily by varying the ethanol-reduction time.     

Efficient one-pot synthesis of Ag nanoparticles loaded on N-doped multiphase TiO2 hollow nanorod arrays with enhanced photocatalytic activity

The simultaneous Ag loaded and N-doped TiO₂ hollow nanorod arrays with various contents of silver (Ag/N-THNAs) were successfully synthesized on glass substrates by one-pot liquid phase deposition (LPD) method using ZnO nanorod arrays as template. The catalysts were characterized by Raman spectrum, field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscope (HRTEM), ultraviolet-vis (UV-vis) absorption spectrum and X-ray photoelectron spectroscopy (XPS). The results suggest that AgNO₃ additive in the precursor solutions not only can promote the anatase-to-rutile phase transition, but also influence the amount of N doping in the samples. The photocatalytic activity of all the samples was evaluated by photodegradation of methylene blue (MB) in aqueous solution. The sample exhibited the highest photocatalytic activity under UV light illumination when the AgNO₃ concentration in the precursor solution was 0.03 M, due to Ag nanoparticles acting as electron sinks; When the AgNO₃ concentration was 0.07 M, the sample performed best under visible light illumination, attributed to the synergetic effects of Ag loading, N doping, and the multiphase structure (anatase/rutile).     

Aerosol-assisted flow synthesis of WxTi1−xO2 solid solution spheres with enhanced photocatalytic activity

In this paper, W_xTi_1−xO₂ solid solutions (x = 0.000, 0.005, 0.010, 0.015, and 0.020) microspheres were synthesized with an aerosol-assisted flow synthesis method. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption, UV-vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the as-prepared catalysts were measured by the degradation of rhodamine B (RhB) under visible light irradiation (λ ≥ 420 nm). All the solid solutions exhibited higher photocatalytic activities than pure TiO₂ and the W_0.015Ti_0.985O₂ solid solution possessed the highest photocatalytic activity. The degradation constant of RhB on W_0.015Ti_0.985O₂ solid solution catalyst was about 15 times of that of the pure TiO₂ and 25 times of that of Degussa P25, respectively. This study provides an effective method to prepare visible light photocatalysts on a large scale.     

Structural, electrical and optical properties of TiO2 doped WO3 thin films

TiO₂ doped WO₃ thin films were deposited onto glass substrates and fluorine doped tin oxide (FTO) coated conducting glass substrates, maintained at 500 °C by pyrolytic decomposition of adequate precursor solution. Equimolar ammonium tungstate ((NH₄)₂WO₄) and titanyl acetyl acetonate (TiAcAc) solutions were mixed together at pH 9 in volume proportions and used as a precursor solution for the deposition of TiO₂ doped WO₃ thin films. Doping concentrations were varied between 4 and 38%. The effect of TiO₂ doping concentration on structural, electrical and optical properties of TiO₂ doped WO₃ thin films were studied. Values of room temperature electrical resistivity, thermoelectric power and band gap energy (E_g) were estimated. The films with 38% TiO₂ doping in WO₃ exhibited lowest resistivity, n-type electrical conductivity and improved electrochromic performance among all the samples. The values of thermoelectric power (TEP) were in the range of 23-56 μV/K and the direct band gap energy varied between 2.72 and 2.86 eV.     

Growth mode and electronic structure of Au nano-clusters on NiO(0 0 1) and TiO2(1 1 0)

The growth mode and electronic structure of Au nano-clusters grown on NiO and TiO₂ were analyzed by reflection high-energy electron diffraction, a field-emission type scanning electron microscope, medium energy ion scattering and photoelectron spectroscopy. Au was deposited on clean NiO(0 0 1)-1 × 1 and TiO₂(1 1 0)-1 × 1 surfaces at room temperature with a Knudsen cell at a rate of 0.25-0.35 ML/min (1 ML = 1.39 × 10¹⁵ atoms/cm²:Au(1 1 1)). Initially two-dimensional (2D) islands with thickness of one Au-atom layer grow epitaxially on NiO(0 0 1) and then neighboring 2D-islands link each other to form three-dimensional (3D)-islands with the c-axis oriented to the [1 1 1] direction. The critical size to form 3D-islands is estimated to be about 5 nm². The shape of the 3D-islands is well approximated by a partial sphere with a diameter d and height h ranging from 2.0 to 11.8 nm and from 0.95 to 4.2 nm, respectively for Au coverage from 0.13 to 4.6 ML. The valence band spectra show that the Au/NiO and Au/TiO₂ surfaces have metallic characters for Au coverage above 0.9 ML. We observed Au 4f spectra and found no binding energy shift for Au/NiO but significant higher binding energy shifts for Au/TiO₂ due to an electron charge transfer from Au to TiO₂. The work function of Au/NiO(0 0 1) gradually increases with increase in Au coverage from 4.4 eV (NiO(0 0 1)) to 5.36 eV (Au(1 1 1)). In contrast, a small Au deposition(0.15 to 1.5 ML) on TiO₂(1 1 0) leads to reduction of the work function, which is correlated with an electron charge transfer from Au to TiO₂ substrate.     

Modification of the electronic properties of the TiO2 (1 1 0) surface upon deposition of the ultrathin conjugated organic layers

A few nm thick 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and Cu-phthalocyanine (CuPc) overlayers were thermally deposited in situ in UHV onto TiO₂ (1 1 0) surface. Atomic composition of the surfaces under study was monitored using Auger electron spectroscopy (AES). The formation of the interfacial potential barrier and the structure of the unoccupied electronic states located 5-25 eV above the Fermi level (E_F) was monitored using a probing beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. The work function values upon the overlayer deposition changed from 4.6 to 4.9 eV at the PTCDA/TiO₂ (1 1 0) interface and from 4.6 to 4.3 eV at the CuPc/TiO₂ (1 1 0) interface. Band bending in the TiO₂ substrate, molecular polarization in the organic film and changes in the work function due to the change in the surface composition were found to contribute to the formation of the interfacial potential barriers. Oxygen admixture related peaks were observed in the AES and in the TCS spectra of the CuPc overlayers. A mechanism of the transformations in the PTCDA and CuPc overlayers on the TiO₂ (1 1 0) upon elevating temperature from 25 to 400 °C was suggested.     

Characterization and activity of visible-light-driven TiO2 photocatalyst codoped with lanthanum and iodine

The novel visible-light-activated La/I/TiO₂ nanocomposition photocatalyst was successfully synthesized using precipitation-dipping method, and characterized by X-ray powder diffraction (XRD), the Brunauer-Emmett-Teller (BET) method, transmission electron microscopy (TEM), thermogravimetry-differential scanning calorimetry (TG-DSC) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The photocatalytic activity of La/I/TiO₂ was evaluated by studying photodegradation of reactive blue 19 as a probe reaction under simulated sunlight irradiation. Photocatalytic experiment results showed that the maximum specific photocatalytic activity of the La/I/TiO₂ photocatalyst appeared when the molar ratio of La/Ti was 2.0 at%, calcined at 350 °C for 2 h, due to the sample with good crystallization, high BET surface area and small crystal size. Under simulated sunlight irradiation, the degradation of reactive blue 19 aqueous solution reached 98.6% in 80 min, which showed La/I/TiO₂ photocatalyst to be much higher photocatalytic activity compared to standard Degussa P25 photocatalyst. The higher visible light activity is due to the codoping of lanthanum and iodine.     

Understanding the solar photo-catalytic activity of TiO2-ITO nanocomposite deposited on low cost substrates

In this work, we report on the photo-catalytic properties of TiO₂-ITO nanocomposite deposited on low cost conventional clay ceramic substrates. The nanocomposite was formed by spraying a solution prepared from the P25 TiO₂ powder (Degussa) mixed with an organometallic paste of a dissolved combination of indium and tin. A TiO₂-ITO powder-like nanocomposite was prepared for X-ray diffraction (XRD) and transmission electron microscopy (TEM) characterization. The mean particle size of the TiO₂-ITO nanocomposite was found to be larger than that of pure TiO₂. The optical features of TiO₂-ITO-based layers (deposited on glass substrates) were investigated using UV-vis spectroscopy. The TiO₂-ITO nanocomposite deposited layers were found to have higher light absorption than the P25 TiO₂ powder. The photo-catalytic properties of the TiO₂-ITO nanocomposite (deposited on low cost clay ceramic substrates) were tested under solar irradiation using a well-known polluting dye. It was shown that the TiO₂-ITO nanocomposite exhibits higher degradation rates towards the pollutant dye than the P25 TiO₂ powder. The optical band gap of the TiO₂-ITO nanocomposite (2.79 eV) was found to be lower than that of pure TiO₂ (3.1 eV), while ITO (indium tin oxide) has a band gap of about 4.2 eV. ITO was found to be entirely transparent to sun light, while it exhibits a slight photo-catalytic activity, signifying the possible existence of an indirect photo-catalysis phenomenon (sensitized semiconductor photocalysis) and potential degradation (oxidation) of the pollutant through electron transfer from the dye to conduction band of the semiconductor. All photo-catalytic activity results were discussed in light of the optical band gap of the various compounds.     

Synthesis and characterization of TiO2 thin films coated on metal substrate

Nanostructured titanium dioxide (TiO₂) thin films have been prepared on metal substrates using a facile layer-by-layer dip-coating method. The phase structure and morphologies of preparing samples were characterized by means of X-ray powder diffraction (XRD) and field-emission scanning electron microscopy (FESEM). The results confirm that films are highly crystalline anatase TiO₂ and free from other phases of titanium dioxide. Scanning electron microscopy (SEM) shows that the nanoparticles are sintered together to form a compact structure. The electrical properties of samples were investigated by cutternt-voltage analysis, the result indicates that a rectifying junction between the nanocrystalline TiO₂ film and metal substrate was formed. The photoelectrochemical characteristics recorded under 1.5 AM illumination indicates that the as-fabricated thin film electrode possesses the highest photocurrent density at 450 °C, which is 1.75 mA/cm² at 0 V vs. Ag/AgCl.     

Thin film transistors based on TiO2 fabricated by using radio-frequency magnetron sputtering

This study demonstrates that nanocrystalline TiO₂ thin films were deposited on ITO/glass substrate by radio-frequency magnetron sputtering. Field-emission scanning electron microscope (FE-SEM) and atomic force microscopic (AFM) images showed the morphology of TiO₂ channel layer with grain size and root-mean-square (RMS) roughness of 15 and 5.39 nm, respectively. TiO₂ thin-film transistors (TFTs) with sputter-SiO₂ gate dielectric layer were also fabricated. It was found that the devices exhibited enhancement mode characteristics with the threshold voltage of 7.5 V. With 8-μm gate length, it was also found that the I_on/off ratio and off-state current were around 1.45×10² and 10 nA, respectively.     

Synthesis and electronic behaviors of TiO2/carbon clusters/Cr2O3 composite materials

Nano-structured TiO₂/carbon clusters/Cr₂O₃ composite material has been successfully obtained by the microwave treatment of a TiO(acac)/Cr(acac)₃/epoxy resin complex. The compositions of the composite materials were determined using ICP, elemental analysis and surface characterization by SEM-EDX, TEM and XRD. ESR spectral examinations suggest the possibility of an electron transfer in the process of TiO₂ → carbon clusters → Cr₂O₃ with an oxidation site at TiO₂ particles and a reduction site at Cr₂O₃ particles. The preliminary experimental results show that the calcined materials could decompose methylene blue under visible-light irradiation.     

Oriented single crystalline TiO2 nano-pillar arrays directly grown on titanium substrate in tetramethylammonium hydroxide solution

Oriented single crystalline titanium dioxide (TiO₂) nano-pillar arrays were directly synthesized on the Ti plate in tetramethylammonium hydroxide (TMAOH) solution by one-pot hydrothermal method. The samples were characterized respectively by means of field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD). Results showed that the TiO₂ nano-pillar with a tetrahydral bipyramidal tip grew vertically on the titanium substrate. HRTEM and Raman results confirmed that the TiO₂ nano-pillar arrays were single crystalline anatase. The controls of morphology, size, and orientation of the nano-pillar could be achieved by varying the solution concentration and hydrothermal temperature. Furthermore, the special morphology of the TiO₂ nano-pillar arrays was caused by the selectively absorption of the tetramethylammonium (TMA) through hydrogen bonds on the lattice planes parallel to (0 0 1) of anatase TiO₂. Less grain boundaries and direct electrical pathway for electron transferring were crucial for the superior photoelectrochemical properties of the single anatase TiO₂ nano-pillar arrays. This approach provides a facile in situ method to synthesize TiO₂ nano-pillar arrays with a special morphology on titanium substrate.     

Synthesis of narrow band gap (V2O5)x-(TiO2)1−x nano-structured layers via micro arc oxidation

V₂O₅-TiO₂ layers with a sheet-like morphology were synthesized by micro arc oxidation process for the first time. Surface morphology and topography of the layers were investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). Phase structure and chemical composition of the layers were also studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. It was revealed that the composite layers had a sheet-like structure average thickness of which was about 100 nm depending on the applied voltage. The layers consisted of anatase, rutile, and vanadium pentoxide phases fractions of which varied with the applied voltage. The optical properties of the layers were also examined employing a UV-vis spectrophotometer. It was found that the absorption edge of the grown composite layers shifted toward the visible wavelengths when compared to MAO-synthesized pure titania layers. The band gap energy of the composite layers was calculated as 2.58 eV. Furthermore, photo-catalytic performance of the layers was examined by measuring the decomposition rate of methylene blue under ultraviolet and visible irradiations. The results demonstrated that about 90% and 68% of methylene blue solution was decomposed after 120 min ultraviolet and visible irradiations over the composite layers, respectively.     

Synthesis and characterization of TiO2/Fe2O3 core-shell nanocomposition film and their photoelectrochemical property

TiO₂/Fe₂O₃ core-shell nanocomposition film has been fabricated via two-step method. TiO₂ nanorod arrays are synthesized by a facile hydrothermal method, and followed by Fe₂O₃ nanoparticles deposited on TiO₂ nanorod arrays through an ordinary chemical bath deposition. The phase structures, morphologies, particle size, chemical compositions of the composites have been characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and ultraviolet-visible (UV-vis) spectrophotometer. The results confirm that Fe₂O₃ nanoparticles of mean size ca. 10 nm coated on the surface of TiO2 NRs. After depositing Fe₂O₃, UV-vis absorption property is induces the shift to the visible-light range, the annealing temperature of 600 °C is the best condition for UV-vis absorption property of TiO₂/Fe₂O₃ nanocomposite film, and increasing Fe content, optical activity are enhanced one by one. The photoelectrochemical (PEC) performances of the as-prepared composite nanorods are determined by measuring the photo-generated currents under illumination of UV-vis light. The TiO₂ NRs modified by Fe₂O₃ show the photocurrent value of 1.36 mA/cm² at 0 V vs Ag/AgCl, which is higher than those of unmodified TiO₂ NRs.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.