Enhanced photoelectrochemical properties and photocatalytic activity of porous TiO2 films with highly dispersed small Au nanoparticles

Small Au nanoparticles (NPs) with mean diameter of 4.1 nm were highly deposited on TiO₂ films via a simple electrostatic self-assembly method. The physically separated Au NPs, with a high surface density of 6.3 × 10¹¹ NPs/cm², were mainly distributed on the top layer of porous TiO₂ films. The deposition of Au NPs induced a negative shift (~ 100 mV) of the apparent flat band potential of Au-TiO₂ electrodes. The charge separation efficiency of the TiO₂ electrode increased from 72.1% to 88.5% by dispersing Au NPs. Whatever redox species were present in the electrolyte, the Au-TiO₂ electrode had higher photovoltage than the TiO₂ electrode. The photovoltage was very sensitive to added redox species such as O₂, O₃, and methanol, and the effect of adsorbed redox species on electron accumulation was discussed. The electrochemical impedance spectroscopic measurements revealed that the charge transfer resistance (R_ct) of Au-TiO₂ films was reduced to 16% of bare TiO₂ electrode, and the decreased R_ct corresponded to the increased photocatalytic activity of Au-TiO₂ films. The beneficial role of uniformly dispersed small Au NPs on the charge separation was discussed. By modifying TiO₂ films with small Au NPs, the photocatalytic activity of TiO₂ films for formaldehyde degradation increased about 2.5 times.     

Microscale meshes of Ti3O5 nano- and microfibers prepared via annealing of C-doped TiO2 thin films

A new technique to produce microscale Ti₃O₅ nano- and microfiber meshes is proposed. When a 3 wt% carbon-doped TiO₂ film on Si(1 0 0) was annealed at 1000 °C in wet nitrogen (0.8%H₂O), the amorphous TiO₂ phase gave rise to crystalline phases of λ-Ti₃O₅ (75%) and rutile + trace of TiO_2−xC_x (25%). From Raman and FTIR Spectroscopy results, it was concluded that rutile is formed at the inner layer located at the interface between the mesh and the Si that was located away from the surface such that the meshes of nano- and microfibers are predominantly composed of Ti₃O₅ grown from the reaction of rutile with Si to form Ti₃O₅ and SiO₂. On the other hand, it was noteworthy that the microscale mesh of nano- and microfibers showed increased photoluminescence compared with amorphous TiO₂. The PL spectrum which had a broad band in the visible spectrum, fitted as three broad Gaussian distributions centered at 571.6 nm (∼2.2 eV), 623.0 nm (∼2.0 eV) and 661.9 nm (∼1.9 eV).     

Surface treatment of TiO2 films for dye-sensitized solar cells using atmospheric-pressure non-equilibrium DC pulse discharge plasma jet

In this paper, we report the utilization of the DC pulse discharge plasma jet technique as a means for the preparation of titanium oxide (TiO₂) films on fluorine dope tin oxide (FTO) coated glass substrates used for dye-sensitized solar cells (DSCs). The TiO₂ film made on these experimental bases exhibited the BET specific surface area of 95 m²/g, the pore volume of 0.3 cm²/g and the TEM particle size of ∼25 nm. The DSCs made by the TiO₂ film exhibited an energy conversion efficiency of 5.7% at 100 mW/cm² light intensity. Consequently, we believe that the optimization between the specific surface area and photocurrent density of TiO₂ film was achieved by the plasma surface treatment which also contributed to the improvement of energy conversion efficiency of DSCs.     

Flame-made single phase Zn2TiO4 nanoparticles

Using zinc naphthenate and titanium tetra isopropoxide (1:1 mol.%) dissolved in ethanol as precursors, single phase Zn₂TiO₄ nanoparticles were synthesized by the flame spray pyrolysis technique. The Zn₂TiO₄ nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. The average diameter of Zn₂TiO₄ spherical particles was in the range of 5 to 10 nm under 5/5 (precursor/oxygen) flame conditions. All peaks can be confirmed to correspond to the cubic structure of Zn₂TiO₄ (JCPDS No. 25-1164). The SEM result showed the presence of agglomerated nanospheres with an average diameter of 10-20 nm. The crystallite sizes of spherical particles were found to be in the range of 5-18 nm from the TEM image. An average BET equivalent particle diameter (d_BET) was calculated using the density of Zn₂TiO₄.     

Charge recombination reduction in dye-sensitized solar cells by depositing ultrapure TiO2 nanoparticles on “inert” BaTiO3 films

Ultrapure TiO₂ nanoparticles (∼5 nm in size) were supported on “inert” BaTiO₃ films by TiCl₄ treatment, which was used to fabricate dye-sensitized solar cells (DSSCs). The optimized electrode, designated as BaTiO₃/TiO₂(4), was obtained upon four cycles of TiCl₄ treatment. DSSC with BaTiO₃/TiO₂(4) electrode exhibits superior power conversion efficiency (PCE) compared to that with conventional anatase TiO₂ (∼25 nm in size) electrode. The interfacial charge recombination kinetics was investigated by electrochemical impedance spectroscopy (EIS) and intensity-modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). In contrast to DSSC with anatase TiO₂ electrode, the dramatically enhanced electron lifetime for DSSC with BaTiO₃/TiO₂(4) electrode could be attributed to the decrease of recombination reaction at the TiO₂ photoelectrode/electrolyte interface. It is proposed that the lower interfacial charge recombination can be related to the relatively shallower trap distributions in DSSC with BaTiO₃/TiO₂(4) electrode.     

Synthesis and electrophoretic deposition of hydrothermally synthesized multilayer TiO2 nanotubes on conductive filters

TiO₂ nanotubes were synthesized by the decomposition of titanium isopropoxide in water and the calcination at 450 °C for 2 h to form TiO₂ nanoparticles. The synthesized TiO₂ in anatase form nanoparticles were processed hydrothermally in 10 M NaOH solution at 130 °C for 24 h to obtain multilayer TiO₂ nanotubes. TEM analysis revealed that the diameters of the tubes were around 10 nm and they are in the length of 100 nm. Subsequently, colloidal suspensions containing 1% wt. Of TiO2 nanotubes were prepared with TEA and butanol and electrophoretic deposition (EPD) experiments were conducted in order to obtain coatings on Ni and carbon filters using a deposition time of 10 min. and an applied voltage of 65 V. It is also shown that multilayer TiO₂ nanotubes having outer diameter around 10 nm and inner diameters of 4.3 nm can be produced using the described technique. EPD is also shown to be an effective technique to coat three dimensional components, such as Ni and C filters for various applications including water and air purification systems.     

Fabrication of TiO2 nanotube film by well-aligned ZnO nanorod array film and sol-gel process

High density TiO₂ nanotube film with hexagonal shape and narrow size distribution was fabricated by templating ZnO nanorod array film and sol-gel process. Well-aligned ZnO nanorod array films obtained by aqueous solution method were used as template to synthesize ZnO/TiO₂ core-shell structure through sol-gel process. Subsequently, TiO₂ nanotube array films survived by removing the ZnO nanorod cores using wet-chemical etching. Polycrystalline anatase TiO₂ nanotube films were ∼ 1.5 μm long and ∼ 100 nm in inter diameter with a wall thickness of ∼ 10 nm.     

Mass-synthesized anatase titania nanocrystals with tunable size and shape via sol-gel in organic solvents with adsorbing ligands

High-quality anatase titania (TiO₂) nanoparticles, nanowires, and nanorods have been mass-synthesized by the modified sol-gel method in the saturated fatty alcohol, acid, and amine systems with adsorbing ligands, respectively. These obtained quasi-spherical TiO₂ nanoparticles showed the mean size of 16.5 nm with a narrow size-distribution. These resulting TiO₂ nanowires had the uniform diameter of 3.8 nm with the length range of 80-180 nm, and TiO₂ nanorods had the uniform diameter of 7.5 nm with the length range of 40-70 nm, respectively. We demonstrated that the shapes, sizes and morphology of these anatase TiO₂ nanocrystals could be controlled systematically by adjusting certain reaction parameters, such as the kind of organic solvents, the alkyl length of organic solvents, and the reaction time. It has been found that the shape of the products was primarily determined by the kind of organic solvents. However, their sizes, size-distributions, and morphology could be controlled by adjusting the alkyl length of organic solvents and the reaction time. Based on the analysis of all experiment results, we have investigated the growth mechanism of these TiO₂ nanocrystals with the different shape. Meanwhile, this synthetic method can be extended further for the preparation of other oxides nanocrystals.     

Rapid synthesis of TiO2 hollow nanostructures with crystallized walls by using CuO as template and microwave heating

In this paper, TiO₂ hollow nanostructures with anatase walls have been rapidly fabricated by using CuO as template and microwave heating. These TiO₂ hollow nanostructures have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Experimental results showed that the TiO₂ shell transformed from amorphous to anatase phase in 3 min, induced by the hot CuO core under microwave irradiation. The diameter of TiO₂ hollow nanostructures is about 50-80 nm, and the length is about 200-300 nm. The thickness of the shell is about 3 nm. This method is promising to be used to synthesize other nanomaterials with a hollow nanostructure.     

Polythiophene thin films electrochemically deposited on sol-gel based TiO2 for photovoltaic applications

In this work, the influence of titanium dioxide (TiO₂) thin films on the efficiency of organic photovoltaic devices based on electrochemically synthesized polythiophene (PT) was investigated. TiO₂ films were produced by sol-gel methods with controlled thickness. The best TiO₂ annealing condition was determined through the investigation of the temperature influence on the electron charge mobility and resistivity in a range between 723 K and 923 K. The PT films were produced by chronoamperometric method in a 3-electrode cell under a controlled atmosphere. High quality PT films were produced onto 40 nm thick TiO₂ layer previously deposited onto fluorine doped tin oxide (FTO) substrate. The morphology of PT films grown on both substrates and its strong influence on the device performance and PT minimum thickness were also investigated. The maximum external quantum efficiency (IPCE) reached was 9% under monochromatic irradiation (λ = 610 nm; 1 W/m²) that is three orders of magnitude higher than that presented by PT-homolayer devices with similar PT thickness. In addition, the open-circuit voltage (V_oc) was about 700 mV and the short-circuit current density (J_sc) was 0.03 A/m² (λ = 610 nm; 7 W/m²). However, as for the PT-homolayer also the TiO₂/PT based devices are characterized by antibatic response when illuminated through FTO. Finally, the Fill Factor (FF) of these devices is low (25%), indicating that the series resistance (R_s), which is strongly dependent of the PT thickness, is too large. This large R_s value is compensated by TiO₂/PT interface morphology and by FTO/TiO₂ and TiO₂/PT interface phenomena producing preferential paths in which the internal electrical field is higher, improving the device efficiency.     

Photocatalytic activity of pulsed laser deposited TiO2 thin films in N2, O2 and CH4

We report on pulsed laser deposition of TiO₂ films on glass substrates in oxygen, methane, nitrogen and mixture of oxygen and nitrogen atmosphere. The nitrogen incorporation into TiO₂ lattice was successfully achieved, as demonstrated by optical absorption and XPS measurements. The absorption edge of the N-doped TiO₂ films was red-shifted up to ∼ 480 nm from 360 nm in case of undoped ones.The photocatalytic activity of TiO₂ films was investigated during toxic Cr(VI) ions photoreduction to Cr(III) state in aqueous media under irradiation with visible and UV light. Under visible light irradiation, TiO₂ films deposited in nitrogen atmosphere showed the highest photocatalytic activity, whereas by UV light exposure the best results were obtained for the TiO₂ structures deposited in pure methane and oxygen atmosphere.     

Structure and CO gas sensing properties of electrospun TiO2 nanofibers

Titanium dioxide (TiO₂) nanofibers were fabricated by electrospinning a hybrid solution, which is a mixture of the TiO₂ sol precursor, polymer, and solvent. The structure and gas sensing properties of TiO₂ nanofibers were investigated. By calcining at 600 °C, the polymeric components were decomposed and a multi-layered random network structure of TiO₂ nanofibers was obtained. Polycrystalline TiO₂ nanofibers consist of tetragonal anatase and rutile TiO₂ phases. The diameter ranged from 400 nm to 500 nm and the grain size was about 15 nm. The TiO₂ nanofibers-based sensor exhibited response to CO concentration as low as 1 ppm at 200 °C.     

Influence of calcination ambient and film thickness on the optical and structural properties of sol-gel TiO2 thin films

Influence of both calcination ambient and film thickness on the optical and structural properties of sol-gel derived TiO₂ thin films have been studied. X-ray diffraction results show that prepared films are in an anatase form of TiO₂. Films calcined in argon or in low vacuum (∼2 × 10⁻¹ mbar) are found to be smaller in crystallite size, more transparent at low wavelength region of ∼300-450 nm, denser, have higher refractive index and band gap energy compared to air-calcined films. Scanning electron microscopic study reveals that surfaces of TiO₂ films calcined in argon or in low vacuum are formed by densely packed nano-sized particulates. Presence of voids and signs of agglomeration can be seen clearly in the surface microstructure of air-calcined films. In the thickness range ∼200-300 nm, band gap energy and crystallite size of TiO₂ films remain practically unaffected with film thickness but refractive index of thinner film is found to be marginally higher than that of thicker film. In this work, it has been shown that apart from temperature and soaking time, partial pressure of oxygen of the ambient is also an important parameter by which crystallite size, microstructure and optical properties of the TiO₂ films may be tailored during calcination period.     

(Eu-Nb)-codoped TiO2 nanopowders synthesized via Ar/O2 radio frequency thermal plasma oxidation processing: Phase composition and photoluminescence properties through energy transfer

(Eu³⁺-Nb⁵⁺)-codoped TiO₂ nanopowders have been prepared by Ar/O₂ radio frequency (RF) thermal plasma oxidizing liquid precursor mists, with various addition contents of dopants (molar ratio of Eu³⁺:Nb⁵⁺ = 1:1). Characterizations have been performed by the combined studies of XRD, TEM, Raman spectra, UV-vis spectroscopy, and excitation and PL spectra. The plasma-generated nanopowders mainly consist of anatase and rutile polymorphs. Doping Nb⁵⁺ cannot have appreciable influence on Eu³⁺ solubility (0.5 at.%) in the TiO₂ host lattice, but can significantly inhibit the increase of rutile weight fraction for TiO₂. 617 nm PL intensity at 350 nm indirect excitation through energy transfer is considerably weaker than that at 467 nm direct excitation, indicating that a defect state level in the TiO₂ host lattice might be lowered below the excited state of Eu³⁺ by doping Nb⁵⁺, which is conceivable from a relatively large amount of oxygen deficiencies yielded in the TiO₂ host lattice.     

Influence of cobalt ion implantation on optical properties of titanium dioxide thin films

Nano-crystalline TiO₂ thin films were synthesized by using sol-gel and spin-coating techniques on glass substrates for photo-catalytic applications. Prior to deposition, a TiO₂ colloidal suspension was synthesized by microwave-induced thermal hydrolysis of the titanium tetrachloride aqueous solution. In this study, the deposited TiO₂ coating with a grain size of 13 ± 2 nm was uniform without aggregation. Co ion implantation into the as-calcined TiO₂ thin films was conducted with fluences of 1 × 10¹⁵-1 × 10¹⁶ doses/cm² at 40 keV. In addition to the emission of TiO₂, the photoluminescence study showed the presence of another Co-related optical center at 405 nm in the Co-implanted TiO₂ thin films. Due to the strong capability of forming impurity compounds between the energetic cobalt ions and TiO₂, the photoluminescence emission and UV-Vis absorption efficiencies were improved.     

Rapid synthesis of homogeneous MnO2/multi-wall carbon nanotubes nanostructure and its electrochemical capacitive behavior

A homogeneous composite of MnO₂/multi-wall carbon nanotubes (MnO₂/MWCNTs) was rapidly and efficiently synthesized by a redox reaction of MnO₄⁻ and Mn²⁺ on the MWCNTs under ultrasonic irradiation. The structure and morphology of the obtained MnO₂ and MnO₂/MWCNTs composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Electrochemical investigation indicated that the maximum specific capacitance of the MnO₂/MWCNTs composite, measured by galvanostatic charge-discharge test, was 315 F g^− 1, compared to the pristine MnO₂ (192 F g^− 1) and MWCNTs electrode (25 F g^− 1), showing the synergistic effect of MWCNTs and MnO₂. The homogeneous hybrid nanostructure and the good conductivity of MWCNTs were considered to be responsible for its preferable electrochemical performances.     

Fabrication of TiO2 nanotubes by anodization of Ti thin films for VOC sensing

Ti thin films were anodized in aqueous HF (0.5 wt.%) and in polar organic (0.5 wt.% NH₄F + ethylene glycol) electrolytes to form TiO₂ nanotube arrays. Ti thin films were deposited on microscope glass substrates and then anodized. Anodization was performed at potentials ranging from 5 V to 20 V for the aqueous HF and from 20 V to 60 V for the polar organic electrolytes over the temperatures range from 0 to 20 °C. The TiO₂ nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX). It has been observed that anodization of the deposited Ti thin films with aqueous HF solution at 0 °C resulted in nanotube-type structures with diameters in the range of 30-80 nm for an applied voltage of 10 V. In addition, the nanotube-type structure is observed for polar organic electrolyte at room temperature at the anodization voltage higher than 40 V. The volatile organic compound (VOC) sensing properties of TiO₂ nanotubes fabricated using different electrolytes were investigated at 200 °C. The maximum sensor response is obtained for carbon tetrachloride. The sensor response is dependent on porosity of TiO₂. The highest sensor response is observed for TiO₂ nanotubes which are synthesized using aqueous HF electrolyte and have very high porosity.     

Microwave assisted fast fabrication of Fe3O4-MWCNTs nanocomposites and their application as MRI contrast agents

Uniform Fe₃O₄ nanoparticles with diameters of 3-5 nm are successfully decorated onto the external walls of multiwall carbon nanotubes (MWCNTs) by in situ high-temperature decomposition of Fe(acac)₃ in polyol solution under the irradiation of microwave. With this method, reaction time of forming Fe₃O₄-MWCNTs nanocomposites has been significantly shortened to 15 min. The resulting Fe₃O₄-MWCNTs nanocomposites show superparamagnetic property at room temperature and can be remained as stable aqueous dispersion for 2 months. Longitudinal relaxivity (r₁) and transverse relaxivity (r₂) of the magnetic MWCNTs are 8.34 Fe mM⁻¹ S⁻¹ and 146 Fe mM⁻¹ S⁻¹ respectively. The much higher r₂ value and the obvious change in the gray scale of MR images confer the Fe₃O₄-MWCNTs nanocomposites as potential candidates for T₂-weighted MRI contrast agents.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

Residual stress effect on luminescence of CeBr3 and its application as a pressure-memory material

Photoluminescence spectra of CeBr₃ powder compacts with various compaction pressures have been measured under ambient conditions and they are found significantly redshifted compared with those of the original powder by nearly 20 nm (∼1440 cm⁻¹) at the compaction pressure of ∼1.0 GPa. The spectral shift increases extremely rapidly with the compaction pressure and then plateaus at ∼1.0 GPa. The observed residual stress effect of the CeBr₃ powder on the luminescence spectra is much larger than that of the EuCl₂ powder reported previously. The luminescence peak wavelength of the compact can be easily tuned between 360 and 380 nm by simply changing the compaction pressure applied to the CeBr₃ powder. With a very large residual stress effect of the CeBr₃ powder on the photoluminescence spectra, this material would make a good pressure-memory material which may be used as a kind of pressure sensor in high-pressure experiments.