Morphology and photocatalytic activity of highly oriented mixed phase titanium dioxide thin films

Thin TiO₂ films on quartz substrates were prepared by spin coating of undoped and metal-ion-doped Sol-Gel precursors. These films were characterised by Scanning Electron Microscopy, Laser Raman Microspectroscopy, X-ray Diffraction and UV-Vis Transmission. The photocatalytic performances of the films were assessed by the photo-degradation of methylene-blue in aqueous solution under UV irradiation. Films exhibited a high degree of orientation and a thermal stabilization of the anatase phase as a result of substrate effects. In the absence of dopants, the rutile phase formed as parallel bands in the anatase which broadened as the transformation progressed. TiO₂ films doped or co-doped with transition metals exhibited the formation of rutile in segregated clusters at temperatures under ~ 800 °C as a result of increased levels of oxygen vacancies. Photocatalytic activity of the films synthesised in this work was low as likely a result of poor TiO₂ surface contact with dye molecules in the solution. The presence of transition metal dopants appears detrimental to photocatalytic activity while the performance of mixed phase films was not observed to differ significantly from single phase material.     

Effect of peak power in reactive high power impulse magnetron sputtering of titanium dioxide

The effect of peak power in a high power impulse magnetron sputtering (HiPIMS) reactive deposition of TiO₂ films has been studied with respect to the deposition rate and coating properties. With increasing peak power not only the ionization of the sputtered material increases but also their energy. In order to correlate the variation in the ion energy distributions with the film properties, the phase composition, density and optical properties of the films grown with different HiPIMS-parameters have been investigated and compared to a film grown using direct current magnetron sputtering (DCMS). All experiments were performed for constant average power and pulse on time (100 W and 35 μs, respectively), different peak powers were achieved by varying the frequency of pulsing. Ion energy distributions for Ti and O and its dependence on the process conditions have been studied. It was found that films with the highest density and highest refractive index were grown under moderate HiPIMS conditions (moderate peak powers) resulting in only a small loss in mass-deposition rate compared to DCMS. It was further found that TiO₂ films with anatase and rutile phases can be grown at room temperature without substrate heating and without post-deposition annealing.     

N-doped TiO2/ZnO composite powder and its photocatalytic performance for degradation of methyl orange

The N-doped TiO₂/ZnO composite powder with a molar ratio of Ti to Zn of 3/1 was prepared via sol–gel process and then ammonia treated with NH₃ mass fractions of 0%, 7%, and 28% for 24 h at room temperature followed by thermal calcinations in air for 2 h at various temperatures of 500, 600, and 700 °C. The as-prepared composite powder was characterized in detail through thermo-gravimetric analyzer, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The results showed that the phase transformation of anatase to rutile has been successfully retarded via the ammonia treating process, leading to the presence of anatase phase in the composite. The particle crystallization of the composite powder was significantly promoted with the increase of the calcining temperature. The photocatalysis evaluation through MO degradation revealed an enhanced photocatalytic activity for the composite powder that might be related to the good crystallization, the presence of anatase phase, and the particle size reduction of the powder.     

Preparation of polyaniline–titanium dioxide hybrid materials in supercritical CO2

Polyaniline–titanium dioxide (PANI–TiO₂) hybrid materials were synthesized in supercritical CO₂ using two different methods. In the first method, separately synthesized TiO₂ particles were mixed with aniline to perform polymerization in supercritical CO₂. The second method included the preparation of aniline–TiO₂ hybrids through a sol–gel reaction of titanium isopropoxide in the presence of aniline. Further polymerization of aniline–TiO₂ hybrids in supercritical CO₂ produced PANI–TiO₂ hybrid particles. The final products showed the intrusion of PANI into the internal structure of TiO₂. The PANI–TiO₂ hybrid materials were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), electrical conductivity (EC), Fourier-transform infrared (FT-IR) and X-ray diffraction (XRD) measurements. PANI–TiO₂ nano-composites synthesized with the first method showed a relatively low electrical conductivity of 3.78 × 10⁻² S/cm at 20 °C. TGA suggested that the particles contained 40.6% TiO₂ by mass and showed a strong interaction at the interface of TiO₂ and PANI. The electrical conductivity of the hybrid particles produced using the second method increased to 7.75 × 10⁻² S/cm and the TGA results showed 34.4% TiO₂ by mass. Through SEM and TEM analyses it was confirmed that the PANI has been interpenetrated into the three-dimensional network of the TiO₂ when the second method was used.     

Comparative study on the photocatalytic behaviour of titanium oxide thermal sprayed coatings from powders and suspensions

This work presents a study of the microstructures and photocatalytic behaviour of titanium oxide coatings obtained by thermal spraying of agglomerated nanopowders and suspensions. Fine TiO₂ Degussa P25 nanopowder, generally considered as the reference material in photocatalytic applications, was used as the material feedstock. HVOF process and suspension thermal spraying were used to prepare photocatalytic titania coatings. The coatings were mainly characterised by means of SEM and X-ray diffraction. The photocatalytic performance was evaluated based on decolouration of the pink dye Rhodamine B and degradation of gaseous acetaldehyde. A lower degree of pollutant degradation was found for deposits prepared by HVOF spraying of granules due principally to the low content of the photocatalytically active phase, i.e. anatase. Complete photocatalytic degradation of the organic compounds was recorded for the suspension-sprayed coatings. Based on the current results, suspension thermal spraying appears to be the better choice for preparing photocatalytically active titanium oxide surfaces for the removal of organic pollutants.     

Investigations on composition and morphology of electrochemical conversion layer/titanium dioxide deposit on stainless steel

In this study, the formation and characterization of conversion coatings modified by a sol-gel TiO₂ deposit were investigated as a way to develop a new photocatalyst for water and air depollution. The conversion coating, characterised by strong interfacial adhesion, high roughness and high surface area facilitates the sol-gel deposition of titania and enhances its adhesion to the substrate. The conversion treatment is carried out in an acid solution. Observation by Scanning Electron Microscopy (SEM) reveals a rough surface with pores and cavities. According to SIMS measurements, the thickness of the initial conversion layer is evaluated at about 1.5 μm. On this pre-functionalised support, the titanium dioxide was deposited by the sol-gel method. The roughness measurements coupled with SIMS analysis allowed a precise evaluation of the surface state of the final layers. The coating consists of two layers: a TiO₂ outer layer and an inner layer containing iron chromium oxides. Characterization by X-ray diffraction (XRD) showed the existence of the TiO₂ anatase structure as the main compound.     

Magonelli相二氧化钛光阳极在量子点敏化太阳能电池中的性能研究

使用产量与性能稳定的工业化生产的黑色二氧化钛制备成QDSSCs的光阳极,通过性能表征与理论计算研究,与常见的Anatase TiO2,Rutile TiO2展开了全面对比。结果表明,由于氧空位的引入导致Magonelli Ti8O15的导带底下降,带隙收缩,吸收光谱范围由紫外光扩展至可见光与近红外,而且吸光度也极大提高。其阻抗也随之减小,明显低于Anatase TiO2,Rutile TiO2。这导致其组装的QDSSCs的性能获得极大提升,尤其是FF与Jsc表现最为显著,最终获得了PCE 5.3%优异成绩。这项工作进一步丰富了黑色二氧化钛的研究,在工业化生产黑色二氧化钛组装太阳能电池领域取得了阶段性成果,为太阳能电池的生产提供了新的可能。     

Effect of Na diffusion from glass substrate on the microstructural and photocatalytic properties of post-annealed TiO2 films synthesised by reactive sputtering

Amorphous columnar TiO₂ films were synthesised by reactive sputtering on cold soda–lime glass substrates (TiO₂/glass films). The films were subsequently heated in order to crystallise the photoactive anatase phase. The surface chemical composition assessment demonstrates the occurrence of metallic Na, the amount of which increases with the annealing temperature. The evolution of the structural, microstructural and photocatalytic properties of the films with the annealing temperature was investigated and compared to that of TiO₂ films deposited in same conditions, but on glass pre-coated with a SiN_x diffusion barrier (TiO₂/SiN_x/glass films). Once crystallised, both series of TiO₂ films exhibit [001] preferential orientation corresponding to the columnar growth. Grain coalescence associated to a modification of the grain shape is only observed in TiO₂/glass films for annealing temperatures higher than 450 °C, whereas neither microstructural nor structural change is observed in TiO₂/SiN_x/glass films. The Na-contaminated TiO₂ films exhibit different photocatalytic behaviour with the annealing temperature compared to the Na-free TiO₂ films. A discussion is finally based on these differences.     

Amphiphilic and photocatalytic behaviors of TiO2 nanotube arrays on Ti prepared via electrochemical oxidation

Amphiphilic TiO₂ nanotube arrays (TiO₂ NTs) were fabricated through electrochemical oxidation of Ti in solution containing H₃PO₄ and NaF. Scanning electron microscopic analysis shows that the as-prepared TiO₂ NTs have an average pore diameter of 100 nm and a wall thickness of 15 nm. The electrochemical oxidation of Ti can be divided into four stages. In the first stage, when the potential is very low, oxygen formation and Ti dissolution are the major reactions. The second stage corresponds to a slightly higher potential, but less than 2.5 V. In this stage, the formation of TiO₂ film occurs. When the potential is increased to the even higher range from 2.5 V to 6 V, the TiO₂ film dissolves and nanoporous surface structure is generated. This is the third stage. Further increase of the potential enters stage four. The high potentials cause the self-organization of the nanostructure and allow the formation of well-aligned TiO₂ NTs. We also found that the change in surface condition of Ti by annealing heat treatment affects the film dissolution kinetics. As compared with TiO₂ thin film, the TiO2 NTs show higher photocatalytic activity on decomposing Rhodamine B. The surface of the TiO₂ NTs can be wetted by both water and oil. Such an amphiphilic property comes from the capillary effect of the nanochannel structure of the TiO₂ NTs. Because of the amphiphilic property and the photocatalytic activity, we conclude that the TiO₂ NTs have the capability of self-cleaning.     

Ionic compounds lamination reaction and characteristics of photosensitive copper indium sulfide on titania nanotube arrays

This study investigates using an inorganic photosensitive CuInS₂ (CIS) coating instead of an organic dye on TiO₂ nanotube arrays (TNAs). The stoichiometric characteristics by use of various deposition parameters such as precursor concentrations (0.1 M, 0.05 M, and 0.01 M) and deposition cycles (1-60 cycles) are then analyzed in relation to the crystallinity and photosensitivity. TNAs are synthesized by anodic oxidation of Ti metal, modified by the TiO₂ film, and are subsequently annealed at 450 °C for 30 min, producing what are named T-TNAs. They show high photocatalytic efficiency and photosensitivity under UV-illumination. The photosensitive CIS coatings on the T-TNAs are processed by an ionic compounds lamination reaction (ICLR) method. The more immersion cycles and the higher the precursor concentration of copper sulfide, the more CIS peeled off as precipitates formed, which result in less indium sulfide deposition being required for reacting with the copper sulfide to reach stoichiometry. Near stoichiometric CIS can be obtained by controlling the precursor concentration and deposition cycles of the ICLR process. Good crystallinity and n-type characteristics are achieved by controlling the precursor concentrations and deposition cycles suitably to obtain a high current density. When the Cu/In ratio is adjusted for n-type characteristics, the current density reaches at least 300 μA/cm² under visible light illumination intensity of 100 mW/cm².     

An efficient protection of stainless steel against corrosion: Combination of a conversion layer and titanium dioxide deposit

In the present work, a novel process has been developed to improve the corrosion properties of ferritic stainless steels. Titanium oxide coatings have been deposited onto stainless steel by sol-gel process after a pre-functionalization of the substrate in a conversion bath. Gel titania was prepared by hydrolysis of a titanium butoxide through a sol-gel process. Duplex systems “conversion layer/uniform TiO₂ coating” have been prepared on stainless steels using a dipping technique and thermal post-treatments at 450 °C. The preparation of sol-gel coatings with specific chemical functions offers tailoring of their structure, texture and thickness and allows the fabrication of large coatings. The morphology and structure of the coatings were analysed using scanning electron microscopy with field effect gun (SEM-FEG), Mass spectroscopy of secondary ions (SIMS) and X-ray diffraction (XRD). The anticorrosion performances and the ageing effects of the coatings have been evaluated in neutral and aggressive media by using several normalized tests.The results show that the conversion layer was not sufficient to protect steel but sol-gel TiO₂ coatings, anchored on the metal substrate via the conversion layer, show good adhesion with the substrate and act as a very efficient protective barrier against corrosion. So, duplex layers with TiO₂ nanoparticle coatings on steels exhibit an excellent corrosion resistance due to a ceramic protective barrier on metal surface. Analysis of the data indicates that the films act as geometric blocking layers against exposure to the corrosive media and increase drastically the lifetime of the substrate.     

Effect of Nd2O3 addition on the surface phase of TiO2 and photocatalytic activity studied by UV Raman spectroscopy

TiO₂ modified with Nd₂O₃ (Nd-TiO₂) nanoparticles were prepared by a co-precipitation method and utilized as the photocatalysts for the degradation of Rhodamine B (RhB). The influence of Nd₂O₃ on the bulk and surface phase, surface area, particle size, and optical response of TiO₂ was investigated by X-ray diffraction (XRD), UV Raman spectroscopy, transmission electron microscopy (TEM), BET, and UV-visible diffuse reflectance spectra. It is found that the crystalline phase and phase composition in the bulk and surface region of Nd-TiO₂ calcined at high temperatures can be tuned by changing the amount of Nd₂O₃. Based on the results from XPS, EDX, XRD, and UV Raman spectra, it is assumed that Nd³⁺ ions do not enter the TiO₂ lattice, but highly disperse onto the Nd-TiO₂ particle surface in the form of Nd₂O₃ crystallites. These crystallites inhibit the agglomeration, growth in crystal size, and anatase-to-rutile phase transformation of TiO₂. In the photocatalytic degradation of RhB reaction, Nd-TiO₂ nanoparticles with higher surface area and wider optical response are more reactive in case of the same surface anatase phase. When the mixed phases of anatase and rutile exist in the surface region of Nd-TiO₂, the synergetic effect over surface area and optical response is the important parameter which determines optimal photocatalytic activity.     

Synthesis of CeO2/TiO2 nanoparticles by laser ablation of Ti target in cerium (III) nitrate hexahydrate (Ce(NO3)3·6H2O) aqueous solution

A new synthesis process, laser ablation in an aqueous solution of target material, was applied to synthesize nanostructured CeO₂/TiO₂ catalyst particles. Reactivity within the laser plume (plasma) can be used to synthesize CeO₂ from an aqueous solution, 2 M cerium (III) nitrate hexahydrate (Ce(NO₃)₃·6H₂O) aqueous solution, and to fabricate TiO₂ from Ti target. CeO₂/TiO₂ nanoparticles were successfully synthesized by the laser ablation of Ti target in 2 M cerium (III) nitrate hexahydrate (Ce(NO₃)₃·6H₂O) aqueous solution. Laser ablation of Ti in a liquid environment and chemical reactions of the solution within a plasma plume are discussed.     

Influence of electrodeposition potential,TiO2 nanoparticles and chromium (III) inhibitor addition on the corrosion protection performance of organosilane coating on aluminium

In this work, the anticorrosion properties of phenyl trimethoxysilane (PTMS) films coated on aluminium 5000 series alloys were studied. PTMS films were deposited at various cathodic potentials. The optimum electrodeposition potential was found to be ?0.8?V vs. SCE. The coatings were also modified by different amounts of nano-TiO₂. In order to introduce corrosion inhibition and a self-repair property of the PTMS film, the addition of chromium (III) corrosion inhibitor in the presence of nano-TiO₂ was studied. The anticorrosion performance of coatings was investigated in a 3.5 wt.% NaCl solution. At optimum deposition potential, the ‘critical’ nano-TiO₂ and Cr(III) contents were both observed, under which the obtained PTMS coatings show the highest anticorrosion performance. The surface morphologies of PTMS coatings were examined by scanning electron microscopy. The results showed that the coatings deposited at ?0.8?V vs. SCE, from 20?ppm of nano-TiO₂ and 0.003 M Cr(III) inhibitor present uniform and compact morphologies.     

Selective single pulse femtosecond laser removal of alumina (Al2O3) from a bilayered Al2O3/TiAlN/steel coating

We studied surface modification of a double layer protective coating on steel induced by single fs laser pulse irradiation in ambient air. The outer alumina (Al₂O₃) layer, which protects against aggressive environments, was 1.7 μm thick and the titanium aluminum nitride (TiAlN) layer in contact with the steel surface had a thickness of 1.9 μm. The pulses (λ = 775 nm, τ = 200 fs) were generated by a Ti:sapphire laser source. The pulse energy was varied from 0.32 μJ to 50 μJ, corresponding to an incident laser fluence of 0.11 J cm^− 2 to 16.47 J cm^− 2. The surface damage threshold was found to be 0.20 J cm^− 2 and the alumina layer removal was initiated at 0.56 J cm^− 2. This selective ablation of alumina was possible in a wide range of fluences, up to the maximum applied, without ablating the TiAlN layer beneath.     

Theoretical study on the electronic and optical properties of (N, Fe)-codoped anatase TiO2 photocatalyst

Electronic and optical properties of pure, N-doped, Fe-doped and (N, Fe)-codoped anatase TiO₂ were evaluated, respectively, by using the density functional theory. The results indicate that the elemental doping narrows the band gap of TiO₂ and realize its visible-light response activity; and incorporation of Fe into N-doped TiO₂ further increases the photocatalytic activity under visible-light irradiation compared with that of the N-doped TiO₂.     

Influence of MnO2 on the sintering behavior and magnetic properties of NiFe2O4 ferrite ceramics

The samples with small amounts of MnO₂ (0, 0.5, 1.0, 1.5, 2.0, and 2.5 wt%, respectively) were prepared via ball-milling process and two-step sintering process from commercial powders (i.e. Fe₂O₃, NiO and MnO₂). Microstructural features, phase transformation, sintering behavior and magnetic properties of Mn-doped NiFe₂O₄ composite ceramics have been investigated by means of scanning electron microscopy (SEM), differential thermal analyzer, X-ray diffraction (XRD), thermal dilatometer and vibrating sample magnetometer (VSM) respectively. The XRD analysis and the result of differential thermal analysis indicate that the reduction of MnO₂ into Mn₂O₃ and the following reduction of Mn₂O₃ into MnO existed in sintering process. No new phases are detected in the ceramic matrix, the crystalline structure of the ceramic matrix is still NiFe₂O₄ spinel structure. Morphology and the detecting result of thermal dilatometer show that MnO₂ can promote the sintering process, the temperature for 1 wt% MnO₂-doped samples to reach the maximum shrinkage rate is 59 °C lower than that of un-doped samples. For 1 wt% MnO₂-doped samples, the value of the saturation magnetization (M_s) and coercivity (H_c) is 15.673 emu/g and 48.316 Oe respectively.     

Composition dependence of structure and optical properties of Cu2ZnSn(S,Se)4 solid solutions: An experimental study

The evolution of structure and optical properties of Cu₂ZnSn (S_xSe_1−x)₄ (CZTSSe) solid solutions in a wide composition range (0 ≤ x ≤ 1) has not been fully elucidated. We have performed comprehensive characterization on the CZTSSe powders with different S/Se ratios, which were synthesized by the solid state reaction method. X-ray diffraction patterns demonstrate that the lattice parameters a and c of CZTSSe decrease lineally when S replace Se gradually, which obeys the Vegard's rule. The A₁ Raman modes of CZTSSe show a typical two-mode behavior. The absorption spectra reveal that the band gap of CZTSSe can be tuned monotonously between 0.96 and 1.5 eV with almost linearity, and a small band gap bowing constant (b ≈ 0.08 eV) is deduced.     

The role of microstructure on pesting during oxidation of MoSi2 and Mo(Si,Al)2 at 773 K

The pesting behavior of MoSi₂ and Mo(Si,Al)₂ has been examined in air at 773 K to clarify the origin and mechanism of pesting phenomena and the effect of aluminum on pesting phenomena. The initial cracks play a much more important role than the grain boundaries and the initial oxide layer in pesting. Mo and Si oxidize to amorphous Mo-Si-O simultaneously with about a 200% volume expansion. Therefore, large stress appears at the cracktips and induce many new cracks. MoO₃ vaporizes from the Mo-Si-O layer on the external surface and crack surfaces causing the oxides in the initial cracks to become porous. Oxygen has a short-circuit path to enter the sample in the cracks. Therefore, the partial pressure of oxygen is sufficiently high to allow oxidation of Mo in the materials. The platelet-like MoO₃ grows on the external surface and also in the cracks. Finally, the sample distintegrates into powder. Pesting of Mo(Si,Al)₂ occurs in the same way, however, its rate is much lower than that of MoSi₂. The role of Al is to decrease the initial crack density of the samples from the melt. Other effects of Al might be to decrease the oxygen flux toward the oxide-intermetallic interface and to increase the plasticity of the amorphous oxide being formed in the cracks.     

The studies of phase relation, microstructure, magnetic transition, magnetocaloric effect in (Gd1−xErx)5Si1.7Ge2.3 compounds

The phase relation, microstructure, Curie temperatures (T_C), magnetic transition, and magnetocaloric effect of (Gd_1−xEr_x)₅Si_1.7Ge_2.3 (x = 0, 0.05, 0.1, 0.15, and 0.2) compounds prepared by arc-melting and then annealing at 1523 K (3 h) using purity Gd (99.9 wt.%) are investigated. The results of XRD patterns and SEM show that the main phases in those samples are mono-clinic Gd₅Si₂Ge₂ type structure. With increase of Er content from x = 0 to 0.2, the values of magnetic transition temperatures (T_C) decrease linearly from 228.7 K to 135.3 K. But the (Gd_1−xEr_x)₅Si_1.7Ge_2.3 compounds display large magnetic entropy near their transition temperatures in a magnetic field of 0-2 T. The maximum magnetic entropy change in (Gd_1−xEr_x)₅Si_1.7Ge_2.3 compounds are 24.56, 14.56, 16.84, 14.20, and 13.22 J/kg K⁻¹ with x = 0, 0.05, 0.1, 0.15, and 0.2, respectively.