Preparation and characterization of Fe-doped TiO2 on fly ash cenospheres for photocatalytic application

Fe³⁺-doped TiO₂ film deposited on fly ash cenosphere (Fe-TiO₂/FAC) was successfully synthesized by the sol-gel method. These fresh photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analyses (TGA). The XRD results showed that Fe element can maintain metastable anatase phase of TiO₂, and effect of temperature showed rutile phase appears in 650 °C for 0.01% Fe-TiO₂/FAC. The SEM analysis revealed the Fe-TiO₂ films on the surface of a fly ash cenosphere with a thickness of 2 μm. The absorption threshold of Fe-TiO₂/FACs shifted to a longer wavelength compared to the photocatalyst without Fe³⁺-doping in the UV-vis absorption spectra. The photocatalytic activity and kinetics of Fe-TiO₂/FAC with varying the iron content and the calcination temperatures were investigated by measuring the photodegradation of methyl blue (MB) during visible light irradiation. Compared with TiO₂/FAC and Fe³⁺-doped TiO₂ powder (Fe-TiO₂), the degradation ratio using Fe-TiO₂/FAC increased by 33% and 30%, respectively, and the best calcined temperature was 450 °C and the optimum doping of Fe/Ti molar ratio was 0.01%. The Fe-TiO₂/FAC particles can float in water due to the low density of FAC in favor of phase separation to recover these photocatalyst after the reaction, and the recovery test shows that calcination contributes to regaining photocatalytic activity of Fe-TiO₂/FAC photocatalyst.     

Reduction of FeO/Pt(1 1 1) thin films by exposure to atomic hydrogen

Using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS) and density functional theory (DFT) calculations we have studied the reduction of ultra-thin films of FeO(1 1 1) grown on Pt(1 1 1) after exposure to atomic hydrogen at room temperature. A number of new ordered, partly-reduced FeO_x structures are identified and as a general trend we reveal that all the reduced FeO_x structures incorporate 2-fold coordinated Fe atoms as opposed to the original 3-fold coordinated Fe atoms in the FeO film. We find that when all the Fe atoms are 2-fold O-coordinated the FeO_x surface structure is resistant to further reduction at room temperature. We observe that water easily dissociates on the most heavily reduced FeO_x, structure in contrast to the initially inert FeO film, and reveal that it is possible to partially re-oxidize the FeO_x film by heating the surface slightly in the presence of water.     

Preparation and characterization of TiO2 photocatalysts co-doped with iron (III) and lanthanum for the degradation of organic pollutants

Titanium dioxide photocatalysts co-doped with iron (III) and lanthanum were prepared by a facile sol-gel method. The structure of catalysts was characterized by X-ray diffraction (XRD), Raman spectroscopy, UV-vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were evaluated by the degradation of methylene blue in aqueous solutions under visible light (λ > 420 nm) and UV light irradiation. Doping with Fe³⁺ results in a lower anatase to rutile (A-R) phase transformation temperature for TiO₂ particles, while doping with La³⁺ inhibits the A-R phase transformation, and co-doping samples indicate that Fe³⁺ partly counteracts the effect of La³⁺ on the A-R transformation property of TiO₂. Fe-TiO₂ has a long tail extending up the absorption edges to 600 nm, whereas La-TiO₂ results in a red shift of the absorption. However, Fe and La have synergistic effect in the absorption of TiO₂. Compared with Fe³⁺ and La³⁺ singly doped TiO₂, the co-doped simple exhibits excellent visible light and UV light activity and the synergistic effect of Fe³⁺ and La³⁺ is responsible for improving the photocatalytic activity.     

Cr掺杂锐钛矿型TiO2（001）薄膜中Cr原子的直接观测

Imaging the doping elements is critical for understanding the photocatalytic activity of doped TiO₂ thin film. But it is still a challenge to characterize the interactions between the dopants and the TiO₂ lattice at the atomic level. Here, we use high angle annular dark-field/annular bright-field scanning transmission electron microscope (HAADF/ABF-STEM) combined with electron energy loss spectroscopy (EELS) to directly image the individual Cr atoms doped in anatase TiO₂(001) thin film from [100] direction. The Cr dopants, which are clearly imaged through the atomic-resolution EELS mappings while can not be seen by HADDF/ABF-STEM, occupy both the substitutional sites of Ti atoms and the interstitial sites of TiO₂ matrix. Most of them preferentially locate at the substitutional sites of Ti atoms. These results provide the direct evidence for the doping structure of Cr-doped A-TiO₂ thin film at the atomic level and also prove the EELS mapping is an excellent technique for characterizing the doped materials.     

The interaction of oxygen molecules with iron films studied with MIES,UPS and XPS

X-ray Photoelectron Spectroscopy (XPS), Metastable Induced Electron Spectroscopy (MIES) and Ultraviolet Photoelectron Spectroscopy (UPS) were applied to study the interaction of oxygen molecules with iron films. Supplementarily, iron oxide was investigated for comparison.With XPS from the Fe 2p_3/2 range contributions of metallic Fe as well as Fe²⁺ and Fe³⁺ can be distinguished. During the interaction with oxygen an oxide film is formed on the iron surface. Nevertheless, XPS still shows metallic contributions even for a surface which is saturated with more than 10⁴ L. The oxide film hinders the dissociation of further impinging oxygen molecules.The interaction of He* atoms with iron oxide surfaces during MIES is dominated by Auger Neutralization. This surprising result follows from the high work function and the fact that intrinsic defects result in a Fermi level pinning to the conduction band.     

Dynamical and structural properties of adsorbed water molecules at the TiO2 rutile-(110) surface: interfacial hydrogen bonding probed by ab-initio molecular dynamics

ABSTRACT

Ab-initio molecular dynamics (AIMD) simulations have been carried out to study a range of different and energetically-accessible adsorbed-water configurations and motifs for their vibrational and structural characteristics, in contact with rutile-(110) interfaces at 100?K. The radial pair distribution function between the titanium atoms at the interface and the hydrogen and oxygen atoms in the water monolayer show an orientation of the water molecules parallel to the surface of titania, and with hydrogen atoms pointed in the opposite direction to the surface. In some cases, a distinctive vibrational frequency region between 2500 and 3000?cm^?1 has also been observed, due to a strong dispersion interaction between water molecules. This behaviour is also seen in experimental studies of thin-film water coverage on TiO₂ surfaces.     

Properties of carbon and iron modified TiO2 photocatalyst synthesized at low temperature and photodegradation of acid orange 7 under visible light

The nanoparticles of TiO₂ modified with carbon and iron were synthesized by sol-gel followed solvothermal method at low temperature. Its chemical composition and optical absorption were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence emission spectroscopy (PL), UV-vis absorption spectroscopy, and electron paramagnetic resonance (EPR). It was found that carbon and iron modification causes the absorption edge of TiO₂ to shift the visible light region. Fe(III) cation could be doped into the matrix of TiO₂, by which could hinder the recombination rate of excited electrons/holes. Superior photocatalytic activity of TiO₂ modified with carbon and iron was observed for the decomposition of acid orange 7 (AO7) under visible light irradiation. The synergistic effects of carbon and iron in modified TiO₂ nanoparticles were responsible for improving visible light photocatalytic activity.     

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.     

结构相变对Fe掺杂TiO2薄膜室温铁磁性的影响

采用直流磁控溅射方法在玻璃基底上制备了不同Fe掺杂浓度的TiO₂薄膜, 并对其晶体结构和磁特性进行了研究.在所有掺杂样品中,均观察到了室温铁磁性, 磁性源于Fe离子与其近邻空间分布的空穴相互作用. 在掺杂量为7%的锐钛矿相薄膜中观察到了最大的磁化强度. 随着Fe掺杂浓度的进一步增加, TiO₂的晶体结构逐渐由锐钛矿相向金红石相转变,并且磁性减弱. 不同结构的TiO₂中Ti–O键长不同,导致替代的磁性Fe离子与空穴的作用强度发生改变, 进而使其磁性发生变化. 关键词： 稀磁半导体 结构相变 铁磁性     

Structural properties of Al2O3 dielectrics grown on TiN metal substrates by atomic layer deposition

We investigated on the structural properties of Al₂O₃ dielectrics grown on TiN metal substrates using an atomic layer deposition technique with tri-methyl-aluminum and either O₃ or H₂O as the precursor and oxidant, respectively. The structural and morphological features of these films were examined by atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy measurements. We find that Al₂O₃ dielectric films with the O₃ oxidant exhibit a rough morphology, a thick TiO₂ film, and a small amount of contaminants such as carbon and hydrogen. The reason for the rapid diffusion of oxygen atoms into the TiN lattice leads to the formation of TiO₂ layer on the TiN substrate. This is due to the higher oxidation potential of the O₃ compared to the H₂O.     

Asymmetry in electrical properties of Al‐doped TiO2 film with respect to bias voltage

The energy diagram of RuO₂/Al‐doped TiO₂/RuO₂ structures was estimated from the capacitance–voltage and leakage current density–voltage curves. The Al‐doping profile in TiO₂ film was varied by changing position of the atomic layer deposition cycle of Al₂O₃ during the atomic layer deposition of 9 nm‐thick TiO₂ film. The interface between the TiO₂ film and the RuO₂ electrode containing Al‐doping layer showed a higher Schottky barrier by 0.1 eV compared with the opposite interface without the doping layer. The evolution of various leakage current profiles upon increasing the bias with opposite polarity could be well explained by the asymmetric Schottky barrier. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Analysis of the production and clusterization of iron atoms under pulsed laser photolysis of Fe(CO)5

Atomic-resonance absorption spectroscopy is used to study the production and loss of iron atoms under dissociation of the Fe(CO)₅ vapor in a quartz reactor that is induced by the pulses of the KrF excimer laser. Iron atoms populate the ground state owing to the quenching of the excited states generated in the course of the laser photolysis and are detected using the resonance absorption at a wavelength of 385.99 nm. The effective quenching rates are in good agreement with the known rates of the quenching of metastable iron atoms by the Fe(CO)₅ molecules. It is demonstrated that a loss of iron atoms is related to the recombination with dimer and trimer formation and the secondary atomic reactions with the Fe(CO)₅, CO, and FeCO molecules. The rates of the main elementary reactions responsible for the loss of iron atoms are determined using the comparison of the experimental results and kinetic simulation data.     

Optical and hydrophilic properties of Cr doped TiO2-SiO2 nanostructure thin film

Cr doped TiO₂-SiO₂ nanostructure thin film on glass substrates was prepared by a sol-gel dip coating process. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structural and chemical properties of the films. A UV-vis spectrophotometer was used to measure the transmittance spectra of the thin film. The hydrophilicity of the thin film during irradiation and storage in a dark place was measured by a contact angle analyzer. The results indicated that Cr doping has a significant effect on the transmittance and super-hydrophilicity of TiO₂-SiO₂ thin film.     

Computer simulation of the hydrophobic hydration of concave surfaces

Hemispherical objects of radius from 6.5 to 12.2 Å were constructed from tessellated icosahedra where the vertices were hydrophobic ‘atoms’. These hemispheres were hydrated in a periodic box of water and molecular dynamics simulations in the NVE ensemble were performed on this solution at 320K. Results show that water molecules in the concave region exhibit a layered structure and have their dipoles preferentially oriented approximately orthogonal to the radial direction of the hemisphere. They possess fewer hydrogen bonds and near neighbours. Changes in the translational dynamics of these water molecules are not detected, but there is an acceleration of the re-orientational dynamics. This work thus represents the first systematic study of the hydration of concave hydrophobic surfaces.     

Surface analysis for LiBq4 growing on ITO and CuPc film using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS)

We have investigated the morphology and surface electron states of LiBq₄ deposited on ITO and CuPc/ITO, using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The AFM observations indicate that LiBq₄ can form a much more uniform film on CuPc than that on ITO. Furthermore, X-ray photoelectron spectroscopy (XPS) is utilized to further demonstrate the AFM results. From the analysis of XPS, we found that LiBq₄ molecules have poor thermal stability, they are seriously oxidized during depositing; but when a CuPc layer is inserted between LiBq₄ and ITO film, the oxidation and surface contamination of LiBq₄ are significantly reduced. It is then concluded that the introduction of a CuPc buffer layer under the LiBq₄ film can improve the film quality of LiBq₄.The XPS results also testified the fact that no coordination bonds between N atoms and B atoms are formed in LiBq₄ molecules, which make LiBq₄ to be potential blue organic light-emitting material.     

Ab initio study of water adsorption on TiO2-terminated (100) surface of SrTiO3 with and without Cr doping

Water molecule adsorption on TiO₂-terminated (100) surface of SrTiO₃ with and without Cr doping is investigated by first principle calculation based on density functional theory. The band gap is shrunk compared with that of bulk due to the existence of defect states on the surface and 3d states of dopants. As a result the absorption energy edge is reduced and locates in the visible region. When adsorbed on the surface, energy levels of water molecules as a whole are lowered with respect to the Fermi energy, but the higher levels are split and electrons are transferred from low levels to high levels due to the decrease of the density of states in low energy region. Weak bonding is formed between water hydrogen atoms and surface oxygen atoms. This bonding causes the electron transferring from substrate to molecule and the occupation of the corresponding states.     

A corrosion-resistance superhydrophobic TiO2 film

A superhydrophobic TiO₂ film with water contact angle greater than 170° on Hastelloy substrate was fabricated through simply dip-coating method from TiO₂ precursor solution containing TiO₂ nanoparticles with the average diameter 25 nm, followed by heat-treatment and modification with fluoroalkylsilane (FAS) molecules. The as-obtained sample was characterized by scanning electron microscopy (SEM), X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), and water contact angle measurement respectively. Moreover, the dynamic light scattering (DLS) size distribution of TiO₂ aggregated particles in the TiO₂ precursor solution containing P25 particles was evaluated by Laser Particle Sizer. It is found that the TiO₂ nanoparticles in TiO₂ precursor solution play a crucial role to form high superhydrophobicity. Simultaneously, the superhydrophobic TiO₂ film still showed great superhydrophobicity after corroded with strong acid or alkali solutions and protected the substrate from corrosion which should be critical to the potential application in industry.     

Theoretical study of the permeation of water through TiO2 nanotubes using molecular dynamics simulation

In this study, the theoretical structures of armchair (6, 6) and zigzag (12, 0) TiO₂ nanotubes (TiNTs) were constructed by rolling the (101) layer of an anatase TiO₂ crystal. The (101) layer was made using Materials Studio (MS) by cutting the cleave plane (101) of the anatase TiO₂ crystal. Based on these structures, the basic properties of TiO₂ nanotubes were investigated using MS. Molecular dynamics simulations were performed using the software NAMD to investigate the status and permeation of water through the TiO₂ nanotubes. Structure analysis shows that both the inner and outer walls of the structures were terminated with oxygen atoms. The thicknesses of single tube walls are smaller than that of a perfect triple layer (2.20?Å) in bulk anatase TiO₂. With regard to the bulk Ti–O bond length, the Ti–O bonds in the outer layer are elongated, and are shortened in the inner layer. Molecular dynamics simulation shows that the water molecules in the nanotubes move back and forth, as in one-dimensional Brownian motion. Moreover, the penetration properties of TiNTs are associated with their radii, with the TiNT with larger radii having better penetration properties. Thus, when used in drug delivery or filtration systems, armchair TiNT has a better effect than zigzag TiNT.     

Formation of iron and iron silicides on silicon and iron surfaces. Role of the deposition rate and volumetric effects

A thin iron film deposited at the rate of 10³ nm/sec on the Si(001) surface and a sandwich structure silicon/iron/Si(111) are studied by Surface Magneto-Optic Kerr Effect, High Resolution Electron Microscopy and X-ray Photoelectron Microscopy methods. The phases present in the structures are identified. Both structures are non-uniform. The ultra-fast-deposited film is magnetically hard (H _c=45 Oe), it contains the silicide Fe₅Si₃. The XPS line shift by +0.55 eV with respect to the pure iron 2p 3/2 level is attributed to Fe₅Si₃. The cross-section image of the sandwich structure shows the presence of enhanced-intermixing channels crossing the Si-rich layer. Iron atoms are the main diffusion species both at the Fe/Si(111) and Si/Fe interfaces. The nature of the volume defect and internal stresses in the transforming iron silicides and their effects on material intermixing and film growth process are discussed.     

Increasing surface hydrophilicity of titania thin films by doping

The hydrophilicity of RF sputtered thin films of: (a) pure TiO₂ and (b) TiO₂ doped with 0.3% Ce, 0.4% Nb, and 0.4% N (atomic percents) was investigated macroscopically by measurements of the contact angle between water and film surface. The results are discussed in terms of the connection of the hydrophilic and photocatalytic properties of the materials with their structure, morphology and optical characteristics. The 280 nm thick films were deposited on optical glass substrates at 250 °C. Film structure and surface morphology were investigated by X-ray diffraction and atomic force microscopy. The surface roughness was derived from atomic force microscopy and ellipsometric data. The contact angle of de-ionized water with film surface was monitored during photo-activation and after irradiating with near-UV light. The surface super-hidrophilicity of all the investigated samples decays, when samples are kept in darkness for 48 h after irradiation. The hydrophilic behavior of the doped TiO₂ thin films is discussed in terms of the effects of surface roughness, phase transformations enhanced by doping and charge carrier recombination.