Synthesis and electrochemical properties of CeO2 nanoparticle modified TiO2 nanotube arrays

In this paper, a cerium dioxide (CeO₂) modified titanium dioxide (TiO₂) nanotube array film was fabricated by electrodeposition of CeO₂ nanoparticles onto an anodized TiO₂ nanotube array. The structural investigation by X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicated that the CeO₂ nanoparticles grew uniformly on the walls of the TiO₂ nanotubes. The composite was composed of cubic-phase CeO₂ crystallites and anatase-phase TiO₂ after annealing at 450 °C. The cyclic voltammetry and chronoamperometric charge/discharge measurement results indicated that the CeO₂ modification obviously increased the charge storage capacity of the TiO₂ nanotubes. The charge transfer process at the surface, that is, the pseudocapacitance, was the dominate mechanism of the charge storage in CeO₂-modified TiO₂ nanotubes. The greater number of surface active sites resulting from uniform application of the CeO₂ nanoparticles to the well-aligned TiO₂ nanotubes contributed to the enhancement of the charge storage density.     

CO hydrogenation to iso-C4 hydrocarbons over CeO2–TiO2 catalysts

CeO₂–TiO₂ (Ce:Ti = 0.25–9, molar ratio) catalysts were synthesized by a sol–gel method and the catalytic performances were evaluated in the selective synthesis of isobutene and isobutane from CO hydrogenation under the reaction conditions of 673–748 K, 1–5 MPa and 720–3000 h⁻¹. The physical properties, such as specific surface area, cumulative pore volume, average pore diameter, crystal phase and size, of the catalysts were characterized by N₂ adsorption/desorption and XRD. All the CeO₂–TiO₂ composite oxides showed higher surface areas than pure TiO₂ and CeO₂. No TiO₂ phase was detected on the samples of CeO₂–TiO₂ in which TiO₂ contents were in the range of 10–50 mol%. Crystalline Ce₂O₃ was detected in CeO₂–TiO₂ (8:2). The reaction conditions, temperature, pressure and space velocity, had obvious influences on the CO conversion and distribution of the products over CeO₂–TiO₂ (8:2) catalyst.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P

TiO₂- and CeO₂-promoted bulk Ni₂P catalysts were prepared by impregnation and in-situ H₂ temperature-programmed reduction method. The prepared catalysts were characterized by XRD and XPS. The hydrogenation activities of the catalysts were studied using 1.5 wt.% 1-heptene in toluene and 1.0 wt.% phenylacetylene in ethanol as the model feeds. The results indicate that bulk Ni₂P possesses low hydrogenation activity but is tunable by simply controlling the content of the additives (TiO₂ or CeO₂), suggesting that TiO₂ and CeO₂ are effective promoters to enhance the hydrogenation activity of Ni₂P.     

Preparation of UO2/TiO2 composite ceramic fuel by sol gel-press forming method

This paper studies the preparation of UO₂/TiO₂ composite ceramic fuel through sol gel-press forming. The research shows that at 1200–1300 °C, UO₂/TiO₂ composite ceramic grains are small, uniform and compact. Among them, UO₂–0.5 wt%TiO₂ has the highest density and good mechanical strength at 1250 °C.     

Al2O3-coated SnO2/TiO2 composite electrode for the dye-sensitized solar cell

A novel Al₂O₃-coated SnO₂/TiO₂ composite electrode has been applied to the dye-sensitized solar cell. In such an electrode, two kinds of energy barriers (SnO₂/TiO₂ and TiO₂/Al₂O₃) were designed to suppress the recombination processes of the photo-generated electrons and holes. After the SnO₂ was modified by colloid TiO₂, the photoelectric conversion efficiency of the SnO₂/TiO₂ composite cell increased to 2.08% by a factor of 2.8 comparing with that of the SnO₂ cell. The Al₂O₃ layer on the SnO₂/TiO₂ composite electrode further suppressed the generation of the dark current, resulting in 37% improvement in device performance comparing with the SnO₂/TiO₂ cell.     

Investigation of surface modification of rutile TiO2 nanoparticles with SiO2/Al2O3 on the properties of polyacrylic composite coating

Surface modification and characterization of TiO₂ nanoparticles as an additive in a polyacrylic clear coating were investigated. For the improvement of nanoparticles dispersion and the decreasing of photocatalytic activity, the surface of nanoparticles was modified with binary SiO₂/Al₂O₃. The surface treatment of TiO₂ nanoparticles was characterized with FTIR. Microstructural analysis was done by AFM. The size, particle size distribution and zeta potential of TiO₂ nanoparticles in water dispersion was measured by DLS method. For the evaluation of particle size and the stability of nanoparticles in water dispersions with higher solid content the electroacoustic spectroscopy was made. To determine the applicability and evaluate the transmittance of the nano-TiO₂ composite coatings UV–VIS spectroscopy in the wavelength range of 200–800 nm was employed. The results showed that surface treatment of TiO₂ nanoparticles with SiO₂/Al₂O₃ improves nanoparticles dispersion and UV protection of the clear polyacrylic composite coating.     

Effect of TiO2 supporting layer on Fe2O3 photoanode for efficient water splitting

For an electrochemical water splitting system, titanate nanotubular particles with a thickness of ∼700 nm produced by a hydrothermal process were repetitively coated on fluorine-doped tin oxide (FTO) glass via layer-by-layer self-assembly method. The obtained titanate/FTO films were dipped in aqueous Fe solution, followed by heat treatment for crystallization at 500 °C for 10 min in air. The UV–vis absorbance of the Fe-oxide/titanate/FTO film showed a red-shifted spectrum compared with the TiO₂/FTO coated film; this red shift was achieved by the formation of thin hematite-Fe₂O₃ and anatase-TiO₂ phases verified using X-ray diffraction and Raman results. The cyclic voltammetry results of the Fe₂O₃/TiO₂/FTO films showed distinct reversible cycle characteristics with large oxidation–reduction peaks with low onset voltage of I–V characteristics under UV–vis light illumination. The prepared Fe₂O₃/TiO₂/FTO film showed much higher photocurrent densities for more efficient water splitting under UV–vis light illumination than did the Fe₂O₃/FTO film. Its maximum photocurrent was almost 3.5 times higher than that obtained with Fe₂O₃/FTO film because of the easy electron collection in the current collector. The large current collection was due to the existence of a TiO₂ base layer beneath the Fe₂O₃ layer.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Direct synthesis of CeO2/SiO2 mesostructured composite materials via sol–gel process

A series of CeO₂/SiO₂ mesostructured composite materials was synthesized by sol–gel process using Pluronic P123 as template, tetraethylorthosilicate as silica source and hexahydrated cerium nitrate as precursor under acid condition. The as-synthesized materials with Ce/Si molar ratio ranging from 0.03 to 0.3 were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), laser Raman spectroscopy (LRS), and N₂ adsorption. Characterization revealed that all samples possess ordered hexagonal mesoporous structure similar to SBA-15 and possess high surface area, large pore volume and uniform pore size. The fact that cerium species are present as highly dispersed CeO₂ nanocrystals in hexagonal matrix was confirmed by XRD combined with high-resolution TEM and selected area electron diffraction (SAED) analysis. Introduction of ceria to silica matrix can cause a distortion of hexagonal ordering structure and decrease pore diameter and increase the wall thickness of mesopores. Moreover, it can be found that this sol–gel route is a feasible, effective and simple method for templating synthesis of CeO₂/SiO₂ composite materials.     

Synthesis of a TiO2 ceramic membrane containing SrCo0.8Fe0.2O3 by the sol-gel method with a wet impregnation process for O2 and N2 permeation

A SrCo_0.8Fe_0.2O₃ impregnated TiO₂ membrane (TiO₂-SrCo_0.8Fe_0.2O₃ membrane) was successfully prepared using a sol-gel method in combination with a wet impregnation process. The membrane was subjected to a single gas permeance test using oxygen (O₂) and nitrogen (N₂). The TiO₂ membrane was immersed in the SrCo_0.8Fe_0.2O₃ solution, dried and then calcined to affix SrCo_0.8Fe_0.2O₃ into the membrane. The effect of the acid/alkoxide (H⁺/Ti⁴⁺) molar ratio of the TiO₂ sol on the TiO₂ phase transformation was investigated. The optimal molar ratio was found to be 0.5, which resulted in nanoparticles with a mean size of 5.30 nm after calcination at 400 °C. The effect of calcination temperature on the phase transformation of TiO₂ and SrCo_0.8Fe_0.2O₃ was investigated by varying the calcination temperature from 300 to 500 °C. X-ray diffraction spectroscopy (XRD) and Fourier transform infrared (FTIR) analysis confirmed that a calcination temperature of 400 °C was preferable for preparing a TiO₂-SrCo_0.8Fe_0.2O₃ membrane with fully crystallized anatase and SrCo_0.8Fe_0.2O₃ phases. The results also showed that polyvinyl alcohol (PVA) and hydroxypropyl cellulose (HPC) were completely removed. Field emission scanning electron microscopy (FESEM) analysis results showed that a crack-free and relatively dense TiO₂ membrane (∼0.75 μm thickness) was created with a multiple dip-coating process and calcination at 400 °C. The gas permeation results show that the TiO₂ and TiO₂-SrCo_0.8Fe_0.2O₃ membranes exhibited high permeances. The TiO₂-SrCo_0.8Fe_0.2O₃ membrane developed provided greater O₂/N₂ selectivity compared to the TiO₂ membrane alone.     

Photocatalytic activity of TiO2 supported on multi-walled carbon nanotubes under simulated solar irradiation

TiO₂ particles supported on multi-walled carbon nanotubes (MWCNTs) were prepared using a sol–gel method to investigate their photocatalytic activity under simulated solar irradiation for the degradation of methyl orange (MO) in aqueous solution. The prepared composites were analyzed using XRD, SEM, EDS and UV–vis absorption spectroscopy. The results of this study indicated that there was little difference in the shape and structure of MWCNTs/TiO₂ composite and pure TiO₂ particles. The composite exhibited enhanced absorption properties in the visible light range compared to pure TiO₂. The degradation of MO by MWCNTs/TiO₂ composite photocatalysts was investigated under irradiation with simulated solar light. The results of this study indicated that MWCNTs played a significant role in improving photocatalytic performance. Different amounts of MWCNTs had different effects on photodegradation efficiency, and the most efficient MO photodegradation was observed for a 2% MWCNT/TiO₂ mass ratio. Photocatalytic reaction kinetics were described using the Langmuir–Hinshelwood (L–H) model. The photocatalyst was reused for eight cycles, and it retained over 95.2% photocatalytic degradation efficiency. Possible decomposition mechanisms were also discussed. The results of this study indicated that photocatalytic reactions with TiO₂ particles supported on MWCNTs under simulated solar light irradiation are feasible and effective for degrading organic dye pollutants.     

Efficient decomposition of organic compounds with FeTiO3/TiO2 heterojunction under visible light irradiation

FeTiO₃/TiO₂, a new heterojunction-type photocatalyst working at visible light, was prepared by a simple sol–gel method. Not only did FeTiO₃/TiO₂ exhibit greatly enhanced photocatalytic activity in decomposing 2-propanol in gas phase and 4-chlorophenol in aqueous solution, but also it induced efficient mineralization of 2-propanol under visible light irradiation (λ ≥ 420 nm). Furthermore, it showed a good photochemical stability in repeated photocatalytic applications. FeTiO₃ showed a profound absorption over the entire visible range, and its valence band (VB) position is close to that of TiO₂. The unusually high photocatalytic efficiency of the FeTiO₃/TiO₂ composite was therefore deduced to be caused by hole transfer between the VB of FeTiO₃ and TiO₂.     

Evaluation of hot corrosion behavior of CSZ,CSZ/micro Al2O3 and CSZ/nano Al2O3 plasma sprayed thermal barrier coatings

Hot corrosion is one of the main destructive factors in thermal barrier coatings (TBCs) which come as a result of molten salt effect on the coating–gas interface. Hot corrosion behavior of three types of plasma sprayed TBCs was evaluated: usual CSZ, layer composite of CSZ/Micro Al₂O₃ and layer composite of CSZ/Nano Al₂O₃ in which Al₂O₃ was as a topcoat on CSZ layer. Hot corrosion studies of plasma sprayed thermal barrier coatings (TBCs) were conducted in 45 wt% Na₂SO₄+55 wt% V₂O₅ molten salt at 1050 °C for 40 h. The graded microstructure of the coatings was examined using scanning electron microscope (SEM) and X-ray diffractometer (XRD) before and after hot corrosion test. The results showed that no damage and hot corrosion products was found on the surface of CSZ/Nano Al₂O₃ coating and monoclinic ZrO₂ fraction was lower in CSZ/Micro Al₂O₃ coating in comparison with usual CSZ. reaction of molten salts with stabilizers of zirconia (Y₂O₃ and CeO₂) that accompanied by formation of monoclinic zirconia, irregular shape crystals of YVO₄, CeVO₄ and semi-cubic crystals of CeO₂ as hot corrosion products, caused the degradation of CSZ coating in usual CSZ and CSZ/Micro Al₂O₃ coating.     

Synthesis and reaction mechanism of Ti3SiC2 ternary compound by carbothermal reduction of TiO2 and SiO2 powder mixtures

The present study aims to investigate synthesis of Ti₃SiC₂ from TiO₂ and SiO₂ powder mixtures by carbothermal reduction method. Equilibrium TiO₂–SiO₂–C ternary phase diagram was used to predict the conditions for the formation of Ti₃SiC₂ at 1800 K under Ar atmosphere. A reactant mixture with a TiO₂:SiO₂ molar ratio of 1.5 and a C content of 68.75 mol% (26.86 wt%) was initially selected among the thermodynamically favorable reactant compositions for the experimental studies. Two different C sources, graphite flakes and pyrolytic C coating, were used to synthesize Ti₃SiC₂ at 1800 K under Ar atmosphere. When graphite flakes were used, the products contained a trace amount of Ti₃SiC₂ phase along with major TiC and minor SiC phases. Whereas, pyrolytic C coating on the oxide particles resulted in the products with much higher Ti₃SiC₂ contents owing to the close contact between the reactants. Optimal C concentration for the C coated oxide mixtures with a TiO₂:SiO₂ molar ratio of 1.5 was determined to be 30.05 wt% under the experimental conditions studied. Ti₃SiC₂ content of the products obtained from this reactant was observed to increase with reaction time to 31 wt% at 75 min beyond which it gradually decreased. XRD studies indicated that the product with the highest ternary carbide content also contained TiC and a trace amount of SiC. SEM-EDS analyses showed that this sample essentially consisted of spherical fine TiC particles and Ti₃SiC₂ nanolaminates. Equilibrium thermodynamic analysis of the TiO₂–SiO₂–C system suggested that the reaction of solid Ti₂O₃ with SiO and CO gases may play a dominant role in the formation of Ti₃SiC₂.     

SnO2 nanoparticle embedded TiO2 nanofibers — Highly efficient photocatalyst for the degradation of rhodamine B

SnO₂ nanoparticle embedded TiO₂ nanofibers were fabricated by a simple electrospinning method. The relationship between the SnO₂/TiO₂ weight ratio and photocatalytic efficiency was investigated from the view point of Rhodamine B decomposition. In addition, electron microscopic analysis, energy dispersive analysis, X-ray diffraction analysis, and photoluminescence study demonstrated that SnO₂ nanoparticle was successfully embedded in TiO₂ nanofibers. TiO₂ nanofibers containing SnO₂ nanoparticle provided an enhanced interfacial region between TiO₂ and SnO₂. SnO₂ nanoparticles embedded TiO₂ nanofibers exhibited highly efficient photocatalytic activity under UV light irradiation due to high charge separation of electron–hole pairs.     

Effect of ceria on the structure and catalytic activity of V2O5/TiO2–ZrO2 for oxidehydrogenation of ethylbenzene to styrene utilizing CO2 as soft oxidant

The present study was undertaken to investigate the influence of ceria on the physicochemical and catalytic properties of V₂O₅/TiO₂–ZrO₂ for oxidative dehydrogenation of ethylbenzene to styrene utilizing CO₂ as a soft oxidant. Monolayer equivalents of ceria, vanadia and ceria–vanadia combination over TiO₂–ZrO₂ (TZ) support were impregnated by a coprecipitation and wet impregnation methods. Synthesized catalysts were characterized by using X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, temperature programmed reduction, transmission electron microscopy and BET surface area methods. The XRD profiles of 550 °C calcined samples revealed amorphous nature of the materials. Upon increasing calcination temperature to 750 °C, in addition to ZrTiO₄ peaks, few other lines due to ZrV₂O₇ and CeVO₄ were observed. The XPS V 2p results revealed the existence of V⁴⁺ and V⁵⁺ species at 550 and 750 °C calcinations temperatures, respectively. TEM analysis suggested the presence of nanosized (<7 nm) particles with narrow range distribution. Raman measurements confirmed the formation ZrTiO₄ under high temperature treatments. TPR measurements suggested a facile reduction of CeO₂–V₂O₅/TZ sample. Among various samples evaluated, the CeO₂–V₂O₅/TZ sample exhibited highest conversion and nearly 100% product selectivity. In particular, the addition of ceria to V₂O₅/TZ suppressed the coke deposition and allowed a stable and high catalytic activity.     

Partial oxidation of ethanol over Pd/CeO2 and Pd/Y2O3 catalysts

The effect of the support nature on the performance of Pd catalysts during partial oxidation of ethanol was studied. H₂, CO₂ and acetaldehyde formation was favored on Pd/CeO₂, whereas CO production was facilitated over Pd/Y₂O₃ catalyst. According to the reaction mechanism, determined by DRIFTS analyses, some reaction pathways are favored depending on the support nature, which can explain the differences observed on products distribution. On Pd/Y₂O₃ catalyst, the production of acetate species was promoted, which explain the higher CO formation, since acetate species can be decomposed to CH₄ and CO at high temperatures. On Pd/CeO₂ catalyst, the acetaldehyde preferentially desorbs and/or decomposes to H₂, CH₄ and CO. The CO formed is further oxidized to CO₂, which seems to be promoted on Pd/CeO₂ catalyst.     

(Ba0.5Sr0.5)TiO3 modification on etched aluminum foil for electrolytic capacitor

A new method was proposed to form (Ba_0.5Sr_0.5)TiO₃–Al₂O₃ composite oxide film on etched aluminum foils. The specimens were covered with (Ba_0.5Sr_0.5)TiO₃ (BST) layer by dip-coating in citrate solution and subsequent heat-treatment under 400–650 °C, finally by anodizing in a hot boracic acid and borate solution. The BST powders heated under different temperatures were characterized by X-ray diffraction (XRD) and the specific capacitance of the coated specimens heat-treated under different temperatures and times was measured. It is found that the specific capacitance increases initially with enhancing the temperature and reaches to maximum at 550 °C, but slightly decreases with the heat-treatment time. The capacitance was increased by about 35% after BST coating.     

Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films

Optically transparent, crack-free, mesoporous anatase TiO₂ thin films were fabricated. The Ag/TiO₂ composite films were prepared by incorporating Ag in the pores of TiO₂ films with an impregnation method via photoreduction. The as-prepared composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectronic spectra (XPS) and N₂ adsorption. The release behavior of silver ions in the mesoporous composite film was also studied. Moreover, the antimicrobial behaviors of the mesoporous film were also investigated by confocal laser scanning microscopy. The antibacterial activities of the composite films were studied by a fluorescence label method using Escherichia coli (E. coli) as a model. The as-prepared mesoporous TiO₂ films showed much higher antimicrobial efficiency than that of glass and commercial P25 TiO₂ spinning film. The facts would result from the high surface area, small crystal size and more active sites for the mesoporous catalysis. After the doping of Ag, a significant improvement for the antimicrobial ability was obtained. To elucidate the roles of the membrane photocatalyst and the doped silver in the antimicrobial activity, cells from a silver-resistant E. coli were used. These results indicated that Ag nanoparticles in the mesoporous were not only an antimicrobial but also an intensifier for photocatalysis. The as-prepared mesoporous composite film is promising in application of photocatalysis, antimicrobial and self-clean technologies.