Synthesis of nano-crystalline Ce0.9Gd0.1O1.95 electrolyte by novel sol–gel thermolysis process for IT-SOFCs

In the present work, nano-crystalline Ce_0.9Gd_0.1O_1.95 (GDC) powder has been successfully prepared by a novel sol–gel thermolysis method using a unique combination of urea and PVA. The gel precursor obtained during the process was calcined at 400 and 600 °C for 2 h. A range of analyzing techniques including XRD, TGA, BET, SEM, EDS and TEM were employed to characterize the physical and chemical properties of obtained powders. GDC gel precursors calcined at 400 and 600 °C were found to have an average crystallite size of 10 and 19 nm, respectively. From the result of XRD patterns, we found that well-crystalline cubic fluorite structure GDC was obtained by calcining the precursor gel at 400 and 600 °C. It has been also found that the sintered samples with lower temperature calcined powder showed better sinterability as well as higher ionic conductivity of 2.21 × 10⁻² S cm⁻¹ at 700 °C in air.     

Synthesis of yttrium aluminum garnet (YAG) powder by homogeneous precipitation combined with supercritical carbon dioxide or ethanol fluid drying

YAG precursors were synthesized by the urea method in aqueous solution using supercritical carbon dioxide and ethanol fluid drying technique, respectively. The composition of the precursors, the phase formation process and the properties of the calcined powders were investigated by means of XRD, IR, TG/DSC, BET, TEM and SEM. Compared with the classically prepared powders at room temperature in air, the amorphous precursor dried by supercritical CO₂ fluid was loosely agglomerated and directly converted to pure YAG at about 900 °C. The resultant YAG powders showed good dispersity with an average crystallite size about 20 nm and specific surface area of 52 m² g⁻¹. However, the precursor dried by supercritical ethanol fluid was crystalline. Extensive phase segregation occurred during the drying process and resulted in the formation of separate phases such as monoclinic Y(OH)₃ and pseudoboehmite. YAM and YAP phases appeared in the calcination process and phase pure were not detected until 1200 °C.     

Escherichia coli inactivation by N, S co-doped commercial TiO2 powders under UV and visible light

Commercial anatase TiO₂ powders (Tayca TKP101, TKP102) were ground with thiourea and annealed at 400 and 500 °C. Diffuse reflectance spectra (DRS) showed that the doping with thiourea shifted the TiO₂ absorption towards the visible region. The absorption was observed to increase with increasing annealing temperature. Using the Kubelka–Munk relations, it was possible to determine the band-gap of the doped TiO₂. Doped Tayca TiO₂ TKP101 showed a band-gap of 2.12 and 2.24 eV calcined at 400 and 500 °C, respectively. Doped Tayca TiO₂ TKP102 calcined at 400 and 500 °C showed in both cases a band-gap of 2.85 eV. X-ray photoelectron spectroscopy (XPS) revealed that these doped TiO₂, TKP101 annealed at 400 °C and TKP102 annealed at 400 and 500 °C present interstitial N-doping while doped TKP101 annealed at 500 °C showed a peak characteristic of substitutional N-doping. S-doped materials calcined at 500 °C presented only anionic S-doping. Nitrogen adsorption studies (BET) showed a loss of specific surface area (SSA) in annealed TiO₂ samples. N- and S co-doped materials showed suitable photocatalytic activity under UV illumination towards Escherichia coli inactivation and also under visible light irradiation (400–500 nm). Applying different annealing temperatures led to a variety of structures for N and S incorporated in the crystalline network. TiO₂ upon annealing showed a varying degree of hydroxylation and particles sizes. This seems to affect the trapping and transfer of the charge carriers generated under light and the semiconductor performance.     

Enhancement of oxygen storage capacity by reductive treatment of Al2O3 and CeO2–ZrO2 solid solution nanocomposite

Oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solution, Ce_xZr_(1−x)O₄, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al₂O₃ and CeZrO₄ (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m²/g) after reductive treatment at 1000 °C. The introduced Al₂O₃ facilitated the regular rearrangement of Ce and Zr ions in CeZrO₄ as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.     

Influence of sulfur on the structural, surface properties and photocatalytic activity of sulfated TiO2

TiO₂ materials were prepared by sol–gel method and then impregnated with sulfuric acid and calcined using different temperatures and atmosphere (air and nitrogen). Systematic variation of these two experimental parameters makes possible to modulate the amount of surface sulfur from the impregnation procedure. The best photocatalyst for liquid phenol degradation was obtained after calcination at 700 °C in air, while gas toluene degradation optimum performance is obtained by calcination at 700 °C in nitrogen from 500 °C. Structural analysis of these materials by XRD, micro-Raman spectroscopy and FE-SEM shows that once calcined at 700 °C the material was a well-crystallized, high surface area anatase structure in all cases. The surface characterization by FTIR and XPS confirms the presence of a higher amount of sulfur species and acidic OH groups in samples partially calcined in nitrogen, and a low XPS O/Ti-atomic ratio with the O 1s peak shifted to higher binding energies (1.8 vs. 2 ± 0.1 and 530.4 eV vs. 529.8 eV, respectively, against the reference materials) for samples calcined at 700 °C, temperature at which most of sulfate species have been evolved. The paper presents an attempt to correlate the contribution of the observed structural defects within the anatase sub-surface layers and surface acidity to the different photoactivity behaviour exhibited for phenol liquid phase and toluene gas phase photodegradation.     

Synthesis of nano-sized Yb3Al5O12 powders by the urea co-precipitation method

Nano-sized polycrystalline ytterbium aluminum garnet (YbAG, Yb₃Al₅O₁₂) powders were successfully synthesized by a simple urea co-precipitation method. The thermal behavior of the YbAG precursor was investigated. The calcined amorphous YbAG precursor was directly converted to 20–30 nm monophase YbAG at as low as temperature 900 °C, without any other intermediate phases. The nano-sized YbAG powders calcined at 900 °C distributed evenly with a slight aggregation, and the specific surface area of the powders reached 29.7 m² g⁻¹. The absorption spectrum of the YbAG powders was measured, and there were two strong absorption peaks centered at 931 and 965 nm. The results did not correspond to the absorption peaks of Yb:YAG crystal exactly, as the lattice parameters were different between YbAG and YAG.     

Microstructure and ionic conductivity properties of gadolinia doped ceria (GdxCe1−xO2−x/2) electrolytes for intermediate temperature SOFCs prepared by the polyol method

Gd_0.1Ce_0.9O_1.95 and Gd_0.2Ce_0.8O_1.9 powders were prepared through the polyol process without using any protective agent. Microstructural and physical properties of the samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG) and impedance analysis methods. The results of the thermogravimetry/differential thermal analysis (TG/DTA) and XRD indicated that a single-phase fluorite structure formed at the relatively low calcination temperature of 500 °C. The XRD patterns of the samples revealed that the crystallite size of the samples increased as calcination temperatures increased. The sintering behavior and ionic conductivity of pellets prepared from gadolinia doped ceria (GDC) powders, which were calcined at 500 °C, were also investigated. The relative densities of the pellets, which were sintered at temperatures above 1300 °C, were higher than 95%. The results of the impedance spectroscopy revealed that the GDC-20 sample that was sintered at 1400 °C exhibited an ionic conductivity of 3.25×10⁻² S cm⁻¹ at 800 °C in air. This result clearly indicates that GDC powder with adequate ionic conductivity can be prepared through the polyol process at low temperatures.     

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.     

Synthesis and characterization of CuO/TiO2 catalysts for low-temperature CO oxidation

In this paper, the CuO/TiO₂ catalysts prepared by the deposition–precipitation (DP) method were extensively investigated for CO oxidation reaction. The structural characters of the CuO/TiO₂ catalysts were comparatively investigated by TG-DTA, XRD, and XPS measurements. It was shown that the catalytic behavior of CuO/TiO₂ catalysts greatly depended on the TiO₂-support calcination temperature, the CuO loading amount and the CuO/TiO₂ catalysts calcination temperature. CuO supported on the anatase phase of TiO₂-support calcined at 400 °C showed better catalytic activity than those supported on TiO₂ calcined at 500 and 700 °C. Among all our investigated catalysts with CuO loading from 2% to 12%, the catalyst with 8 wt% CuO loading exhibited the highest catalytic activity. The optimum calcination temperature of the CuO/TiO₂ catalysts was 300 °C. The XRD results indicated that the catalytic activity of the CuO/TiO₂ catalysts was related to the crystal phase and particle size of TiO₂ support and CuO active component.     

Nafion-TiO2 composite DMFC membranes: physico-chemical properties of the filler versus electrochemical performance

TiO₂ nanometric powders were prepared via a sol-gel procedure and calcined at various temperatures to obtain different surface and bulk properties. The calcined powders were used as fillers in composite Nafion membranes for application in high temperature direct methanol fuel cells (DMFCs). The powder physico-chemical properties were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and pH measurements. The observed characteristics were correlated to the DMFC electrochemical behaviour. Analysis of the high temperature conductivity and DMFC performance reveals a significant influence of the surface characteristics of the ceramic oxide, such as oxygen functional groups and surface area, on the membrane electrochemical behaviour. A maximum DMFC power density of 350 mW cm⁻² was achieved under oxygen feed at 145 °C in a pressurized DMFC (2.5 bar, anode and cathode) equipped with TiO₂ nano-particles based composite membranes.     

Thermal expansion behavior of Cu/Cu2O cermets with different Cu structures

Cu/Cu₂O cermets were prepared with Cu₂O matrix imbedded with branch-like or spherical Cu powders. The coefficients of thermal expansion (CTE) of them were tested. The CTE curves can be divided into three segments. From 25 °C to 150 °C, CTEs were found to decrease with temperatures. The CTEs were influenced by the structure of the conductor phase. For cermets prepared with spherical Cu, the increase in CTEs was basically linear with temperatures above 150 °C. In contrast, cermets with same Cu content prepared with branch-like Cu had a CTE with an increasing rate as the temperature rose from 150 °C to 900 °C, and the increasing rates in these temperature range are much higher than those prepared with spherical Cu.     

Lyothermal synthesis of nanocrystalline BaSnO3 powders

The synthesis of BaSnO₃ powders has been investigated at lyothermal conditions (temperature of 250 °C; t = 6 h), starting from SnO₂·xH₂O and Ba(OH)₂ and methanol, ethanol, isopropanol and acetone as solvents. Among them isopropanol was found to be the most suitable medium for preparing BaSnO₃. By addition of the modifier Genapol X-080 during the processing, the BET specific surface area of the end-powder was increased by a factor of 10. The as-prepared powder consisted of BaSn(OH)₆. The thermal behavior, the crystallization behavior and the structure evolution of the powder during heating treatment have been studied with the TG–DTA–MS, XRD and FTIR. The weight loss of the as-prepared powder of about 12 wt% heated up to 1200 °C is mainly attributed to the dehydration around 260 °C which leads to the structure rearrangement and the building of the [SnO₆] octahedra. At this temperature BaSn(OH)₆ converts to an amorphous phase, from which BaSnO₃ nucleates and grows with increasing temperature. The obtained BaSnO₃ powders had a BET specific surface area of 16.56 m²/g and a primary crystallite size of 49 nm.     

Low temperature synthesis of single-phase α-Fe2O3 nano-powders by using simple but novel chemical methods

Two simple chemical methodologies have been described for the preparation of single-phase α-Fe₂O₃ nano powder with particle size ∼ 20-30 nm. Precursor powders were synthesized by reacting aqueous solutions of ferric nitrate and PVA and sucrose (method 1) and EDTA (method 2) and then evaporating the resulting solutions to dryness. The precursors were subsequently calcined in air for 2.30 hr at different temperatures ranging from 250 to 450 °C. The synthesized powders were characterised using TG-DSC analysis, X-Ray Diffraction, BET surface area measurement, SEM and TEM. DC electrical resistivity of the synthesized materials was measured by the two-probe method. The synthetic routes described here provide simple but cost-effective methods to produce single phase, α-Fe₂O₃ nanopowder at a comparatively low temperature.     

Effect of calcination temperature on the structural properties and photocatalytic activities of solvothermal synthesized TiO2 hollow nanoparticles

TiO₂ hollow nanoparticles were prepared by the solvothermal method, calcined at different temperatures and characterized by XRD, BET, SEM, PL and FT-IR. The effects of morphology, size and calcination temperature on the photocatalytic activity of the prepared materials were discussed in detail. It was found that the calcination temperature altered the crystallinity, morphology, surface area, and the porous structure. The photocatalytic activity of the TiO₂ powders evaluated through photocatalytic degradation of gaseous acetone under UV-light irradiation, showed TiO₂ calcined at 250 °C to exhibit a higher photocatalytic activity than commercial powders (Degussa P25).     

Calcination and sintering characteristics of limestone under O2/CO2 combustion atmosphere

The O₂/CO₂ coal combustion technology is an innovative combustion technology that can control CO₂, SO₂ and NO_x emissions simultaneously. Calcination and sintering characteristics of limestone under O₂/CO₂ atmosphere were investigated in this paper. The pore size, the specific pore volume and the specific surface area of CaO calcined were measured by N₂ adsorption method. The grain size of CaO calcined was determined by XRD analysis. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere are less than that of CaO calcined in air at the same temperature. And the pore diameter of CaO calcined in O₂/CO₂ atmosphere is larger than that in air. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere increase initially with temperature, and then decline as temperature exceeds 1000 °C. The peaks of the specific pore volume and the specific surface area appear at 1000 °C. The specific surface area decreases with increase in the grain size of CaO calcined. The correlations of the grain size with the specific surface area and the specific pore volume can be expressed as L = 744.67 + 464.64 lg(1 / S) and L = − 608.5 + 1342.42 lg(1 / ε), respectively. Sintering has influence on the pore structure of CaO calcined by means of influencing the grain size of CaO.     

One-step synthesis of fine SrTiO3 particles using SrSO4 ore under alkaline hydrothermal conditions

The employment of mineral SrSO₄ crystals and powders for preparing SrTiO₃ compound was investigated, with coexistence of Ti(OH)₄·4.5H₂O gel under hydrothermal conditions, at various temperatures (150–250 °C) for different reaction intervals (0.08–96 h) in KOH solutions with different concentrations. The complete dissolution of the SrSO₄ crystal occurred at 250 °C for 96 h in a 5 M KOH solution, resulting in the synthesis of SrTiO₃ particles with two different shapes (peanut-like and cubic). In contrast, very fine SrTiO₃ pseudospherical particles were crystallized when SrSO₄ powders were employed as precursor. Variations on the SrTiO₃ particle shape and size were found to be caused by the differences in the dissolution rate of the SrSO₄ phase in the alkaline KOH solution. The crystallization of SrTiO₃ particles was achieved by a bulk dissolution–precipitation mechanism of the raw precursors, and this mechanism was further accelerated by increasing the reaction temperature and concentration of the alkaline media. Kinetic data depicted that the activation energy required for the formation of SrTiO₃ powders from the complete consumption of a SrSO₄ single crystal plate under hydrothermal conditions, is 27.9 kJ mol⁻¹. In contrast, when SrSO₄ powders were employed (28–38 μm), the formation of SrTiO₃ powder proceeded very fast even for a short reaction interval of 3 h at 250 °C in a 5 M KOH solution.     

Synthesis and electrical properties of Ce0.8Sm0.2O1.9 ceramics for IT-SOFC electrolytes by urea-combustion technique

Fine Ce_0.8Sm_0.2O_1.9 (SDC) powders with a fluorite cubic phase were prepared using a urea-combustion technique. The sinterability and microstructural evolution of the resulting ceramics were investigated. The results indicate that the ceramics sintered above 1350 °C display relative densities of about 98.5% along with significant grain growth. With respect to their electrical conduction properties, the specimens sintered above 1350 °C exhibit an excellent total ionic conductivity of 0.082 S cm⁻¹ at 800 °C in air. However, when measured in an N₂ + 33.3%H₂ atmosphere, a pronounced Warburg feature appears in the impedance plots of the SDC ceramics, together with a significant increase of the total conductivity at measuring temperatures above 550 °C, due to the introduction of a mixed Ce⁴⁺/Ce³⁺ valence state and the generation of the electronic conduction in the reducing atmosphere.     

Synthesis of lanthanum beta-alumina powders by the polymeric precursor technique

La-β-Al₂O₃ (LaAl₁₁O₁₈) powders were synthesized by the polymeric precursor technique using lanthanum nitrate and aluminum nitrate. The transformations during thermal treatment of the precursor solution with ethylene glycol and citric acid were evaluated by thermal analysis. Fourier transform infrared spectroscopy analysis was performed after calcinations of the polymeric resin for determination of residual carbon. The specific surface area was evaluated by the BET method. Fine powders with ∼121 m²/g specific surface area and 20 nm average particle size were obtained and observed by scanning and transmission electron microscopy. Nearly single phase LaAl₁₁O₁₈ was obtained after pressing and sintering these powders at 1600 °C with small additions of MgO. The sintered pellets were characterized by X-ray diffraction and scanning electron microscopy. Impedance spectroscopy measurements carried out in the 1000–1200 °C range show the electrolytic behavior of the La-β-Al₂O₃ pellets, suggesting their application as solid electrolytes in high temperature potentiometric oxygen sensors.     

Facile preparation of Na-free anatase TiO2 film with highly photocatalytic activity on soda-lime glass

Na-free anatase TiO₂ film was prepared on soda-lime glass (SL-glass) from a TiF₄ aqueous solution upon addition of boric acid at 60 °C. It was found that the as-prepared TiO₂ film before calcination showed a higher photocatalytic activity than the calcined sample (500 °C). This could be attributed to the fact that the calcined TiO₂ film contained decent Na⁺ ions, which was diffused from the SL-glass substrate into the TiO₂ film during calcination, resulting in the decrease of photocatalytic activity.     

Oxidation of ethane on high specific surface SmCoO3 and PrCoO3 perovskites

An adapted sol–gel method allowed synthesizing SmCoO₃ and PrCoO₃ oxides with high specific surface (ca. 28 m² g⁻¹) and a relatively clean perovskite phase at 600 °C, a temperature much lower than the one required in ceramic methods. The perovskites were investigated as catalysts for the oxidation of ethane in the temperature range 300–400 °C. Both catalysts were very active: ethane was activated already at 300 °C, i.e., 100 °C below the temperatures previously reported for perovskites. The main product was CO₂ on both catalysts, but on PrCoO₃ oxidehydrogenation (ODH) to ethylene was observed already at 300 °C, with the low selectivity. Even so, this was quite unusual for simple perovskites, and for such a low temperature. TPR data showed that praseodymium decreases the reducibility of Co³⁺ in the perovskite, what could explain the observed ODH, and suggest it proceeds via a Mars–van Krevelen mechanism. Kinetic study showed a similar apparent activation energy for both catalysts (ca. 80 kJ/mol), but a difference in the nature of the participating oxygen species: while on PrCoO₃ both adsorbed and lattice species contribute to the reaction, on SmCoO₃ contribution of adsorbed species is practically negligible, due to its very high oxygen lability. The results show that these simple perovskites may be promising catalysts for ethane oxidation at relatively low temperatures.