Eutectic structure from amorphous Al2O3-ZrO2-Y2O3 system by rapid quenching technique for potential hybrid solar cell application

Abstract

Ternary Al₂O₃-ZrO₂-Y₂O₃ samples with a eutectic composition were prepared using the rapid quenching method, with some samples further annealed at 1300°C for 30?min and then slow cooled. The microstructural evolution was observed with XRD, SEM, and TEM. The SEM and TEM observations of the ternary samples agreed with the XRD. The rapid quenched sample was an amorphous phase with a small amount of crystalline phase mixed in. Observations showed that the rapid quenched and annealed sample was completely crystalline with a granular structure and well defined crystals of 40-60?nm in size.     

Evaluation of Ni/Y2O3/Al2O3 catalysts for hydrogen production by autothermal reforming of methane

Ni/xY₂O₃–Al₂O₃ (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al₂O₃ catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H₂-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH₄ conversion increased with elevating levels of Y₂O₃ from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY₂O₃–Al₂O₃ catalysts maintained high activity after 24 h on stream, while Ni/Al₂O₃ had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.     

Sol-gel synthesis of Er3+:Y3Al5O12/TiO2Ta2O5/MoO2 composite membrane for visible-light driving photocatalytic hydrogen generation

By using TiO₂ and Ta₂O₅ colloids, a stable and efficient visible-light driven photocatalyst, Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ composite membrane, was successfully prepared via sol–gel dip coating method at room temperature. The XRD, FTIR, SEM, TEM and EDX results confirm that approximately spherical Er³⁺:Y₃Al₅O₁₂ nanoparticles were embedded in TiO₂Ta₂O₅ matrix. UV–vis absorption and PL spectra of Er³⁺:Y₃Al₅O₁₂ were also determined to confirm the visible absorption and ultraviolet emission. The photocatalytic hydrogen generation was carried out by using methanol as sacrificial reagent in aqueous solution under visible-light irradiation. Furthermore, some main influence factors such as heat-treated temperature, heat-treated time and molar ratio of TiO₂ and Ta₂O₅ on visible-light photocatalytic hydrogen generation activity of Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ composite membrane were studied in detail. The experimental results showed that the photocatalytic hydrogen generation activity of Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ composite membrane heat-treated at 550 °C for 3.0 h was highest when the molar ratio of TiO₂ and Ta₂O₅ was adopted as 1.00:0.50. And that a high level photocatalytic activity can be still maintained after four cycles. In addition, a possible mechanism for the visible-light photocatalytic hydrogen generation of the Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ membrane was proposed based on PL spectra.     

Syngas production via CO2 reforming of methane over plasma assisted synthesized Ni‐Co/Al2O3‐ZrO2 nanocatalysts with different Ni‐loadings

Ni‐Co/Al₂O₃‐ZrO₂ nanocatalysts with 5, 10 and 15 wt.% nominal Ni content have been prepared by impregnation followed by a non‐thermal plasma treatment, characterized and tested for dry reforming of methane. For nanocatalysts characterization the following techniques have been used: XRD, FESEM, TEM, EDX dot‐mapping, BET, FTIR and XPS. The dry reforming of methane was carried out at different temperatures (550‐850 °C) using a feed mixture of CH₄:CO₂ (1:1). Among the nanocatalysts studied, the catalyst with the medium Ni content (10 wt.%) was the most active in dry reforming of methane. This higher activity exhibited by Ni‐Co/Al₂O₃‐ZrO₂ catalyst with medium Ni content (10 wt.% ) can be attributed to small and well dispersed particles of Ni within the catalyst. Apart from the narrow surface particle size distribution in the case of Ni(10 wt.%)‐Co/Al₂O₃‐ZrO₂, the presence of small active components with average size of 7.5 nm is proposed to be the reason for the superior performance of the catalyst. Ni(10 wt.%)‐Co/Al₂O₃‐ZrO₂ nanocatalyst had maximum surface area and the lower surface area was observed in the case of Ni(5 wt.%)‐Co/Al₂O₃‐ZrO₂ and Ni(15 wt.%)‐Co/Al₂O₃‐ZrO₂ due to the formation of the larger agglomeration and higher mean particle size of nickel particles, respectively. Although, GHSV enhancment had inverse effect on product yield but yield reduction for Ni‐Co/Al₂O₃‐ZrO₂ catalyst with 10 wt.% Ni was less drastic at high GHSVs. According to XRD and XPS, existence of NiAl₂O₄ confirms strong interaction between Ni and support but higher loadings of Ni resulted in less NiAl₂O₄; loser interaction between support and active phase. Small particles of active components and well‐defined dispersion of them in Ni(10 wt.%)‐Co/Al₂O₃‐ZrO₂ nanocatalyst resulted in stability of the catalyst for either feed conversion or H₂/CO molar ratio. Copyright © 2013 John Wiley & Sons, Ltd.     

Oxide ionic conductivity and crystallographic properties of tetragonal type Bi2O3-based solid electrolyte doped with Ho2O3

Abstract

In the present work, the authors have investigated the binary system of (Bi₂O₃)_1–x(Ho₂O₃)_x. For the stabilisation of the tetragonal type solid solution, small amounts of Ho₂O₃ were doped into the monoclinic Bi₂O₃ via solid state reactions in the stoichiometric range 0·01≤x≤0·1. The crystal formula of the formed solid solution was determined as Bi(III)_4–4xHo(II)_4xO_6–2xVo_(2+2x) (where Vo is the oxide ion vacancy) according to the XRD and SEM microprobe results. In the crystal formula, stoichiometric values of x were 0·04≤x≤0·08, 0·03≤x≤0·09, 0·02≤x≤0·09 and 0·04≤x≤0·09 for annealing temperatures at 750, 800, 805 (quench) and 760°C (quench) respectively. The four probe electrical conductivity measurements showed that the studied system had an oxide ionic type electrical conductivity behaviour, which is increased with increasing dopant concentration and temperature. The obtained solid electrolyte system has an oxygen non-stoichiometry characteristic, and it contains O^2– vacancies, which have disordered arrangements in its tetragonal crystal structure. The increase in the amount of Ho₂O₃ doping and temperature causes an increasing degree of the disordering of oxygen vacancies and a decrease in the activation energy E_a.     

Effect of pre-treatment and calcination temperature on Al2O3-ZrO2 supported Ni-Co catalysts for dry reforming of methane

In this paper, the effect of pre-treatment and calcination temperature on a series of 5%Co/Al₂O₃-ZrO₂, 5%Ni/Al₂O₃-ZrO₂ and 2.5%Co-2.5%Ni/Al₂O₃-ZrO₂ catalysts for dry reforming of methane was investigated. Main focus of our research was to improve the catalyst stability by proper pre-treatment and reaction conditions. The first approach aimed at the catalyst pre-treatment by using bimetallic systems and the second strategy at the in situ suppression of coke. The catalytic activity of bimetallic system was indeed higher compared to the monometallic in the temperature range of 500–800 °C (space velocity 18000 ml h⁻¹·g_cat⁻¹, CH₄/CO₂ = 1). The bimetallic catalyst calcined at 800 °C showed highest CH₄ conversion without deactivation and gave a H₂/CO ratio of 91% and 0.96, respectively, and good stability with less coke deposition over 28 h at 800 °C reaction temperature. This improvement is assigned to the synergism between Co and Ni, their high dispersion according to interaction with support. It has been shown in our work that pretreatment temperatures and atmospheres have strong impact on stability of the catalyst. TEM, XRD and TPO investigations confirmed that the slight catalyst deactivation was related to the formation of multiwall carbon nanotubes with hollow inner tube structure. The addition of small amounts of steam or oxygen during DRM improved both the catalyst activity and stability as the bimetallic catalyst lost around 9.4% conversion in DRM, 5.4% in presence of water and only 3.2% in presence of O₂.     

Nickel catalysts supported on ZrO2, Y2O3-stabilized ZrO2 and CaO-stabilized ZrO2 for the steam reforming of ethanol: Effect of the support and nickel load

Catalysts with various nickel loads were prepared on supports of ZrO₂, ZrO₂–Y₂O₃ and ZrO₂–CaO, characterized by XRD and TPR and tested for activity in ethanol steam reforming. XRD of the supports identified the monoclinic crystalline phase in the ZrO₂ and cubic phases in the ZrO₂–Y₂O₃ and ZrO₂–CaO supports. In the catalysts, the nickel impregnated on the supports was identified as the NiO phase. In the TPR analysis, peaks were observed showing the NiO phase having different interactions with the supports. In the catalytic tests, practically all the catalysts achieved 100% ethanol conversion, H₂ yield was near 70% and the gaseous concentrations of the other co-products varied in accordance with the equilibrium among them, affected principally by the supports. It was observed that when the ZrO₂ was modified with Y₂O₃ and CaO, there were big changes in the CO and CO₂ concentrations, which were attributed to the rise in the number of oxygen vacancies, permitting high-oxygen mobility and affecting the gaseous equilibrium. The liquid products analysis showed a low selectivity to liquid co-products during the reforming reactions.     

Effect of Co2O3 as sintering aid on perovskite BaCe0.8Y0.2O3-δ proton conductive membrane for hydrogen separation

BaCe_0.8Y_0.2O_3-δ proton conductor powder was prepared by sol-gel method, and the effects of sintering temperature and sintering aids addition on the mechanical properties and hydrogen permeability of BaCe_0.8Y_0.2O_3-δ proton conductor were investigated. XRD tests showed that when the addition of sintering aid Co₂O₃ reached 5%, the BaCe_0.8Y_0.2O_3-δ proton conductor still showed a good perovskite phase. The sintering temperature of the sample with sintering aid is significantly lower than that of the blank sample. SEM shows that the addition of Co₂O₃, the proton conductor grains are closely arranged, the mechanical properties are increased, and the hydrogen permeability is significantly improved.     

Ni/Pd-promoted Al2O3–La2O3 catalyst for hydrogen production from polyethylene terephthalate waste via steam reforming

Ni/Pd-co-promoted Al₂O₃–La₂O₃ catalysts for selective hydrogen production from polyethylene terephthalate (PET) plastic waste via steam reforming process has been investigated. The catalysts were prepared by impregnation method and were characterized using XRD, BET, TPD-CO₂, TPR-H₂, SEM, TGA and DTA. The results showed that Ni-Pd-co-impregnated Al₂O₃–La₂O₃ catalyst has excellent activity for the production of hydrogen with a prolong stability. The feed conversion of 87% was achieved over 10% Ni/Al₂O₃ catalyst which increased to 93.87% in the case of 10% Ni-1% Pd/Al₂O₃–La₂O₃ catalysts with an H₂ fraction of 0.60. The catalyst performance in term of H₂ selectivity and feed conversion was further investigated under various operating parameters, e.g., temperatures, feed flow rates, feed ratios and PET concentrations. It was found that the temperature has positive effects on H₂ selectivity and conversion, yet feed flow rate has the adverse effects. In addition, PET concentrations showed improved in H₂ selectivity in comparison to when only phenol as a solvent was involved. The Ni particles, which are the noble-based active species are more effective, thus offered good hydrogen production in the PET steam reforming process. Incorporation of La₂O₃ as support and Pd as a promoter to the Ni/Al₂O₃ catalyst significantly increased catalyst stability. The Ni–Pd/Al₂O₃–Al₂O₃ catalyst showed remarkable activity even after 36 h along with the production of carbon nanotubes, while H₂ selectivity and feed conversion was only slightly decreased.     

Efficiency and effectiveness enhancement of an intercooler of two‐stage air compressor by low‐cost Al2O3/water nanofluids

The present study was aimed to utilize low‐cost alumina (Al₂O₃) nanoparticles for improving the heat transfer behavior in an intercooler of two‐stage air compressor. Experimental investigation was carried out with three different volume concentrations of 0.5%, 0.75%, and 1.0% Al₂O₃/water nanofluids to assess the performance of the intercooler, that is, counterflow heat exchanger at different loads. Thermal properties such as thermal conductivity and overall heat transfer coefficient of nanofluid increased substantially with increasing concentration of Al₂O₃ nanoparticles. Specific heat capacity of nanofluids were lower than base water. The intercooler performance parameters such as effectiveness and efficiency improved appreciably with the employment of nanofluid. The efficiency increased by about 6.1% with maximum concentration of nanofluid, that is, 1% at 3‐bar compressor load. It is concluded from the study that high concentration of Al₂O₃ nanoparticles dispersion in water would offer better heat transfer performance of the intercooler.     

Influence of tungsten loading on CO2/O2 reforming of methane over Co‐W–promoted NiO‐Al2O3 nanocatalyst designed by sol‐gel‐plasma

Co‐W–promoted NiAl₂O₄ nanocatalyst with various amount of tungsten (0, 1, 3, and 7 wt.%) was fabricated via hybrid sol‐gel‐plasma method. The nanocatalysts were evaluated by XRD, FESEM, EDX, BET, and FTIR analyses. The samples were utilized in CO₂/O₂ reforming of methane to syngas. EDX results proved the existence of all the applied elements in synthesis. FESEM and BET results illustrated that tungsten addition led to lower surface area, larger particle size, and roughly worse particles scattering. Therefore, Co‐NiAl₂O₄ (NCW0A) presented higher yield; however, yields were reduced for the other samples due to the covering impact of tungsten. As a result of time on streams performance (2880 minutes and at 750°C), the 7 wt.% tungsten promoted sample exhibited stable but lower yield (Y_H2 = 64%). Moreover, NCW1A exhibited more stable and higher yield than NCW0A. Optimum operating parameters were obtained as GHSV = 24 l/g_cat.h, CH₄/CO₂ = 1, and CH₄/CO₂/O₂ = 1/1/0.08. TG‐DTG, EDX, and FESEM analyses were applied for the used samples. TG‐DTG graphs demonstrated that by rising of tungsten loading, lighter and lower amount of coke was formed. Some agglomerations were observed in the EDX images of NCW0A and NCW1A while lower agglomeration was found for the tungsten‐rich sample. Carbon fiber formation was detected in the FESEM images of the used NCW0A while for the others, amount of the deposited coke and carbon fibers decreased.     

The steam reforming of guaiacol for hydrogen via Ni/Al2O3: The influence of dispersion

In this paper, three Ni/Al₂O₃ catalysts with different structure were prepared by different methods. The differences between the catalysts had been compared by H₂ temperature program reduction (H₂-TPR), X-ray diffraction, thermogravimetric analysis, scanning electron microscope, transmission electron microscope, and X-ray photoelectron spectroscopy. The results showed that synthesis method had significant effect on the combination of Ni particle with carrier. The method of coprecipitation could help to improve the combination of Ni and Al₂O₃, and the effect was further enhanced after adding polyethylene glycol (PEG). Due to the enhanced interaction between the active metal and the carrier, the NiO could be easily deoxidized and hard to sinter, which could obtain smaller and more dispersed Ni particles. Moreover, the addition of PEG improved the Ni particle size and its dispersion, and promoted the formation of the unique acicular Al₂O₃. The performance of guaiacol steam catalytic reforming via different catalysts was further analyzed, and the results showed the catalyst obtained by coprecipitation method with PEG exhibited best activity with 73.8% guaiacol conversion and 23.1 wt% H₂ yield.     

High-performance mesoporous (AlN/Al2O3) for enhanced NH3 yield during chemical looping ammonia generation technology

Chemical looping ammonia generation (CLAG), including the N-sorption/desorption steps of the N-carrier, is increasingly important due to the high demand for formation of carbon-free fuel. The N-sorption step, the synthesis of aluminum nitride (AlN) by the carbothermal reduction, has been widely studied for improving the purity and stability of aluminum nitride. However, there are few studies on how to enhance the porosity and thus N-desorption reactivity of AlN, one of the key issues for the CLAG. Therefore, in this paper, a supported Al-based nitrogen carrier (AlN/Al₂O₃) with mesoporous structure, in which 5% of Y₂O₃ was added as a catalyst, was developed with excess aluminum oxide (γ-Al₂O₃) and the corresponding N-desorption of the generated N-carrier was studied with a stationary bed reactor, X-ray diffraction (XRD), Brunner-Emmet-Teller (BET) measurements, Raman spectra and scanning electron microscope (SEM). The results showed that using the excess aluminum oxide in N-sorption step significantly led to the significant improvement in N-carrier's porosity and thus N-desorption reactivity, which did not vary with change in carbon types. Also, the N-sorption performance of γ-Al₂O₃ with carbon black was better than that with graphite due to their different carbon crystal structures. In addition, the effect of other parameters including the mole ratio of Al₂O₃:C, reaction temperature on the N-sorption performance of the N-carrier were studied. It was found that the specific surface area of the mesoporous structured Al-based AlN, synthesized with mole ratio of Al₂O₃: C being 3:3 at 1200 °C, reached to>70 m²/g, which was the best one for good NH₃ synthesis performance.     

Thermal, structural and crystallization kinetics of SiO2-BaO-ZnO-B2O3-Al2O3 glass samples as a sealant for SOFC

The present work describes the development of a glass-ceramic in SiO₂-BaO-ZnO-B₂O₃-Al₂O₃ system. The prepared glass samples were found to have good compatibility to act as a sealant in planar solid oxide fuel cell (SOFC) in terms of coefficient of thermal expansion (TEC) and glass transition temperature (T_g). The crystallization kinetics of present glass samples were investigated by various characterization techniques such as differential thermal analyzer (DTA), Dilatometery, X-Ray diffraction (XRD) and scanning electron microscopy (SEM). The crystallization behavior of the chosen glass samples was influenced by replacing B₂O₃ with Al₂O₃. With the addition of Al₂O₃ there is increase in glass transition temperature (T_g) and glass crystallization temperature (T_c). Also with the addition of Al₂O₃ crystallization phenomenon is hindered. XRD and SEM study was done at various temperatures for different time durations. The detail of the above discussed study is done in the present paper.     

Ce promoting effect on the activity and coke formation of Ni catalysts supported on mesoporous nanocrystalline γ-Al2O3 in autothermal reforming of methane

In this study methane autothermal reforming (ATR) was investigated over Ni/Al₂O₃ and Ni/Al₂O₃–CeO₂ catalysts. The catalyst carriers were prepared through a facile one-step method, which produced mesoporous nanocrystalline carriers for Ni catalysts. The samples were characterized by XRD, TPR, BET, TPO and SEM characterization techniques and the catalytic activity and stability were also studied at different conditions (GHSV and feed ratio) in methane ATR. It was found that the nickel catalyst supported on 3 wt.% Ce–Al₂O₃ exhibited higher activity compared to the catalysts supported on the Al₂O₃ and promoted Al₂O₃ with 1 and 6 wt.% Ce. The results also showed that the nickel catalyst supported on 3 wt.% Ce–Al₂O₃ possessed the highest resistance against carbon deposition in ATR reaction.     

A heat-resistant ceramic with increased mechanical strength on the basis of aluminum titanate synthesized with concentrated solar radiation

The mechanical properties of an aluminum titanate-based ceramic are increased by decreasing the grain growth kinetic of the initial material, which is synthesized by melting in a solar furnace. The thermomechanical properties are improved if the following additives are introduced: mullite, spinel, and a eutectic of Al₂O₃-ZrO₂.     

Characterization of molten salt doped with different size nanoparticles of Al2O3

This paper aims to study the effect on the characteristics of molten salt because of the dispersion of different size nanoparticles of Al₂O₃. The eutectic mixture of 54 wt% KNO₃ and 46 wt% NaNO₃ was selected as the base salt. Five different size nanoparticles of Al₂O₃, 80, 135, 200, 300, and 1000 nm, were dispersed into the base salt at a mass concentration of 1% to make the nanomaterials by a two‐step method, respectively. Thermal properties of the base salt and the samples with Al₂O₃ nanoparticles, including the melting point temperature, fusion heat, specific heat capacity, and thermal diffusivity, were measured with differential scanning calorimeter (DSC) and Xenon Flash Apparatus (XFA). On the basis of the measured specific heat capacities and thermal diffusivities, their thermal conductivities in the solid state were calculated at discrete specified temperatures. The results showed that the dispersions of 200‐ and 135‐nm Al₂O₃ nanoparticles could enhance the average solid and liquid specific heat capacities by up to 17.2% and 19.7%, respectively. The research on thermal diffusivity and thermal conductivity also verified that the influences of different size nanoparticles were different. Although no new strong intensity peaks or peak position variations were found in the diffraction patterns of the two samples with 80‐ and 1000‐nm nanoparticles of Al₂O₃, the larger deviations in the lower wavenumber region still meant possible crystalline structure variation because of the dispersion of Al₂O₃ nanoparticles. Scanning electronic microscope (SEM) images showed the inhomogeneity and the agglomeration of dispersed nanoparticles in the base salt, and the formation of a nanolayer around the nanoparticles could be a possible explanation to the thermal‐physical property variation.     

Facile synthesis of M-CuFe2O4 (M= Al2O3, CeO2, La2O3, ZrO2, Mn2O3) catalysts using a one-pot method and their applications in high-temperature water gas shift reaction

Water gas shift reaction is an essential process of hydrogen production and carbon monoxide removal from syngas. In this study, the promotional effect of ZrO₂, CeO₂, La₂O₃, Al₂O₃, and Mn₂O₃ was investigated on the CO conversion and thermal stability of the copper ferrite in high-temperature water gas shift reaction (HTSR) and hydrogen purification. The powders were synthesized by a simple solid-state route and characterized by XRD, H2-TPR, SEM, FT-IR, TG-DTA, and BET analyses. Promoters (ZrO₂, CeO₂, La₂O₃, Al₂O3, and Mn₂O₃) could affect the WGSR performance in activity and stability. In the M-CuFe2O4 catalyst, alumina acts as a texture promoter and aids in the fine dispersion of copper ferrite. The results indicated that the surface area of the Al₂O₃–CuFe₂O₄ (210 m²/g) catalyst was higher than the other samples. This catalyst presented higher CO conversion in HTSR and had higher stability at 1000 min on stream. It was found that the incorporation of different contents of alumina had a significant influence on the textural and catalytic properties of the CuFe₂O₄-based catalysts. The 30%Al₂O₃–70%CuFe₂O₄ catalyst exhibited the highest CO conversion of 65% at 350 °C, uniform pore size distribution, and intense interaction between copper ferrite and alumina, causing the effective stabilization of the active phase in the catalyst structure. The findings of this study represent that the solid-state method, due to its simplicity and creation of a mesoporous structure, can also be applied for the preparation of many heterogeneous metal oxide catalysts.     

Fabrication of oxide pellets containing lumped Gd2O3 using Y2O3‐stabilized ZrO2 for burnable absorber fuel applications

In this paper, the fabrication of novel burnable absorber fuel concepts with oxide pellets, containing either a lumped Gd₂O₃ rod, a mini‐pellet, or a spherical particle in the centerline of the oxide pellet, is investigated to propose the lumped Gd₂O₃ burnable absorber fuel concept to improve nuclear fuel performance with longer fuel cycle lengths and better fuel utilization. The unique characteristic of the lumped Gd₂O₃ burnable absorber fuel is its high spatial self‐shielding factor that reduces its burnout rate and, therefore, improves the reactivity control. Oxide pellets containing lumped Gd₂O₃ were fabricated by using a combination of cold isostatic pressing and microwave sintering at 1500°C to understand the potential technical issues in the fabrication of duplex burnable absorber fuel. The effect of the sintering temperature on the densification and phase transformation of 8 wt.% yttria‐stabilized zirconia, a surrogate for UO₂, was investigated. Spherical Gd₂O₃ particles were fabricated by the drip casting of a Gd₂O₃‐based Na alginate solution. The fabrication of duplex oxide pellets by using presintered Gd₂O₃ mini‐pellets resulted in internal cracks at the interface between the Gd₂O₃ and 8 wt.% yttria‐stabilized zirconia layers because of the mismatch of their densification. However, the formation of interfacial cracks was eliminated by controlling the initial sintered density of the lumped Gd₂O₃.