Flame Spray Synthesis of Nanoscale La0.6Sr0.4Co0.2Fe0.8O3–δ and Ba0.5Sr0.5Co0.8Fe0.2O3–δ as Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

Electrochemical performance and degradation was analysed by conductivity measurements as well as thermogravimetric analysis (TGA) under different atmospheres. CO₂ was identified as a critical parameter in terms of carbonate formation from Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–δ and causes a strong increase in the material resistivity, whereas La_0.6Sr_0.4Co_0.2Fe_0.8O_3–δ is unaffected. The oxygen exchange kinetic of both compositions is affected by CO₂ containing atmospheres.     

Electrochemical Performance of PrBaCo2O5+δ and Sm0.5Sr0.5CoO3−δ Infiltrated Ce0.9Gd0.1O1.95 Cathodes

Cathodes with PrBaCo₂O_5+δ (PBC) and Sm_0.5Sr_0.5CoO_3−δ (SSC) infiltrated on Ce_0.9Gd_0.1O_1.95 (CGO) backbones are prepared using metal nitrates as precursors and ethanol as wetting agent. Electrochemical impedance spectra (EIS) are measured from cathode/CGO/cathode symmetrical cells in 400–650 °C under humidified air. The results indicate that interfacial area specific resistance (ASR) value decreases and then increases with infiltrate loading and minimum values occur at 50 wt.% loading (relative to sum of infiltrate and backbone) for both PBC and SSC infiltrates. ASR values of PBC infiltrated cathodes are lower than that of corresponding SSC infiltrated cathodes in general, and in particular ASR values as low as 1.36 × 10⁻² and 2.27 × 10⁻² Ω cm² are obtained at 650 °C in air for 50 wt.% PBC and 50 wt.% SSC infiltrated cathodes, respectively. Conductivity values of CGO electrolyte increase with infiltrate loading and agree with the reported values when the loading reaches 50 wt.%.     

Sm0.5Sr0.5CoO3–Sm0.2Ce0.8O1.9 Composite Oxygen Electrodes for Solid Oxide Electrolysis Cells

In this paper, a series of Sm_0.5Sr_0.5CoO₃–Sm_0.2Ce_0.8O_1.9 (SSC–SDC) composite with different ratios were prepared and characterized as oxygen electrodes for solid oxide electrolysis cells (SOECs). Yttria‐stabilized zirconia (YSZ) was selected as the electrolyte with a SDC barrier layer to avoid detrimental solid state interaction between SSC and YSZ. At 850 °C, the impedance spectra showed that the optimum SDC content in the composite electrode was found to be about 30 wt.%, which showed a much lower area specific resistance of 0.03 Ω cm². The electrochemical performances of a Ni–YSZ hydrogen electrode supported YSZ membrane SOEC with the SSC–SDC73 oxygen electrode were also measured at 750–850 °C. The hydrogen production rate calculated from the Faraday's law was 327 mL cm^–2 h^–1 at 850 °C at an electrolysis voltage of 1.3 V with a steam concentration of ∼40%, which indicated that the SSC–SDC73 was a promising oxygen electrode candidate for high temperature electrolysis cells.     

Co‐synthesis of Sm0.5Sr0.5CoO3‐Sm0.2Ce0.8O1.9 Composite Cathode with Enhanced Electrochemical Property for Intermediate Temperature SOFCs

A 70 wt.% Sm_0.5Sr_0.5CoO₃ – 30 wt.% Sm_0.2Ce_0.8O_1.9 (SSC–SDC73) composite cathode was co‐synthesized by a facile one‐step sol–gel method, which showed lower polarization resistance and overpotential than those of physically mixed SSC–SDC73 cathode. The polarization resistance of co‐synthesized SSC–SDC73 cathode at 800 °C was as low as 0.03 Ω cm² in air. Scanning electron microscopy (SEM) images showed that the enhanced electrochemical property was mainly attributed to the smaller grains and good dispersion of SSC and SDC phases within the composite cathode, leading to an increase in three‐phase boundary length. The dependence of polarization resistance with oxygen partial pressure indicated that the rate‐limiting step for oxygen reduction reaction was the dissociation of molecular oxygen to atomic oxygen process. An anode supported fuel cell with a co‐synthesized SSC–SDC73 cathode exhibited a peak power density of 924 mW cm⁻² at 800 °C. Our results suggested that co‐synthesized composite was a promising cathode for intermediate temperature solid oxide fuel cells (IT‐SOFCs).     

Characterization of Ba0.5Sr0.5Co0.7In0.1Fe0.2O3−δ as the Cathode Material for Proton‐conducting SOFCs

Ba_0.5Sr_0.5Co_0.7In_0.1Fe_0.2O_3−δ powders are successfully synthesized as the cathode materials for proton‐conducting solid oxide fuel cells (SOFCs). The prepared cells consisting of the structure of a BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7)‐NiO anode substrate, a BZCY7 electrolyte membrane and a cathode layer, are measured from 600 to 700 °C with humidified hydrogen (ca. 3% H₂O) as the fuel. The electrochemical results show that the cell exhibits a high power density which could obtain an open‐circuit potential of 0.986 V and a maximum power density of 400.84 mW cm⁻² at 700 °C. The polarization resistance measured at the open‐circuit condition is only 0.15 Ω cm² at 700 °C.     

Enhancement of the oxygen desorption/absorption property of BaFe1−xInxO3−δ by In substitution for Fe site

Oxygen desorption/absorption behavior of In‐substituted BaFeO_3?δ [BaFe_1?xIn_xO_3?δ] was evaluated using thermogravimetry, high‐temperature X‐ray diffraction, and iodometry. By In substitution of 10% into BaFeO_3?δ with ordered distribution of oxide ion vacancy, the structural change to cubic perovskite structure occurred, accompanied by the rearrangement of oxide ion vacancy in random and by the increase in the average valence of Fe ions. The amount of desorbed oxygen per Fe ion was enhanced by only 10% In substitution, which could be attributed to the random distribution of oxide ion vacancies. Among the In‐substituted specimens with almost constant valence of Fe ion, BaFe_0.9In_0.1O_3?δ with the highest value of Fe content exhibited the largest amount of desorbed oxygen from the lattice, indicating that this material could be regarded as a promising candidate for oxygen storage materials.     

Performance of Cobalt‐free La0.6Sr0.4Fe0.9Ni0.1O3–δ Cathode Material for Intermediate Temperature Solid Oxide Fuel Cells

A series of cobalt‐free perovskite‐type cathode materials La_0.6Sr_0.4Fe_1–xNi_xO_3–δ (0 ≤ x ≤ 0.15) for intermediate temperature solid oxide fuel cells (IT‐SOFCs) are prepared by a citric‐nitrate process. The conductivities of the cathode materials are measured as functions of temperature (300–800 °C) in air by AC impedance method, and the La_0.6Sr_0.4Fe_0.9Ni_0.1O_3–δ (LSFN10) has the highest conductivity to be 160 S cm^–1 at 400 °C. A single IT‐SOFC based on LSFN10 cathode, BaZr_0.1Ce_0.7Y_0.2O_3–δ electrolyte membrane and Ni–BaZr_0.1Ce_0.7Y_0.2O_3–δ anode substrate was fabricated by a simple spin‐coating process, and the performances of the cell using hydrogen as fuel and air as the oxidant were researched by electrochemical methods at 600–700 °C. The maximum power densities of the cell are 405 mW cm^–2 at 700 °C, 238 mW cm^–2 at 650 °C, and 140 mW cm^–2 at 600 °C, respectively. The results indicate that the LSFN10 is a promising cathode material for proton conducting IT‐SOFCs.     

Degradation mechanism analysis of Ba0.5Sr0.5Co0.8Fe0.2O3‐δ membranes at intermediate‐low temperatures

The degradation of the permeation flux of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ membranes has typically been attributed to the phase transformation of the material at intermediate temperatures. In this study, the effect of the interfacial oxygen exchange steps was considered to give an overall view of the degradation mechanism. The changes in the interfacial exchange resistances, bulk resistance, and morphologies of the membranes were investigated via physical characterizations and a permeation model. The interfacial oxygen exchange resistances increased more quickly with time than bulk resistance. Meanwhile, BaSO₄ particles were detected on both surfaces of the membranes, and their contents reached maximum at 650°C. However, after the membrane surfaces were coated by Sm_0.5Sr_0.5CoO_3‐δ porous layers, the interfacial oxygen exchange resistances kept constant and the degradation rates were slowed down. The degradation was predominated by the increase of interfacial oxygen exchange resistances induced by the enrichment of BaSO₄ particles on membrane surfaces. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3879–3888, 2015     

Perovskite oxide absorbents for oxygen separation

The fixed‐bed oxygen absorption processes of the series of Ba_1?xSr_xCo_0.8Fe_0.2O_3?δ oxides were studied by oxygen partial pressure swing absorption in the temperature range of 300–850°C. The results show that SrCo_0.8Fe_0.2O_3?δ, with the smallest A‐site ion radius, has the largest oxygen absorption capacity (0.402 mmol/g) at 500°C. The oxygen absorption and desorption kinetics fit well with the pseudo‐second‐order kinetics model. Comparing the modeling absorption rate coefficient k₂ with the desorption rate coefficient k₂′, all the oxides studied had higher oxygen absorption rates than oxygen desorption ones. In addition, the combined results of X‐ray diffraction analysis, O₂‐TPD, room temperature iodometric titration, and thermogravimetric analysis explained the relationship between the oxygen absorption capacities and the average radii of the A‐site ions for this series of Ba_1?xSr_xCo_0.8Fe_0.2O_3?δ in the temperature range of 300–600°C. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

The catalytic activity of the ceramic superconductor YBa2Cu3O7 − δ

The superconductivity of the ceramic solid YBa₂Cu₃O_{7 ? δ}, prepared by heating Y₂O₃, BaCO₃ and CuO at 920°C for 22 h, was checked by the Meissner effect. Chemical analysis established the formula of the compound prepared. A thermostated aqueous suspension of the superconductor, treated with a solution of H₂O₂, produced oxygen, whose volume was measured at intervals in a gas burette. From the initial rates of the first-order reaction at different temperatures, the activation enthalpy and entropy were 16 kJ mol^?1 and ?210 J K^?1 mol^?1 respectively. The rates of gas evolution were similar to those obtained when a MnO₂ sample was used as a catalyst. Neither the superconductor nor its semiconductor phase photocatalysed the decomposition of KMnO₄ solution. Evidence of the catalysed decomposition of N₂H⁺₅ by the superconductor is presented.     

Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Structural elucidation and iron oxidation states in situ formed β‐Ca3(PO4)2/α‐Fe2O3 composites

A detailed structural analysis on the in situ synthesized β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites is demonstrated. Compositional ratios, the influence and occupancy of iron at the β‐Ca₃(PO₄)₂ lattice, oxidation state of iron in the composites are derived from analytical techniques involving XRD, FT‐IR, Raman, refinement of the powder X‐ray diffraction and X‐ray photoelectron spectroscopy. Iron exists in the Fe³⁺ state throughout the investigated systems and favors its occupancy at the Ca²⁺(5) site of β‐Ca₃(PO₄)₂ until critical limit, and thereafter crystallizes as α‐Fe₂O₃ at ambient conditions. Fe³⁺ occupancy at the β‐Ca₃(PO₄)₂ lattice yields a Ca₉Fe(PO₄)₇ structure that is isostructural with its counterpart. A strong rise in the soft ferromagnetic behavior of β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites is obvious that depends on the content of α‐Fe₂O₃ in the composites. Overall, the diverse level of iron inclusions at the calcium phosphate system with a Ca/P ratio of 1.5 yields a structurally stable β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites with assorted compositional ratios.     

Improving the oxygen permeability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ membranes by a surface-coating layer of GdBaCo2O5+δ

A GdBaCo₂O_5+δ layer was coated on the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes to enhance their oxygen permeability by employing the fast oxygen adsorption/desorption surface-exchange properties of the GdBaCo₂O_5+δ material. The oxygen flux of the coated and uncoated Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes was measured in the temperature range of 600–850 °C. The results reveal that the oxygen-permeation flux of the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes coated by a GdBaCo₂O_5+δ layer shows significant enhancement. The GdBaCo₂O_5+δ layer coated on the oxygen desorption side (He side) has much effect than that coated on the oxygen adsorption side (air side). At 850 °C, the oxygen flux with a single coating layer on the air side can rise 16%, while a single coating on the helium side will result into a rise of 23%.     

A Performance Study of Solid Oxide Fuel Cells With BaZr0.1Ce0.7Y0.2O3–δ Electrolyte Developed by Spray‐Modified Pressing Method

Fuel cells with BaZr_0.1Ce_0.7Y_0.2O_3–δ (BZCY) proton‐conducting electrolyte is fabricated using spray‐modified pressing method. In the present study the spray‐modified pressing technology is developed to prepare thin electrolyte layers on porous Ni‐BZCY anode supports. SEM data show the BZCY electrolyte film is uniform and dense, well‐bonded with the anode substrate. An anode‐supported fuel cell with BZCY electrolyte and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–δ (BSCF) cathode is characterized from 600 to 700 °C using hydrogen as fuel and ambient air as oxidant. Maximum power density of 536 mW cm^–2 along with a 1.01 V OCV at 700 °C is obtained. Impedance spectra show that Ohmic resistances contribute minor parts to the total ones, for instance, only ~23% when operating at 600 °C. The results demonstrate that spray‐modified pressing technology offers a simple and effective way to fabricate quality electrolyte film suitable to operate in intermediate temperature.     

Bio‐Based Hybrid Magnetic Latex Particles Containing Encapsulated γ ‐Fe2O3 by Miniemulsion Copolymerization of Soybean Oil‐Acrylated Methyl Ester and Styrene

This work reports the use of acrylated fatty acid methyl ester (AFAME) as a biomonomer for the synthesis of bio‐based hybrid magnetic particles poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ produced by miniemulsion polymerization. Poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ can be tailored for use in various fields by varying the content of AFAME. The strategy employed is to encapsulate superparamagnetic iron oxide nanoparticles (SPIONs) as γ‐Fe₂O₃ into a styrene/AFAME‐based copolymer matrix. Raman spectroscopy is employed to ensure the formation of the SPIONs (γ‐Fe₂O₃) obtained by a co‐precipitation technique followed by oxidation of Fe₃O₄. The functionalization of SPIONs with oleic acid (OA) is carried out to increase the SPIONs–monomer affinity. The presence of OA on the surface of γ‐Fe₂O₃ is certified by identification of main absorption bands by fourier‐transform infrared spectroscopy (FTIR). Thermal analysis (differential thermogravimetry/differential thermo analysis and differential scanning calorimetry) results of poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ show an increase in AFAME content leading to a lower copolymer glass transition temperature (T _g). Dynamic light scattering (DLS) measurements result in poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ particles with diameter in the range of 100–150 nm. It is also observed by transmission electron microscopy (TEM) and cryo‐TEM techniques that γ‐Fe₂O₃ particles are successfully encapsulated into the poly(styrene‐co‐AFAME) matrix.     

Statistical Optimization of the Biodiesel Production Process Using a Magnetic Core‐Mesoporous Shell KOH/Fe3O4@γ‐Al2O3 Nanocatalyst

A magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was synthesized using the Fe₃O₄@γ‐Al₂O₃ core‐shell structure as support and KOH as active component. The prepared samples were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDS), Fourier transform infrared (FTIR), Brunauer‐Emmett‐Teller (BET), and vibrating sample magnetometry (VSM) techniques. Transesterification of canola oil to methyl esters (biodiesel) in the presence of the magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was investigated. Response surface methodology (RSM) based on the Box‐Behnken design (BBD) was employed to optimize the influence of important operating variables on the yield of biodiesel. A biodiesel yield of 97.4 % was achieved under optimum reaction conditions. There was an excellent agreement between experimental and predicted results.     

Fabrication of BaZr0.1Ce0.7Y0.2O3 – δ ‐Based Proton‐Conducting Solid Oxide Fuel Cells Co‐Fired at 1,150 °C

Dense proton‐conducting BaZr_0.1Ce_0.7Y_0.2O_{3 – δ} (BZCY) electrolyte membranes were successfully fabricated on NiO–BZCY anode substrates at a low temperature of 1,150 °C via a combined co‐press and co‐firing process. To fabricate full cells, the LaSr₃Co_1.5Fe_1.5O_{10 – δ}–BZCY composite cathode layer was fixed to the electrolyte membrane by two means of one‐step co‐firing and two‐step co‐firing, respectively. The SEM results revealed that the cathode layer bonded more closely to the electrolyte membrane via the one‐step co‐firing process. Correspondingly, determined from the electrochemical impedance spectroscopy measured under open current conditions, the electrode polarisation and Ohmic resistances of the one‐step co‐fired cell were dramatically lower than the other one for its excellent interface adhesion. With humidified hydrogen (2% H₂O) as the fuel and static air as the oxidant, the maximum power density of the one‐step co‐fired single cell achieved 328 mW cm^–2 at 700 °C, showing a much better performance than that of the two‐step co‐fired single cell, which was 264 mW cm^–2 at 700 °C.     

Treatment of Volatile Organic Compounds with a Pt/Co3O4‐CeO2 Catalyst

For emission control of volatile organic compounds (VOC), e.g., in the painting and printing industries, conventional Pt/Al₂O₃ and Co₃O₄‐CeO₂ catalysts are used. On the Pt/Al₂O₃ catalyst, aromatic hydrocarbons containing a benzene ring such as toluene can be oxidized at a lower complete oxidation temperature than on Co₃O₄‐CeO₂, under typical treatment conditions. However, ethyl acetate and isopropyl alcohol can be oxidized at a lower complete oxidation temperature on Co₃O₄‐CeO₂ than on Pt/Al₂O₃. In this study, platinum was directly supported on Co₃O₄‐CeO₂. Using chloroplatinic acid, the platinum cohered and the catalytic activity did not improve. But when the platinum was supported using platinum colloid coated with dispersant, high‐dispersion support of the platinum on the Co₃O₄‐CeO₂ surface was achieved, and toluene, ethyl acetate, and isopropyl alcohol could be oxidized at less than 250 °C.     

Preparation of γ‐Fe2O3 Catalysts and their deNOx Performance: Effects of Precipitation Conditions

Magnetic γ‐Fe₂O₃ catalysts were prepared by microwave‐assisted coprecipitation utilizing the direct‐titrate and back‐titrate precipitation technique with different precipitants, namely, (NH₄)₂CO₃, NaOH, Na₂CO₃, and NH₄OH, which were evaluated in the selective catalytic reduction of NO_x with NH₃. The optimum γ‐Fe₂O₃ catalyst preparation method was direct titration with NH₄OH as the precipitant, which exhibits high deNO_x efficiency. This direct titration was effective to maintain the proper crystallization degree of γ‐Fe₂O₃, improve the pore structure, and suppress the formation of α‐Fe₂O₃ phase, being advantageous to get tiny and uniform discrete γ‐Fe₂O₃ particles with high activity in selective catalytic reduction. NH₄⁺‐based precipitants in direct titration leads to an increase of the surface O/Fe atom ratio, and more lattice oxygen sites are exposed to the crystal surface.