The enhancement of oxygen flux on Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) hollow fibers using silver surface modification

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) hollow fibers were fabricated using a phase inversion/sintering method. As oxygen permeation of BSCF hollow fibers is controlled by the rate surface exchange kinetics, catalytic Ag particles were coated on both inner and outer surfaces using chemical deposition method, as verified by SEM and EDX. The Ag coated BSCF membranes showed up to 100% increase in oxygen permeation at 700 °C, and improvements lower than 10% were measured at 950 °C as compared with unmodified membranes. It was found that Ag catalyst surface loading was non-homogenous and concentrated on the perovskite grain boundaries. As a result, lighter Ag surface loading delivered improved oxygen flux while oxygen flux reached a maximum even though in the presence of excess catalyst loading. The catalytic activity of Ag was beneficial in enhancing surface reaction kinetics up to 850 °C attributed to the spillover effect. Above this temperature, the increase in oxygen permeation rate was marginally diminished due to the reduction of the spillover effect.     

Oxygen surface exchange kinetics of SrTi(1-x)Fe(x)O(3-δ) mixed conducting oxides

The oxygen surface exchange kinetics of mixed conducting perovskite oxides SrTi(1-x)Fe(x)O(3-δ) (x = 0, 0.01, 0.05, 0.35, 0.5) has been investigated as a function of temperature and oxygen partial pressure using the pulse-response (18)O-(16)O isotope exchange (PIE) technique. Arrhenius activation energies range from 140 kJ mol(-1) for x = 0 to 86 kJ mol(-1) for x = 0.5. Extrapolating the temperature dependence to the intermediate temperature range, 500-600 °C, indicates that the rate of oxygen exchange, in air, increases with increasing iron mole fraction, but saturates at the highest iron mole fraction for the given series. The observed behavior is concomitant with corresponding increases in both electronic and ionic conductivity with increasing x in SrTi(1-x)Fe(x)O(3-δ). Including literature data of related perovskite-type oxides Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-δ), La(0.6)Sr(0.4)CoO(3-δ), and Sm(0.5)Sr(0.5)CoO(3-δ), a linear relationship is observed in the log-log plot between oxygen exchange rate and oxide ionic conductivity with a slope fairly close to unity, suggesting that it is the magnitude of the oxide ionic conductivity that governs the rate of oxygen exchange in these solids. The distribution of oxygen isotopomers ((16)O(2), (16)O(18)O, (18)O(2)) in the effluent pulse can be interpreted on the basis of a two-step exchange mechanism for the isotopic exchange reaction. Accordingly, the observed power law dependence of the overall surface exchange rate on oxygen partial pressure turns out to be an apparent one, depending on the relative rates of both steps involved in the adopted two-step scheme. Supplementary research is, however, required to elucidate which of the two possible reaction schemes better reflects the actual kinetics of oxygen surface exchange on SrTi(1-x)Fe(x)O(3-δ).     

Mixed conductivity, nonstoichiometric oxygen, and oxygen permeation properties in Co-Doped Sr3Ti2O(7-δ)

Electrical conductivity and oxygen permeation rates in Co-doped Sr(3)Ti(2)O(7-δ) with Ruddesden-Popper type structures were investigated. The effects of metal dopants (M) in the Ti site of Sr(3)Ti(2)(M)O(7-δ) on the mixed conductivity were also studied. Doping of Sr(3)Ti(2)O(7-δ) with Co was found to be effective for improving the electrical conductivity as well as the oxygen permeation rate, which could be assigned to the increased oxygen vacancy concentration by doping Co(3+) into Ti(4+) sites. The nonstoichiometric oxygen of these oxides was measured by using a thermal gravimetric method. The creation of oxygen vacancies, which is compensated with Co(3+) doping, leads to higher oxide ion conductivity. The oxygen permeation rate monotonously increased with increasing amounts of Co in the Ti site. Sr(3)Ti(0.8)Co(1.2)O(7-δ) exhibited high oxide ion conductivity and a large oxygen permeation rate. The highest oxygen permeation rate achieved a value of 2.02 cc min(-1) cm(-2) at 1273 K for Sr(3)Ti(0.8)Co(1.2)O(7-δ). Neutron diffraction analysis and redox titration suggests that the oxygen diffusion occurs through oxygen vacancies in the perovskite block, but not through excess oxygen in the rock salt block.     

颗粒弥散Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ基复合透氧膜材料的制备、结构与性能研究

Dense oxygen permeable membranes are expected to have great impact on oxygen production and oxygen involved industrial processes. Ba0.5Sr0.5Co0.8Fe0.2O3-δ is of highest oxygen permeability at elevated temperatures. A novel composite ceramic preparation route for Ba0.5Sr0.5Co0.8Fe0.2O3-δ was developed by directly produced stable BaZrO3 based secondary phase particles(SPP) via addition of ZrO2 and iso molar excess BaO, aiming at improving mechanical properties. It revealed that as synthesized composites could get a well developed and fine grained microstructure, there being secondary phase particles as the grain growth inhibitor, and the mechanical properties and oxygen permeation are improved. For the composite with addition of 10% ZrO2+10% BaO, a well developed and fine grained microstructure has been obtained. Compared to the pure phase BSCF5582, the three point bending strength of the composite with addition of 5% ZrO2+5% BaO increases by 68% and its oxygen permeation rate is much higher below 850℃ with the smaller apparent activation energy. Additionally, the electrical properties of the composites are also affected by the inclusion of SPP: conductivity decreases with the SPP content increasing, while the hysteresis of conductivity declines due to the relative stable carrier concentration.     

Oxygen permeation of BSCF membrane with varying thickness and surface coating

The oxygen permeation of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) membranes was measured between 750 and 900 °C as a function of membrane thickness with or without La_0.7Sr_0.3CoO₃ (LSC) coating layer under controlled PO₂-gradient$P_{{\text{O}}_2}\text{-gradient}$ (Air/He). In order to see the relative effects of bulk diffusion and surface-exchange kinetics, the thickness of membrane was varied from 0.5 to 2.0 mm. The oxygen-permeation flux at 900 °C increased with LSC coating from that of uncoated membrane. For example, it increased ∼1.8 times for 1 mm-thick BSCF membrane. The characteristic membrane thickness (L_C) which divides the bulk-diffusion limit and surface-exchange kinetics limit was estimated using the modified Wagner equation. The L_C values were 0.55 and 1.10 mm at 900 °C for the coated and uncoated BSCF membranes, respectively, and decreased with decreasing temperature.     

Influence of CO2 on Oxygen Surface Exchange Kinetics of Mixed-Conducting Ba0.5Sr0.5Co0.8Fe0.2O3?δ Oxide

The poisoning effect of CO₂ on the oxygen surface exchange kinetics of BSCF (Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ) is investigated with a novel pulse isotopic exchange technique. The surface exchange rate of BSCF severely decreases after in situ exposure to CO₂, which is ascribed to carbonate formation on the material surface. The detrimental effect of CO₂ starts at a low temperature of 375 ^oC and concentration as low as 1%, and becomes more pronounced at higher temperatures. Degradation of the surface exchange kinetics is associated with a rapid loss of oxygen permeation performance of BSCF in CO₂.     

Cation interdiffusion model for enhanced oxygen kinetics at oxide heterostructure interfaces

An interface between the perovskite La(0.8)Sr(0.2)CoO(3-δ) (LSC-113) and the K(2)NiF(4)-type (La(0.5)Sr(0.5))(2)CoO(4-δ) (LSC-214) heterostructure was recently shown to enhance oxygen surface exchange and the rate of the oxygen reduction reaction (ORR) by orders of magnitude compared to either the LSC-113 or LSC-214 phase alone. This result is of interest to develop better optimized materials for solid-state electrochemical devices, e.g. solid oxide fuel cells. The effect has been attributed to the interface itself, rather than changes in the bulk LSC-113 or LSC-214 phases. Using density functional theory (DFT)-based simulations, we demonstrate that there is a ～0.9 eV (～1.3 eV) energy gain for exchanging a Sr from LSC-113(25%Sr) (LSC-113(40%Sr)) with a La from LSC-214(50%Sr). These changes in energy create a large driving force for interdiffusion across the heterostructure interface from Sr into LSC-214 and La into LSC-113. We estimate that the Sr concentrations (in the LSC-214 phase) in a typical experimental temperature range of 500-600 °C and in equilibrium with LSC-113(25%Sr) and LSC-113(40%Sr), may be about 75% Sr and 90% Sr, respectively. Based on the bulk behavior of the LSC-214 phase (Vashook et al., Solid State Ionics, 2000, 138, 99-104), an Sr enrichment from x = 0.5 to x = 0.75 in (La(1-x)Sr(x))(2)CoO(4-δ) is expected to enhance the oxygen vacancy concentration by 2-2.5 orders of magnitude under typical experimental conditions. An increased vacancy concentration in LSC-214 near the interface can explain most of the enhanced oxygen kinetics observed up until now in these heterostructures.     

高温固体氧化物电解池钙钛矿型氧电极材料Ba_xSr_(1-x)Co_(0.8)Fe_(0.2)O_(3-δ)结构计算与性能研究

研究和开发高性能的钙钛矿型混合电导氧化物是目前高温固体氧化物电解池(SOEC)氧电极材料研究的热点.选择BaxSr1-xCo0.8Fe0.2O3-δ系列材料,通过对材料的容差因子、关口半径、晶格自由体积等计算,以及对平均键能、B位离子的变价能力、催化活性等方面的分析,确定了A位最佳配比.对优化出的Ba0.5Sr0.5Co0.8Fe0.2O3-δ材料的电化学性能进行了研究,并与自制的La0.2Sr0.8MnO3(LSM)氧电极材料进行了比较.结果表明:850℃下阳极极化阻抗(ASR)仅为0.07Ωcm2,远低于LSM;将其应用于SOEC氧电极进行高温电解制氢试验,产氢速率为相同条件下LSM的2.3倍,说明将Ba0.5Sr0.5Co0.8Fe0.2O3-δ用作SOEC阳极材料具有很好的应用前景.     

Fast oxygen exchange kinetics of pore-free Bi(1-x)Sr(x)FeO(3-δ) thin films

The oxygen incorporation/extraction kinetics of the potential solid oxide fuel cell (SOFC) cathode material Bi(1-x)Sr(x)FeO(3-δ) with x = 0.5 and 0.8 was studied by electrochemical impedance spectroscopy on geometrically well-defined pore-free thin film electrodes. The oxygen exchange rate was found to be higher than that of La(1-x)Sr(x)FeO(3-δ) and-among cobalt-free perovskites-only surpassed by Ba(1-x)Sr(x)FeO(3-δ) which is however known to be unstable in a SOFC environment.     

Solid oxide fuel cells with both high voltage and power output by utilizing beneficial interfacial reaction

An intriguing cell concept by applying proton-conducting oxide as the ionic conducting phase in the anode and taking advantage of beneficial interfacial reaction between anode and electrolyte is proposed to successfully achieve both high open circuit voltage (OCV) and power output for SOFCs with thin-film samarium doped ceria (SDC) electrolyte at temperatures higher than 600 °C. The fuel cells were fabricated by conventional route without introducing an additional processing step. A very thin and dense interfacial layer (2-3 μm) with compositional gradient was created by in situ reaction between anode and electrolyte although the anode substrate had high surface roughness (>5 μm), which is, however, beneficial for increasing triple phase boundaries where electrode reactions happen. A fuel cell with Ni-BaZr(0.4)Ce(0.4)Y(0.2)O(3) anode, thin-film SDC electrolyte and Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) cathode has an OCV as high as 1.022 V and delivered a power density of 462 mW cm(-2) at 0.7 V at 600 °C. It greatly promises an intriguing fuel cell concept for efficient power generation.     

氧渗透膜反应器的烷烃氧化脱氢

研究了乙烷和丙烷在催化膜反应器中的氧化脱氢反应．所用的膜材料为La2Ni0.9V0.1O4＋δ和Ba0.5Sr0.5Co0.8Fe0.2O3-δ．为了平衡氧气通量和额外的均匀气相反应,实验选择在中温段进行（550或者650℃）．实验结果表明膜的氧渗透通量和膜表面上主要激活烷烃的活性位在获得高的烷烃转化率过程中起决定性作用．乙烷和丙烷的氧化脱氢实验数据均符合Mars-van Krevelen机理,其中烷烃和膜表面的晶格氧反应产生相应的烯烃．同时证明了气相和膜表面的氧浓度是决定烯烃选择性的关键．     

Influence of grain size on the oxygen permeation performance of perovskite-type (Ba0.5Sr0.5)(Fe0.8Zn0.2)O3−δ membranes

The effect of grain size distribution in perovskite-type (Ba_0.5Sr_0.5)(Fe_0.8Zn_0.2)O_3−δ (BSFZ) ceramics on their oxygen permeation behaviour has been investigated by variation of calcination temperature in powder production and sintering time for the ceramics. The membranes were examined via scanning electron microscopy (SEM), transmission electron microscopy (TEM) and oxygen permeation experiments. We found that the dwell time during sintering has an important influence on the microstructure of the ceramic. The longer the dwell time, the further proceeds the grain coarsening, which affects the oxygen permeation in a positive way and leads to an enhanced permeation. Supplementary, decreasing calcination temperature in perovskite powder synthesis delivers fine powders with grain sizes less than one micrometer and thus smaller grains in the ceramic. Unfortunately, the grain size distribution in sintered membranes is not constant through membrane cross-sections since grains in the bulk are smaller compared to those at the surface which is not favorable for the oxygen permeation of the ceramics. The activation energy was determined to be in the range of 51–53 kJ/mol and its variation does not exhibit a dependence of grain size changes. High-resolution transmission electron microscopy proved that grain boundaries are atomically thin without any interfacial phases. We come to the conclusion that the transport rate of the oxygen permeation is limited predominantly by bulk diffusion and due to the fact that grain boundaries in BSFZ act as barriers for bulk diffusion, this material is a high mobility material.     

Electrical properties and defect chemistry of TiO2 single crystal. III. Equilibration kinetics and chemical diffusion

The equilibration kinetics of high-purity single-crystal TiO(2) were monitored using measurements of electrical conductivity in the temperature range 1073-1323 K and oxygen activity, p(O(2)), range 10(-13) to 75 kPa. The kinetics data were used to determine the chemical diffusion coefficient (D(chem)) within narrow ranges of p(O(2)). There was observed a complex effect of the p(O(2)) on the D(chem), which exhibits a maximum at the n-p transition. The effect of the p(O(2)) on the D(chem) was discussed in terms of the defect disorder and the related semiconducting properties. The activation energy of the D(chem), which also varies with the p(O(2)), exhibits a maximum at p(O(2)) = approximately 10(4) Pa (143 kJ/mol).     

Electrical properties of niobium-doped titanium dioxide. 2. Equilibration kinetics

The present work reports isothermal gas/solid equilibration kinetics for Nb-doped TiO(2) (0.65 atom %) at elevated temperatures (1073-1298 K) within narrow ranges of oxygen activity spanning between 10(-13) Pa and 75 kPa. The equilibration kinetics were monitored using electrical conductivity measurements. The kinetic data were used to determine the chemical diffusion coefficient (D(chem)). D(chem) as a function of p(O(2)) exhibits a complex dependence, which is considered in terms of defect disorder and the related concentrations of electronic charge carriers. The activation energy of D(chem) in the p(O(2)) range 10 Pa < p(O(2)) < 75 kPa varies in the range 88.0-98.2 kJ/mol. It is important to note that the chemical diffusion coefficient in strongly reduced conditions [p(O(2)) = 10(-9) Pa] exhibits a negative temperature dependence of D(chem) (-67.2 kJ/mol). This finding indicates that under these conditions transport in a chemical potential gradient is consistent with metallic charge transport.     

Studies on the performance stability of mixed conducting BSCFO membranes in medium temperature oxygen permeation

A permeation study using bare Ba0.5Sr0.5Co0.8Fe0.2Ox membranes shows that stable oxygen fluxes are only achieved when operating the membrane at temperatures higher than 1023 K and indicates therefore that short contact time membrane reactors will be most suitable for future upgrading of light hydrocarbons.     

甲烷部分氧化制合成气的钙钛矿型致密透氧膜反应器的数值模拟(英文)

采用等温理论模型,以甲烷催化氧化制合成气为模型反应,模拟非担载钙钛矿型致密透氧膜反应器的性能。分别研究了Ｌａ_０．２Ｂａ_０．８Ｆｅ_０．８Ｃｏ_０．２Ｏ_(３－δ)、Ｌ３０．２Ｓｒ０．８Ｆｅ０．８Ｃｏ０．２Ｏ３－δ和ＳｒＦｅＣｏ０．５Ｏｘ三种透氧速率不同的膜材料、膜反应器的尺寸以及反应工艺条件对ＣＨ４转化率、ＣＯ选择性和Ｈ２／ＣＯ摩尔比的影响,对膜反应实验具有指导意义。     

Syngas Production Using an Oxygen-Permeating Membrane Reactor with Cofeed of Methane and Carbon Dioxide

MethaneutilizationhasbeendrawingconsiderableattentionrecentlyduetothelargeamountofnatUralgasavailabletobeupgradedandtheworldwidedemandforlow-costtransportationfuelsl'2.Amongthemanyconversionroutes,partialoxidationofmethane(POM)tosyngasprovedanewwayforthepotentialalternativetotoday'sindustrialsteamreformingprocesses.HoweveT,althoughveryactivecatalystsforthePOMtosyngashavebeenreported,large-scaleplantshavenotyetbeenconstructed.AIargeadiabatictemperatUreriseatthefrontoftheco-bedeasilycausesre…     

Mixed-conducting perovskite-type Sr_xBi_(1-X)FeO_(3-δ)oxygen-permeating membranes

SrxBi1-xFeO3- (SBF) series mixed conductors were synthesized using Standard ceramic method. The properties of such materials were characterized by XRD, O2-TPD techniques. Ab-normal crystal phenomena were found and explained and correlated with the oxygen permeation results. By analysis of the critical radius (rc), the degree of openness of the lattice (Fv) and the average metal-oxygen bonding energy of the perovskite lattice (ABE), it was proposed that the oxygen permeation flux is determined mainly by the oxygen diffusion rate in bulk when 1-x≤0.5, and by the concentration of oxygen vacancy when 1-x≥ 0.5. The stability of Sr0.5Bi0.5FeO3- was also investigated, and the high stability of it was attributed to the stable BO6 octahedra.     

Thermal characterization and compatibility studies of perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) oxide with Cr2O3 at high temperature

The chemical compatibility of perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) oxides with Cr₂O₃ has been examined between room temperature and 1,100 °C. Differential thermal analysis and thermogravimetric analysis were used to analyze the thermal behavior of BSCF–Cr₂O₃ binary mixtures in all composition ranges (0–100 mass% BSCF). The reaction products were identified by X-ray analysis after heating at 700–1,100 °C. As we expected, it was found that perovskite-type BSCF oxide had a poor chemical compatibility with the Cr₂O₃ oxide. In particular, the decomposition process of the BSCF–Cr₂O₃ binary mixture is quite complex and it starts at about 700–750 °C. The mixtures of BSCF and Cr₂O₃ oxides reacted forming mixed complex oxides based on (Ba/Sr)FeO₃, (Co/Fe)CrO₄, and (Ba/Sr)CrO₄ mixtures.     

混合导体透氧膜反应器中甲烷部分氧化反应的催化行为(英文)

应用组成为Ba0.5Sr0.5Co0.8Fe0.2O3-(的钙钛矿型混合导体陶瓷膜制成膜反应器。该膜在进行氧分离的同时具有活化甲烷氧化偶联的催化功能。随着温度升高和膜的富氧端氧分压的增大,透氧量有所增加。在空气、氦气的氧分压梯度下,850(C,膜厚度为1.5 mm时,JO2可达到1.2 mL/(cm3(min)。同时在800(C~900(C温度范围内,该膜对于甲烷转化为乙烷和乙烯一般只具有0.5%~3.5%的低转化率,而选择性可达40%~70%。在反应尾气中发现了大量的未反应的分子氧,说明过量的氧与甲烷未经催化反应的气相反应导致了C2的选择性相对较低。OCM膜反应模式情况下的透氧量与空气、氦气梯度情况下的透氧量相比只有微小增加,这与POM膜反应模式情况下透氧量大量增加显著不同。