Preparation and hydrogen permeation properties of BaCe_(0.95)Nd_(0.05)O_(3-δ) membranes

Dense mixed proton and electron conducting membrane made of BaCe_(0.95)Nd_(0.05)O_(3-δ)(BCNd5)was prepared by pressing followed by sintering.X-ray diffraction(XRD)was used to characterize the phase structure of both the powder and the sintered membranes.The microstructure of the sintered membranes was studied by scanning electron microscopy(SEM).Hydrogen permeation through the BCNd5 membrane was studied using a high temperature permeator.The hydrogen permeation fluxes under wet conditions are higher than those under dry conditions,which is due to H~ hopping via surface OH groups.At 925℃,a hydrogen permeation flux of 0.02 mL/min cm~2 was obtained under wet condition,which recommends BCNd5 as a potential material for hydrogen-selective membranes.     

SrCe_(0.95)Y_(0.05)O_3-δ在中温区的电化学性质及其在常压合成氨中的应用

SrCe0.95Y0.05O3-δ是一种高温质子导体,本研究采用溶胶—凝胶法合成了 SrCe0.95Y0.05O3-δ纳米粉体,并以该粉体烧制得固体复合氧化物电解质陶瓷,测 定了其在中温区间(400-600℃)的电导率,结果表明不同气氛对其电导率有很大影 响．用该陶瓷在固态质子传导电他中常压下以氮气和氢气为原料合成了氨,并研究 了影响氨合成的关键因素,确定了合适的工作温度,在常压下480℃时氨的产率可 达10^-9mol/(s.cm^-2)以上．     

Novel Ba_(0.5)Sr_(0.5)Fe_(0.8)Zn_(0.2)O_(3-δ) membranes for POM

A novel cobalt-free perovskite based on Ba_(0.5)Sr_(0.5)Fe_(0.8)Zn_(0.2)O_(3-δ)(BSFZ)were prepared by EDTA-citric acid method.The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray diffraction(HTXRD).The thermal expansion coefficient of BSFZ is 10.5×10~(-6)K~(-1),which is lower than that of cobalt-based perovskite materials.The BSFZ membrane was also used to construct reactors for the partial oxidation of methane(POM)to syngas.Results show that the BSFZ membrane...     

Ce_(0.8)Nd_(0.2)O_(1.9)-La_(0.95)Sr_(0.05)Ga_(0.9)Mg_(0.1)O_(3-δ)固体复合电解质的结构和电性能

采用溶胶-凝胶法分别制备La0.95Sr0.05Ga0.9Mg0.1O3-δ(LSGM)和Ce0.8Nd0.2O1.9(NDC)电解质,并在NDC溶胶中加入0-15%(w,质量分数)的LSGM预烧粉体制得NDC-LSGM复合电解质,研究不同质量比复合电解质的结构和电性能.采用X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)和X能量色散谱仪(EDS)对样品进行结构表征,交流(AC)阻抗谱测试样品导电性能.结果表明:NDC-LSGM复合体系主要由立方萤石结构相、钙钛矿结构相和杂质相组成;LSGM的添加可促进晶粒的生长,产生大量相界面,清除或降低SiO2有害影响,明显提高晶界导电性;LSGM质量分数为10%的样品NL10具有最高晶界电导率和总电导率,400°C时NL10的晶界电导率σgb和总电导率σt分别为12.15×10-4和3.49×10-4S cm-1,与NDC的σgb(1.41×10-4S cm-1)和σt(1.20×10-4S cm-1)相比分别提高了7.62和1.91倍,总电导率的提高主要归因于晶界电导率的影响.     

Perovskite Sr_(0.9)Fe_(0.9)Zr_(0.1)O_(3-δ):Redox-stable Structure,Oxygen Vacancy,Electrical Properties and Steam Electrolysis Performance

Many researchers have studied on perovskite oxide for its unique structure.Perovskite oxides,ABO_(3-δ),with different A and B metals have shown wide applications in many fields,in particular solid oxide electrolysers.SrFeO_(3-δ),typical perovskite oxides,in which iron is the mixed-valence cation with the capacity to change the chemical valence,have a wide range of oxygen nonstoichiometry.In this study,Sr_(0.9)Fe_(0.9)Zr_(0.1)O_(3-δ)(SFZO) is synthesized and then treated in 5%H_2/Ar and air at high temperature,exhibiting excellent redox stability.Redox-stable structure,oxygen vacancy and electrical properties of SFZO are investigated.Steam electrolysis is then performed with SFZO cathode under 5%H_2O/5%H_2/Ar and 5%H_2O/Ar atmospheres,respectively.The present results indicate that the SFZO is a novel promising cathode material for solid oxide steam electrolyser.     

BaCe_(0.8)Zr_(0.1)La_(0.1)O_(3-α)陶瓷的制备和电性能研究

以高温固相反应法制备了BaCe0.8Zr0.1La0.1O3-α陶瓷,用粉末X-射线衍射(XRD)和扫描电镜(SEM)对其晶体结构和断面形貌进行了表征。以陶瓷材料为固体电解质、多孔性铂为电极,用交流阻抗谱技术测定了材料在500～900℃下不同气体气氛中的电导率;用气体浓差电池方法测定了材料在干燥空气和湿润空气中的离子迁移数;研究了材料的离子导电特性。结果表明,该陶瓷材料为单一钙钛矿型BaCeO3斜方晶结构。在500～900℃下,干燥和湿润的氧气、空气和氮气中,材料的电导率随着温度升高和氧分压增大而增大。在干燥的空气中,材料的氧离子迁移数为0.06～0.17,表现为氧离子与电子空穴的混合导电性,其中,电子空穴导电为主导。在湿润的空气中,材料的质子迁移数为0.52～0.01,氧离子迁移数为0.14～0.27,表现为质子、氧离子和电子空穴的混合导电性,其中,在500～550℃下,质子导电为主导;高于550℃,电子空穴导电为主导。     

Efficient CO_2 Electrolysis with Fluorite Structure Nanoparticles Modified Perovskite Structure La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3-δ) Cathode

Perovskite structure La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3-δ)(LSCM) cathode with unique structure can electrolyze CO_2 to CO in solid oxide electrolysers(SOEs).However,the cell performance is restricted by its electro-catalysis activity.In this work,fluorite structure nanoparticles(CeO_(2-δ)) are impregnated on LSCM cathode to improve the electro-catalysis activity.X-ray diffraction(XRD),scanning electron microscope(SEM) and X-ray photoelectron spectroscopy(XPS) together approve that the fluorite structure nanoparticles are uniformly distributed on the perovskite structure LSCM scaffold.Electrochemical measurements illustrate that direct CO_2 electrolysis with 10%mol CeO_(2-δ) impregnated LSCM cathode exhibits excellent performance for current density(0.5 A×cm~(-2)) and current efficiency(～95%) at 800 ℃ under 1.6 V.It is believed that the enhanced performance of directed CO_2 electrolysis may be due to the synergetic effect of fluorite structure CeO_(2-δ) nanoparticles and perovskite structure LSCM ceramic electrode.     

Ni/Ce_(0.75)Zr_(0.25)O_2界面催化CO_2甲烷化密度泛函理论研究

将温室气体CO_2催化加氢转化为CH_4,有利于碳资源化利用和减轻环境污染,是具有一定现实意义的模型化反应.实验发现,氧化物负载型催化剂对CO_2甲烷化过程展现出较高的催化活性和稳定性,但其催化机理和界面作用机制并未得到清楚认识.基于DFT+U计算方法,本文系统研究了复合氧化物Ce_(0.75)Zr_(0.25)O_2负载Ni体系催化CO_2甲烷化复杂基元过程.结果表明,在Ni/Ce_(0.75)Zr_(0.25)O_2(110)体系中,CO_2甲烷化反应涉及CO_2分解和甲酸盐两条途径,且CO_2的分解途径占主导地位,整个反应的控制步骤为CO_2吸附过程.产物甲烷是由界面上CO_2解离加氢产生的CH基团进一步在金属Ni活性位上加氢生成,揭示了该催化体系中载体与负载物之间存在协同催化作用,即载体界面主要发生碳氧化物的脱氧加氢,碳氢中间物种的加氢反应在Ni上发生.     

Nd_(1 x)Ba_(2-x)Cu_3O_(7-δ)超导体的热处理

通过对Nd1 xBa2 -xCu3O7-δ的两种样品 (烧结样品和区域熔炼样品 )的XRD谱图分析 ,研究了高温氩气氛下热处理对样品中Nd对Ba的取代值x的影响 ,同时比较了不同样品的Tc 和Jc 值。研究表明 ,氩气下 95 0℃热处理可以减少Nd对Ba的取代 ,Tc 和Jc 都有不同程度的提高。对不同固溶度x值的Nd1 xBa2 -xCu3O7-δ进行吸氧热处理 ,样品在热处理前后分别作XRD分析。从XRD谱图可以看出 :当x <0 4时 ,样品经吸氧后可以从四方相转变为正交相 ,而当x >0 4时 ,样品虽经长时间吸氧也不能使其从四方相转变为正交相     

Hydrogen Permeation Properties of Perovskite-type BaCe_(0.9)Mn_(0.1)O_(3-δ)Dense Ceramic Membrane

In recent years, mixed-conducting oxides, in which both protonic and electronic charge carriers exist, have received increasing attentions1. Ceramic membranes made of such materials are semipermeable to hydrogen at elevated temperatures. In the early 1980s, Iwahara et al. first reported protonic conduction in SrCeO3-based materials2. Later, BaCeO3 system was extensively studied because of its higher conductivities. However, the electronic conductivity of rare earth doped-BaCeO3 ceramic…     

A dense oxygen separation membrane with a layered morphologic structure

A configuration of dense mixed ionic and electronic conducting (MIEC) membrane with layered morphological structure for oxygen separation, which combines the benefits of high oxygen permeation flux of cobalt-based membrane, high chemical stability of iron-based perovskite and high mechanical strength of thick membrane, was studied. The membrane is normally composed of two layers; each layer is a dense MIEC oxide. The substrate layer is a thick dense membrane with high oxygen permeability but relatively lower chemical stability. The feasibility of dense thick Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF5582) membrane as the substrate layer and Ba_0.5Sr_0.5Co_0.2Fe_0.8O_3−δ (BSCF5528) as the thin-film layer was mainly experimentally investigated. Both the BSCF5582 and the BSCF5528 show the same cubic perovskite structure and the similar lattice constant with no detrimental reaction products formed. By optimizing fabrication parameters of a simple dry pressing process, dual-layered membrane, free of cracks, was successfully fabricated. The oxygen permeation flux of a dual-layered membrane with the thin-film BSCF5528 layer facing to the sweep gas reached 2.1 mL cm⁻² min⁻¹ [STP] (1.56 × 10⁻⁶ mol cm⁻² s⁻¹) at 900 °C, which is about 3.5 times higher than that of the BSCF5528 membrane (0.6 mL cm⁻² min⁻¹, [STP] (4.46 × 10⁻⁷ mol cm⁻² s⁻¹) under the same conditions.     

Preparation and hydrogen permeation properties of BaCe0.95Nd0.0503-δ membranes

Dense mixed proton and electron conducting membrane made of BaCe0.95Nd0.05O3-δ(BCNd5)was prepared by pressing followed by sintering.X-ray diffraction(XRD)was used to characterize the phase structure of both the powder and the sintered membranes.The microstructure of the sintered membranes was studied by scanning electron microscopy(SEM).Hydrogen permeation through the BCNd5 membrane was studied using a high temperature permeator.The hydrogen permeation fluxes under wet conditions are higher than those under dry conditions,which is due to H hopping via surface OH groups.At 925℃,a hydrogen permeation flux of 0.02 mL/min cm2 was obtained under wet condition.which recommends BCNd5 as a potential material for hydrogen-selective membranes.     

Preparation and hydrogen permeation properties of BaCeo.95Nd0.05O3-δ membranes

Dense mixed proton and electron conducting membrane made of BaCe0.95Nd0.05O3-δ （BCNd5） was prepared by pressing followed by sintering. X-ray diffraction （XRD） was used to characterize the phase structure of both the powder and the sintered membranes. The microstructure of the sintered membranes was studied by scanning electron microscopy （SEM）. Hydrogen permeation through the BCNd5 membrane was studied using a high temperature permeator. The hydrogen permeation fluxes under wet conditions are higher than those under dry conditions, which is due to H^＋ hopping via surface OH groups. At 925℃, a hydrogen permeation flux of 0.02 mL/min cm^2 was obtained under wet condition, which recommends BCNd5 as a potential material for hydrogen-selective membranes.     

Preparation and hydrogen permeation of BaCe0.95Nd0.05O3−δ membranes

A mixed proton–electron conducting perovskite made of BaCe_0.95Nd_0.05O_3−δ (BCN) was prepared by EDTA/citric acid complexing method. The precursor was characterized by differential scanning calorimetry (DSC), thermogravimetry (TG), and X-ray diffraction (XRD). In order to learn the perovskite formation process during the calcination, the intermediate, i.e. the sample calcined at 750 °C for 5 h, was investigated by scanning (STEM), energy-filtered (EFTEM), and high-resolution transmission electron microscopy (HRTEM) as well as electron energy-loss spectroscopy (EELS). The results revealed that the perovskite structure was formed via a solid-state reaction between barium–cerium mixed carbonate and cerium–neodymium mixed oxide particles. Dense mixed proton–electron conducting BCN membranes were made by pressing BCN powder followed by sintering. The microstructure of the sintered membranes was investigated by scanning electron microscopy (SEM). Hydrogen permeation through the BCN membrane was studied using a high-temperature permeator. The hydrogen permeation fluxes under wet conditions are higher than those under dry conditions, which is due to increased proton concentrations in the H⁺ hopping via OH groups. The hydrogen permeation increased with increasing hydrogen and steam concentrations in the feed. For a steam concentration of 15 vol.%, the hydrogen permeation flux reaches 0.026 ml/min cm².     

Mechanical stability and transport properties of the Sn-promoted SrCo0.8Fe0.2O3−δ ceramic membrane

In this article, the phase compositions, thermal, mechanical and transport properties of both the SrCo_0.8Fe_0.2O_3−δ (SCF) and the SrCo_0.8Fe_0.1Sn_0.1O_3−δ (SSCF) ceramic membranes were investigated systematically. As compared with the SCF membrane, the SSCF one had a more promoted thermal shock resistance, which related to its small thermal expansion coefficient between them and an enhanced composite structure for it. For the SCF membrane, a permeation rate of 1.9 × 10⁻⁶ mol cm⁻² s⁻¹ was obtained at 1000 °C and under the oxygen partial pressure gradient of P_O2 (h)/P_O2 (l) = 0.209 atm/0.012 atm; however, the permeation rate was 2.5 × 10⁻⁶ mol cm⁻² s⁻¹ for the SSCF one in the same measuring condition. In addition, both peak values of total electrical conductivity (σ_e) for SSCF sample appeared with increasing temperature. The second peak value of σ_e for SSCF one was regarded as the contribution from its minor phase, which appeared with the mixed conducting behavior resulting from partly Co-dissolving into its lattice.     

Systematic investigation on new SrCo1−yNbyO3−δ ceramic membranes with high oxygen semi-permeability

SrCo_1−yNb_yO_3−δ (y = 0.025–0.4) were synthesized for oxygen separation application. The crystal structure, phase stability, oxygen nonstoichiometry, electrical conductivity, and oxygen permeability of the oxides were systematically investigated. Cubic perovskite, with enhanced phase stability at higher Nb concentration, was obtained at y = 0.025–0.2. However, the further increase in niobium concentration led to the formation of impurity phase. The niobium doping concentration also had a significant effect on electrical conductivity and oxygen permeability of the membranes. SrCo_0.9Nb_0.1O_3−δ exhibited the highest electrical conductivity and oxygen permeability among the others. It reached a permeation flux of ∼2.80 × 10⁻⁶ mol cm⁻² s⁻¹ at 900 °C for a 1.0-mm membrane under an air/helium oxygen gradient. The further investigation demonstrated the oxygen permeation process was mainly rate-limited by the oxygen bulk diffusion process.     

Oxygen permeation through a Ce0.8Sm0.2O2−δ–La0.8Sr0.2CrO3−δ dual-phase composite membrane

A composite of oxygen ion conducting oxide Ce_0.8Sm_0.2O_2−δ (60 vol.%) and electron conducting oxide La_0.8Sr_0.2CrO_3−δ was prepared by sintering a powder compact at a temperature of 1550 °C. No significant reaction between the two constituent oxides was observed under preparation and oxygen permeation conditions. Appreciable oxygen permeation fluxes through the composite membrane were measured at elevated temperatures with one side of it exposed to the ambient air and the other side to a flowing helium gas stream. The oxygen flux initially increased with time, and took a long time to reach a steady value. A steady oxygen permeation flux as high as 1.4 × 10⁻⁷ mol cm⁻² s⁻¹ was obtained with a 0.3 mm thick membrane at 950 °C under a relatively small oxygen partial pressure difference of 0.21 bar/0.0092 bar. It was revealed that the overall oxygen permeation process was mainly limited by the transport in the bulk of the membrane in the range of the membrane thickness greater than 1.0 mm, and the limitation by the surface oxygen exchange came into play at reduced thickness of 0.6 mm.     

Evaluation of La0.5Sr0.5FeO3 − δ membrane reactors for partial oxidation of methane

Dense planar and tubular oxygen separation membranes of La_0.5Sr_0.5FeO_{3 −  δ} were studied in the partial oxidation of methane to syngas process. The oxygen permeation properties were obtained from the analysis of the outlet gas and compared with the data calculated from conductivity measurements. For the planar reactor, the selectivity achieved 95% and the CH₄ conversion was 95–99% at 900 °C with pure methane. For the tubular reactor, the CO selectivity and CH₄ conversion were 90% and 100%, respectively, under the same conditions. In both cases, the H₂/CO ratio was 1.6–1.9. No degradation of membranes was observed after 250 h of operation.     

Hydrogen permeability of 2.5 μm palladium–silver membranes deposited on ceramic supports

The permeability of hydrogen selective Pd-based membranes was tested in different experimental conditions. The membranes were obtained by depositing palladium–silver films onto ceramic porous supports, with film composition of about 20 wt% of silver and thicknesses of about 2.5 μm. Their permeance was measured at 400 °C at total trans-membrane pressures between 0.2 and 6 bar, using pure feeds of H₂ and N₂, as well as H₂/N₂ and H₂/CO mixtures; the temperature dependence of permeability was investigated using pure H₂ feeds at 300, 400 and 500 °C. The membranes exhibit a very attractive behavior, maintaining a virtually infinite selectivity throughout the testing, with permeance values among the highest values reported in literature for similar membranes. Permeation of pure hydrogen accurately follows Sieverts’ law and confirms the presence of a chemisorption–dissociation–diffusion mechanism, characterised by the transport of atomic hydrogen through the Pd–Ag layer as the limiting step. In the case of H₂/N₂ mixtures, the high membrane permeance originates also significant concentration polarization phenomena resulting in apparent deviations from Sieverts’ behavior; the presence of CO in the feed may reduce hydrogen permeability even by 75%, although this effect is shown to be fully reversible after a subsequent air treatment at 400 °C. The temperature dependence of the membrane permeability is of Arrhenius type, with an activation energy of about 17 kJ/mol, that is, close to what is reported for Pd–Ag membranes following Sieverts’ behavior.