多层膜结构BaCe0.9Nd0.1O3-δ的制备及其在常压合成氨中的应用

用干压法制备了Ni-BaCe0.9Nd01O3-δ多孔金属陶瓷阳极,并在阳极基膜上制备出致密的BaCe0.9Nd0.1O3-δ固体电解质薄膜.薄膜的厚度约为40 μm,致密均匀.测定了多层膜结构BaCe0.9Nd0.1O3-δ在干燥氮气/湿润氢气气氛中的电导率,结果表明其电导率要比厚膜BaCe0.9Nd0.1O3-δ和SrCe0.95Y0.05O3-δ(SCY)要高.将多层膜材料用于固态质子传导电池中,在常压下以氮气和氢气为原料合成了氨气.结果表明,与SCY固体电解质比较,氨的产率提高了一个数量级以上.     

BaCe0.5Zr0.4Y0.1O3-δ粉体的溶胶-凝胶法和高温固相法制备及性能表征

分别通过溶胶-凝胶法和高温固相反应法制备了BaCe0.5Zr0.4Y0.1O3-δ粉体.采用热重-差热分析(TG-DTA),粉末X射线衍射(XRD),扫描电子显微镜(SEM),傅立叶红外衍射(FT-IR),N2吸附-脱附等方法对所制备的粉体进行了表征.结果表明:用溶胶-凝胶法在1200 ℃×10 h可以合成纯的BaCe0.5Zr0.4Y0.1O3-δ粉体,合成温度比传统的高温固相反应法降低400 ℃左右;溶胶-凝胶法合成粉体具有多孔结构特征,与固相法合成粉体相比具有较高的比表面积.但致密化试验表明:溶胶-凝胶法合成粉体与固相法合成粉体相比具有较低的烧结活性.溶胶-凝胶法合成粉体颗粒表面残余的有机基团和颗粒内部的大量微孔将在致密化过程中产生空间位阻,从而影响高温下原子的迁移,阻碍材料的致密化过程.     

Ca、Ce双掺杂烧绿石型复合氧化物的合成及离子导电性能研究

Pyrochlore-type rare earth complex oxides of La_2-αCa_αZr_2-βCe_βO_7-δ were synthesized by the sol-gel method. The structure of the samples was characterized by X-ray diffraction (XRD). The ionic conduction in solid electrolyte of the sintered samples was examined using electrochemical methods at 400～800 ℃. The result indicated that the samples were pyrochlore-type structure, conductivities of the Ca and Ce doped samples were largely increased. Ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid state proton conducting cell reactor. The ammonia evolution rate of doped samples is larger than that of the undoped ones, which indicates that the samples are proton conductor and the ability of protonic conductivity is mainly decided by hole concentration.     

BaCe0.9Nd0.1O3-δ柠檬酸盐法合成、表征及其在中温区的电导率

A precursor of BaCe_0.9Nd_0.1O_3-δ solid electrolyte was synthesized by the sol-gel method and sintered at 1400℃.The obtained gels and powder were characterized by differential and ther mogravimetric thermal analysis(TG-DTA),X-ray diffraction(XRD), transmissi on electron microscopy(TEM).Using the sintered samples as solid electrolyte and silver-palladium alloy as electrodes,electrical conductivities under different gas ambiences at intermediate temperature (400～600℃) were measured. In moist hydrogen atmosphere, the conduction is a little higher than that of dry hydrogen atmosphere. In hydrogen atmosphere, proton conduction may predominate, leading to an increase in conductivity and a decrease in activation energy.     

钙钛矿型A位掺杂复合氧化物La1-xSrxCoO3-6的光催化活性研究

用柠檬酸溶胶-凝胶法制备了钙钛矿型La1-xSrxCoO3-6复合氧化物，用XRD、XPS、EDS、红外、紫外等技术进行了表征，测定了其对活性艳红等水溶性染料光催化脱色的活性．结果表明：在A位掺Sr^2＋，由于产生较多氧空位，表面非晶格活性氧量增加，使LaCoO3的光催化活性明显提高，其中La1-xSrxCoO3-6效果最佳．     

BaCe0.5Zr0.4Y0.1O3-α的溶胶-凝胶法制备及其电性能

采用溶胶-凝胶法, 以低于固相合成法150～250 ℃的温度进行烧结, 分别制备了BaCe0.9Y0.1O3-α和BaCe0.5Zr0.4Y0.1O3-α固体电解质. 应用AUTOLAB PGSTA 30型电化学工作站测定了两种电解质在不同温度下的阻抗谱, 在350～800 ℃范围内电导率分别为1.62×10-4～6.43×10-3 S·cm-1, 2.52×10-5～3.73×10-3 S·cm-1, 电导激活能分别为0.54和0.84 eV. 同时用高温固相合成法合成了BaCe0.9Y0.1O3-α质子导体, 在相同条件下其电导率为1×10-4～4×10-3 S·cm-1, 激活能为0.50 eV. 实验结果表明 用溶胶-凝胶法得到的材料在烧结温度低于固相合成法150～250 ℃的情况下, 制备出的样品电导率高;对于同一质子导体BaCe0.9Y0.1O3-α, 用Zr代替部分Ce, 固体电解质的电导率明显降低.     

钙钛矿型氧化物A(Mg、Ca、Sr)TiO_3的结构及其光催化性能研究

钙钛矿型ABO_3复合氧化物具有良好的热稳定性、催化性能、磁性、导电性以及传感等性质~([1-5]).目前钙钛矿结构复合氧化物以其优异的性能已成为光催化领域的研究热点之一~([6-9]).在钙钛矿型ABO_3复合氧化物中,A位金属可以起到稳定结构的作用,而B位金属为活性位.但是,当B位金属相同A位金属不同的一类钙钛矿型氧化物作为催化剂时,影响其光催化活性的主要因素很少见文献报道.     

铈酸钡和钇掺杂的铈酸钡复合氧化物的制备及其在钌基氨合成催化剂中的应用

 采用柠檬酸法合成了 BaCeO3 和掺杂 Y3+的 BaCe0.9Y0.1O3-δ 复合氧化物, 以 Ru3(CO)12 为前体, 利用浸渍法制备了 Ru/BaCeO3 和 Ru/BaCe0.9Y0.1O3-δ 催化剂. 通过 X 射线衍射、扫描电镜和透射电镜技术对样品进行了表征, 并在固定床反应器中考察了催化剂的氨合成反应活性. 结果表明, 载体 BaCeO3 的稳定性优于 BaCe0.9Y0.1O3-δ, 但 Ru/BaCe0.9Y0.1O3-δ 催化剂的氨合成活性明显高于 Ru/BaCeO3, 在 3.0 MPa, 15 000 h1, 425 oC 反应时, Ru/BaCe0.9Y0.1O3-δ 催化剂上氨合成反应速率达到 432.5 ml/(g•h), 是 Ru/BaCeO3 催化剂的 1.6 倍. 这种活性和稳定性的显著差异来自载体中 Ce4+ 与 Ru 纳米粒子间的电子作用.     

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．     

BaZr0.45Ce0.45Y0.1O3-δ的合成及其电性能研究

采用高温固相反应制备了电导率高、化学稳定性较好的新型高温质子导体BaZr0.45Ce0.45Y0.1O3-δ材料.运用X射线衍射仪、扫描电子显微镜分别对不同烧结温度试样的晶型、微观形貌进行了表征,并应用IM6e型电化学工作站测定了其不同温度下的阻抗谱.结果表明1600℃为最佳的烧结温度,此温度烧结试样具有最高的电导率,800℃约为1.06×10-2S·cm-1,电导活化能为0.76 ev.     

阳极支撑BZCY电解质及GBFN阴极膜在常压合成氨中的性能研究

采用硝酸盐-柠檬酸法制备了 BaZr0.1 Ce0.7 Y0.2 O3-α(BZCY)质子电解质及GdBaFeNiO5+δ(GBFN)阴极材料,用浆料旋涂法结合后续的热处理在NiO-BZCY阳极支撑体上制备致密的BZCY电解质薄膜,在电解质薄膜上制备多孔性GBFN阴极膜,成功地组装成合成氨膜反应器.以氢、氮气为反应气体,通过电解方法进行了常压合成氨试验.结果显示,BZCY及GBFN分别具有钙钛矿型及双钙钛矿型结构,NiO与BZ-CY具有良好的化学兼容性,合成氨产率高达1.63 ×10-8 mol·s-1·cm-2,高于迄今所报道的类似方法的合成氨产率.这与BZCY电解质膜优良的导电性能、GBFN膜优良的极化性能密切相关.Ag对GBFN的修饰也有利于氨产率的提高.     

SDC和SSC在低温常压电化学合成氨中的性能研究

用溶胶—凝胶法制备了Ce0.8Sm0.2O2-δ(SDC)和Sm0.5Sr0.5CoO 3-δ（SSC）超细粉体,采用XRD、TEM和SEM等对粉体进行了观察和表征。分别以Ni-SDC和SSC为阴极, 磺化聚砜质子交换膜为电解质, Ni- SDC金属陶瓷为阳极,银-铂网做集流体组成单电池,在25℃～120℃温度范围内研究了其电导率随温度变化关系及在电化学合成氨中的性能。结果表明：在25℃～120℃温度范围内,使用Ni-SDC和SSC为阴极均有氨气生成,而SSC对电化学合成氨的性能优于Ni-SDC, 在80℃时氨产率达到了6.5×10-9 mol•s-1•cm-2。     

Atmospheric Pressure Ammonia Synthesis Using Non-thermal Plasma Assisted Catalysis

This paper described a novel and green approach on catalytic ammonia synthesis using non-thermal plasma (NTP). The process studied in this paper involves the synthesis and absorption of ammonia under atmospheric pressure and low temperature. The effects of operational parameters including applied voltage, frequency, gas component and flow rate on ammonia synthesis under NTP conditions are studied in this paper. In addition, different selected catalysts and absorbents were investigated under different conditions of NTP treatment and the ammonia efficiency was reported and analyzed. Ru catalyst with carbon nanotube support, along with Cs promoter and micro porous absorbents including Molecular Sieve 13X and Amberlyst 15 yield the highest ammonia efficiency in this process. Results further indicated that frequency and applied voltage of 10,000 Hz and 6000 V, with N₂:H₂ feed ratio of 3:1 provided the optimized efficiency of ammonia synthesis of 2.3 gNH₃/kWh.     

La0.9M0.1Ga0.8Mg0.2O3-α的中温质子导电性及其在常压合成氨中的应用

采用水热沉淀法制备了La0.9M0.1Ga0.8 Mg0.2O3-a(M=Ca2+,Sr2+,Ba2+)陶瓷样品的前驱体,沉淀剂来自尿素在水热条件下的水解产物.前驱体经煅烧和烧结后得到陶瓷样品.XRD显示样品具有单一的斜方晶LaGaO3钙钛矿结构.同位素效应和氢的电化学透过(氢泵)实验证明陶瓷样品具有质子导电性.用AC阻抗谱法测定了样品在300~600℃、氢气气氛中的质子电导率,其人小取决于La位掺杂的碱土金属离子:σ(M=Sr2+)>σ(M=Ba2+)>σ(M=Ca2+).以La0.9M0.1Ga0.8Mg0.2O3-a为固体电解质进行了常压合成氨,最佳合成温度为520℃.当施加的电流密度为1mA-cm-2、合成温度为520℃时,氨产率分别为:1.63X 10-9 mol·s-1cm-2(M=Ca2+),2.53X 10-9 mol·s-1·cm-2(M=Sr2+)和2.04X10-9mol·s-1,cm-2(M=Ba2+).     

Ammonia Synthesis at Room Temperature and Atmospheric Pressure from N2: A Boron-Radical Approach

Ammonia, NH₃, is an essential molecule, being part of fertilizers. It is currently synthesized via the Haber–Bosch process, from the very stable dinitrogen molecule, N₂ and dihydrogen, H₂. This process requires high temperatures and pressures, thereby generating ca 1.6 % of the global CO₂ emissions. Alternative strategies are needed to realize the functionalization of N₂ to NH₃ under mild conditions. Here, we show that boron-centered radicals provide a means of activating N₂ at room temperature and atmospheric pressure whilst allowing a radical process to occur, leading to the production of borylamines. Subsequent hydrolysis released NH₄⁺, the acidic form of NH₃. EPR spectroscopy supported the intermediacy of radicals in the process, corroborated by DFT calculations, which rationalized the mechanism of the N₂ functionalization by R₂B radicals.     

常温常压高效电化学合成氨催化体系的设计新策略

<正>氨是一种重要的生产原料。除传统工农业用途之外,氨还具有含氢量高(质量比达17.6%)、易液化、易储运等优点。若能实现绿色高效合成氨,势必能为其作为清洁储氢、储能材料等重要应用提供基础。目前,工业上广泛采用的Haber-Bosch方法需要在高温高压(300–500°C,100–200 atm (1atm=100 kPa))等苛刻条件下促进氮分子的活化。其能量和氢气都来自于化石燃料(如甲烷等),因而消耗大量的化石能源,并造成大量的二氧化碳排