阴极催化剂Sm1.5Sr0.5MO4 (M＝Ni, Co, Fe)在低温常压下合成氨

利用溶胶—凝胶法制备了复合氧化物Sm1.5Sr0.5MO4 (M＝Ni, Co, Fe)(SSM),并利用XRD和SEM等对样品进行表征。用Nafion膜作电解质、以SSM作为阴极、Ni-SDC金属陶瓷为阳极、银-铂网做集流体组成单电池,在温度为25℃～100℃的低温常压下以干燥氮气和湿的氢气为原料进行电化学合成氨气测定,同时研究了影响氨合成的关键因素,确定了合适的工作温度,实验结果表明,最高氨产率可达到1.05×10-8mol·s-1·cm-2。     

利用Nafion膜和SFCN在低温常压下电化学合成氨

用溶胶-凝胶法制备了Ce0.8Sm0.2O2δ（SDC）和SmFe0.7Cu0.3-xNixO3（x=0,0.1,0.2,0.3）（SFCN）系列超细粉体,用XRD、TEM和SEM等方法对其进行了表征.分别将NiO-SDC和SFCN系列超细粉体干压成片并烧结成陶瓷,以SFCN系列陶瓷片为阴极,Nafion膜为电解质,NiO-SDC还原后得到的Ni-SDC金属陶瓷为阳极,银-铂网为集流体组成单电池,在低温常压下研究了其在电化学合成氨中的性能.结果表明：在25-100℃和施加电压的条件下,使用SFCN系列陶瓷片为阴极时均有氨气在阴极生成,其中SmFe0.7Cu0.1Ni0.2O3作阴极时电化学合成氨的性能最佳,在80℃时氨的合成速率为1.13×10^-8mol·s^-1·cm^-2,其电流效率为90.4%.     

Electrochemical synthesis of ammonia using a cell with a Nafion membrane and SmFe0.7Cu0.3?xNixO3 (x = 0?0.3) cathode at atmospheric pressure and lower temperature

Samaria-doped ceria Ce_0.8Sm_0.2O_2−δ (SDC) and SmFe_0.7Cu_0.3−x Ni _x O₃ have been synthesized by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The electrochemical synthesis of ammonia was investigated at atmospheric pressure and low temperature, using the SFCN materials as the cathode, a Nafion membrane as the electrolyte, nickel-doped SDC (Ni-SDC) as the anode and silver-platinum paste as the current collector. Ammonia was synthesized from 25 to 100°C when the SFCN materials were used as cathode, with SmFe_0.7Cu_0.1Ni_0.2O₃ giving the highest rates of ammonia formation. The maximum rate of evolution of ammonia was 1.13 × 10⁻⁸ mol·cm⁻²·s⁻¹ at 80°C, and the current efficiency reached as high as 90.4%. Supported by the National Natural Science Foundation of China (Grant No. 20863007)     

Electrochemical synthesis of ammonia using a cell with a Nafion membrane and SmFe_(0.7)Cu_(0.3-x)Ni_xO_3(x=0―0.3) cathode at atmospheric pressure and lower temperature

Samaria-doped ceria Ce0.8Sm0.2O2-δ(SDC) and SmFe0.7Cu0.3-xNixO3 have been synthesized by the sol-gel method and characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM) and scanning electron microscopy(SEM).The electrochemical synthesis of ammonia was investigated at atmospheric pressure and low temperature,using the SFCN materials as the cathode,a Nafion membrane as the electrolyte,nickel-doped SDC(Ni-SDC) as the anode and silver-platinum paste as the current collector.Ammonia was synt...     

钴掺杂Sr1.5La0.5MnO4的合成及高温电化学性能研究

采用EDTA-柠檬酸法合成了中温固体氧化物燃料电池阴极材料Sr_1.5La_0.5Mn_1-xCo_xO₄（SLMCO_x）,并利用粉末X射线衍射（XRD）、X射线光电子能谱（XPS）以及电化学交流阻抗谱（EIS）进行表征。结果表明,该材料与Ce_0.9Gd_0.1O_1.95（CGO）在1 200℃烧结12 h不发生化学反应。随着Co掺入量的增加,氧化物中Mn³⁺和Co²⁺含量增多,晶格氧含量降低,晶格畸变率增大。交流阻抗谱（EIS）测试结果显示,钴的掺杂明显降低电极的极化电阻,其中Sr_1.5La_0.5Mn_0.7Co_0.3O₄阴极在700℃空气中的极化电阻为0.62 Ω·cm²,明显小于Sr_1.5La_0.5MnO₄阴极在750℃的极化电阻（1.5 Ω·cm²）,表明钴掺杂的Sr_1.5La_0.5Mn_1-xCo_xO₄是一种潜在的IT-SOFC阴极材料。     

钴掺杂Sr1.5La0.5MnO4的合成及高温电化学性能研究

采用EDTA-柠檬酸法合成了中温固体氧化物燃料电池阴极材料Sr_(1.5)La_(0.5)Mn_(1-x)Co_xO_4(SLMCOx),并利用粉末X射线衍射(XRD)、X射线光电子能谱(XPS)以及电化学交流阻抗谱(EIS)进行表征。结果表明,该材料与Ce0.9Gd0.1O1.95(CGO)在1 200℃烧结12 h不发生化学反应。随着Co掺入量的增加,氧化物中Mn~(3+)和Co~(2+)含量增多,晶格氧含量降低,晶格畸变率增大。交流阻抗谱(EIS)测试结果显示,钴的掺杂明显降低电极的极化电阻,其中Sr_(1.5)La_(0.5)Mn_(0.7)Co_(0.3)O_4阴极在700℃空气中的极化电阻为0.62Ω·cm~2,明显小于Sr_(1.5)La_(0.5)MnO_4阴极在750℃的极化电阻(1.5Ω·cm~2),表明钴掺杂的Sr_(1.5)La_(0.5)Mn_(1-x)CoxO_4是一种潜在的IT-SOFC阴极材料。     

5V锂离子电池正极材料LiNi_(0.5)Mn_(1.5)O_4的低温燃烧法合成及性能研究

以IANO_3、Ni(NO_3)_2·6H_2O、Mn(NO_3)_2和CO(NH_2)_2为原料,采用低温燃烧法成功合成了5V锂离子电池正极材料LINi_(0.5)Mn_(15)O_4.通过XRD、SEM、循环伏安和恒电流充放电实验对合成样品进行了表征.结果表明,在850℃合成的正极材料LiNi_(0.5)Mn_(1.5)O_4具有立方尖晶石结构,规则的八面体晶形,粒度适中,比较均匀.合成产物具有良好的电化学性能,其充放电电压平稳,放电平台高达4.7V,4V放电平台几乎消失;放电容量达到124.92mAh/g,50次循环后放电容量仍可达到120.84mAh/g.     

载体乳化液膜法同步进行亚稳相PbCrO4纳米粒子的仿生合成与铅铬废水的处理

采用一种新型的纳米材料仿生合成方法——载体乳化液膜法,在煤油-Span-80-N7301乳化液膜体系中,以电镀废水中常见的Cr(Ⅵ)溶液为外相,蓄电池、油漆等行业废水常见的Pb(Ⅱ)溶液为内相,通过对生物体内囊泡结构的形态和离子传输功能模拟,室温下成功合成了能稳定存在的直径为5～15nm的正交亚稳相PbCrO4纳米粒子．使用XRD,TEM对产物结构和形貌进行了表征．首次通过FT-IR和UV-vis对所得产物和普通块体材料的光学性质做了比较．并对乳化液膜体系控制产物晶型和尺寸的机理进行了初步的探讨．此方法也有望用于对不同类型工业废水的耦合处理．     

Sulfonated Microporous Polymer Membranes with Fast and Selective Ion Transport for Electrochemical Energy Conversion and Storage

Membranes which allow fast and selective transport of protons and cations are required for a wide range of electrochemical energy conversion and storage devices, such as proton‐exchange membrane (PEM) fuel cells (PEMFCs) and redox flow batteries (RFBs). Herein we report a new approach to designing solution‐processable ion‐selective polymer membranes with both intrinsic microporosity and ion‐conductive functionality. Polymers are synthesized with rigid and contorted backbones, which incorporate hydrophobic fluorinated and hydrophilic sulfonic acid functional groups, to produce membranes with negatively charged subnanometer‐sized confined ionic channels. The ready transport of protons and cations through these membranes, and the high selectivity towards nanometer‐sized redox‐active molecules, enable efficient and stable operation of an aqueous alkaline quinone redox flow battery and a hydrogen PEM fuel cell.     

Hydrothermal Synthesis and Electrochemical Properties of Complex Cu(CH3C6H4COOH)2(2,2''-bipy)·(H2O)

The title complex has been synthesized by 4-methylbenzoic acid and 2,2'-bipyridine (bipy) in the mixed solvent of water and methanol. It crystallizes in the triclinic system, space group (P1-) with a = 0.7047(3), b = 1.1217(5), c = 1.6718(7) nm, α = 103.826(7), β = 90.772(6), γ = 104.195(6)°, C26H25CuN2O5.50, Mr = 517.02, V = 1.2404(9) nm3, Dc = 1.384 g/cm3, Z = 2, F(000) = 536, μ(MoKα= 0.921 mm-1, R = 0.0782 and wR = 0.2172. Structural analysis shows that the copper atom is coordinated with three oxygen atoms from two 4-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2'-bipyridine, giving a distorted square-pyramid coordination geometry. The cyclic voltametric behavior of the complex has also been described.     

Hydrothermal Synthesis and Electrochemical Properties of Complex Cu(CH_3C_6H_4COOH)_2(2,2′-bipy)·(H_2O)

1 INTRODUCTION Inorganic-organic coordination framework has captured the interest of chemists due to its potential applications in adsorption, catalyst, separation and host-guest recognition. Generally, it builds upon the coordination of rigid multi-dentate bridge ligands with proper center metallic ions, and furthermore, weak interactions like hydrogen bond are involved[1, 2]. As an excellent N-donating ligand, 2,2?-bipyridine could coordinate with most transition metals to ge- nerate co…     

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of the Copper(II) Complex [Cu_4O_4(phen)_4(ClC_6H_4COO)_2(H_2O)_2]·(H_2O)_3

1 INTRODUCTION As we all know, copper is a necessary trace element for human body. For example, a large number of bi- nuclear or multi-nuclear transition metallic complex- es exist in active centers of some metalloprotein[1]. In the 1960’s, Bertand and Bock et al[2] reported the first tetra-nuclear copper complex with Cu4O3 unit. In 1996, a cyclo-tetranucleate complex bridged by pyridine was synthesized by Zhang Hua etc[3]. In 1999, Tan Xiangshi and coworkers[4] presented a cubic tet…     

Synthesis and Characterization of Phenolphthalein‐Containing Sulfonated Poly(arylene ether phosphine oxide)s by Direct Polycondensation for Proton Exchange Membrane

A series of novel phenolphthalein‐containing sulfonated poly(arylene ether phosphine oxide)s (sPAEPP) with various sulfonation degrees were synthesized by direct polycondensation. The structure of sPAEPP was confirmed by ¹H‐NMR, ¹³C‐NMR, and IR spectroscopy. The high‐molecular weight of these polymers was determined by gel permeation chromatography (GPC). The transparent, tough, and flexible membranes could be achieved by solution casting. The macroscopic properties and microstructure of the obtained membranes were investigated in detail. The results showed that these sPAEPP membranes displayed excellent properties in terms of swelling, proton conductivity, and methanol permeability. For example, sPAEPP‐100 membrane exhibited an appropriate water uptake of 33.1%, a swelling ratio of only 11.7% (lower than 20.1% of Nafion 117), a proton conductivity of 0.11 S cm^?1 (similar to that of Nafion 117) at 80 °C, and a methanol permeability of 4.82 × 10^?7 cm² s^?1. Meanwhile, it also presented outstanding oxidative stability. Atomic force microscope (AFM) micrographs showed that the hydrophilic domains of the sPAEPP‐100 membrane formed connected and narrow ionic channels, which contributed to its high proton conductivity and good dimensional stability. As a result, sPAEPP‐100 membrane displays excellent application prospect for fuel cells. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1097–1104     

二苯乙醇酸铜配合物的合成、晶体结构、电化学和荧光性质

以二苯乙醇酸为配体合成了1个新的化合物[Cu(2,2′-bipy)(BAA)][Cu(2,2′-bipy)(BAA)(H2O)]2.(H2O)3(BAA=二苯乙醇酸阴离子,2,2′-bipy=2,2′-联吡啶)。该化合物晶体属三斜晶系,空间群P1,晶胞参数:a=1.121 7(5)nm,b=1.360 2(6)nm,c=2.335 2(10)nm,α=99.260(6)°,β=101.223(8)°,γ=94.805(8)°,V=3.425(3)nm3,Dc=1.385 g.cm-3,Z=6,μ(Mo Kα)=0.992 mm-1,F(000)=1 474,最终偏离因子R1=0.0561,wR2=0.1128。在标题化合物的不对称单元中有3个单核铜(Ⅱ)配合物,且3个中心铜(Ⅱ)离子的配位数不完全相同,如Cu(1)离子的配位数是4,而Cu(2)和Cu(3)离子的配位数都是5。本文还测定了标题化合物的电化学性能和荧光性能,结果表明:在电化学过程中配合物的电子转移是准可逆的,电子转移数为2个;配合物在478 nm的光激发下可发射荧光。     

Reactions of 2,3-Dioxopyrrolo[2,1-a]isoquinolines with Ammonia and Aliphatic Amines

2,3-Dioxopyrrolo[2,1-a]isoquinolines, with either a tertiary amide substituent at position 1 or no substituent, react with ammonia and aliphatic amines with ring opening to form the corresponding enamino keto amides.     

Synthesis of functional derivatives of 2-methylenecyclopentane and 2-methylenecyclohexane based on the allylborylation of imines,nitriles, isocyanates,and isothiocyanates by cycloalkenylmethyl(dipropyl)boranes

A study has been made of the allylborylation of imines, nitriles, isocyanates, and isothiocyanates by the action of cycloalkenylmethyl(dipropyl)boranes. Preparative methods have been developed for obtaining amines, phenylamides, and phenylthioamides of the 2-methylenecyclopentane and 2-methylenecyclohexane series.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2597–2604, November, 1992.     

水合烟酸钡的合成、±结构表征和热化学性质

选择烟酸和氢氧化钡作为反应物, 利用室温固相合成方法, 借助于球磨技术, 合成了一种新的化合物——水合烟酸钡. 利用化学分析、元素分析、FTIR和X射线粉末衍射等方法确定了它的组成和结构为Ba(Nic)2·3H2O(s). 利用精密自动绝热热量计直接测定了此化合物在78-400 K温区的摩尔热容. 在热容曲线上出现了一个明显的吸热峰, 通过对热容曲线的解析, 得到了相变过程的峰温、相变焓和相变熵分别为(327.097±1.082) K、(16.793±0.084) kJ·mol-1和(51.340±0.164) J·K-1·mol-1. 将该温区的摩尔热容实验值用最小二乘法拟合得到摩尔热容(Cp,m)对温度(T)的多项式方程, 并且在此基础上计算出了它的舒平热容值和各种热力学函数值. 另外, 依据Hess定律, 通过设计合理的热化学循环, 选择体积为100 mL、浓度为0.5 mol·L-1的盐酸作为量热溶剂, 利用等温环境溶解-反应热量计分别测量固相反应的反应物和产物在所选溶剂中的溶解焓, 利用溶解焓确定固相反应的反应焓为⊿rH0m=-(84.12±0.38) kJ·mol-1. 最后, 利用固相反应的反应焓和其它反应物和产物已知的热力学数据计算出水合烟酸钡的标准摩尔生成焓为⊿fH0m[Ba(Nic)2·3H2O(s)]=-(2115.13±1.90) kJ·mol-1.     

Reaction of Mo(CO)_6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et_4N]_3[Mo_2(CO)_6(μ-OC_6H_4OCH_2C_6H_5)_3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359(2), b = 18.378(3), c = 24.952(2), β = 102.268(4)°, V = 6882.3(16) 3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm3, F(000) = 2832 and μ = 0.424 mm-1. The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections (I > 2σ(I)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) , indicating no metal- metal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

稀土—4—（2—吡啶偶氮）间苯二酚螯合物的高效液相色谱分离和测定

本文讨论了反相离子对液相色谱法分离和检测稀土-4-(2-吡啶偶氮)间苯二酚螯合物的各种条件,在12 min内完成了9种稀土螫合物的分离,校正曲线的线性范围是(ppm):La(0.01～3.20),Ce(0.03～2.8),Pr(0.06～3.5),Nd(0.05～3.8),Sm(0.01～3.0),Eu(0.05～3.4),Tb(0.02～3.0),Ho(0.01～3.4),Er(0.06～4.0).变异系数小于1.2％.