Interaction of An(VI) (An = U, Np, Pu) and Np(V) with 2,3-pyridinedicarboxylic (quinolinic) acid (H2Quin): Complexation in aqueous solutions, synthesis and structure of the complexes [UO2(HQuin)2], [(NpO2)2(HQuin)2(C6H4NO3)2]·2H2O, and [PuO2Quin(H2O)]

Complexation of An(VI) (An = U, Np, Pu), and Np(V) with 2,3-pyridinedicarboxylic (quinolinic, H₂Quin) acid in aqueous solutions was studied. Np(V) can form 1: 1 and 1: 2 complexes, and An(VI), also 1: 3 complexes (at pH ? 6 and [H₂Quin] ? 0.1 M). Quinolinate ion can coordinate to actinide(VI) and (V) ions in solutions in different modes. The apparent stability constants of the complexes in a wide pH range and the concentration stability constants of the An(VI) complexes were measured. In the series from Pu(VI) to U(VI), the stability of the complexes slightly increases. Crystalline complexes [UO₂(HQuin)₂], [(NpO₂)₂(HQuin)₂(HL)₂]·2H₂O (HL is N-protonated 2-hydroxypyridine-3-carboxylic acid anion), and [PuO₂Quin(H₂O)] were synthesized, and their structures were determined by single crystal X-ray diffraction. Different types of coordination of quinolinate ions to actinide ions are also observed in the crystalline complexes.     

Fabrication, growth mechanism, and characterization of α-Fe(2)O(3) nanorods

This work reports the facile synthesis of α-Fe(2)O(3) nanorods and nano-hexagons and its application as sunlight-driven photocatalysis. The obtained products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), scanning electron microscopy (SEM), diffused reflectance spectroscopy (DRUV-vis), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The phase and crystallinity were confirmed from the XRD study. Electron microscopy study clearly indicates the formation of different morphologies of nanocrystals. These hematite nanostructures were used as a model system for studying the shape-dependent photocatalytic degradation of phenol, methylene blue, and congo red. Amongst all the nanostructured semiconductors, Pt-doped hematite nanorod showed 55% efficiency towards the decolonization of methylene blue and 63% toward congo red under sun light illumination. The difference in photocatalytic activity is discussed in terms of their crystallize size and morphological ordering.     

温度传感器(2)

4.利用磁特性的温度传感器在随温度不同磁性能发生很大变化的材料中有热敏铁氧体和磁补偿合金,这里仅就第一种材料来谈一谈。热敏铁氧体的实用温度范围中包括居里温度Tc,即产生磁体二次相变的温度。改变铁氧体的成份可自由     

Phase Formation in the Systems α(δ)-FeOOH–M(OH)2–H2O (M = Mn, Co, Zn)

The sequence of chemical transformations induced in the systems ()-FeOOH–M(OH)₂–H₂O (M = Mn, Co, Zn) by heat treatment in the range 125–200°C is studied. The results demonstrate that the kinetics of M(II) ferrite formation, the chemical and phase compositions of the product, and its particle size distribution depend on the heat-treatment temperature, the pH of the suspension (or NaOH concentration), the FeOOH polymorph used as a starting reagent, and the starting-mixture composition.     

A_2B_7型La_(0.63)(Pr,Nd,Y,Sm,Gd)_(0.2)Mg_(0.17)Ni_(3.1)Co_(0.3)Al_(0.1)储氢合金微观组织和电化学性能研究

用Pr、Nd、Y、Sm和Gd按一定比例组成混合稀土对La进行部分替代,通过分别增加混合稀土中各元素的含量获得5种合金试样(分别用Pr0.6、Nd0.6、Y0.6、Sm0.6和Gd0.6表示),研究了混合稀土组成对A2B7型La_(0.63)(Pr,Nd,Y,Sm,Gd)_(0.2)Mg_(0.17)Ni_(3.1)Co_(0.3)Al_(0.1)退火合金微观结构与电化学性能的影响规律。合金相结构分析表明,合金微观组织均由主相2H-Ce2Ni7型和CaCu5型第二相组成,其中Y0.6合金的Ce2Ni7型相丰度最高(93.3%(质量分数))。合金中Ce2Ni7型和CaCu5型相晶胞体积均随A端元素平均原子半径的减小而逐渐降低。电化学分析表明,合金放氢平台压力为0.013~0.054 MPa,最大储氢量(Hmax/M)为1.23%~1.42%(质量分数),其中Y0.6合金具有最高的电化学放电容量(404.4 mAh/g)和最佳的容量保持率(S100=93.50%);合金电极高倍率放电性能HRD按试样Gd0.6、Sm0.6、Y0.6、Nd0.6、Pr0.6顺序依次减小。混合稀土中适量增加Y元素可显著提高和改善合金电极的综合电化学性能。     

New Pb-Based 1222 Cuprates, (Pb0.5B0.5)Sr2(RE2−x−y Ce x Sr y )Cu2O z (RE = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y)

New Pb-based layered cuprates with the 1222 structure have been synthesized in the (Pb_0.5B_0.5)Sr₂ (RE_2−x−y Ce _x Sr _y )Cu₂O _z (RE = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y) systems. The almost-single-phase samples in the systems can be obtained for a nominal composition of x=0.7 and y=0.1. The crystal structure of the samples has a tetragonal symmetry, the lattice parameters of a and c are increasing with increasing the ionic radius of RE element. Despite treatment under high O₂ pressure of 100 atm, the samples are semiconductors with the transport process characteristic of three-dimensional variable range hopping conduction.     

UV-induced photodecomposition of 2, 2′, 4, 4′, 6, 6′-hexanitrostillbene (HNS)

HNS (2, 2′, 4, 4′, 6, 6′-hexanitrostillbene) is a heat-resistant photosensitive explosive widely used in the booster charge. Investigation of the photodecomposition mechanism may provide important information for controlling and enhancing the detonation performance, also for the lifetime prediction. The UV-induced photodecomposition of HNS has been subjected to experimental studies. The UV-Vis spectra, X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance spectra (EPR) demonstrate the formation of NO₂ free radicals and nitroso derivatives of HNS upon UV irradiation, which proves well known facts that C-NO₂ breaking and removal of oxygen from the nitro group take part in the photodecomposition of HNS.     

Transport and Cu K-XANES Studies of (Hg,Cr)Sr2(Ca,Y)Cu2O6 + δ

The nominal (Hg_0.7Cr_0.3)Sr₂(Ca_0.7Y_0.3)Cu₂O_{6 +} , referred to as (Hg,Cr)-1212, were successfully synthesized at high temperature in partial vacuum. The samples were subsequently annealed in Ar or O₂ annealed at 300°C under ambient pressure. No T _c was observed in any of these samples down to 12 K which is in contrast to high pressure synthesized Y-free (Hg,Cr)-1212 phase where the latter exhibits a superconductivity at 80 K. The divalent state of Cu, as shown by XANES in the as-prepared (Hg,Cr)-1212, is not affected either by Ar or O₂ annealing. Depletion of holes due to trivalent Y substitution at the Ca-site, and a relatively higher 'a' lattice parameter (3.851 Å) are the apparent reasons for the non-superconducting nature of the samples.     

Synthesis and crystal structure of a new Np(V) oxalate, Na4(NpO2)2(C2O4)3·6H2O

A new oxalate complex, Na₄(NpO₂)₂(C₂O₄)₃·6H₂O, with the Np:C₂O₄ ratio of 2:3 was synthesized and studied by single crystal X-ray diffraction. In the crystal, the NpO ₂ ⁺ cations and oxalate anions are bound in open networks [(NpO₂)₂(C₂O₄)₃] _n ^4n- parallel to the bc plane. The Na(1) cations are accommodated in large voids of the neptunyl oxalate networks with the formation of crimped mixed-cation layers of the composition [Na₂(NpO₂)₂(C₂O₄)₃] _n ^2n- . The negative charge of the layers is compensated by the Na(2) cations arranged between the layers. The Np atoms have a pentagonal bipyramidal coordination surrounding with the equatorial plane formed by the oxygen atoms of three oxalate anions. The structure contains tridentate-bridging and tetradentate-bridging oxalate anions.     

Mg_2(Si,Sn)基热电材料研究进展

热电材料又称温差电材料,是利用固体中载流子和声子的输运及其相互作用实现热电相互转换的新型功能材料。热电材料可以将太阳辐射、工业废热、汽车尾气余热等转换成电能,对缓解污染和能源压力有重要意义。此外,热电制冷器件也具有低噪音、无污染、体积小和反应灵敏等压缩机制冷所不具备的优点,近年来受到研究者的广泛关注。材料的热电转换性能通过热电优值ZT表征,如何提高热电转换效率(即提高ZT值)成为研究者关注的热点。作为最具潜质的中温区热电材料之一,Mg2(Si,Sn)基热电材料由于其低廉的成本和无毒无害等优点,过去十几年被广泛研究。近年来,研究者们尝试了多种方法(如高频感应熔炼、固相反应加热压烧结、两步固相反应加放电等离子烧结和快速凝固加等离子活化烧结等)来获得高质量的Mg2(Si,Sn)块体。除此之外,研究者们还利用能带工程、单元素和双元素掺杂等方法来进一步提高材料的ZT值,这些方法可以使合金的ZT值从0.5提高到1.55。但是这类基于固相反应加烧结来制备纳米级晶粒块体材料的方法存在反应不完全和服役过程中晶粒易发生长大等问题。而且由于Mg元素极高的化学活泼性和挥发性,以及组成合金的各元素之间较大的熔点差,给熔炼法制备Mg2(Si,Sn)块体材料带来了很大的困难,极大地限制了材料热电性能的优化。因此,如何制备高质量的Mg2(Si,Sn)块体材料成为亟待解决的难题。本文综述了Mg2(Si,Sn)基热电材料制备方法的最新研究进展,以及能带工程和掺杂元素的选择等ZT值优化途径,提出存在的问题和未来的发展方向。同时,本文提出采用材料定向凝固方法制备Mg2(Si,Sn)单晶材料,并利用单晶各向异性来优化其热电性能,此方法有望解决纳米级晶粒块体材料服役过程中出现晶粒长大而导致的性能恶化问题,同时为此类合金热电材料的性能优化提供了新的思路。     

Monodisperse α-Fe(2)O(3)@SiO(2)@Au core/shell nanocomposite spheres: synthesis, characterization and properties

A new hybrid spherical structure α-Fe(2)O(3)@SiO(2)@Au with a size of about 141?nm was designed, with a hematite cubic core surrounded by a thick silica shell and further decorated with gold nanoparticles. The monodisperse α-Fe(2)O(3)@SiO(2) spheres were first prepared by a sol-gel process based on the modified St?ber method. Subsequently, the surface of the α-Fe(2)O(3)@SiO(2) particles was functionalized by-NH(2) functional groups. The electrostatic attraction of -NH(2) groups will attach the negatively charged Au nanoparticles to the amino-functionalized α-Fe(2)O(3)@SiO(2) nanospheres in order to prepare α-Fe(2)O(3)@SiO(2) monodisperse hybrid spheres. The M(H) hysteresis loop for α-Fe(2)O(3)@SiO(2) and α-Fe(2)O(3)@SiO(2)@Au spheres indicates that the nanocomposite spheres exhibit superparamagnetic characteristics at room temperature. The optical properties and the application of these hybrid nanocomposites as catalysts for the conversion of CO to CO(2) have also been studied.     

Crystal structure of mixed-valent Np(IV)/Np(V) chloride, [Np(NpO2)6(H2O)8(OH)Cl9]·H2O

A new mixed-valent Np(IV)/Np(V) chloride, [Np(NpO₂)₆(H₂O)₈(OH)Cl₉]·H₂O, was synthesized, and its crystal structure was determined. The crystals consist of NpO ₂ ⁺ and Np⁴⁺ cations, of Cl^? and OH^? anions, of coordination-bonded water molecules, and of water molecules of crystallization. The Np(V) atom, Np(1), has pentagonal bipyramidal coordination surrounding with O atoms in the apical position and with the equatorial plane formed by three Cl^? anions, O atom of the adjacent NpO ₂ ⁺ cation, and O atom of water molecule. The mutual coordination of the neptunyl(V) ions, cation-cation (CC) interaction, links the Np(1) coordination polyhedra via common vertices into rings around sixfold axes, with the Np(V)?Np(V) distance in these fragments of 4.276 Å. The ring fragments are linked with each other via common equatorial edges of the bipyramids into layers perpendicular to c-axis. The Np(IV) atom, Np(2), has coordination surrounding in the form of tricapped trigonal prism (CN 9) with the tetragonal lateral faces formed by the O atoms of the NpO ₂ ⁺ cations and the capping positions occupied by the O atoms of two water molecules and one hydroxy group. The Np(2) atoms act in CC interactions as coordination center for six NpO ₂ ⁺ ions, with the Np(IV)?Np(V) distance of 4.183 Å. The Np(2) polyhedra are arranged in the crystal between layers of the Np(1) coordination polyhedra, linking them with each other.     

Magnetocrystalline Anisotropies of RFe_(10)V_2 (R=Y, Tb, Dy, Ho, and Er) and Their Hydrides

The magnetocrystalline anisotropies of RFe10V2 (R=Y, Tb, Dy, Ho and Er) and their hydrides were studied by X-ray diffraction, magnetization and a.c. susceptibility measurements. The uniaxial anisotropy of Fe-sublattice and R-sublattice with positive second order Stevens αJ in RFe10V2 compounds is weakened by hydrogenation, while that of R-sublattice with negative αJ (Er) enhanced. Such a change of anisotropy causes planar-easy magnetic structures in RFe10V2 (R=Tb and Dy) at room temperature and induces spin reorientation in HoFe10V2 after hydrogenation. The change of anisotropy of R-sublattice after hydrogenation may be owed to a decrease of the second order crystalline coefficient.     

K_2Ln(NO_3)_5·2H_2O(Ln=La,Ce,Pr,Nd,Sm)的晶体生长和热重-差热分析研究

本文生长出了K2Ln（NO3）5.2H2O（Ln=La；Ce；Pr；Nd；Sm）的单晶，并对其进行了晶体结构及差热-热重分析研究．结果表明，K2Ln（NO3）5.2H2O（Ln=La；Ce；Pr；Nd）的晶体属正交晶系，Fdd2空间群．首次生长出KPrN单晶并用直接法解出其晶体结构．解得KPrN的晶胞参数为：a=11．2210（10）,b=21．411（3），c=12．208（2）,Z=6；R=0．0240．对KLnN加热，则依次出现脱水、熔化、不可逆相变和NO的分解过程（K2Ce（NO3）5·2H2O除外）K2Ln（NO3）5·2H2O（Ln＝La；Nd；Sm）的NO分三步分解，K2Ln（NO3）5·2H。O（Ln=Ce；Pr）的NO分两步分解·KNO3和Ln（NO3）3·nH2O的混合物在225℃左右生成K2Ln（NO3）5     

Synthesis and crystal structure of americium(V) dichromate, Cs3AmO2(Cr2O7)2·H2O

A new Am(V) chromate complex with outer-sphere cesium cation, Cs₃AmO₂(Cr₂O₇)₂·H₂O, was prepared from aqueous solution. Its composition and structure were determined by single crystal X-ray diffraction. The Am(V) atom has coordination surrounding in the form of a distorted pentagonal bipyramid with the O atoms of the AmO ₂ ⁺ group in apical positions. The equator of the bipyramid is formed by the O atoms of four dichromate groups and of the water molecule. The mean bond lengths (Å) are as follows: Am=O 1.802(5), Am-O(Cr₂O₇) 2.443(6), and Am-O_w 2.519(6). The Am(V) pentagonal bipyramids are combined via bidentate bridging Cr₂O ₇ ^2? anions into infinite chains [AmO₂(Cr₂O₇)₂H₂O] _n ^3? arranged in layers parallel to the series of diagonal planes (111). A system of hydrogen bonds links the chains in a layer and the layers with each other. The Cs cations are arranged between the layers, forming cationic interlayers.     

{[Cd(Ⅱ)L(NCS)2](DMF)2}n(L=1,4-二[2-(2-吡啶基)苯并咪唑基]丁烷)的合成,晶体结构与荧光光谱研究

合成了一种新的包含咪唑基团的双端四齿鳌合配体1,4-二[2-(2-吡啶基)苯并咪唑基]丁烷,并用其作为桥联配体与金属离子共同构筑配位聚合物.用Cd2 金属离子和L在DMF/H2O混合溶液中,存在KSCN的条件下,合成一种新型的一维链状配位聚合物{[Cd(Ⅱ)L(NCS)2](DMF)2}n(L=1,4-二[2-(2-吡啶基)苯并咪唑基]丁烷).单晶X-射线分析仪分析表明,该晶体属三斜晶系,P-1空间群,晶胞参数为:a=8.869(1)A,b=11.278(2)A,c=19.328(4)A,α=89.83(3)°,β=89.52(3)°,γ=74.28(3)°,V=1860.9(7)(A)3,Z=2,7250个独立衍射点中,6039个可观测点满足F2≥2σ(F2o),R=0.0543,wR2=0.1442.它是由一维的锯齿形链[Cd(Ⅱ)L(NCS)2]n和游离的DMF分子组成.在链内金属原子与来自于2个具有不同结构的配体L中的4个N原子和2个SCN-阴离子中的2个N原子形成八面体配位.该固态配合物在室温下用389nm的紫外光激发时在453nm处发射出强的荧光.