Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound〔Et_4N〕_2〔Mo_2(CO)_8(SC_6H_4-NH_2-p)_2〕

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｅｘｉｓｔｅｎｃｅａｎｄｓｉｇｎｉｆｉｃａｎｃｅｏｆｔｈｅｍｏｌｙｂｄｅｎｕｍ ｓｕｌｆｕｒｂｏｎｄｉｎｇｉｎｍｏｌｙｂｄｅｎｕｍｅｎｚｙｍｅｓ〔１〕ｈａｖｅｓｔｉｍｕｌａｔｅｄｔｈｅｓｔｕｄｉｅｓｏｎｔｈｅｃｈｅｍｉ...     

芳香基苯并咪唑衍生物的合成、表征及抑菌活性研究

在微波辐射下,通过二茂铁磺酰氯和相应的苯并咪唑合成了4种芳香基苯并咪唑衍生物。经^1H NMR、MS及元素分析确证产物结构。通过X线衍射测定了化合物4a的晶体结构。用琼脂稀释法测定化合物抑菌活性,并与对照药剂50%多菌灵可湿性粉剂比较,结果表明化合物4a～4d对番茄早疫病菌、烟草赤星病菌和小麦赤霉病菌有与对照药剂近似的抑菌活性。     

Synthesis and structure of the new complex hydride Li2BH4NH2

The structure of the new complex hydride Li(2)BH(4)NH(2), determined through Rietveld analysis of synchrotron X-ray and neutron powder diffraction data, comprises a hexagonal array of discrete (LiNH(2))(6) clusters dispersed in a LiBH(4) matrix.     

溶胶-凝胶法制备Fe掺杂MgF2催化剂及其催化1，1-二氟乙烷(R152a)脱HF反应的性能

通过助剂掺杂的方法解决MgF2催化剂高温失活的问题。采用溶胶-凝胶法制备了一系列Fe^3+掺杂的高比表面MgF2催化剂,并通过N2吸附-脱附测试、X射线衍射(XRD)、能量色散X射线光谱(EDS)和NH3程序升温脱附技术(NH3-TPD)、电子自旋共振(ESR)、X射线光电子能谱(XPS)等对FeF3/MgF2催化剂的物化性质进行了表征。结果表明,一定量(物质的量分数小于20%)的Fe^3+掺杂可以有效地减少MgF2晶粒度,且随着Fe^3+掺杂量的增加,催化剂的比表面积、酸性及1,1-二氟乙烷(R152a,C2H4F2)脱HF反应的催化活性均呈现增加趋势,但当Fe^3+掺杂量超过20%时,催化剂明显失活。     

固相反应合成LiCoPO4中间体的反应动力学

以磷酸二氢铵、醋酸钴和氢氧化锂为原料, 用低温固相反应合成含Li⁺的NH₄CoPO₄前驱体, 再经过高温焙烧合成LiCoPO₄粉体. 应用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和热重-差热分析(TG-DTA)等技术对合成产物进行表征. 结果表明: 焙烧气氛影响中间体的生成, 含Li⁺的前驱体NH₄CoPO₄在210-500 °C的空气中发生脱水脱氨反应, 制备过程存在“酸碱共同体”的中间体(CoHPO₄·LiCoPO₄·Co₂(OH)PO₄·Li₃PO₄). 中间体生成反应遵循界面反应幂律机理, 表观活化能约50.0 kJ?mol^-1, 过程机理函数为g(x)=(1-α)^-1. 中间体继续脱水反应生成LiCoPO₄, 平均表观活化能约为54.2 kJ?mol^-1. 物系非晶化和晶化过程对中间体的存在没有直接的影响, 高温对中间体的分解产物LiCoPO₄和LiCoPO₄的晶体生长有利, 在550 °C以上温度中间体可分解得到完整的LiCoPO₄晶体.     

Ab initio structure study from in-house powder diffraction of a novel ZnS(EN)0.5 structure with layered wurtzite ZnS fragment

The solvothermal reaction of elemental zinc with sulfur in ethylenediamine (en) as solvent yields [ZnS-0.5(NH2CH2CH2NH2)], 1, an unprecedented ethylenediamine pillared ZnS layered compound, containing two dimensional (2-D) boat-type 6-membered rings, which was characterized by ab initio structure solution from powder diffraction data (SDPD).     

冰晶石型氟化物(NH_4)_3FeF_6的水热合成及其磁学性质

首次采用水热法合成了冰晶石型氟化合物(NH_4)_3FeF_6,其结构和性质经X-射线粉末衍射、扫描电子显微镜和差热-热重分析表征。(NH_4)_3FeF_6属立方晶系,空间群Fm-3m,晶胞参数a=b=c=0.913 0 nm。对磁化率进行了表征。结果表明:随着温度降低,磁有序与晶体特征和孤立的磁单元有关。     

一个含有连续氢键的晶态Ni(Ⅱ)⁃MOF的合成、结构及质子传导性能

选用柔性多羧酸有机配体与过渡金属离子Ni(Ⅱ)在水热条件下得到Ni?MOF[Ni2(L)(Nphen)2(H2O)4]n(1)(H4L=5,5'?(丁基?1,4?二氧)间苯二甲酸,Nphen=5?硝基?1,10?邻二氮杂菲)。单晶结构分析表明,配合物1中存在连续氢键作用,这将有利于质子的传导。红外、X射线粉末衍射以及热重分析等表征结果表明,配合物具有良好的纯度和稳定性。将配合物1的颗粒与Nafion混合形成复合膜,并对其进行了电化学研究。结果表明配合物1的掺杂能够明显改善Nafion膜的质子传导行为,复合膜的质子电导率比纯Nafion膜提升24.08%。     

Unmasking melon by a complementary approach employing electron diffraction, solid-state NMR spectroscopy, and theoretical calculations-structural characterization of a carbon nitride polymer

Poly(aminoimino)heptazine, otherwise known as Liebig's melon, whose composition and structure has been subject to multitudinous speculations, was synthesized from melamine at 630 degrees C under the pressure of ammonia. Electron diffraction, solid-state NMR spectroscopy, and theoretical calculations revealed that the nanocrystalline material exhibits domains well-ordered in two dimensions, thereby allowing the structure solution in projection by electron diffraction. Melon ([C(6)N(7)(NH(2))(NH)](n), plane group p2 gg, a=16.7, b=12.4 A, gamma=90 degrees, Z=4), is composed of layers made up from infinite 1D chains of NH-bridged melem (C(6)N(7)(NH(2))(3)) monomers. The strands adopt a zigzag-type geometry and are tightly linked by hydrogen bonds to give a 2D planar array. The inter-layer distance was determined to be 3.2 A from X-ray powder diffraction. The presence of heptazine building blocks, as well as NH and NH(2) groups was confirmed by (13)C and (15)N solid-state NMR spectroscopy using (15)N-labeled melon. The degree of condensation of the heptazine core was further substantiated by a (15)N direct excitation measurement. Magnetization exchange observed between all (15)N nuclei using a fp-RFDR experiment, together with the CP-MAS data and elemental analysis, suggests that the sample is mainly homogeneous in terms of its basic composition and molecular building blocks. Semiempirical, force field, and DFT/plane wave calculations under periodic boundary conditions corroborate the structure model obtained by electron diffraction. The overall planarity of the layers is confirmed and a good agreement is obtained between the experimental and calculated NMR chemical shift parameters. The polymeric character and thermal stability of melon might render this polymer a pre-stage of g-C(3)N(4) and portend its use as a promising inert material for a variety of applications in materials and surface science.     

Electric Conductivity of α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Suspensions in Carbonate and Carbonate-Chloride Melts

The temperature dependence of the specific electric conductivity of suspensions based on carbonate and carbonate-chloride melts immobilized with α-Al₂O₃ powder was studied. For carbonate-chloride melts immobilized with α-Al₂O₃, the decrease in the specific electric conductivity considerably exceeded the effect associated with a decrease in the volume fraction of charge carriers. The Raman spectroscopy and Xray diffraction analysis showed that there was no chemical interaction of α-Al₂O₃ with the carbonate and carbonate-chloride melt that could lead to the formation of additional nonconducting phases in these systems in the temperature range under study.     

一种基于碘化铅的有机/无机杂化钙钛矿材料传输性能的研究

合成了一种新型的有机/无机杂化钙钛矿(NH3C6H4OC6H4NH3)PbI4, 采用元素分析、紫外-可见光吸收光谱、X射线衍射和透射电镜对其结构进行了表征, 结果表明这种材料具有规则的层状结构, 有序性高. 对这种材料的薄膜进行了伏安测试, 结果表明该材料属于n型半导体, 其电子迁移率达到0.065 cm2&#8226;V－1&#8226;s－1, 在光电器件领域有着潜在的应用前景.     

碳酸钇铵复盐结晶的形成及影响因素

对碳酸氢铵沉淀钇时碳酸钇铵复盐结晶的形成条件与ｐＨ变化特征进行了研究,发现其结晶过程与平衡溶液ｐＨ有对应关系。溶液ｐＨ由碳酸钇铵结晶化反应和碳酸氢铵的水解反应所控制。根据溶液ｐＨ的变化可以判断结晶反应是否发生或完成,以及结晶速度的快慢和结晶的程度。Ｘ－射线衍射及差热－热重分析结果表明,产物为复盐结晶２,加料方式对结晶的形成有很大影响。     

Gelatin-containing calcium hydroxyapatites: Synthesis and physicochemical characterization

The CaCl₂-(NH₄-)₂HPO₄-NH₃-H₂O-gelatin system was studied at 25°C using the solubility (residual concentrations) method. Stoichiometric nanocrystalline (11–15.4 nm) gelatin-containing calcium hydroxyapatites (HAs) were found to form. They were characterized by chemical analysis, thermal analysis, Xray powder diffraction, and IR spectroscopy. Original Russian Text ? Zh.A. Ezhova, N.A. Zakharov, E.M. Koval’, V.T. Kalinnikov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 3, pp. 526–530.     

Analysis of Roman wall paintings found in Verona

The present paper deals with the analysis of roman wall paintings fragments recovered from twelve buildings of Verona, Italy. The analytical techniques used were Optical Microscopy, Scanning Electron Microscopy (SEM) equipped with an EDS microanalysis detector, Xray powder diffraction (XRD) Fourier Transform infrared spectroscopy (FTIR) and Raman Spectroscopy. The wall preparation generally consisted of three layer: the pictorial layer, an intonachino layer of hydrated lime and a plaster one made of slaked lime and sand. The pigments found in the studied domus are different reflecting the taste and culture of Xa Regio of Italy but also the economical possibilities of the dominus and the building period.     

氧钒(Ⅳ)碱式碳酸铵的氨解和纳米VN的制备

氮化钒(VN)具有十分高的热、化学稳定性和强的机械性能,用于切削工具和结构材料。VN作为催化剂,具有高催化活性、高选择性、良好的稳定性和抗中毒性能;其催化行为类似Pt、Pd和Rh,是这些稀贵金属的经济的代用物。细的球状     

Structure of ternary imide Li2Ca(NH)2 and hydrogen storage mechanisms in amide-hydride system

The crystal structure of the ternary imide Li 2Ca(NH) 2 has been determined using neutron powder diffraction data on a deuterated sample. The structure consists of infinite layers of edge-shared Ca[NH] 6 octahedra, which are separated by Li cations. The mobile Li (+) ions in such two-dimensional channels defined by Ca[NH] 6 octahedra layers are shown to have a great impact on the hydrogenation properties of the imide. Through detailed structural analysis on the products at various stages of desorption and absorption of the amide-hydride mixture, we proposed a dehydrogenation mechanism involving the mobile small ions in both amide and hydride and a hydrogen storage mechanism for the ternary imide.     

磁性阳离子交换树脂的结构与性能分析

利用古埃磁天平法、扫描电镜、粉末Ｘ射线衍射以及分光光度法等检测了化学转化法制备的磁性阳离子交换树脂。结果表明,所制备的树脂内部磁性物质为Ｆｅ３Ｏ４,且在 树脂内部的孔道及表面分布均匀,均被封锁在树脂内部,因而,这类磁性树脂在碱性和中性盐溶液中具有较高的稳定性。此外,树脂的磁化过程并不影响其交换容量。     

Formation of MoS2 inorganic fullerenes (IFs) by the reaction of MoO3 nanobelts and S

The reaction of MoO3 and S at temperatures higher than 300 degrees C in an argon atmosphere provides a convenient and effective method for the synthesis of MoS2 nanocrystalline substances. MoS2 nanotubes and fullerene-like nanoparticles have been obtained by the reaction at 850 degrees C under well-controlled conditions. The influences of reaction temperature and duration were carefully investigated in this paper. All of the nanostructures were characterized by Xray powder diffraction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). A stepwise reaction model and rolling mechanism were proposed based on the experimental results.     

DTA和XRD用于(14-x)SrCO3-xCaCO3-24CuO系统合成spin-ladder化合物Sr14-xCaxCu24O41的研究

The (14-x)SrCO3xCaCO324CuO system was investigated by means of differential thermal analysis (DTA) technique combined with the powder Xray diffraction (XRD) technique, and the relationship of its thermal behavior with the synthesis of spin-ladder compound Sr14-xCaxCu24O41 was first analyzed in detail. It is found that the DTA curve (x≤5.6) exhibits two endothermic peaks and could be divided into three reaction stages, corresponding to the solid state reaction to synthesize single-phase Sr14-xCaxCu24O41. The DTA curve (x≥8.4) shows three big endothermic peaks below 1000 ℃. The intensity and the position of the first endothermic peak around 800 ℃ is depending on the content of CaCO3 in the system, while the third endothermic peak is the crucial factor of the synthesis of single-phase compound.     

Structural chemistry, monoclinic-to-orthorhombic phase transition, and CO2 adsorption behavior of the small pore scandium terephthalate, Sc2(O2CC6H4)CO2)3, and its nitro- and amino-functionalized derivatives

The crystal structure of the small pore scandium terephthalate Sc(2)(O(2)CC(6)H(4)CO(2))(3) (hereafter Sc(2)BDC(3), BDC = 1,4-benzenedicarboxylate) has been investigated as a function of temperature and of functionalization, and its performance as an adsorbent for CO(2) has been examined. The structure of Sc(2)BDC(3) has been followed in vacuo over the temperature range 140 to 523 K by high resolution synchrotron X-ray powder diffraction, revealing a phase change at 225 K from monoclinic C2/c (low temperature) to Fddd (high temperature). The orthorhombic form shows negative thermal expansivity of 2.4 × 10(-5) K(-1): Rietveld analysis shows that this results largely from a decrease in the c axis, which is caused by carboxylate group rotation. (2)H wide-line and MAS NMR of deuterated Sc(2)BDC(3) indicates reorientation of phenyl groups via π flips at temperatures above 298 K. The same framework solid has also been prepared using monofunctionalized terephthalate linkers containing -NH(2) and -NO(2) groups. The structure of Sc(2)(NH(2)-BDC)(3) has been determined by Rietveld analysis of synchrotron powder diffraction at 100 and 298 K and found to be orthorhombic at both temperatures, whereas the structure of Sc(2)(NO(2)-BDC)(3) has been determined by single crystal diffraction at 298 K and Rietveld analysis of synchrotron powder diffraction at 100, 298, 373, and 473 K and is found to be monoclinic at all temperatures. Partial ordering of functional groups is observed in each structure. CO(2) adsorption at 196 and 273 K indicates that whereas Sc(2)BDC(3) has the largest capacity, Sc(2)(NH(2)-BDC)(3) shows the highest uptake at low partial pressure because of strong -NH(2)···CO(2) interactions. Remarkably, Sc(2)(NO(2)-BDC)(3) adsorbs 2.6 mmol CO(2) g(-1) at 196 K (P/P(0) = 0.5), suggesting that the -NO(2) groups are able to rotate to allow CO(2) molecules to diffuse along the narrow channels.