Ultrathin ruthenium(II) complex-H4SiW12O40 multilayer film

A dipolar Ru(II) complex, [(bpy)2Ru(bpbh)Ru(bpy)2](ClO4)4 {where bpbh = 1,6-bis-[2-(2-pyridyl) benzimidazoyl]hexane, bpy = 2,2'-bipyridine}, was synthesized and characterized. A multilayer film of at least 18 layers was successfully prepared by alternating adsorption of H4SiW12O40 and [Ru2(bpy)4(bpbh)](ClO4)4 by electrostatic layer-by-layer self-assembly. The multilayer films were studied by ultraviolet-visible and X-ray photoelectron spectroscopy, atomic force microscopy, and cyclic voltammetry.     

一维含能金属有机框架的合成与性能研究

为制备高能绿色起爆药,以5,5'-偶氮四唑钠盐为前驱体,硝酸亚铁提供金属离子,采用溶剂挥发法合成了一维含能金属有机框架化合物[Fe(ATZ)(H2O)4·2H2O]n.利用红外光谱、元素分析、X射线单晶衍射对其结构进行了表征和分析,用差式扫描量热仪分析了该化合物的热分解性能.基于最大放热原则,应用广义的Kamlet-Jacobs方法计算了化合物的爆轰性能,并对其撞击感度进行了测试.结果表明,该一维含能金属有机框架化合物的理论爆热、爆压、爆速分别为2 294.73 kJ/mol、34.54 GPa和8.83 km/s,撞击感度H50为39.0 cm,具有典型起爆药的特征,可作为一种优异的高能绿色起爆药.     

Synthesis,characterization and photovoltaic properties of phase pure Cu<Subscript>2</Subscript>SnSe<Subscript>3</Subscript> nanostructures using molecular precursors

Phase pure Cu₂SnSe₃ (CTSe) nanostructures have been synthesized using metal selenolates, [Me₂Sn{SeC₅H₃(Me-3)N}₂] (molecular structure of [Me₂Sn{SeC₅H₃(Me-3)N}₂] has been established by single crystal X-ray analysis) and [Cu{SeC₅H₃(Me-3)N}]₄ as molecular precursors in oleylamine (OLA) and tri-n-octylphosphine oxide (TOPO). The effect of temperature on final composition of nanostructures has also been investigated. Powder X-ray diffraction, Raman and X-ray photoelectron spectroscopy (XPS) were used to investigate the crystal structure, phase purity and homogeneity of the nanostructures while the electron microscopy revealed the morphology of the nanostructures. Superconducting quantum interference device (SQUID) measurements of CTSe nanostructures showed weak magnetic ordering at low temperature (below 50 K) attributed to the presence of some defect centres in the sample. The CTSe nanostructure possess an optical band gap of 1.7 eV deduced from diffuse reflectance spectroscopy (DRS) and showed photo response which makes them promising candidate for alternative low cost photon absorber material.     

Molecular structure,photoluminescent and electroluminescent properties of bis(2-(4-methyl-2-hydroxyphenyl)benzothiazolate) zinc with excellent electron-transport characteristics

In this article, the molecular structure, photoluminescent and electroluminescent properties of bis(2-(4-methyl-2-hydroxyphenyl) benzothiazolate) zinc (Zn(4-MeBTZ)₂) with good electron-transport characteristics were reported. This complex was identified as triclinic structure with the strong intermolecular π–π stacking interactions between the benzothiazolate/phenoxido rings and weak intramolecular hydrogen bonds by X-ray single-crystal diffraction. Quantum chemical method has been employed to investigate electron structure and charge transport property. The blue-green light emission was observed by fabricating double-layer devices using Zn(4-MeBTZ)₂ as electron-transport and NPB as hole-transport material. The performance of organic light-emitting devices based on Zn(4-MeBTZ)₂ is much better than that of the devices based on [Zn(BTZ)₂]₂.     

Novel expansion/shrinkage modulation of 2D layered MOF triggered by clathrate formation with CO(2) molecules

Crystal-to-crystal transformation from a 3D interpenetrated-type MOF {[Cu(BF(4))(2)(bpy)(H(2)O)(2)] (bpy)} (1) to a 2D square-grid-type [Cu(BF(4))(2)(bpy)(2)] (2) (bpy = 4,4'-bipyridine) was observed. It was derived from dehydration and confirmed by in situ FT-IR, TG, and elemental analysis. Moreover, we elucidate the novel expansion/shrinkage dynamic modulation of 2 triggered by clathrate formation with gas molecules.     

Modelling,structural, thermal,optical and vibrational studies of a new organic–inorganic hybrid material (C<Subscript>5</Subscript>H<Subscript>16</Subscript>N<Subscript>2</Subscript>)Cd<Subscript>1.5</Subscript>Cl<Subscript>5</Subscript>

Chemical preparation, theoretical calculations, X-ray single-crystal diffraction, thermal analysis, electrochemical measurements, IR, Raman and UV spectroscopic investigations of a novel organic–inorganic hybrid material (C₅H₁₆N₂)Cd_1.5Cl₅ are described. The structure provides a new interesting example of infinite inorganic chains of [Cd_1.5Cl₅]\(_{\mathbf {n}}^{\boldsymbol {2\mathrm {n}-}}\) following the a crystallographic direction. The [Cd_1.5Cl₅]^2? anions are interconnected by N–H ? Cl hydrogen bonds. The Hirshfeld surface and associated fingerprint plots of the compound are presented to explore the nature of intermolecular interactions and their relative contributions in building the solid-state architecture. IR and Raman spectra are reported and discussed on the basis of group theoretical analysis and quantum chemical density functional theory (DFT) calculation. The molecular HOMO–LUMO compositions and their respective energy gaps are also drawn to explain the activity of our compound. Thermal analysis reveals the anhydrous character of the compound.     

Measurement and Prediction of the Thermal Conductivity of Tricyanomethanide- and Tetracyanoborate-Based Imidazolium Ionic Liquids

The thermal conductivity of ten ionic liquids (ILs) based on the anions \([\mathrm{C(CN)}_{3}]^{-}\) (tricyanomethanide) and \([\mathrm{B(CN)}_{4}]^{-}\) (tetracyanoborate) carrying a homologous series of the [alkyl-MIM] \(^{+}\) (1-alkyl-3-methylimidazolium) cations [EMIM] \(^{+}\) (ethyl), [BMIM] \(^{+}\) (butyl) [HMIM] \(^{+}\) (hexyl), [OMIM] \(^{+}\) (octyl), [DMIM] \(^{+}\) (decyl) was measured by a steady-state guarded parallel-plate instrument in the temperature range between (283.15 and 353.15) K at atmospheric pressure with a total uncertainty of 5 % ( \(k\,=\,2\) ). Furthermore, the refractive index required for data evaluation and the density, which is an important property in the developed prediction method for the thermal conductivity, were determined. In general, the measured thermal conductivities of the probed ILs decrease with increasing temperature and increasing alkyl-chain length of the cation. Regarding the influence of the anion, somewhat smaller values for the \([\mathrm{B(CN)}_{4}]^{-}\) -based ILs compared to the \([\mathrm{C(CN)}_{3}]^{-}\) -based ILs carrying the same cation are observed. Our previously developed simple prediction method for the thermal conductivity of ILs at 293.15 K using only information on the molar mass and the density could be improved. By the combination of this approach with the temperature dependence of the density, an extended empirical correlation additionally describing the temperature dependence of the thermal conductivity of ILs is recommended. This correlation represents all experimental thermal-conductivity data in the literature with a standard deviation of less than 7 %.     

N-(邻硝基苯基)-N′-(甲氧基羰基)硫脲及其过渡金属配合物的NMR研究

本文测定了四个N-(邻硝基苯基)-N＇-(甲氧基羰基)硫脲(H_2omt)(1)及其过渡金属配合物{Cd(Homt)_2 (bpy)(2)、Zn(Homt)_2(phen)(3)、[Cu (H_2om＇t)_2Cl]_2}(4)的~1H、~(13)CNMR谱,归属了它们的所有谱线,对于它们的化学位移与配位行为作了简单讨论。     

Directed synthesis of a new decamolybdate-encapsulated nanocage framework by mixed-ligands for light-driven hydrogen generation

Clean Technologies and Environmental Policy - A new compound [CuICuII2(bpy)(pzta)2][HMo10O34] {CuICuII2-Mo10, pzta = 3-(pyrid-4-yl) pyrazole and bpy = 4,4’-bipyridine}...     

Nafion-tris(2-2'-bipyridyl)ruthenium(II) Ultrathin Langmuir-Schaefer films: redox catalysis and electrochemiluminescent properties

A simple procedure to incorporate tris(2-2'-bipyridyl)ruthenium(II), [Ru(bpy)3]2+, into Nafion Langmuir-Schaefer (LS) films is described. Nafion LS films (tens of nanometers thick) were formed on quartz glass and indium tin oxide (ITO) directly from Nafion-[Ru(bpy)3]2+ Langmuir films assembled at the water-air interface. This procedure allowed the direct incorporation of [Ru(bpy)3]2+ into Nafion films without the need for subsequent loading. UV-vis spectroscopy confirmed the successful incorporation of [Ru(bpy)3]2+ within the LS films and showed that the amount of [Ru(bpy)3]2+ immobilized in this way scaled with film thickness. Voltammetric studies on ITO-modified electrodes confirmed the successful incorporation of [Ru(bpy)3]2+ and demonstrated that [Ru(bpy)3]2+ was retained within the ultrathin films over a long time scale. These electrodes were tested for the electrocatalytic reduction of tripropylamine. Significant catalysis was observed due to the rapid turnover of [Ru(bpy)3]2+/3+ between the electrode surface and outer boundary of the film, as a direct consequence of the ultrathin film dimensions. Concomitant electrochemiluminescence (ECL) was demonstrated highlighting the potential of this material for sensing applications.     

A new nanostructured material based on fluorophosphate incorporated into a zinc–aluminium layered double hydroxide by ion exchange

Layered double hydroxides (LDHs), also called anionic clays, consist of cationic brucite-like layers and exchangeable interlayer anions. These hydrotalcite-like compounds, with Zn and Al in the layers and chloride in the interlayer space, were prepared following the coprecipitation method at constant pH. The effect of pH, aging time and anion concentration on the intercalation of fluorophosphate \((\hbox {PO}_{3}\hbox {F}^{2-}\), FP) in the [Zn–Al] LDH was investigated. The best crystalline material, with high exchange extent, was obtained by carrying out the exchange at 25\({^{\circ }}\hbox {C}\) in a 0.03 M FP solution at pH 7 with at least 42 h of aging time. A mechanism for the FP intercalation was confirmed by X-ray diffraction, infrared spectroscopy and thermogravimetry (TG) analyses (TG and DTG curves).     

Metal organic chemical vapour deposition of vertically aligned ZnO nanowires using oxygen donor adducts

Vertically aligned zinc oxide (ZnO) nanowires (NWs) have been grown by liquid injection Metal Organic Chemical Vapour Deposition, using oxygen donor adducts of Me2Zn. The growth and characterisation of the nanowires grown using [Me2Zn(L)] where L = monodentate ethers, tetrahydrofuran (C4H8O) (1), tetrahydropyran (C5H10O) (2), furan (C4H4O) (3) and the bidentate ethers, 1,2-dimethoxyethane (C4H12O2,) (4) 1,4-dioxane (C4H8O2) (5) and 1,4-thioxane (C4H8SO) (6) is discussed. Single crystal X-ray structures of (4), (5), (6) have been established and are included here. The ZnO NWs were deposited in the absence of a seed catalyst on Si(111) and F-doped SnO2/glass substrates over the temperature range 350-600 degrees C. X-ray diffraction (XRD) data shows that the nanowires grown from all adduct precursors were deposited in the wurtzitic phase.     

Zn^2＋掺杂的YBCO薄膜的超导性能研究

采用溶胶-凝胶法在LaAlO3（LAO）单晶衬底上制备了Zn^2＋掺杂的YBCO薄膜,用X射线衍射（XRD）、高分辨透射电子显微镜（HRTEM）以及标准四引线法分别研究了Zn^2＋掺杂的YBCO薄膜的微观结构、生长取向以及超导性能。结果表明,随Zn2＋掺杂浓度的增大薄膜的临界电流密度提高,而临界转变温度下降、临界转变温区变宽;但当掺杂量〉0.5%（摩尔分数）时,会影响YBCO的c轴取向生长,导致超导性能变差。通过优化掺杂比例后得到Zn2＋掺杂0.5%（摩尔分数）的YBCO薄膜具有最好的综合超导性能,其TC为91.3K,ΔT为1.1K,Jc约为1.54MA/cm^2（77K,0T）。     

Ni_(0.5)Zn_(0.5)Fe_2O_4铁氧体的制备及其电磁损耗性能

以Zn(NO3)2.6H2O、Ni(NO3)2.6H2O和Fe(NO3)3.9H2O及柠檬酸为原料,采用溶胶-凝胶法制备前驱体,在1 200℃下煅烧3 h合成ZnFe2O4和Ni0.5Zn0.5Fe2O4铁氧体粉体。利用差热分析、X射线衍射、扫描电镜、透射电镜和红外光谱等测试手段对产物进行分析和表征。结果表明:ZnFe2O4和Ni0.5Zn0.5Fe2O4属于立方晶系尖晶石结构,结晶完整,晶粒大小在100 nm左右。在0.2~1.8 GHz的频率下对产品进行了电磁损耗性能测试,发现Ni0.5Zn0.5Fe2O4具有较好的电磁损耗特性。     

{H3[PMo12O40]/Pt/PAMAM}复合膜的制备及对甲醇的电催化氧化

采用循环伏安法在玻碳电极上制备了{H3[PMo12O40]/Pt/PAMAM}复合膜,用X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、电子能谱技术(EDS)、原子力显微镜(AFM)和循环伏安法(CV)研究了膜的组成、形貌及其对甲醇的电催化氧化活性。结果表明,Pt纳米粒子在PAMAM基底上分散均匀;最外层沉积H3[PMo12O40]后,与相同条件下制备的Pt/PAMAM膜相比,{H3[PMo12O40]/Pt/PAMAM}复合膜修饰电极对甲醇的氧化有更强的电催化活性。     

Enhanced electrogenerated chemiluminescence in the presence of fluorinated alcohols

The electrochemistry, UV-vis absorption, photoluminescence (PL), and coreactant electrogenerated chemiluminescence (ECL) of Ru(bpy)3(2+) (where bpy=2,2'-bipyridine) have been obtained in a series of hydroxylic solvents. The solvents included fluorinated and nonfluorinated alcohols and alcohol/water mixtures. Tri-n-propylamine was used as the oxidative-reductive ECL coreactant. Blue shifts of up to 30 nm in PL emission wavelength maximums are observed compared to a Ru(bpy)3(2+)/H2O standard due to interactions of the polar excited state (i.e., *Ru(bpy)3(2+)) with the solvent media. For example, Ru(bpy)3(2+) in water has an emission maximum of 599 nm while in the more polar hexafluoropropanol and trifluoroethanol it is 562 and 571 nm, respectively. ECL spectra are similar to PL spectra, indicating the same excited state is formed in both experiments. The difference between the electrochemically reversible oxidation (Ru(bpy)3(2+/3+)) and first reduction (Ru(bpy)2(2+/1+)) correlates well with the energy gap observed in the luminescence experiments. Although the ECL is linear in all solvents with [Ru(bpy)3(2+)] ranging from 100 to 0.1 nm, little correlation between the polarity of the solvent and the ECL efficiency (phiecl=number of photons per redox event) was observed. However, dramatic increases in phiecl ranging from 6- to 270-fold were seen in mixed alcohol/water solutions.     

层状硫化锌的溶剂热法制备

以乙酸锌Zn(CH3COO)2.2H2O为锌源、硫脲SC(NH2)2为硫源、水与乙二胺的混合溶液为反应溶剂、十二烷基磺酸钠C12H25SO3Na形成的胶束为模板,利用溶剂热法制备了具有层状微观形貌的ZnS粉体材料。利用XRD、SEM、EDS等测试手段进行表征,结果表明,所得ZnS粉体材料结晶良好,层状形貌明显;层状ZnS粉体材料在435nm附近有较宽的发射峰,且发光性能明显优于球状ZnS粉体材料。     

静电纺丝技术制备NiOZnTiO3TiO2同轴三层纳米电缆及其形成机制

采用静电纺丝技术, 通过改进实验装置, 在最佳的纺丝条件下制备了 [Ni(CH₃COO)₂+PVP]-[Zn(CH₃COO)₂+PVP]-[Ti(OC₄H₉)₄+CH₃COOH+PVP] 前驱体复合电缆, 在600℃下将其进行热处理, 制备出了NiO-ZnTiO₃-TiO₂同轴三层纳米电缆。采用热重-差热 (TG-DTA)、 X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 扫描电子显微镜(SEM)和透射电子显微镜(TEM)等分析技术对样品进行了表征。对NiO-ZnTiO₃-TiO₂ 同轴三层纳米电缆的形成机制进行了讨论。结果表明, 所得产物为NiO-ZnTiO₃-TiO₂同轴三层纳米电缆。芯层为NiO, 直径大约为(42.024±4.405) nm; 中间层为ZnTiO₃, 厚度大约为(55.385±7.681) nm; 壳层为TiO₂, 厚度大约为(70.747±7.373) nm。      

Sorption processes and XRD analysis of a natural zeolite exchanged with Pb(2+), Cd(2+) and Zn(2+) cations

In this study the Pb(2+), Cd(2+) and Zn(2+) adsorption capacity of a natural zeolite was evaluated in batch tests at a constant pH of 5.5 by polluting this mineral with solutions containing increasing concentrations of the three cations to obtain adsorption isotherms. In addition X-ray powder diffraction (XRD) was used to investigate the changes of zeolite structure caused by the exchange with cations of different ionic radius. The zeolite adsorption capacity for the three cations was Zn>Pb>Cd. Moreover a sequential extraction procedure [H(2)O, 0.05 M Ca(NO(3))(2) and 0.02 M EDTA] was applied to zeolite samples used in the adsorption experiments to determine the chemical form of the cations bound to the sorbent. Using this approach it was shown that low concentrations of Pb(2+), Cd(2+) and Zn(2+) were present as water-soluble and exchangeable fractions (<25% of the Me adsorbed), while EDTA extracted most of the adsorbed cations from the zeolite (>27% of the Me adsorbed). The XRD pattern of zeolite, analysed according to the Rietveld method, showed that the main mineralogical phase involved in the adsorption process was clinoptilolite. Besides structure information showed that the incorporation of Pb(2+), Cd(2+) and Zn(2+), into the zeolite frameworks changed slightly but appreciably the lattice parameters. XRD analysis also showed the occurrence of some isomorphic substitution phenomena where the Al(3+) ions of the clinoptilolite framework were replaced by exchanged Pb(2+) cations in the course of the ion exchange reaction. This mechanism was instead less evident in the patterns of the samples doped with Cd(2+) and Zn(2+) cations.     

Antioxidant redox sensors based on DNA modified carbon screen-printed electrodes

Antioxidant redox sensors based on DNA modified carbon screen-printed electrodes were developed. The carbon ink was doped with TiO2 nanoparticles, onto which double-strand DNA was adsorbed. A redox mediator, namely, tris-2,2'-bipyridine ruthenium(II) [Ru(bpy)3(2+)] was electrooxidized on the electrode surface to subsequently oxidize both the adsorbed ds-DNA and the antioxidants in solution. The resulting oxidation damage of the adsorbed ds-DNA was then detected by square wave voltammetry in a second solution containing only Ru(bpy)3Cl2 at a low concentration (microM). A kinetic model was developed to study the protecting role of antioxidants in aqueous solutions. The electrochemical sensor has been applied to evaluate the redox antioxidant capacity of different molecules.