The Low Temperature Polarised Electronic Spectra of Some Tetragonal Nickel(II) Haloacetate Complexes

We have recently reported the single crystal electronic spectra of some substituted ethylenediamine complexes of nickel(II), discussing both cis (1) and trans (2) examples. We have also reported data for their cobalt(II) analogs (3). These were analysed using the Normalised Spherical Harmonic Hamiltonian (NSH) (4) and the Orbital Angular Overlap Model (OAM) (5) approaches. We have     

2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶及镍(Ⅱ)配合物的合成与光谱学研究

合成并表征了有机配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶(L)及其镍(Ⅱ)配合物,采用元素分析确定目标配合物组成为C15H21N3O4Ni.H2O,通过对比分析的方法讨论了配位前后游离配体L和镍(Ⅱ)配合物的核磁共振氢谱、核磁共振碳谱、红外吸收光谱和紫外-可见吸收光谱的谱学性质,进而推断出镍(Ⅱ)配合物的结构。结果表明,配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶以2个酰胺负离子N和1个吡啶环N原子为配位原子,与中心金属离子Ni(Ⅱ)通过三齿形式配位;配合物中Ni(Ⅱ)采取dsp2杂化轨道方式与配位原子构成配位键,中心金属Ni(Ⅱ)的配位数为4,1个Ni(Ⅱ)与1个三齿配体L和1个水分子配位,形成平面正方形构型的低自旋镍(Ⅱ)配合物。     

Are transition-metal borides promising for Na ion batteries? A first-principles study on transition-metal boride monolayer

Although two-dimensional (2D) materials have been proposed as the promising candidates for Na ion batteries (NIBs), electrode materials with high specific capacity and moderate diffusion energy barriers are still scare. Here, we firstly demonstrated that transition-metal borides (TMB) are much more promising electrode materials than other transition metal compounds. Density functional theory (DFT) calculations are performed to investigate the electronic properties and Na storage capability of TMB monolayer, which is realized in recent experiments. TMB monolayer forms strong chemical interaction with Na atoms, and the diffusion energy barrier of Na atoms is much lower than LIBs. Importantly, TMB monolayer exhibits a very high Na storage capacity. Such exceptional properties, including high stoichiometry (namely TMBNa₂), excellent electronic conductivity, moderate Na diffusion and high operating voltage, endow TMB monolayers as very promising anode materials for NIBs.     

CO chemisorption on two-dimensional cobalt clusters: A surface science approach to cluster chemistry

We have studied the CO chemisorption properties of small two-dimensional clusters (islands) and of monolayers and multilayers of cobalt deposited on Cu(100). The behaviour of one monolayer of cobalt is indistinguishable from the multilayers indicating weak influence of the copper support twoards the adsorption of CO. Below one monolayer of cobalt we observed the appearance of new peaks in the thermal desorption spectrum of CO related to the increasingly large number of edge atoms and small size of the cobalt islands. Of particular interest is the number of CO molecules bound per cobalt atom as a function of island size. This number was found to vary from 0.65, with the compression structure formed on the monolayer and multilayer cobalt coverages, up to approximately 3 when the cobalt coverage decreased to 0.002 monolayers.     

PDC材料烧结过程中钴在金刚石层中的扩散熔渗迁移机制

 讨论了PDC材料烧结过程中钴在金刚石层中的固相扩散、钴液熔渗、两次钴高浓度峰的“波浪”式迁移过程中的运动规律及其作用机制,并根据实验观测的数据进行了有关计算。结果表明：在5.8 GPa、1 300 ℃条件下,钴的扩散系数D≈1.6×10^-7 cm²/s,是一般常压及相同温度条件下钴固相扩散系数（3×10^-10 cm²/s）和相同压力条件下钴的液相扩散系数（5×10^-5 cm²/s）的中间值;对于粒度W≥10 μm的金刚石烧结体系,钴液熔渗作用时间非常短暂,略大于0.5 s,而对于W≤1 μm的超细金刚石烧结体系而言,钴熔渗作用时间为28 s,比粒度W≥10 μm的金刚石烧结要长得多;两次钴高浓度峰的迁移速度分别约为50 μm/s和100 μm/s。     

Synthesis, characterization and analytical applications of Ni(II)-ion imprinted polymer

Ion recognition-based separation techniques have received much attention because of their high selectivity for target ions. In this study, we have prepared a novel ion imprinted polymer (IIP) to remove nickel ions with high selectivity. The imprinted polymer was prepared by copolymerization of 2-hydroxy ethyl methacrylate (HEMA) with nickel vinylbenzoate complex in the presence of ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The polymerization was carried out in bulk with free radical initiation using 2-methoxy ethanol as a solvent and porogen. The adsorbed nickel was completely eluted with 15 mL of 1 M HCl. Control polymer was also prepared by similar experimental conditions without using imprint ion. The above synthesized polymers were characterized by surface area measurements, FT-IR, microanalysis and SEM analysis. The adsorption capacity of IIP and CP was found to be 1.51 and 0.65 mmol g⁻¹, respectively. The optimal pH for quantitative enrichment was 6.5. Nature of eluent, eluent concentration and eluent volume were also studied. The relative selectivity factor (α_r) values of Ni(II)/Zn(II), Ni(II)/Cu(II) and Ni(II)/Co(II) were 78.6, 111.1 and 91.6, respectively. Five replicate determinations of 30 μg L⁻¹ of Ni(II) gave a mean absorbance of 0.067 with a relative standard deviation of 1.06%. The lowest concentration determined by GTA-AAS below which the recovery becomes non-quantitative is 6 μg L⁻¹. IIP was tested for removal of Ni(II) from sea water sample.     

Reactive epitaxy of cobalt disilicide on Si(111)

A study of the mechanism governing the initial stages in silicide formation under deposition of 1–10 monolayers of cobalt on a heated Si(111) 7×7 crystal is reported. The structural data were obtained by an original method of diffraction of inelastically scattered medium-energy electrons, which maps the atomic structure of surface layers in real space. The elemental composition of the near-surface region to be analyzed was investigated by Auger electron spectroscopy. Reactive epitaxy is shown to stimulate epitaxial growth of a B-oriented CoSi₂(111) film on Si(111). In the initial stages of cobalt deposition (1–3 monolayers), the growth proceeds through island formation. The near-surface layer of a CoSi₂(111) film about 30 Å thick does not differ in elemental composition from the bulk cobalt disilicide, and the film terminates in a Si-Co-Si monolayer triad.     

Luminescence Properties of Metal(II)-Diethyldithiocarbamate Chelate Complex Particles and Its Analytical Application

In a suitable pH buffer solutions, sodium diethyldithiocarbamate (DDTC) reacts with some divalence metal ions M(II) to form (M–DDTC) _n chelate complex nanoparticles, which exhibit different luminescence properties. There is a strongest luminescence peak at 470 nm for the Co(II)–DDTC system, three peaks at 330, 470, and 630 nm for the Cu(II)–DDTC system, three peaks at 420, 470, and 630 nm for the Cd(II)–DDTC system, four peaks at 350, 400, 435, and 470 nm for the Ni(II)–DDTC system, two peaks at 408 and 470 nm for the Pb(II)–DDTC system, two peaks at 415 and 470 nm for the Fe(II)–DDTC system. The different luminescence properties of (M–DDTC) _n chelate complex nanoparticles was explained. Under the optimal conditions, the luminescence intensity of (Co–DDTC) _n chelate complex nanoparticles at 470 nm (F _{470 nm}) is linear to Co(II) concentration in the range of 0.012–1.44 μg/mL. The detection limit is 0.0023 μg/mL. A novel luminescence method has been proposed for the determination of cobalt in Vitamin B₁₂ samples, with satisfactory results.     

Spectrophotometric Determination of Cobalt with Di-2-Pyridyl Ketone Benzoylhydrazone

Abstract

A method for the spectrophotometric determination of cobalt (II) by complexation with di-2-pyridyl ketone benzoylhydrazone (DPKBH) in 50% (v/v) ethanolic solution is described. Cobalt (II) forms a 1:2 complex with DPKBH. The complex has maximum absorbance at 370 nm. Beer's law is obeyed over the range 0.1 – 2.8 μg.ml^?1. The effect of pH, effect of excess reagent, stability of the complex and the tolerance limit of many metal ions have been reported. The method is applied to the determination of cobalt in different alloys containing other metals ions.     

Evaluation of elastic modulus of cantilever beam by TA-ESPI

The paper proposes an evaluation technique for the elastic modulus of a cantilever beam by vibration analysis based on time average electronic speckle pattern interferometry (TA-ESPI) and Euler-Bernoulli equation. General approaches for the measurement of elastic modulus of a thin film are the Nano indentation test, Buldge test, Micro-tensile test, and so on. They each have strength and weakness in the preparation of the test specimen and the analysis of experimental results. ESPI is a type of laser speckle interferometry technique offering non-contact, high-resolution and whole-field measurement. The technique is a common measurement method for vibration mode visualization and surface displacement. Whole-field vibration mode shape (surface displacement distribution) at resonance frequency can be visualized by ESPI. And the maximum surface displacement distribution from ESPI can be used to find the resonance frequency for each vibration mode shape. And the elastic modules of a test material can be easily estimated from the measured resonance frequency and Euler-Bernoulli equation. The TA-ESPI vibration analysis technique can be used to find the elastic modulus of a material requiring simple preparation process and analysis.     

Luminescence behavior of tetraaza macrocylic nickel (II) complexes and non-linear Stern-Volmer quenching

Macrocylic dicarbinolamine nickel (II) complexes with diimine moiety in their ligand exhibited luminescence, when irradiated at their charge transfer band. The Stern-Volmer (S-V) plots of one of the complexes in DMF medium exhibited positive curvature, when FeC1₃ was used as a quencher, while the same complex showed negative curvature when nitrobenzene was used as a quencher. The mechanism for the luminescence quenching of the macrocyclic complex has also been discussed.     

新型对称巯基卟啉及其钴配合物的合成和性质研究

本文用一种新型的方法合成了一种新型卟啉及其钴配合物。用元素分析、紫外-可见、红外、核磁共振等进行了表征。用循环伏安法和差示脉冲法对钴卟啉配合物进行了电化学性质研究。     

Aqueous Cobalt(II) ion as a Nitrogen-14 Chemical Shift Reagent and Its Application to the Determination of Betaine,Glycerophosphorylcholine and Ammonium Ion

Aqueous cobalt(II) ion is shown to be an effective chemical shift reagent for nitrogen-14 nuclear magnetic resonance spectroscopy. Addition of an 8 fold excess of cobalt (II) ion to a mixture of betaine, glycerophosphorylcholine and ammonium ion results in baseline resolution of the three components. The chemical shift of each component is a function of cobalt concentration up to a molar ratio of about 4:1 after which, the shifts     

Structural Chemistry of Some Imidazole Complexes

Synthesis of benzimidazole and 4 (Imidazole 1-yl) acetophenone complexes derived from cobalt(II), nickel(II), copper(II), palladium(II) and platinum(IV) salts were carried out. The elemental analyses suggest the formation of 1:2 and 1:4 stoichiometries (M:L). Electronic spectra and magnetic susceptibility measurements are used to infer the structures. The i.r. spectra of the ligands and their complexes are used to identify the type of bonding. Thermal analysis and electrical conductivity measurements were investigated in the temperature range 30–250°C. The results indicate slight semiconducting properties.     

Evaluation of cerium doped tin oxide nanoparticles as a sensitive sensor for selective detection and extraction of cobalt

Chemo-sensor technology demands to design a single, preconcentrator based sensing system having higher sensitivity, sufficient selectivity and efficient removal of metal ions with simple operating and recognition methodology. Here we effectively deliberated Ce doped SnO₂ nanoparticles based sensing system which can be exploited for the recognition and extraction of Co(II) ions in a single step by strong interaction between Ce doped SnO₂ nanoparticles and Co(II). The sensing ability of Ce doped SnO₂ nanoparticles were deliberated for a selective removal of cobalt using inductively coupled plasma-optical emission spectrometry. The sensing ability of Ce doped SnO₂ is studied for various metal ions, such as Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II) and Zn(II) but the designed sensor was most selective toward Co(II) which was 5000 time more sensitive to Co(II) rather than different interfering metal ions. In addition, the desorption study for regeneration of Ce doped SnO₂ nanoparticles was carried out. This novel approach provides a new route for simultaneous detection and removal of Co(II) in a single step and can be a time and cost alternative tool for environmental safety.     

Studies on Some Schiff Base Complexes of CoII,NiII and CuII Derived from Salicylaldehyde and O-Nitrobenzaldehyde

Schiff bases of the type salicylidene 2-aminobenzothiazole and o-nitrobenzylidene 2-aminobenzothiazole were prepared by condensation of 2-aminobenzothiazole with salicylaldehyde and o-nitrobenzaldehyde. The bases react with cobalt(II), nickel(II) and copper(II) chlorides to give 1:1 and 1:2 complexes. Electronic spectra, magnetic susceptibility measurements and infrared data are used to infer the structures. The thermal decomposition of the complexes and evaluation of the thermodynamic parameters are also reported.     

Reaction diffusion and interdiffusion in some binary metallic systems

This paper reviews studies from the Münster laboratory on multiphase and interdiffusion performed on several binary metallic systems. Optical microscopy and electron microprobe analysis were used to study interdiffusion and growth of the intermetallic layer(s) in infinite diffusion couples. Both methods have resolutions at the micron level. Thus, the results summarised in this paper concern the diffusion-controlled regime of the reaction diffusion process. We first remind the reader of some of the basics of multiphase diffusion and interdiffusion. Then we discuss results reported for the following systems: cobalt–niobium, nickel–niobium, nickel–aluminium and magnesium–aluminium. In the case of Co₂Nb we also compare interdiffusion and tracer diffusion of the components. Multiphase diffusion experiments also contain information about solid–solid equilibria of the phase diagram(s).     

Alloy formation at the Ni–Al interface for nickel films deposited on Al(110) surfaces

Alloy formation at the Ni–Al interface for thin nickel films deposited on Al(110) surfaces has been studied using high-energy ion scattering/channeling (HEIS) and X-ray photoelectron spectroscopy (XPS). For nickel atoms deposited at room temperature on Al(110), a large amount of nickel–aluminum intermixing occurs at the interface. For the first two monolayers (ML) of deposited nickel, an NiAl-like compound is formed. The intermixing continues with a different rate, forming an Ni₃Al-like compound for nickel coverages from 2 to 8 ML, at which point a nickel metal film begins to grow on the surface. Nickel atoms deposited at 250°C on the Al(110) surface exhibit no surface compound formation, but diffuse up to 400 Å into the aluminum substrate. Interatomic potentials based on the embedded-atom method (EAM) are used in a Monte Carlo approach to simulate the evolution of the Ni–Al(110) interface as a function of the nickel coverage. The calculated ion-scattering yields and X-ray photoelectron intensities from nickel and aluminum atoms in these simulated interfaces are in good quantitative agreement with the experimental results. The simulations show a high-density Ni–Al alloy forming at the Al(110) surface which apparently inhibits outward diffusion of aluminum, leading to the more nickel-rich alloy and finally nickel film growth. The ion-scattering simulations show an unusually large amount of backscattering occurring below the Ni–Al(110) interface, apparently associated with defocusing of the incident ion beam.     

Étude de l'adsorption par ellipsométrie: adsorption du Xe/(0001) graphite

The adsorption isotherms of xenon on the perfectly homogeneous (0001) face of graphite are known with great accuracy through classical volumetric measurements, LEED and Auger diffusion. Ellipsometric measurements have led to the same results. The formation of five successive monolayers and two phase transitions in the first monolayer have been shown. The ellipsometric signal Δ which is related to the formation of one monolayer varies linearly with the layer number, with only a slight discrepancy for n= 4.5. In the first monolayer the ellipsometric signal Δ varies linearly with the coverage ratio θ, 0 < 9 < 1. The detection sensibility corresponds to $\text{1}\text{100th}$ of a monolayer.