C K‐edge NEXAFS study of fluorocarbon formation on carbon anodes in molten NaF–AlF3–CaF2

Operational instability from processes occurring at the anode during the production of aluminum in the commercial Hall‐Héroult process may lead to an increase in undesirable fluorocarbon emissions, higher energy use, and shorter plant life. One contribution to this instability may be the possible formation of a fluorocarbon film at the electrode interface. Here, the surface composition of graphite anodes after electrolysis in molten NaF–AlF₃–CaF₂ at 990 °C is investigated for evidence of fluorocarbon formation using C K‐edge near edge X‐ray absorption fine structure. Fluorocarbon is identified on an anode surface after prolonged anode effect (very high overpotential with increased cell resistance) and also on an anode surface after normal electrolysis without anode effect. This provides evidence that fluorocarbon formation may occur prior to anode effect lowering the surface tension of the anode and therefore resulting in dewetting to contribute to the onset of the anode effect. Confirmation that such compounds form furthers our understanding of electrochemical reactions of graphite with fluoride and of the fundamental processes that occur in an aluminum smelter cell. Copyright © 2013 John Wiley & Sons, Ltd.     

Cloud point extraction of aluminum (III) in water samples and determination by electrothermal atomic absorption spectrometry,flame atomic absorption spectrometry and UV-visible spectrophotometry

Cloud point extraction was applied as a preconcentration step for the determination of trace level of Al(III) in water samples with electrothermal atomic absorption spectrometry (ETAAS), flame atomic absorption spectrometry (FAAS) and UV-visible spectrophotometry. The aluminum was extracted as aluminum-Eriochrome Cyanine R (ECR) complex, at pH 6 by micelles of the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114). The investigations showed that the same CPE procedure can be used for different detection techniques. The results obtained from these techniques were evaluated. Under the optimal conditions, limit of detection obtained with ETAAS, FAAS and UV-visible spectrophotometry were 0.03 ng mL^?1, 0.06 µg mL^?1 and 0.01 µg mL^?1, respectively. The accuracy of the procedure was tested by analysing certified reference material. The method was successfully applied to determination of aluminum in water samples and dialysis fluid.     

Formation of Quaternary Stereogenic Centers by Copper‐Catalyzed Asymmetric Conjugate Addition Reactions of Alkenylaluminums to Trisubstituted Enones

Alkenylaluminums undergo asymmetric copper‐catalyzed conjugate addition (ACA) to β‐substituted enones allowing the formation of stereogenic all‐carbon quaternary centers. Phosphinamine–copper complexes proved to be particularly active and selective compared with phosphoramidite ligands. After extensive optimization, high enantioselectivities (up to 96 % ee) were obtained for the addition of alkenylalanes to β‐substituted enones. Two strategies for the generation of the requisite alkenylaluminums were explored allowing for the introduction of aryl‐ and alkyl‐substituted alkenyl nucleophiles. Moreover, alkyl‐substituted phosphinamine (SimplePhos) ligands were identified for the first time as highly efficient ligands for the Cu‐catalyzed ACA.     

Selective Dimerization of Lewis‐Acid/Base‐Stabilized Phosphanylalanes

The reaction of [{(CO)₅W}PRH₂] (R=H, Ph) with H₃Al ? NR₃ (R=Et, Me) leads to the formation of four‐membered heterocyclic compounds [({(CO)₅W}P(H)AlH ? NEt₃)₂] and [({(CO)₅W}PhPAlH ? NMe₃)₂]. Upon dissolving the solid compounds, fast equilibria between the isomers are observed on the NMR timescale. Further insight into the stability and reactivity of the isomers was gained by applying theoretical methods. DFT calculations predict that hydrogen elimination in the case of [({(CO)₅W}PhPAlH ? NMe₃)₂] may be reversible.     

苯基硫脲对6063铝合金表面化学镀镍层电化学性能的影响

采用极化曲线及交流阻抗技术研究了不同浓度的苯基硫脲(稳定剂)对6063铝合金表面镍层的电化学性能的影响。极化曲线结果表明,镀液中加入苯基硫脲后的镀镍层比基体铝合金具有更正的腐蚀电位(Ecorr)、小孔(点)腐蚀电位(Epit)及更低的腐蚀电流(icorr)。为了解释镍层的电化学性能,建立了等效电路模型,并拟合出了表面电阻(Rcoat)及电容(Qcoat),电荷转移电阻(Rct)及双电层电容(Qdl)等腐蚀参数。交流阻抗研究结果表明,加入6～10 mg/L苯基硫脲后的镀镍层具有较高的表面电阻(Rcoat)、电荷转移电阻(Rct)及较低的表面电容与双电层电容(Qcoat与Qdl)。镀镍层的交流阻抗谱及极化曲线的测试结果表明,制备的镀层具有较好的耐腐蚀性能,并且相互吻合。采用扫描电子显微镜及能谱对化学镀镍层的表面形貌及成份进行了分析。结果显示,表面处于较均匀的状态,磷元素的质量分数超过10%。     

Reaction of a Dialumene‐Benzene Adduct with Diphenylacetylene: Formation of 3,4‐Dialuminacyclobutene and 5,6‐Dialuminabicyclo[2.1.1]hex‐2‐ene Derivatives

Reaction of a dialumene‐benzene adduct bearing bulky aryl substituents with diphenylacetylene was found to give a novel 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene derivative in addition to the 3,4‐dialuminacyclobutene derivative, the formal [2+2]cycloadduct of an intermediary dialumene with diphenylacetylene. The molecular structure of the newly obtained 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene has been elucidated by X‐ray crystallographic analysis.     

The Research of Sulfuric Acidic Recycling of Aluminum Industry Fluorine-containing Waste Products

The article presents the method of recycling aluminum industry fluorine-containing waste products to produce hydrogen fluoride. We carried out the estimate of the thermodynamic parameters of sulfuric acidic recycling of fluorine-containing waste products. We considered the necessity of waste products preliminary oxidizing roast stage to reduce carbonic constituent due to the interaction between carbonic constituent blocks of the sulfuric acid and waste products. We also carried out the researches for kinetic characteristics and to determine the optimal conditions for the to recycle sulfuric acidic in the fluorine-containing waste products.     

Photonic Floquet topological insulators in atomic ensembles

The feasibility of realizing a photonic Floquet topological insulator (PFTI) in an atomic ensemble is demonstrated. The interference of three coupling fields will split energy levels periodically, to form a periodic refractive index structure with honeycomb profile that can be adjusted by different frequency detunings and intensities of the coupling fields. This in turn will affect the appearance of Dirac cones in momentum space. When the honeycomb lattice sites are helically ordered along the propagation direction, gaps open at Dirac points, and one obtains a PFTI in an atomic vapor. An obliquely incident beam will be able to move along the zigzag edge of the lattice without scattering energy into the PFTI, due to the confinement of edge states. The appearance of Dirac cones and the formation of a photonic Floquet topological insulator can be shut down by the third‐order nonlinear susceptibility and opened up by the fifth‐order one.

     

A Mesoionic Diselenolene Anion and the Corresponding Radical Dianion

Dichalcogenolenes are archetypal redox non-innocent ligands with numerous applications. Herein, a diselenolene ligand with fundamentally different electronic properties is described. A mesoionic diselenolene was prepared by selenation of a C2-protected imidazolium salt. This ligand is diamagnetic, which is in contrast to the paramagnetic nature of standard dichalcogenolene monoanions. The new ligand is also redox-active, as demonstrated by isolation of a stable diselenolene radical dianion. The unique electronic properties of the new ligand give rise to unusual coordination chemistry. Thus, preparation of a hexacoordinate aluminum tris(diselenolene) complex and a Lewis acidic aluminate complex with two ligand-centered unpaired electrons was achieved.