C−H Activation of Inert Arenes using a Photochemically Activated Guanidinato-Magnesium(I) Compound

UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg}₂] 3 (Priso=[(DipN)₂CNPrⁱ₂]⁻, Dip=2,6-diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C−H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg}₂(μ-H)(μ-Ar)] 4 – 9 . In contrast to similar reactions reported for β-diketiminate coordinated counterparts of 3 , these C−H activations proceed with little regioselectivity, though they are considerably faster. Reaction of 3 with an excess of the pyridine, p-NC₅H₄Bu^t (py^But), gave [(Priso)Mg(py^ButH)(py^But)₂] 10 , presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(py^But⋅)(py^But)₂] 11 , which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C−H activations. One of these involves photochemical cleavage of the Mg−Mg bond of 3 , generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give “Birch-like” products, which subsequently rearrange via C−H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of 3 leads to an intramolecular aliphatic C−H activation process and formation of an alkyl-bridged magnesium(II) species, [{Mg(μ-Priso^−H)}₂] 12 . Furthermore, irradiation of a 1 : 1 mixture of 3 and the β-diketiminato dimagnesium(I) compound, [{(^DipNacnac)Mg}₂] (^DipNacnac=[HC(MeCNDip)₂]⁻), effects a “scrambling” reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg−Mg(^DipNacnac)] 13 . Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated 3 is dominated by a broad featureless signal, indicating the presence of a doublet radical species.     

Revealing the Reaction and Fading Mechanism of FeSe2 Cathodes for Rechargeable Magnesium Batteries

Rechargeable Mg batteries (RMBs) are advantageous large-scale energy-storage devices because of the high abundance and high safety, but exploring high-performance cathodes remains the largest difficulty for their development. Compared with oxides and sulfides, selenides show better Mg-storage performance because the weaker interaction with the Mg²⁺ cation favors fast kinetics. Herein, nanorod-like FeSe₂ was synthesized and investigated as a cathode for RMBs. Compared with microspheres and microparticles, nanorods exhibit higher capacity and better rate capability with a smaller particle size. The FeSe₂ nanorods show a high capacity of 191 mAh g⁻¹ at 50 mA g⁻¹ and a good rate performance of 39 mAh g⁻¹ at 1000 mA g⁻¹. Ex situ characterizations demonstrate the Mg²⁺ intercalation mechanism for FeSe₂, and a slight conversion reaction occurs on the surface of the particles. The capacity fading is mainly because of the dissolution of Fe²⁺, which is caused by the reaction between Fe²⁺ and Cl⁻ of the electrolyte during the charge process on the surface of the particles. The surface of FeSe₂ is mainly selenium after long cycling, which may also dissolve in the electrolyte during cycling. The present work develops a new type of Mg²⁺ intercalation cathode for RMBs. More importantly, the fading mechanism revealed herein has considered the specificity of Mg battery electrolyte and would assist a better understanding of selenide cathodes for RMBs.     

探究镁与氯化钠溶液反应的微观过程*

镁在常温下和水发生反应的速率较慢,这是因为镁表面存在氢氧化镁附着层的保护作用,但是镁可以和NaCl溶液发生较快的反应,在产生大量气泡的同时生成白色固体。通过对白色固体进行分析发现,在有Cl^-的环境下氢氧化镁会逐渐转化为碱式氯化镁,同时也会导致溶液pH的升高。经过实验探究发现,镁在不同浓度NaCl溶液中的反应现象存在差异,在反应过程中溶解氧含量也会下降。     

An investigation on surface tensions of Pb-free solder materials

Surface tensions of some Pb-free solder systems such as Ag–Bi–Sn with cross-sections Ag/Bi = 1/1, Ag/Bi = 1/2, Ag/Bi = 2/1, In–Sn–Zn with cross-sections Sn/In = 1/1, Sn/In = 1/3 and (Ag₇Cu₃)_100?x Sn_x with cross-section Ag/Cu = 7/3 are calculated from the sub-binary surface tension data using the models, such as the Muggianu, Kohler, Toop models, Butler’s equation and Chou’s General Solution Model (GSM) at 873, 923 and 1073 K, respectively. The surface tension of In–Sn–Zn increases wavily with increasing amount of Zn and it is found that the best models are the GSM for both cross-sections in question while GSM becomes the best model for (Ag₇Cu₃)_100?x Sn_x alloy in the whole experimental range. Moreover, the surface tension of (Ag₇Cu₃)_100?x Sn_x decreases slightly with increasing amount of Sn. The Muggianu, Butler and Butler models are determined as the best models for the cross-sections in the order given above for entire measurement range, respectively, and the surface tension of Ag–Bi–Sn decreases slightly with an increasing amount of Bi and Ag but increases with increasing Sn in liquid alloys.     

Microstructures and soft magnetic properties of Fe80P20-xSix (x = 4.5–6.5) amorphous ribbons

Fe-based amorphous ribbons with excellent soft magnetic properties and mechanical properties were prepared in the Fe–Si–P ternary system. Enhanced soft magnetic properties could be achieved through annealing treatment of the ribbons for 1 h at 325 °C, which is far below the glass transition temperatures (462–474 °C). Icosahedral medium-range ordering with a size range of around 2 nm occurred throughout the amorphous matrix during the low-temperature annealing treatment. The annealed ribbons exhibited improved magnetic saturation of over 185 emu/g while maintaining good mechanical flexibility. During icosahedral ordering, the distance between the Fe atoms and the coordination number within the amorphous ribbon can be optimised for achieving high magnetic saturation. However, nanocrystallisation of the SiP and Fe₂P transition phases embedded within the amorphous matrix occurred after the annealing treatment for 1 h at 385 °C, which caused deterioration of the soft magnetic properties and mechanical flexibility of the ribbons. Therefore, the combination of high magnetic saturation and mechanical flexibility of the amorphous ribbons could be optimised through low-temperature annealing treatment without any nanocrystallisation.     

Spectral probing of carrier traps in Si–Ge alloy nanocrystals

Photogenerated carriers in Si–Ge alloy nanocrystals (NCs) prepared by co‐sputtering method were investigated by mean of transient induced absorption. The carrier relaxation features multiple components, with three decay life times of τ ≈ 600 fs, 12 ps, and 15 ns, established for Si_0.2Ge_0.8 alloy NCs of a mean crystal size of 9 nm and standard deviation of 3 nm. Deep carrier traps, identified at the boundary between the NCs and the SiO₂ host with the ionization energy of about 1 eV, are characterized by a long‐range Coulombic potential. These are responsible for rapid depletion of free carrier population within a few picoseconds after the excitation, which explains the low emissivity of the investigated materials, and also sheds light on the generally low luminescence of Si/Ge and Ge NCs. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

First-principles study of fundamental properties and electronic structure of alloys

We have performed first-principles calculations using full-potential augmented-plane-wave method to investigate the fundamental properties of the Cd_1–xZn_xTe alloys. The composition dependence of the lattice constant and the bulk modulus have been estimated from total energy calculations. By means of the analytical fitting the band structures in the vicinity of the Brillouin center a complete set of effective electron- and hole-masses have also been derived. In order to further understand the effects of the chemical bonding on the above macroscopic properties we then studied the relaxation behaviors and the changes of the electronic states upon alloying for x=0.25 system. The results presented here yield a general understanding of the fundamental properties for the Cd_1–xZn_xTe crystals studies.     

3D ordered macro-/mesoporous Ni_xCo_(100-x) alloys as high-performance bifunctional electrocatalysts for overall water splitting

Electrochemical water splitting is a facile and effective route to generate pure hydrogen and oxygen.However,the sluggish kinetics of hydrogen evolution reaction(HER) and especially oxygen evolution reaction(OER) hinder the water splitting efficiency.Meanwhile,the high-cost of noble-metal catalysts limit their actual application.It is thus highly urgent to exploit an economical and earthabundant bifunctional HER and OER electrocatalyst to simplify procedure and reduce cost.Herein,we synthesize the three-dimensionally ordered macro-/mesoporous(3 DOM/m) Ni_xCo_(100-x) alloys with distinctive structure and large surface area via a dual-templating technique.Among them,the3 DOM/m Ni_(61)Co_(39) shows the lowest overpotentials of 121 mV and 241 mV at 10 mA/cm~2 for HER and OER,respectively.Furthermore,when employed for water splitting,the Ni_(61)Co_(39) only requires 1.60 V to approach 10 mA/cm2 and presents excellent stability.These encouraging performances of the Ni_(61)Co_(39)render it a promising bifunctional catalyst for overall water splitting.     

Development of Surface Nano-Crystallization in Alloys by Surface Mechanical Attrition Treatment (SMAT)

Nanometer-sized grain structures that exhibit a large number of grain boundaries on the surface of a bulk material demonstrate excellent properties relative to their coarse-grained (CG) equivalents. Surface modification using surface mechanical attrition treatment (SMAT) is an option that cab be used to tailor the corrosion, tribological, mechanical, and chemical reaction properties of a surface. SMAT is an effective route to create the nanostructured surface layer. The SMAT process has unique advantages compared with the other coating and deposition techniques for surface nanocrystallization. For example, SMAT does not alter the chemical composition of the nanocrystalline surface layer in the matrix. In addition, SMAT has been demonstrated to activate the material surface layer by surface modification and enhance the atomic diffusivity. This article presents a review of the advantages offered by the SMAT technique for the creation of high performance surface layers. The influence of the created nanocrystalline layer on mechanical, physical, and chemical properties is assessed. Developments and the current status of the surface nanolayer that are formed are evaluated from a physical approach. Finally, prospects for the future development of grain refinement on the surface of a material matrix and potential applications are presented.