Stabilization of High‐Valence Ruthenium with Silicotungstate Ligands: Preparation,Structural Characterization,and Redox Studies of Ruthenium(III)‐Substituted α‐Keggin‐Type Silicotungstates with Pyridine Ligands, [SiW11O39RuIII(Py)]5−

Ruthenium(III)‐substituted α‐Keggin‐type silicotungstates with pyridine‐based ligands, [SiW₁₁O₃₉Ru^III(Py)]^5?, (Py: pyridine ( 1 ), 4‐pyridine‐carboxylic acid ( 2 ), 4,4′‐bipyridine ( 3 ), 4‐pyridine‐acetamide ( 4 ), and 4‐pyridine‐methanol ( 5 )) were prepared by reacting [SiW₁₁O₃₉Ru^III(H₂O)]^5? with the pyridine derivatives in water at 80 °C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and ¹H NMR spectroscopy, elemental analysis, titration, and X‐ray absorption near‐edge structure (XANES) analysis (Ru K‐edge and L₃‐edge). Single‐crystal X‐ray analysis of compounds 2 , 3 , and 4 revealed that Ru^III was incorporated in the α‐Keggin framework and was coordinated by pyridine derivatives through a Ru? N bond. In the solid state, compounds 2 and 3 formed a dimer through π? π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated Ru^III–Py was reversibly oxidized into the Ru^IV–Py derivative and reduced into the Ru^II–Py derivative.     

High‐Loading Nano‐SnO2 Encapsulated in situ in Three‐Dimensional Rigid Porous Carbon for Superior Lithium‐Ion Batteries

Tin oxide nanoparticles (SnO₂ NPs) have been encapsulated in situ in a three‐dimensional ordered space structure. Within this composite, ordered mesoporous carbon (OMC) acts as a carbon framework showing a desirable ordered mesoporous structure with an average pore size (≈6 nm) and a high surface area (470.3 m² g^?1), and the SnO₂ NPs (≈10 nm) are highly loaded (up to 80 wt %) and homogeneously distributed within the OMC matrix. As an anode material for lithium‐ion batteries, a SnO₂@OMC composite material can deliver an initial charge capacity of 943 mAh g^?1 and retain 68.9 % of the initial capacity after 50 cycles at a current density of 50 mA g^?1, even exhibit a capacity of 503 mA h g^?1 after 100 cycles at 160 mA g^?1. In situ encapsulation of the SnO₂ NPs within an OMC framework contributes to a higher capacity and a better cycling stability and rate capability in comparison with bare OMC and OMC ex situ loaded with SnO₂ particles (SnO₂/OMC). The significantly improved electrochemical performance of the SnO₂@OMC composite can be attributed to the multifunctional OMC matrix, which can facilitate electrolyte infiltration, accelerate charge transfer, and lithium‐ion diffusion, and act as a favorable buffer to release reaction strains for lithiation/delithiation of the SnO₂ NPs.     

Molecular dynamics simulations of structural disordering and forming defects in a milling process for selenium

In our previous paper, structural changes of selenium powders ground by a planetary ball mill at various rotational speeds were investigated for the nanostructural modification of particles using mechanical grinding process. The experimental results indicated that the amorphisation of Se by grinding accompanies lattice strain, and the lattice strain arises from impact energy which is more than an energy related to intermolecular interaction. In this paper, molecular dynamics simulations of selenium have been carried out under compressing conditions of various pressure strengths for obtaining information of the lattice strain at atomic level. Then, dynamical behaviour of atomic configuration has been discussed in this process. The structural disordering and formation of the structural defects were estimated by deviations of bond length and angle and the number of created defects before and after compressing from simulated results. The disordering took place during compressing at various pressure strengths, and the disordered atoms return to their initial positions at lower pressure. Stable disordered state and defects after the compression can however remain by compression at more than a certain pressure strength mainly associated with binding energy of selenium.