Characterization and performance of cobalt-free perovskite-type La0.6Ba0.4Fe0.8Ni0.2O3 − δ cathode material for intermediate-temperature solid oxide fuel cells

Ionics - A novel cobalt-free perovskite La0.6Ba0.4Fe0.8Ni0.2O3 − δ (LBFN) powder was synthesized using a combustion method. The phase composition, electrical conductivity, thermal...     

Synergistic effect of methyl phenyl silicone resin and DOPO on the flame retardancy of epoxy resins

Polymers based on styrene (STY) and divinylbenzene (DVB) are widely used for water treatment. The chemical modification of these materials, with the introduction of chemical groups, increases their selectivity for certain types of contaminants. The incorporation of magnetic particles makes these systems useful for removing contaminants from aquifers, due to their magnetic attraction of certain residues. In this work, STY–DVB resins (unmodified, sulfonated, and impregnated with nickel and cobalt particles) were analyzed by thermogravimetry. The thermal stabilities of all the samples were compared, showing that sulfonation reduces the thermal stability of the resin, but the incorporation of metal particles restores that stability, with the extent of this recovery depending on the type of metal. This result shows that even when the incorporation of metal particles does not involve removal of contaminants by magnetic attraction, this inclusion is still justified because it increases the material’s thermal stability and also makes it more efficient for removing certain types of non-metallic contaminants, as observed in a previous study. Besides this, the thermogravimetric analysis was highly useful to ascertain the changes caused to the materials, including allowing inferences on the semi-quantitative results of the degree of sulfonation and confirming that metal compounds are not only physical mixtures.     

The Photo‐Nazarov Reaction: Scope and Application

The reaction conditions and scope of the photo‐Nazarov reaction of aryl vinyl ketones were investigated. In contrast to the conventional acid‐catalyzed methods, this photolytic electrocyclization proceeds in the neutral or basic conditions. Irradiating substrates bearing various aromatic rings, acid‐sensitive groups, cyclohexenyl, cycloheptenyl, and unsaturated pyran with UV‐light (254 nm) smoothly yielded hexahydrofluorenones and related structures. This photo‐Nazarov reaction could also be applicable to the substrates carrying β‐alkyl groups on the enone, which gave corresponding polycyclic rings containing quaternary centers. These photo‐electrocyclized products may prove useful for synthesizing a variety of natural products and their derivatives. Further application of this mild photo‐Nazarov reaction in the synthesis of taiwaniaquinol B was achieved.     

One-pot synthesis–assembly–separation of cucurbit[6]uril via SO3H-functionalized ionic liquids

A novel microwave-assisted route to synthesize cucurbit[n]uril in SO₃H-functionalized ionic liquids was reported, which enabled the automatic separation of cucurbit[6]uril through anion assembly. For the first time, the route has realized synthesis–assembly–separation of cucurbit[6]uril in one pot. The reaction yield and separation efficiency can be tuned by choice of anionic groups in ionic liquids.     

Electrochemical Phase Evolution of Metal-Based Pre-Catalysts for High-Rate Polysulfide Conversion

In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li-S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal-based pre-catalysts (Co₄N) in working Li-S batteries that renders highly active electrocatalysts (CoS_x). Electrochemical cycling induces the transformation from single-crystalline Co₄N to polycrystalline CoS_x that are rich in active sites. This transformation propels all-phase polysulfide-involving reactions. Consequently, Co₄N enables stable operation of high-rate (10 C, 16.7 mA cm⁻²) and electrolyte-starved (4.7 μL mg_S⁻¹) Li-S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low-valence metal compounds.     

Helical Coordination Polymers Based on Keggin-type POMs and N-donor Ligand

Two new 1D helical coordination polymers based on polyoxometalate were synthesized by self-assembly of Keggin-type POMs and copper salts in the presence of triangular N-heterocyclic derivatives or long-chain N-containing carboxylate ligand, that are, (H₃O)[{Cu(H₂tpim)₂}{SiMo₁₂O₄₀}] · 0.5H₂O [Htpim = 2,4,5-tri(4-pyridyl)-imidazole] ( 1 ) and [Cu₂(Hcpp)₃(cpp)(H₂O)][PMo₁₂O₄₀] · 2H₂O [Hcpp = 1-(4-cyanobenzyl)-3–2-yl)pyrazole] ( 2 ). Their structures were determined by single-crystal X-ray diffraction and further characterized by elemental analyses and TG analyses. Compounds 1 and 2 exhibit (1D→2D) interdigitated architectures assembled from 1D helical chains. In compound 1 , the achiral 2D interdigitated nets containing left- and right-handed helixes are further interdigitated with each other to form a 3D supramolecular framework. In compound 2 , adjacent 2D interdigitated layers with opposite chirality are further extended by supramolecular interactions into a 3D supramolecular network, in which non-coordinating Keggin-type POMs as guests are encapsulated.     

Three-dimensional Octameric Assembly of Icosahedral M13 Units in [Au8Ag57(Dppp)4(C6H11S)32Cl2]Cl and its [Au8Ag55(Dppp)4(C6H11S)34][BPh4]2 Derivative

The high-dimensional (that is, three-dimensional (3D)) assembly of nanomaterials is an effective means of improving their properties; however, achieving this assembly at the atomic level remains challenging. Herein, we obtained a novel nanocluster, [Au₈Ag₅₇(Dppp)₄(C₆H₁₁S)₃₂C_l2]Cl (Dppp=1,3-bis(diphenylphosphino)propane) showing a 3D octameric assembly mode involving the kernel penetration of eight complete icosahedral Au@Ag₁₀Au₂ units for the first time. The atomically precise structure was determined by single-crystal X-ray diffraction, and further confirmed by thermogravimetric analysis, X-ray photoelectron spectroscopy, and electrospray ionization mass spectrometry measurements. Furthermore, ligand-induced transformation prompted the conversion of [Au₈Ag₅₇(Dppp)₄(C₆H₁₁S)₃₂Cl₂]Cl, with complete octameric fusion into [Au₈Ag₅₅(Dppp)₄(C₆H₁₁S)₃₄][BPh₄]₂, with incomplete octameric fusion. These observations will hopefully facilitate further research on the assembly of M₁₃ nanobuilding blocks.