Rapid Interception of CnF2n+1(O)SO. Radical with Copper-Based Carbene: A Novel Access to Perfluoroalkanesulfinate Ester

In this communication, an unprecedented interception of C_nF_2n+1(O)SO^. radical with a copper-based carbene has been established. Distinguished by wide substrate scopes and mild reaction conditions, this novel radical–carbene coupling reaction (RCC reaction) provides a fundamentally different and mechanistically interesting strategy for the synthesis of perfluoroalkanesulfinate esters.     

Advantageous Interfacial Effects of AgPd/g-C3N4 for Photocatalytic Hydrogen Evolution: Electronic Structure and H2O Dissociation

Bimetallic AgPd nanoparticles have been synthesized before, but the interfacial electronic effects of AgPd on the photocatalytic performance have been investigated less. In this work, the results of hydrogen evolution suggest that the bimetallic AgPd/g-C₃N₄ sample has superior activity to Ag/g-C₃N₄ and Pd/g-C₃N₄ photocatalysts. The UV/Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, CO adsorption diffuse reflectance FTIR spectroscopy, and FTIR results demonstrate that in the AgPd/g-C₃N₄, the surface electronic structures of Pd and Ag are changed, which is beneficial for faster photogenerated electron transfer and greater H₂O molecule adsorption. In situ ESR spectra suggest that, under visible light irradiation, there is more H₂O dissociation to radical species on the AgPd/g-C₃N₄ photocatalyst. Furthermore, DFT calculations confirm the interfacial electronic effects of AgPd/g-C₃N₄, that is, Pd^δ−⋅⋅⋅Ag^δ+, and the activation energy of H₂O molecule dissociation on AgPd/g-C₃N₄ is the lowest, which is the main contributor to the enhanced photocatalytic H₂ evolution.     

Lattice-confined Ru clusters for hydrogen oxidation reaction with high CO-tolerance

正Hydrogen has been considering as a promising renewable energy source and a viable alternative for fossil-fuels in the future [1,2]. Hydrogen oxidation reaction (HOR) and its reverse reaction are two significant reactions for applying hydrogen as electrochemical energy. On the other hand,platinum is believed to be the best electrocatalyst for HOR,although several drawbacks including high cost, scarcity,low CO tolerance, and depressed catalytic activities in alkaline environments, hinder the development of hydrogen application [1]. Hence, it is highly desired to develop Pt-free HOR catalysts with high activity, high stability, low cost, and good resistance to CO poisoning [3].     

Effects of C3-aromatic heterocycles on 1,3,5-triaryl-2-pyrazoline sulfonium salt photoacid generators as light-emitting diode-sensitive cationic photoinitiators

Four 1,5-diphenyl-3-aromatic heterocyclyl-2-pyrazoline-based sulfonium salt photoacid generators (PAGs) with different aromatic heterocycles substituted on C3 atom and dimethyl sulfonium group on C5 atom were synthesized. These PAGs were highly photosensitive in the 365–425 nm light-emitting diode region, and the intramolecular charge transfer from the pyrazoline ring to sulfonium salts induced efficient photolysis and high Φ_H⁺. The heterocycles as well as their substituted positions significantly influenced the energy of the S₂ orbital, which was determined by the electrochemical and absorption properties of the PAGs. The raising of the S₂ orbital energy enlarged the energy gap of S₀–S₂ and S₁–S₂, resulting in blue shift of the absorption spectra and increase in the quantum yield of photoacid generation (Φ_H⁺), respectively. When the energy of excited electrons was higher than that of the S₂ orbital, the transition from S₀ to S₂ (π–π*) occurred before the C-S cleavage on S₁ and the PAGs showed high Φ_H⁺ values (0.52–0.72). The transition from S₀ to S₁ (π–σ*) occurred when the energy of electrons is lower than that of the S₂ orbital, and the PAGs showed low Φ_H⁺ value. The photopolymerization kinetics demonstrated that these PAGs were highly efficient cationic photoinitiators.     

Influence of an inserted bar on the flow regimes in the hopper

We investigated the influence of an inserted bar on the hopper flow experimentally.Three geometrical parameters,size of upper outlet D1,size of lower outlet D0,and the height of bar H,are variables here.With varying H we found three regimes:one transition from clogging to a surface flow and another transition from a surface flow to a dense flow.For the dense flow,the flow rate follows Beverloo’s law and there is a saturation of inclination of free surfaceθ.We plotted the velocity field and there is a uniform linear relation between the particle velocity and depth from the free surface.We also found that the required value of D₁ to guarantee the connectivity of flow is little smaller than D₀.For the transition from a surface flow to a dense flow,there is a jump of flow rate and the minimumθfor flowing is two degrees larger than the repose angle.     

A new MnxOy/carbon nanorods derived from bimetallic Zn/Mn metal–organic framework as an efficient oxygen reduction reaction electrocatalyst for alkaline Zn-Air batteries

Journal of Solid State Electrochemistry - In this work, nanorods like bimetallic Zn/Mn metal–organic-frameworks (MOFs) are proposed as the precursor for preparing MnxOy/porous carbon...     

Extraction of uranium in caustic sludge from the production of nuclear fuel components by countercurrent dissolution and acid curing

Journal of Radioanalytical and Nuclear Chemistry - The uraniferous caustic sludge (UCS) produced in the production of uranium fuel components was hardly to leach directly, due to its very low-grade...     

The Cu-catalyzed C–P coupling of phosphonate esters with arylboronic acids

Copper-catalyzed C–P cross coupling of phosphonate esters with arylboronic acids has been developed. The reaction provided an efficient method for aryl phosphonates under mild conditions.