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.     

XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

Development of Lysosome-Targeted Fluorescent Probes for Cys by Regulating the Boron-dipyrromethene (BODIPY) Molecular Structure

Our previous discovery suggested that substituents on the 1,7 positions delicately modulate the sensing ability of the meso-arylmercapto boron-dipyrromethene (BODIPY) to biothiols. In this work, the impact of delicate modulations on the sensing ability is investigated. Therefore, 1,7-dimethyl, 3,5-diaryl substituted BODIPY is designed and developed and its conformationally restricted species with a meso-arylmercapto moiety ( DM-BDP-SAr and DM-BDP-R-SAr ) as selective fluorescent probes for Cys. Moreover, the lysosome-target probes ( Lyso-S and Lyso-D ) based on DM-BDP-SAr carrying one or two morpholinoethoxy moieties were developed. They were able to detect Cys selectively in vitro with low detection limits. Both Lyso-S and Lyso-D localized nicely in lysosomes in living HeLa cells and exhibited red fluorescence for Cys. Moreover, a novel fluorescence quenching mechanism was proposed from the calculations by density functional theory (DFT). The probes may go through intersystem crossing (from singlet excited state to triplet excited state) to result in fluorescence quenching.     

Air-Stable Hexagonal Bipyramidal Dysprosium(III) Single-Ion Magnets with Nearly Perfect D6h Local Symmetry

Eight-coordinated Dy^III centres with D_6h symmetry are expected to act as high-performance single-molecule magnets (SMMs) due to the simultaneous fulfilment of magnetic axiality and a high coordination number (a requisite for air stability). But the experimental realization is challenging due to the requirement of six coordinating atoms in the equatorial plane of the hexagonal bipyramid; this is usually too crowded for the central Dy^III ion. Here a hexaaza macrocyclic Schiff base ligand and finetuned axial alkoxide/phenol-type ligands are used to show that a family of hexagonal bipyramidal Dy^III complexes can be isolated. Among them, three complexes possess nearly perfect D_6h local symmetry. The highest effective magnetic reversal barrier is found at 1338(3) K and an open hysteresis temperature of 6 K at the field sweeping rate of 1.2 mT s⁻¹; this represents a new record for D_6h SMMs.     

TBOR-shaped electro-optic modulator with dual output based on double-layer graphene

We proposed an electro-optic modulator with two-bus one-ring (TBOR) structure to improve the extinction ratio and reduce insert loss. It has a dual output compared with one-bus one-ring structure. In addition, double-layer graphene makes it possible for the modulation in the visible to mid-infrared wavelength range. It shows that this new electro-optic modulator can present two switching states well with low insertion loss, high absorption and high extinction ratio. At $\lambda =1550\text{ nm}$, when the switching states are based on the chemical potential, ${\mu }_{\mathrm{c}}=0.38\text{ eV}$ and ${\mu }_{\mathrm{c}}=0.4\text{ eV}$, the insertion losses of both output ports are less than 2 dB, the absorption of the output port coupled via a micro-ring reaches 45 dB and the extinction ratio reaches 14 dB. When the refractive index of the dielectric material is 4.2, the applied voltage will be less than 1.2 V, thus can be used in low-voltage CMOS technology.     

Facile preparation of Ag/Ag2WO4/g‐C3N4 ternary plasmonic photocatalyst and its visible‐light photocatalytic activity

Introducing plasmonic metals into semiconductor materials has been proven to be an attractive strategy for enhancing photocatalytic activity in the visible region. In this work, a novel and efficient Ag/Ag₂WO₄/g‐C₃N₄ (AACN) ternary plasmonic photocatalyst was successfully synthesized using a facile one‐step in situ hydrothermal method. The composition, structure, morphology and optical absorption properties of AACN were investigated using X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and UV–visible diffuse reflectance spectroscopy, respectively. Photocatalytic performance of AACN was evaluated via rhodamine B and tetracycline degradation. The results indicated that AACN had excellent photocatalytic performance for rhodamine B degradation with a rate constant of 0.0125 min^?1, which was higher than those of Ag₂WO₄ and Ag/Ag₂WO₄. Characterization and photocatalytic tests showed that the strong coupling effect between the Ag/Ag₂WO₄ nanoparticles and the exfoliated ultrathin g‐C₃N₄ nanosheets was superior for visible‐light responsivity and reduced the recombination rate of photogenerated electrons and holes. A proposed mechanism is also discussed according to the band energy structure and the experimental results.     

An experimental study on the fire characteristics of new and aged building wires using a cone calorimeter

Journal of Thermal Analysis and Calorimetry - The fire behavior of one flame-retardant PVC cable used as building wire is investigated in this work. Bench scale tests were performed using a cone...     

Internal plasticization of poly(vinyl) chloride using glutamic acid as a branched linker to incorporate four plasticizers per anchor point

Internal plasticization of polyvinyl chloride (PVC) using thermal azide‐alkyne Huisgen dipolar cycloaddition between azidized PVC and electron‐poor acetylenediamides incorporating a branched glutamic acid linker resulted in incorporation of four plasticizing moieties per attachment point on the polymer chain. A systematic study incorporating either alkyl or polyethylene glycol esters provided materials with varying degrees of plasticization, with depressed T_g values ranging from ?1 °C to 62 °C. Three interesting trends were observed. First, T_g values of PVC bearing various internal plasticizers were shown to decrease with increasing chain length of the plasticizing ester. Second, branched internal plasticizers bearing triethylene glycol chains had lower T_g values compared to those with similar length long‐chain alkyl groups. Finally, thermogravimetric analysis of these internally plasticized PVC samples revealed that these branched internal plasticizers bearing alkyl chains are more thermally stable than similarity branched plasticizers bearing triethylene glycol units. These internal tetra‐plasticizers were synthesized and attached to PVC‐azide in three simple synthetic steps. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1821–1835