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.     

Crosslinking‐induced morphology change of latex nanoparticles: A study of RAFT‐mediated polymerization in aqueous dispersed media using amphiphilic double‐brush copolymers as reactive surfactants

Amphiphilic double‐brush copolymers (DBCs) with each graft site quantitatively carrying both a hydrophilic poly(ethylene oxide) (PEO) graft and a hydrophobic polystyrene (PSt) graft are synthesized by sequential reversible addition‐fragmentation chain transfer (RAFT) polymerization and ring‐opening metathesis polymerization (ROMP). These DBCs are used as both surfactants and polyfunctional RAFT agents in the radical polymerization of St in aqueous dispersed media. Miniemulsions with narrowly dispersed St‐based nanodroplets are readily obtained after ultrasonication of the reaction mixtures. Without the presence of crosslinker, chain‐extension polymerization of St from the DBCs yields well‐defined polymeric latexes with narrow size distributions. However, with the presence of divinylbenzene (DVB) as the crosslinker, vesicular polymeric nanoparticles are formed as the major product. Such crosslinking‐induced change in morphology of the resulting latex nanomaterials may be ascribed to the increase of interfacial curvature in the heterophase systems during crosslinking polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3250–3259     

Bilinear formalism,lump solution,lumpoff and instanton/rogue wave solution of a (3+1)-dimensional B-type Kadomtsev–Petviashvili equation

Nonlinear Dynamics - We consider the simplified (3+1)-dimensional B-type Kadomtsev–Petviashvili equation. We use the binary Bell polynomial theory to construct a bilinear form of the...     

Saliency detection based on superpixels clustering and stereo disparity

Reliable saliency detection can be used to quickly and effectively locate objects in images. In this paper, a novel algorithm for saliency detection based on superpixels clustering and stereo disparity (SDC) is proposed. Firstly, we use an improved superpixels clustering method to decompose the given image. Then, the disparity of each superpixel is computed by a modified stereo correspondence algorithm. Finally, a new measure which combines stereo disparity with color contrast and spatial coherence is defined to evaluate the saliency of each superpixel. From the experiments we can see that regions with high disparity can get higher saliency value, and the saliency maps have the same resolution with the source images, objects in the map have clear boundaries. Due to the use of superpixel and stereo disparity information, the proposed method is computationally efficient and outperforms some state-of-the-art colorbased saliency detection methods.     

Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst

We report the polymerization of phenyl isocyanides with the chiral palladium(II) initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer(rac-1), and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac-1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester(1 s) and 4-isocyanobenzoyl-D-alanine decyl ester(1 r), revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations.It turned out that the monomer reactivity ratio of 1 s was higher than that of 1 r with chiral ligands. The results clearly demonstrated the inclination for incorporation of the 1 s enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated,and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium(II) catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.     

The First One‐Pot Synthesis of Metal–Organic Frameworks Functionalised with Two Transition‐Metal Complexes

The synthesis of a metal–organic framework (UiO‐67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one‐pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X‐ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO‐67 with a very wide range of loadings (from 4 to 43 mol %) of an iridium complex ([IrCp*(bpydc)(Cl)Cl]^2?; bpydc=2,2′‐bipyridine‐5,5′‐dicarboxylate, Cp*=pentamethylcyclopentadienyl) through a pre‐functionalisation methodology.     

Insights into the Control of Optoelectronic Properties in Mixed-Stacking Charge-Transfer Complexes

Although cocrystallization has provided a promising platform to develop new organic optoelectronic materials, it is still a big challenge to purposely design and achieve specific optoelectronic properties. Herein, a series of mixed-stacking cocrystals (TMFA, TMCA, and TMTQ) were designed and synthesized, and the regulatory effects of the acceptors on the co-assembly behavior, charge-transfer nature, energy-level structures, and optoelectronic characteristics were systematically investigated. The results demonstrate that it is feasible to achieve effective charge-transport tuning and photoresponse switching by carefully regulating the intermolecular charge transfer and energy orbitals. The inherent mechanisms underlying the change in these optoelectronic behaviors were analyzed in depth and elucidated to provide clear guidelines for future development of new optoelectronic materials. In addition, due to the excellent photoresponsive characteristics of TMCA, TMCA-based phototransistors were investigated with varying light wavelength and optical power, and TMCA shows the best performance among all reported cocrystals under UV illumination.     

食品药品检验机构仪器设备计量信息的标准化管理

建立食品药品检验机构仪器设备计量的信息化规范管理方法。总结了传统人工计量管理的弊端,提出计量信息化管理的流程,将计量信息化管理分为计量计划申报、计量应急申报、计量信息登记、计量结果确认4个步骤,详细介绍了4个步骤中信息管理的主要内容及注意事项。建立食品药品检验机构仪器设备计量信息化管理的标准化规程,可以为仪器设备计量信息的动态监管提供支持。     

Nanoscale Broadband Viscoelastic Spectroscopy of Soft Materials Using Iterative Control

A novel approach to nanoscale broadband viscoelastic spectroscopy is presented. The proposed approach utilizes the recently developed modeling-free inversion-based iterative control (MIIC) technique to achieve accurate measurement of the material response to the applied excitation force over a broad frequency band. Scanning probe microscope (SPM) and nanoindenter have become enabling tools to quantitatively measure the mechanical properties of a wide variety of materials at nanoscale. Current nanomechanical measurement, however, is limited by the slow measurement speed: the nanomechanical measurement is slow and narrow-banded and thus not capable of measuring rate-dependent phenomena of materials. As a result, large measurement (temporal) errors are generated when material is undergoing dynamic evolution during the measurement. The low-speed operation of SPM is due to the inability of current approaches to (1) rapidly excite the broadband nanomechanical behavior of materials, and (2) compensate for the convolution of the hardware adverse effects with the material response during high-speed measurements. These adverse effects include the hysteresis of the piezo actuator (used to position the probe relative to the sample); the vibrational dynamics of the piezo actuator and the cantilever along with the related mechanical mounting; and the dynamics uncertainties caused by the probe variation and the operation condition. In the proposed approach, an input force signal with frequency characteristics of band-limited white-noise is utilized to rapidly excite the nanomechanical response of materials over a broad frequency range. The MIIC technique is used to compensate for the hardware adverse effects, thereby allowing the precise application of such an excitation force and measurement of the material response (to the applied force). The proposed approach is illustrated by implementing it to measure the frequency-dependent plane-strain modulus of poly(dimethylsiloxane) (PDMS) over a broad frequency range extending over 3 orders of magnitude (~1 Hz to 4.5 kHz).