In Situ Observation of Hot Carrier Transfer at Plasmonic Au/Metal-Organic Frameworks (MOFs) Interfaces

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal-organic frameworks (MOFs, NH₂−MIL-125 and MIL-125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon-excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti₈O₈(OH)₄ cluster) of the MOF structure, and the plasmon-excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4-benzenedicarboxylate−NH₂). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular-level manipulation of interface charge transfer on plasmonic photocatalysts.     

二苯并噻吩在分散型钼催化剂和原位产生的氢存在下的加氢脱硫Ⅳ. 集总动力学(英)

研究了水／ 甲苯乳化液中二苯并噻吩（ 硫芴） 在分散型钼酸、磷钼酸和四硫代钼酸铵催化剂存在下的加氢脱硫反应． 反应在高压釜中于３４０ ℃及三种不同的气氛即Ｈ２ , Ｈ２／Ｈ２Ｏ 和ＣＯ／Ｈ２Ｏ（ＣＯ 和Ｈ２Ｏ 经水煤气转换反应（ ＷＧＳＲ） 产生原位氢） 的存在下进行． 用ＧＣ 和ＧＣＭＳ鉴定、分析了气体和液体产物的组成． 在此基础上,提出了包含直接氢解和加氢脱硫两个反应途径的硫芴加氢反应网络,并采用最优化法计算了反应网络的速率常数． 结果表明： 对所研究的９ 个反应体系,反应网络的模型预测值与试验值十分吻合; 加氢路径比氢解路径至少快１ 倍,硫芴的加氢比联苯的加氢快１ 倍,部分加氢的中间产物１ ,２ ,３ ,４四氢硫芴和１ ,２ ,３ ,４ ,１０,１１六氢硫芴的氢解比硫芴直接氢解快１０ 倍以上; 对硫芴的加氢脱硫反应,在分散型钼存在下,原位产生的氢比加入的氢气更为有效．     

Smart Nanovalves with Thermoresponsive Amphiphilic Triblock Copolymer Brushes

Nanochannels modified with stimuli-responsive copolymer brushes offer a smart nanovalve mechanism. The potential application of these special nanovalves is wide-ranging and includes the areas of drug delivery and signal transduction, as well as molecular machines. In this study, molecular dynamics simulations were performed to study nanovalve systems that use thermo-responsive amphiphilic triblock copolymer brushes grafted onto the surface of the nanochannel. Varying the system temperature facilitated the extension/collapse transition of the copolymer brushes, which resulted in the opening/closing of the nanochannels. The results of the investigation of the effect of the grafting density and the composition of the copolymers on the conformational transition behavior showed that the composition of copolymer has a significant influence on the nanovalve system. A remarkable result is the effectiveness of the use of intermediate or relatively low grafting density in obtaining an ideal controlling effect on the nanochannels. Our work provides a fundamental understanding of nanovalves that utilize thermo-responsive copolymers, and guidance for the design of a smart nanochannel.     

Electrohydrodynamics of spherical polyampholyte‐grafted nanoparticles: Multiscale simulations by coupling of molecular dynamics and lattice‐boltzmann method

We perform multiscale simulations based on the coupling of molecular dynamics and lattice‐Boltzmann (LB) method to study the electrohydrodynamics of a polyampholyte‐grafted spherical nanoparticle. The long‐range hydrodynamic interactions are modeled by coupling the movement of particles to a LB fluid. Our results indicate that the net‐neutral soft particle moves with a nonzero mobility under applied electric fields. We systematically explore the effects of different parameters, including the chain length, grafting density, electric field, and charge sequence, on the structures of the polymer layer and the electrophoretic mobility of the soft particle. It shows that the mobility of nanoparticles has remarkable dependence on these parameters. We find that the deformation of the polyampholyte chains and the ion distribution play dominant roles in modulating the electrokinetic behavior of the polyampholyte‐grafted particle. The enhancement or reduction in the accumulation of counterions around monomers can be attributed to the polymer layer structure and the conformational transition of the chains in the electric field. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1435–1447     

Physical deposition behavior of charged amphiphilic diblock copolymers: Effect of charge distribution and electric field

Coarse-grained molecular dynamics simulations are used to investigate physical deposition behavior of charged amphiphlic diblock copolymers. The effects of solvent selectivity, charge distribution in amphiphlic diblock copolymers, and electric field strength on deposition conformations are studied qualitatively. Flat amphiphilic bilayers, which consist of hydrophilic monolayer and hydrophobic brush, are formed by physical deposition of charged amphiphlic diblock copolymers in nonselective solvents. For physically deposited amphiphlic diblock copolymers in selective solvents, amphiphilic bilayers consist of disc-shaped hydrophilic monolayers and hydrophobic nanospheres are found. This study sheds light on the formation of various amphiphlic diblock copolymer deposition conformations in different solvents and interaction mechanism of different components. Furthermore, the evolution of physical deposition process of charged amphiphlic diblock copolymers layer offers new insight to the controlling of amphiphilic bilayer thickness, hydrophobic nanosphere size, and interface property of depositional amphiphlic diblock copolymers.     

Activation of Water in Titanium Dioxide Photocatalysis by Formation of Surface Hydrogen Bonds: An In Situ IR Spectroscopy Study

The hole‐driving oxidation of titanium‐coordinated water molecules on the surface of TiO₂ is both thermodynamically and kinetically unfavorable. By avoiding the direct coordinative adsorption of water molecules to the surface Ti sites, the water can be activated to realize its oxidation. When TiO₂ surface is covered by the H‐bonding acceptor F, the first‐layer water adsorption mode is switched from Ti coordination to a dual H‐bonding adsorption on adjacent surface F sites. Detailed in situ IR spectroscopy and isotope‐labeling studies reveal that the adsorbed water molecules by dual H‐bonding can be oxidized to O₂ even in the absence of any electron scavengers. Combined with theoretical calculations, it is proposed that the formation of the dual H‐bonding structure can not only enable the hole transfer to the water molecules thermodynamically, but also facilitate kinetically the cleavage of O? H bonds by proton‐coupled electron transfer process during water oxidation.     

利用复矩阵的高阶直接积分算法

本文提出一个直接积分结构动力学方程的高阶无条件稳定算法,并给出于利用复矩阵运算的实现方法。用本文算法,每个时间步中只需求解 N×N 阶复值线性代数方程组一次。此法的算法特性和作者以前发表的 DC 法(1990)完全相同,但缩短了计算时间并解除了对系统矩阵的若干限制(经典阻尼等)。通过几个算例对方法的精度作了考察。     

Global Hopf Bifurcation Analysis of a Nicholson’s Blowflies Equation of Neutral Type

We investigate Hopf bifurcations in a delayed Nicholson’s blowflies equation of neutral type, derived from the Gurtin–MacCamy model. A key parameter that determines the direction of the Hopf bifurcation and the stability of the bifurcating periodic solutions is derived. Global extension of local Hopf branches is established by combining a global Hopf bifurcation theorem with a Bendixson criterion for higher dimensional ordinary differential equations. We show that a branch of slowly varying periodic solutions and a branch of fast oscillating periodic solutions coexist for all large delays.