DFT Study of the BH4− Hydrolysis on Au(111) Surface

The mechanism of the catalytic hydrolysis of BH₄⁻ on Au(111) as studied by DFT is reported. The results are compared to the analogous process on Ag(111) that was recently reported. It is found that the borohydride species are adsorbed stronger on the Au⁰-NP surface than on the Ag⁰-NP surface. The electron affinity of the Au is larger than that of Ag. The results indicate that only two steps of hydrolysis are happening on the Au(111) surface and the reaction mechanism differs significantly from that on the Ag(111) surface. These remarkable results were experimentally verified. Upon hydrolysis, only three hydrogens of BH₄⁻ are transferred to the Au surface, not all four, and H₂ generation is enhanced in the presence of surface H atoms. Thus, it is proposed that the BH₄⁻ hydrolysis and reduction mechanisms catalyzed by M⁰-NPs depend considerably on the nature of the metal.     

Mechanisms of Methylenecyclobutane Hydrogenation over Supported Metal Catalysts Studied by Parahydrogen-Induced Polarization Technique

In this work the mechanism of methylenecyclobutane hydrogenation over titania-supported Rh, Pt and Pd catalysts was investigated using parahydrogen-induced polarization (PHIP) technique. It was found that methylenecyclobutane hydrogenation leads to formation of a mixture of reaction products including cyclic (1-methylcyclobutene, methylcyclobutane), linear (1-pentene, cis-2-pentene, trans-2-pentene, pentane) and branched (isoprene, 2-methyl-1-butene, 2-methyl-2-butene, isopentane) compounds. Generally, at lower temperatures (150–350 °C) the major reaction product was methylcyclobutane while higher temperature of 450 °C favors the formation of branched products isoprene, 2-methyl-1-butene and 2-methyl-2-butene. PHIP effects were detected for all reaction products except methylenecyclobutane isomers 1-methylcyclobutene and isoprene implying that the corresponding compounds can incorporate two atoms from the same parahydrogen molecule in a pairwise manner in the course of the reaction in particular positions. The mechanisms were proposed for the formation of these products based on PHIP results.     

MOF-253 immobilized Pd and Cu as recyclable and efficient green catalysts for Sonogashira reaction

MOF-253·Pd(OAc)₂ and MOF-253·CuI were prepared, characterized, and evaluated firstly as heterogeneous co-catalysts, which showed high catalytic activity in Sonogashira coupling reaction of various substituted (hetero)aryl halides with terminal alkynes at 70–120 °C, and afforded the corresponding products in 45–99% yields with high TON (～2722 for Pd). The best result was achieved with an extremely low Pd (0.036 mol%) and Cu (0.397 mol%) loading. Moreover, the catalysts can be reused at least five times without significantly reducing the activity. Besides, Hg(0) and PVP-poisoning experiments confirmed that the present catalysts were efficient and heterogeneous catalysts in this coupling reaction.     

基于用户簇分布模型的三维异构蜂窝网络覆盖概率分析

采用随机几何理论分析异构蜂窝网络性能时,通常假设用户均匀分布且独立于基站。但在实际的异构蜂窝网络中,小基站一般部署在热点地区或覆盖盲区,因此,小基站与用户的空间位置存在相关性。针对三维空间中蜂窝用户以小基站为父节点的Matern簇过程和Thomas簇过程进行建模,再采用最大信号干扰比(signal to interference ratio, SIR)的小区接入准则,在瑞利衰落信道下推导出下行链路的覆盖概率;通过蒙特卡罗仿真验证理论结果,分析用户簇过程的半径或方差、SIR门限值、小基站密度和小基站功率对覆盖概率的影响,并比较三维用户簇分布模型、三维用户均匀分布模型和二维用户簇分布模型的网络性能。实验结果表明基于三维用户簇分布模型的异构蜂窝网络具有较好的覆盖概率。     

Reliability inference with extended sequential order statistics

In this article, we will address the complexity of non-identical components in multi-component systems. Most technical systems can be described as such since either component types or component functions within the system vary amongst components. While most reliability related work resorts to the assumption of homogeneous components, we aim to address the often more realistic assumption of heterogeneous components extending the model of Extended Sequential Order Statistics by two inferential methods. Firstly, the derivation of Maximum Likelihood Estimates including a simulation study demonstrating their good performance for large enough sample size. Secondly, we introduce a likelihood ratio test to test whether components can be assumed identical accompanied by a power study. Both methods are powerful tools in reliability contexts. The former increases our understanding of component behaviour, especially upon failure of other components. This knowledge empowers system operators to make better decisions regarding maintenance schedules and failure time prediction. The latter supports operators in their quest of identifying component equivalence. Therefore, both methods can be used to achieve meaningful results in real life applications.     

Flow Synthesis of Plasmonic Gold Nanoshells via a Microreactor

Gold nanoshells with tunable surface plasmon resonances are a promising material for optical and biomedical applications. They are produced through seed‐mediated growth, in which gold nanoparticles (AuNPs) are seeded on the core particle surface followed by growth of the gold seeds into a shell. However, synthetic gold nanoshell production is typically a multistep, time‐consuming batch‐type process, and a simple and scalable process remains a challenge. In the present study, a continuous flow process for the seed‐mediated growth of silica–gold nanoshells is established by exploiting the excellent mixing performance of a microreactor. In the AuNP‐seeding step, the reduction of gold ions in the presence of core particles in the microreactor enables the one‐step flow synthesis of gold‐decorated silica particles through heterogeneous nucleation. Flow shell growth is also realized using the microreactor by selecting an appropriate reducing agent. Because self‐nucleation in the bulk solution phase is suppressed in the microreactor system, no washing is needed after each step, thus enabling the connection of the microreactors for the seeding and shell growth steps into a sequential flow process to synthesize gold nanoshells. The established system is simple and robust, thus making it a promising technology for producing gold nanoshells in an industrial setting.     

离散异质多智能体系统的分组一致性控制

针对一类混合异质多智能体系统的分组一致性控制问题进行了研究。具体分析了由一阶智能体和二阶智能体组成的混合异质系统,研究其在离散情况下的分组一致性。基于两个合理的假设提出了线性控制协议,运用代数图论、稳定性理论和矩阵理论,分析协议作用下闭环系统的系统矩阵及动态特性,取得了系统渐近实现分组一致性的充分条件,该条件与系统拓扑结构、采样周期以及控制参数有关。结论同时适用于有向拓扑与无向拓扑,最后通过仿真实例对所得分析结果进行了验证。     

Tailoring the Optical Absorption of Water‐Stable ZrIV‐ and HfIV‐Based Metal–Organic Framework Photocatalysts

New Zr^IV‐ and Hf^IV‐based metal–organic framework photocatalysts, termed VNU‐1 and VNU‐2 (where VNU=Vietnam National University), were synthesized and their resulting structures fully characterized. By employing a highly π‐conjugated linker, namely 1,4‐bis(2‐[4‐carboxyphenyl]ethynyl)benzene, the optical absorption properties were effectively red‐shifted into the visible light region. This strategy, coupled with the high water stability of the materials, led to enhanced MOF‐driven photocatalytic degradation, under ultraviolet‐visible light, of organic dye pollutants commonly found in wastewater.     

Two-phase flow in heterogeneous porous media: The method of large-scale averaging

The analysis of two-phase flow in porous media begins with the Stokes equations and an appropriate set of boundary conditions. Local volume averaging can then be used to produce the well known extension of Darcy's law for two-phase flow. In addition, a method of closure exists that can be used to predict the individual permeability tensors for each phase. For a heterogeneous porous medium, the local volume average closure problem becomes exceedingly complex and an alternate theoretical resolution of the problem is necessary. This is provided by the method of large-scale averaging which is used to average the Darcy-scale equations over a region that is large compared to the length scale of the heterogeneities. In this paper we present the derivation of the large-scale averaged continuity and momentum equations, and we develop a method of closure that can be used to predict the large-scale permeability tensors and the large-scale capillary pressure. The closure problem is limited by the principle of local mechanical equilibrium. This means that the local fluid distribution is determined by capillary pressure-saturation relations and is not constrained by the solution of an evolutionary transport equation. Special attention is given to the fact that both fluids can be trapped in regions where the saturation is equal to the irreducible saturation, in addition to being trapped in regions where the saturation is greater than the irreducible saturation. Theoretical results are given for stratified porous media and a two-dimensional model for a heterogeneous porous medium.