Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

驻波声场中单分散细颗粒的相互作用特性

利用外加声场促进悬浮在气相中的细颗粒发生相互作用,进而引起颗粒的碰撞和凝并,使得颗粒平均粒径增大、数目浓度降低,是控制细颗粒排放的重要技术途径.为探究驻波声场中单分散细颗粒的相互作用,建立包含曳力、重力、声尾流效应的颗粒相互作用模型,采用四阶经典龙格-库塔算法和二阶隐式亚当斯插值算法对模型进行求解.将数值模拟得到的颗粒声波夹带速度和相互作用过程与相应的解析解和实验结果进行对比,验证模型的准确性.进而研究颗粒初始条件和直径对相互作用特性的影响.结果表明,初始时刻颗粒中心连线越接近声波波动方向、颗粒位置越接近波腹点,颗粒间的声尾流效应就越强,颗粒发生碰撞所需要的时间就越短.研究还发现,颗粒直径对颗粒相互作用的影响取决于初始时刻颗粒中心连线偏离声波波动方向的程度.当偏离较小时,颗粒直径越大,颗粒发生碰撞所需要的时间越短;当偏离很大时,直径较小的颗粒能够发生碰撞,而直径较大的颗粒则无法发生碰撞.     

New Electroweak Model Without a Higgs Particle

A new unified electroweak model is proposed in this paper. In this unified electroweak model, Higgsmechanism is not used, so no Higgs particle exists in the model. In order to keep the masses of intermediate gaugebosons non-zero, two sets of gauge fields will be introduced. In order to introduce symmetry breaking and to help tointroduce the masses of all fields, a vacuum potential is needed. Except for those terms concerning Higgs particle, thefundamental dynamical properties of this model are similar to those of the standard model. And in a proper limit, thismodel will approximately return to the standard model. The purpose of this paper is not to say that the Higgs particledoes not exist in Nature, it is only to prove that, without a Higgs particle, we can also set up a unified electroweak modelwhich is consistent with present experiments.     

考虑到束-波相互作用的速调管离子噪声二维模拟

采用粒子模拟的方法并考虑电子束与电磁波的相互作用，首次直接得到了速调管输出信号的离子噪声图像，阐述了束电子、二次电子、离子、电磁场之间的相互作用的动力学过程. 指出离子噪声所表现出来的相位波动是由电子束速度的波动引起的，电子束速度的变化来源于管内离子数量的变化，离子的数量的变化又与电子束状态变化相互影响，这是离子噪声产生的根本原因. 二次电子对离子噪声产生过程的影响甚微，但是其行为却反映了离子噪声的形成机理. 离子噪声引发的输出信号幅度波动取决于电子束速度和半径的改变，与离子行为密切相关. 关键词： 离子噪声 速调管 粒子模拟 电子束     

An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

束晕-混沌的复杂性理论与控制方法及其应用前景

本文系统论述涉及强流加速器等强流离子束装置中产生的束晕-混沌的复杂性理论与控制方法及其应用前景。强流离子束在核材料生产与增殖、洁净核能、放射性废物嬗变、放射性药物生产、重离子聚变、高能物理、核科学与工程、国防与民用工业和医疗等许多方面都有极其重要的应用潜力和诱人的发展前景。尤其是，近年来强流加速器驱动的放射性洁净核能系统是国内外关注的热门课题，因为它比常规核电更安全、更干净、更便宜。但是，强流离子束形成的束晕-混沌的复杂性现象已引起了国内外广泛关注，需要加以抑制、控制和消除这类现象，解决这一难题已经成为强流离子束应用中的关键问题之一。目前不仅必须深入研究这类束晕-混沌的复杂特性及其产生的物理机制，而且需要研究如何实现对束晕-混沌的有效控制，并寻求和发展其新理论、新方法和新技术。这就向强流离子束物理和非线性-复杂性科学及其技术提出了一系列极富挑战性的新课题。本文结合国内外的研究概况，根据我们多年来的研究成果，特别是我们首创性地提出了一些束晕-混沌的有效控制方法，它们包括：非线性反馈控制法，小波反馈控制法，变结构控制法，延迟反馈控制法，参数自适应控制法等，进行重点的介绍。对上述课题当前的主要进展及相关问题进行系统的总结和比较全面综述的评论。最后，指出该领域今后的研究方向，以推动这个崭新领域的深入研究和应用发展。     

Transport of Neutrally Buoyant and Dense Variably Sized Colloids in a Two-Dimensional Fracture with Anisotropic Aperture

The transport of monodisperse as well as polydisperse colloid suspensions in a two-dimensional, water saturated fracture with spatially variable and anisotropic aperture is investigated with a particle tracking model. Both neutrally buoyant and dense colloid suspensions are considered. Although flow and transport in fractured subsurface formations have been studied extensively by numerous investigators, the transport of dense, polydisperse colloid suspensions in a fracture with spatially variable and anisotropic aperture has not been previously explored. Simulated snapshots and breakthrough curves of ensemble averages of several realizations of a log-normally distributed aperture field show that polydisperse colloids exhibit greater spreading than monodisperse colloids, and dense colloids show greater retardation than neutrally buoyant colloids. Moreover, it is demonstrated that aperture anisotropy oriented along the flow direction substantially increases colloid spreading; whereas, aperture anisotropy oriented transverse to the flow direction retards colloid movement.     

CFD在燃煤细粒子凝聚过程中的应用

燃煤产生的细粒子富集了大量的有毒痕量元素,对大气环境和人类健康造成严重危害。本文针对燃煤细粒子的形成过程,在计算流体力学(CFD)的基础上,结合气溶胶动力学理论,模拟了烟气中细粒子在圆柱形流场中由于碰撞而凝聚的过程,并通过计算结果分析细粒子颗粒特征参量(速度、质量、直径和颗粒数目)随流场的变化趋势,为深入研究燃煤细粒子的形成演化机理提供理论基础。