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.     

遥感相机自动检焦技术研究

将基于图像处理的自动检焦技术应用于线阵CCD推扫成像的空间遥感相机中。图像法检焦的关键在于对焦评价函数的选取。通常对焦评价函数是在摄影目标不变的情况下得出的,而推扫成像的线阵CCD相机在任意时刻所拍摄的景物都是不同的,这就给对焦评价函数的选取增加了难度。用功率谱的方法对任意景物在空间频域进行分析表明,功率谱对于自然景物具有一定的不变性。由此建立了基于功率谱的对焦评价函数,采用小波去噪与亮度归一化相结合的图像预处理技术有效地去除了图像噪声和亮度变化对对焦精度的影响。通过对功率谱评价函数进行加权处理,提高了对焦评价函数曲线的灵敏度。仿真实验表明了所构造的对焦评价函数是可行的。     

红外热像仪参数的双黑体测量装置

对红外热像仪参数双黑体测量装置的工作原理进行了介绍。装置采用双黑体及反射型靶标为温差辐射源，可实现黑体温度温差准直辐射的定期校准和红外热像仪参数测量量值的溯源，也可实现红外热像仪参数的可控性，以及对它进行稳定的、可复现的精确测量。推导出利用红外热像仪参数双黑体测量装置测量信号传递函数SiTF数学模型，分析了红外热像仪参数测量装置的客观因素——仪器常数，针对仪器常数对SiTF测量的影响进行了试验。试验结果表明，仪器常数对红外热像仪SiTF参数测量精度影响较大，并同时影响时域与空域NETD及3D噪声的准确测量。     

Entropy for frame bundle systems and Grassmann bundle systems induced by a diffeomorphism

A Liao hyperbolic diffeomorphism has equal measure entropy and topological entropy to that of its induced systems on frame bundles and Grassmann bundles. This solves a problem Liao posed in 1996 for Liao hyperbolic diffeomorphisms.     

Using multi-exposure of color fringes to measure the beating motion of a moth

A multi-exposure of color fringes method has been developed to improve the capture speed of a conventional color CCD camera. In the method, four groups of projected fringe patterns encoded with different colors and different directions are stored in one CCD frame. Therefore the capture frequency of the conventional CCD can be improved to 200 Hz. It is available to measure the insect wings with low beating frequency, such as dragonfly, moth, or butterfly, whose beating frequency is about 30–40 Hz. We have used the method to measure the beating motion of a moth successfully.     

大口径宽视场双波段扫描红外相机光学设计

通过分析计算,设计了一种大口径宽视场折射式红外相机光学系统。该系统设计用于超长线阵扫描红外相机的地面演示成像,它能同时对短波2μm—3μm、中波3μm—4.5μm双波段成像,且同时具有24°的大视场和150mm的宽口径,成像质量接近衍射极限。该系统在航天遥感领域应用广泛。     

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.     

FJZ-250型高速分幅相机时间测量不确定度分析

FJZ-250型高速转镜分幅相机因转镜速度的不可重复性，光机结构的构造原理和控制系统各路高压触发时间的漂移，导致了时间测量的不确定度。为此，须对相机测量数据进行校正。阐述了校正方法、提供了逐幅校正位置误差的修正系数。若以预置转速对应的名义周期值去处理测量结果，则相机的时间测量合成小确定度将达1％，对名义周期值和名义幅间间隔时间值进行修正后，则可降至0.3％。     

Variational Derivative for Buckling Loads of Beams and Frames

The finite-difference method is a numerical technique for obtaining approximate solutions to differential equations. The main objective of the present study is to give a new aspect to the finite-difference method by using a variational derivative. By applying this formulation, accurate values of the buckling loads of beams and frames with various end supports are obtained. The performance of this formulation is verified by comparison with numerical examples in the literature __________ Published in Prikladnaya Mekhanika, Vol. 41, No. 7, pp. 139–144, July 2005.     

Stable Ergodicity and Frame Flows

In this note we show that all diffeomorphisms close enough to the time-one map of the frame flow on certain negatively curved manifolds are ergodic. As a simple corollary we deduce that the frame flows are ergodic for all compact manifolds with curvature pinched sufficiently close to –1, thus providing results in the case of manifolds of dimension 7 or 8 which were missing from the results of Brin and Karcher.