基于热解ZIF-8的氮掺杂碳电化学氧还原合成过氧化氢催化剂

氧气的两电子还原反应(2e-ORR)是绿色、安全的H₂O₂合成路线. 本工作以Zn²⁺和2-甲基咪唑合成的沸石型咪唑酸框架-8 (ZIF-8)为前驱体, 通过高温热解炭化, 利用ZIF-8中的锌在高温下的可挥发性, 制备了非金属氮掺杂石墨化多孔碳材料(p-ZIF), 系统考察了ZIF-8热解炭化温度(900、950和1000 ℃)对催化剂结构和2e-ORR催化性能的影响. p-ZIF不仅保留了ZIF-8规整的菱形十二面体形貌, 而且氮含量高, 拥有高的比表面积和多级孔结构. 在酸性条件下的2e-ORR反应中, 三个p-ZIF催化剂均显示了较低的过电位和较低的Tafel斜率, 而且稳定性良好. 其中在H₂O₂选择性最高的p-ZIF-950催化剂上, 过电位为86 mV, H₂O₂选择性最高可达89.2%. 在6 h恒电位反应中, p-ZIF-950催化剂能够以87 mmol•g_cat^-1•h^-1的恒定速率产生H₂O₂. 根据多种表征结果, 推测p-ZIF催化剂的孔径尺寸和石墨N含量是影响其2e-ORR催化性能的主要因素.     

液滴在超疏水植物叶面的沉积：实验和分子动力学模拟

农药液滴在靶标植物叶面的动态沉积对于提高农药利用率具有重要的意义,特别是在超疏水植物叶面的动态沉积。在本文中,我们利用生物基表面活性剂和甘油之间的氢键作用来增强液滴在超疏水植物叶面的有效沉积。在较低浓度的山梨醇-烷基胺表面活性剂溶液中,添加0.001%的甘油,可有效抑制液滴在不同超疏水/疏水植物叶片表面的弹跳和飞溅行为。结果表明,甘油的加入并没有显著改变山梨醇-烷基胺表面活性剂溶液的表面张力、粘度和聚集体的形态。核磁共振波谱(DOSY)显示,甘油加速了山梨醇-烷基胺表面活性剂分子的扩散速度。利用分子动力学模拟,对山梨醇-烷基胺表面活性剂/甘油体系的能量演化及表面活性剂相对于固体表面距离的分布进行了研究。这项目工作不仅为抑制液滴在植物叶面的弹跳飞溅提供了一种建设性的方法,而且为选择农用表面活性剂提供了理论基础。     

卡西酮类新精神活性物质的差分拉曼光谱分析研究

通过对14种卡西酮类新精神活性物质标准品的差分拉曼光谱分析研究,建立了一种简便快速、准确可靠、无损检材的卡西酮类新精神活性物质的分析方法。设置差分拉曼光谱仪激光光源785nm,激光功率200mW,积分时间1s,扫描范围为2400～200 cm^-1,对14种常见卡西酮类标准品样品进行了检验分析。可以通过对差分拉曼光谱的分析区分所有14种卡西酮类物质。利用该方法可以对卡西酮类物质进行快速无损的检验,该方法可以用于公安机关实际办案。     

外电场作用下离子液体振动光谱变化的分子动力学模拟研究

Vibrational spectroscopy is a powerful tool for studying the microstructure of liquids, and anatomizing the nature of the vibrational spectrum (VS) is promising for investigating changes in the properties of liquid structures under external conditions. In this study, molecular dynamics (MD) simulations have been performed to explore changes in the VS of 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim][PF₆]) ionic liquid (IL) under an external electric field (EEF) ranging from 0 to 10 V·nm^-1 at 350 K. First, the vibrational spectra for [Emim][PF₆] IL as well as its cation and anion are separately obtained, and the peaks are strictly assigned. The results demonstrate that the VS calculated by MD simulation can well reproduce the main characteristic peaks in the experimentally measured spectrum. Then, the vibrational spectra of the IL under various EEFs from 0 to 10 V·nm^-1 are investigated, and the intrinsic origin of the changes in the vibrational bands (VBs) at 50, 183, 3196, and 3396 cm^-1 is analyzed. Our simulation results indicate that the intensities of the VBs at 50 and 183 cm^-1 are enhanced. In addition, the VB at 50 cm^-1 is redshifted by about 16 cm^-1 as the EEF is varied from 0 to 2 V·nm^-1, and the redshift wavenumber increases to 33 cm^-1 as the EEF is increased to 3 V·nm^-1 and beyond. However, the intensities of the VBs at 3196 and 3396 cm^-1 show an obvious decrease. Meanwhile, the VB at 3396 cm^-1 is redshifted by about 16 cm^-1 when the EEF increases to 3 V·nm^-1, and the redshift increases to 33 cm^-1 with an increase in the EEF beyond 4 V·nm^-1. The intensity of the VB at 50 cm^-1 increases because of the increase in the total dipole moment of each anion and cation (from 4.34 to 5.46 D), and the redshift is attributed to the decrease in the average interaction energy per ion pair (from -378.7 to -298.0 kJ·mol^-1) with increasing EEF. The intensity of the VB at 183 cm^-1 increases on account of the more consistent orientations for cations in the system with increasing EEF. The VB at 3196 cm^-1 weakens visibly because a greater number of hydrogen atoms appear around the carbon atoms on the methyl/ethyl side chains and the vibrations of the corresponding carbon-hydrogen bonds are suppressed under the action of the EEF. Furthermore, the intensity of the VB at 3396 cm^-1 decreases due to the decrease in the intermolecular ⁺C-H···F^- hydrogen bonds (HBs), while the relaxation effect that is beneficial for the formation of HBs simultaneously exists in the system under the varying EEF, thus causing a redshift of the VB at 3396 cm^-1.     

Preparation and chiral resolution properties of bridged bis(cyclodextrin)s hybrid spheres for high performance liquid chromatography

Selenium-bridged bis(β-cyclodextrin)s organic–inorganic hybrid silica material with regular spherical shape as new type of chiral stationary phase was directly synthesized under the one-pot hydrothermal synthesis method, and the chiral stationary phase was further characterized by infrared spectroscopy, scanning electron microscopy, thermogravimetry, and elemental analysis. The results of chiral separation showed that eight chiral compounds including various types of chiral alcohols and flavanone were successfully separated in the reversed-phase separation mode by high performance liquid chromatography, which showed the better chiral resolution effect than that on the C2 position of single β-cyclodextrin. The mechanism of chiral separation was likely due to multiple interactions such as inclusion, hydrogen bonding, electrostatic interaction, dipole–dipole interaction, and the synergistic effect of two cyclodextrins during the chiral resolution process. The synergy of the two cyclodextrins has great potential for development in chiral resolution.     

超快电子衍射技术及其应用

时间和空间上实时观测原子运动对于自然科学研究有着非常重大的意义, 而超快电子衍射(UED)技术同时具备飞秒激光脉冲的高时间分辨特性和电子衍射技术的高空间特性, 可以为实时观测原子级分辨尺度物质的结构变化提供一种有效工具. 本文综述了超快电子衍射技术的发展历史、实验方法以及相关应用, 并且展望了超快电子衍射技术未来的发展.     

延性金属层裂自由面速度曲线物理涵义解读

对延性金属层裂自由面速度曲线上典型特征所蕴含的物理涵义进行了新的解读. 揭示了自由面速度曲线上宏观响应特征和微孔洞成核、长大和聚集的微损伤演化动力学之间的关联: Pullback信号的临界点对应于微孔洞的成核,Pullback幅值表征了损伤成核或起始的条件——成核强度; Pullback信号之后的回跳斜率代表了损伤演化速率, Pullback 信号后速度回跳幅值从一定程度上反映了损伤程度; Pullback信号之后的振荡周期模式反映了损伤的局域化状态.     

Rb87冷原子电磁感应透明吸收曲线不对称性的分析

研究了耦合光共振时Rb⁸⁷冷原子D1线Λ形能级体系中电磁感应透明吸收曲线的不对称现象.发现间隔为814 MHz的另一个激发态能级导致了不对称现象.不对称现象的根本原因是受激拉曼散射, 同时发现透明窗口两侧不对称的吸收峰的幅值比与耦合光强成正比.理论拟合与实验数据符合得较好.     

X‐ray‐induced Cu deposition and patterning on insulators at room temperature

X‐ray irradiation is shown to trigger the deposition of Cu from solution, at room temperature, on a wide variety of insulating substrates: glass, passivated Si, TiN/Ti/SiO₂/Si and photoresists like PMMA and SU‐8. The process is suitable for patterning and the products can be used as seeds for electroplating of thicker overlayers.     

Optoelectronic Oscillator Based on Polarization Modulation

Abstract

A polarization modulator together with a polarizer can implement phase modulation, intensity modulation with tunable chirp, and frequency-doubling intensity modulation. If an optical filter is incorporated, frequency-quadrupling and frequency-sextupling intensity modulations and a microwave photonic phase shifter can also be realized. By using a polarization modulator to replace the intensity modulator in an optoelectronic oscillator, various new features are enabled. In this article, an analytical model for the polarization modulator-based systems is established. The recent development in employing polarization modulators for constructing optoelectronic oscillators is discussed. The emerging applications enabled by the polarization modulator-based optoelectronic oscillators and the possible future development are also discussed.