Interface Engineering in Two‐Dimensional Heterostructures: Towards an Advanced Catalyst for Ullmann Couplings

The design of advanced catalysts for organic reactions is of profound significance. During such processes, electrophilicity and nucleophilicity play vital roles in the activation of chemical bonds and ultimately speed up organic reactions. Herein, we demonstrate a new way to regulate the electro‐ and nucleophilicity of catalysts for organic transformations. Interface engineering in two‐dimensional heteronanostructures triggered electron transfer across the interface. The catalyst was thus rendered more electropositive, which led to superior performance in Ullmann reactions. In the presence of the engineered 2D Cu₂S/MoS₂ heteronanostructure, the coupling of iodobenzene and para‐chlorophenol gave the desired product in 92 % yield under mild conditions (100 °C). Furthermore, the catalyst exhibited excellent stability as well as high recyclability with a yield of 89 % after five cycles. We propose that interface engineering could be widely employed for the development of new catalysts for organic reactions.     

The Mosaic Structure of Zeolite Crystals

Zeolites are widely used in many commercial processes, mostly as catalysts or adsorbents. Understanding their intimate structure at the nanoscale is the key to control their properties and design the best materials for their ever increasing uses. Herein, we report a new and controllable fluoride treatment for the non‐discriminate extraction of zeolite framework cations. This sheds new light on the sub‐structure of commercially relevant zeolite crystals: they are segmented along defect zones exposing numerous nanometer‐sized crystalline domains, separated by low‐angle boundaries, in what were apparent single‐crystals. The concentration, morphology, and distribution of such domains analyzed by electron tomography indicate that this is a common phenomenon in zeolites, independent of their structure and chemical composition. This is a milestone to better understand their growth mechanism and rationally design superior catalysts and adsorbents.     

Influence of Steric Hindrance of N‐Heterocyclic Ancillary Ligands on the Structure and Magnetic Properties of Manganese(II) Coordination Polymers

Three biphenyl‐3,5‐dicarboxylic acid (H₂ L ) based coordination polymers, namely, [Mn₃( L )₃(2,2′‐bpy)₂]_n ( 1 ), {[Mn( L )(phen)] · (MeOH)}_n ( 2 ), and [Mn( L )(dipt)]_n ( 3 ), (2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and dipt = 2,9‐dimethyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction and analyses of their magnetic properties. 1 is a trinuclear manganese structure with a 2D motifs, which can join by hydrogen bond bridges to give 3D supramolecular architectures. 2 has a dinuclear center forming a 1D supramolecular ladder chain. The mononuclear complex 3 displays 1D metal‐organic chains driven by μ₂‐ L linkers. Their structural differences were investigated, revealing that the influence of steric hindrance on the structures of acid‐based coordination polymers is realized through changing the N‐heterocyclic ancillaries of diverse steric hindrance. Obviously, with decreasing of the steric hindrance of the N‐donor ligand, complexes 1 – 3 show structures from 1D to 2D and mononuclear to multinuclear. Magnetic susceptibility measurements indicate that 1 and 2 have dominating antiferromagnetic couplings between metal ions, whereas compound 3 is paramagnetic.     

Non-metallic gold nanoclusters for oxygen activation and aerobic oxidation

In this review, oxygen activation and their aerobic oxidation over the Au nanoclusters are presented. The size-specificity, ligand engineering, and doping effects and the proposed reactions’ mechanism and the structure-activity relationships at the atomic level are also discussed.     

中美无机化学课程比较与探讨*——以美国康奈尔大学与河北工业大学无机化学课程为例

以河北工业大学和美国康奈尔大学的无机化学课程为例,从教材设置、教学方法和课程考核评价方式等方面对该课程教学进行了对比探讨,以期构建一套符合我国国情且具有国际视野的无机化学新的课程体系,能为国内高校本科无机化学课程的教学改革提供参考,提高其教育教学质量,促进本科人才培养。     

新工科背景下大型仪器培训体系的创新与实践——以扫描电镜为例

针对传统大型仪器培训体系存在的定位不准、内容不足、方案陈旧等局限性,结合“新工科”人才培养理念,围绕开放共享、科研导向、育人为本、安全高效的大型仪器培训方针,充分挖掘大型仪器设备的资源价值,释放科技资源潜力,初步建立了以扫描电镜为主体的远程培训、实体培训、应用培训、动态监管“四位一体”的新型大型仪器培训体系,形成了一个闭环的、高效的大型仪器培训管理模式,具有一定的推广和借鉴价值。     

Flexible Alkylene Bridges as a Tool To Engineer Crystal Distyrylbenzene Structures Enabling Highly Fluorescent Monomeric Emission

To design ultrabright fluorescent solid dyes, a crystal engineering strategy that enables monomeric emission by blocking intermolecular electronic interactions is required. We introduced propylene moieties to distyrylbenzene (DSB) as bridges between the phenyl rings either side of its C=C bonds. The bridged DSB derivatives formed compact crystals that emit colors similar to those of the same molecules in dilute solution, with high quantum yields. The introduction of flexible seven-membered rings to the DSB core produced moderate distortion and steric hindrance in the DSB π-plane. However, owing to this strategy, it was possible to control the molecular arrangement with almost no decrease in the crystal density, and intermolecular electronic interactions were suppressed. The bridged DSB crystal structure differs from other DSB derivative structures; thus, bridging affords access to novel crystalline systems. This design strategy has important implications in many fields and is more effective than the conventional photofunctional molecular crystal design strategies.     

结构动力优化设计述评与展望

结构动力优化设计是当前工程结构设计研究领域中的前沿性课题。文中着重从结构动力特性优化、结构动力响应设计、结构动力灵敏度分析和基于可靠性的结构动力优化设计等四个专题方面对结构动力优化设计研究的发展与现状进行了述评,并粗略地展望了结构动力优化研究未来的发展趋势。      

端部激励相位差下斜拉索的非线性振动

斜拉桥中拉索承受着多种端部激励,可激发大幅空间振动．以斜拉索为对象,探究不同端部激励间相位差对其非线性振动的影响．首先,推导斜拉索无量纲离散控制方程,引入考虑相位的三向端部激励得到一般化模型;然后,针对拉索下端存在的纵桥向、竖向和横桥向激励的两两组合,受大幅或小幅激励,及其在主共振区或主参数共振区几组因素,共计12种工况,采用数值分析法分别研究了各工况下不同激励相位差时的斜拉索稳态响应．研究发现：激励相位差能加剧与激励频率相近的面内、外模态振动;在任意端部激励组合下,激励相位差不仅可使斜拉索非线性振动出现定量变化,还可改变内共振的表现形式．面内、外激励组合下,相位差对拉索响应幅值的影响以π为周期变化,且当相位差趋于π/2 + kπ (k = 0, 1, 2…)时影响最为突出;而面内激励组合下,以2π为变化周期,当相位差为π + 2kπ (k = 0, 1, 2, …)时其对稳态幅值的影响最显著．其原因是：面外激励关于拉索所在的竖直面对称,故其本质上以π为周期;而面内激励无此对称性,仍以2π为周期．因此,有无面外激励参与决定了激励间相位差对斜拉索响应的影响规律．     

土木工程结构健康监测系统的研究状况与进展

土木工程结构健康监测的研究是近年来国际学术研究的热点问题之一,涉及许多不同的研究领域,如数据采集系统、信号处理、结构分析等.阐述了实施土木工程结构健康监测的必要性和迫切性,介绍了结构健康监测系统的概念、组成及其应用,分析研究了结构健康监测系统的各个子系统的功能、特点和实现方法,重点讨论了实现各子系统的理论、方法和存在的若干力学问题,论述了结构健康监测在国内外土木工程领域的应用状况,最后对结构健康监测领域的几个重要问题做了展望.