Highly effective and chemoselective hydrodeoxygenation of aromatic alcohols

Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon–nitrogen hybrid material-supported Co catalysts. The C–OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C–N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.

Porous carbon–nitrogen hybrid material-supported Co catalysts can effectively promote the chemoselective hydrodeoxygenation reaction of a various of aromatic alcohols in ethanol and hydrogen atmosphere, under relatively mild conditions.     

The Impact of Foaming Effect on the Physical and Mechanical Properties of Foam Glasses with Molecular-Level Insights

Foaming effect strongly impacts the physical and mechanical properties of foam glass materials, but an understanding of its mechanism especially at the molecular level is still limited. In this study, the foaming effects of dextrin, a mixture of dextrin and carbon, and different carbon allotropes are investigated with respect to surface morphology as well as physical and mechanical properties, in which 1 wt.% carbon black is identified as an optimal choice for a well-balanced material property. More importantly, the different foaming effects are elucidated by all-atomistic molecular dynamics simulations with molecular-level insights into the structure–property relationships. The results show that smaller pores and more uniform pore structure benefit the mechanical properties of the foam glass samples. The foam glass samples show excellent chemical and thermal stability with 1 wt.% carbon as the foaming agent. Furthermore, the foaming effects of CaSO₄ and Na₂HPO₄ are investigated, which both create more uniform pore structures. This work may inspire more systematic approaches to control foaming effect for customized engineering needs by establishing molecular-level structure–property–process relationships, thereby, leading to efficient production of foam glass materials with desired foaming effects.     

Mo/HZSM-5催化剂上甲烷无氧芳构化反应——HZSM-5分子筛脱铝的影响

采用两种不同的脱铝方法对HZSM-5分子筛进行了预处理,并利用MAS NMR和吸附吡啶的FT-IR对分子筛的结构和酸性质进行了表征,考察了分子筛的脱铝程度对Mo基催化剂上甲烷芳构化反应性能的影响.结果表明,HZSM-5分子筛的酸性过强或B酸量不足,均会导致催化剂严重积炭,但积炭成因不同.母体HZSM-5分子筛上的强B酸中心的存在可促使催化剂上反应中间物种深度脱氢,造成催化剂在反应过程中严重积炭.经水热处理的HZSM-5分子筛,骨架铝脱出严重,造成B酸活性中心不足以及部分微孔阻塞,不利于C2中间物种芳构化,导致芳烃选择性显著降低.经高温N2处理的HZSM-5分子筛,骨架铝脱出相对缓和,在消除母体分子筛上强B酸中心的同时,保留了较多的弱B酸中心,既可满足C2中间物种芳构化反应的需要,又可有效抑制催化剂积炭,导致甲烷芳构化反应性能显著改善.     

1.3 GHz超导腔磁通排出效应研究

设计并搭建了一套高精度的磁场测量和补偿系统,并结合中国科学院高能物理研究所(IHEP)的2K超导腔垂直测试平台对1.3 GHz单加速间隙超导腔的磁通排出效应开展了实验研究:利用研制的磁场测量和补偿系统能够精密地测量超导腔赤道位置磁场,并能够将磁场补偿至小于5.0×10-8 T;并对超导腔不同表面温度梯度下的磁通排出效应进行了测量分析;对钉扎了磁场的超导腔进行了射频性能测试,研究了超导腔电阻对磁通钉扎的敏感度,以及在不同电场梯度下超导腔的表面电阻变化情况。结果表明,研制的高精度磁场测量和补偿系统能够满足超导腔磁通排出研究的需求;高的超导腔表面温度梯度有利于磁通的排出;磁通钉扎电阻的敏感度随着加速电场梯度的增加而增大,导致超导腔的性能下降。此实验研究也为后续超导腔的研制奠定了一定基础。     

Halogen bond between hypervalent halogens YF3/YF5 (Y=Cl,Br, I) and H2X (X= O,S, Se)

ABSTRACT

The complexes of H₂X (X?=?O, S, Se) with hypervalent halogens YF₃ and YF₅ (Y?=?Cl, Br, I) have been studied. The σ-hole on the Y atom participates in a halogen bond with the lone pair on the chalcogen atom. In addition, some secondary interactions coexist with the halogen bond in most complexes. The interaction energy correlates with the nature of both X and Y atoms. In most cases, the complex is more stable for the heavier Y atom and the lighter X atom. Of course, there are some exceptions in H₂X···YF₃. YF₃ forms a more stable complex with H₂X than does YF₅. These complexes are dominated by electrostatic interaction and the halogen bond involving H₂S and H₂Se exhibits some covalent character.

Halogen bond plays an important role in chemical reactions and multivalent halogens can regulate chemical reactions by participating in a halogen bond. Thus we compare the effect of the chalcogen electron donor on the strength and nature of halogen bonding involving multivalent halogens.     

基于石墨烯/石墨烯卷轴复合薄膜高灵敏度柔性压力传感器

一维导电材料例如纳米线,大量应用于柔性压力传感器中. 但是一维材料和基底之间接触时相互作用力较弱,使得传感器灵敏度、响应时间、和循环寿命等性能指标有待进一步提高. 针对这些问题,设计了石墨烯/石墨烯卷轴多分子层复合薄膜作为传感器导电层. 石墨烯卷轴具有一维结构,而石墨烯的二维结构可以牢固地固定卷轴,以确保高导电性复合薄膜与基底之间的粘附性,同时整体结构的导电通道得到了增加. 由于一维和二维结构的协同效应,实现了应变灵敏度系数3.5 kPa^-1、 响应时间小于50 ms、能够稳定工作1000次以上的压阻传感器.     

Spin-exchange relaxation of naturally abundant Rb in a K-Rb-~(21)Ne self-compensated atomic comagnetometer

The total effective spin-exchange relaxation of naturally abundant Rb in a K–Rb–21Ne comagnetometer is analyzed,and the results show that the coexistence of 87Rb and 85Rb isotopes in the same volume can lead to a large extra spinexchange broadening compared to pure 87Rb.This broadening mainly comes from the contribution of the equivalent reduction in the Rb spin-exchange rate.On this basis,an approximate relaxation model is proposed and experimentally demonstrated to be more accurate than that from a previous work.This study also provides a method for determining the properties of alkali-metal vapor cells.     

光锥与TDI-CCD耦合监控中测试目标的一种实现方法

为了给光锥与时间延迟积分电荷耦合器件耦合监控装置提供有效的被测运动条纹,分析了传统推扫成像实验装置的不足之处,设计了电子显示目标滚屏运动装置.采用光学相机对印刷条纹静止成像,并用TDI-CCD数字相机对监视器屏幕上的运动条纹动态成像.实验结果表明,该方案解决了高分辨率的鉴别率图样无法在监视器或投影仪上精确显示的困难.与传统的实验室模拟装置相比,该方案提高了鉴别率条纹的运动稳定性,减小了条纹运动速率与TDI-CCD扫描行频间的失配误差,不仅能够对耦合过程实施监控,而且还能用于耦合系统的像质评价.     

连续梁在周期荷载下的动力稳定性简化分析方法

对于一般任意支撑的连续梁结构动力稳定性问题,已有的计算方法求解过程都很复杂,给工程设计带来极大的不便．本文提出了一个简化的分析方法,利用现有的商业软件,只需求得连续梁的自然频率及静力屈曲（失稳）荷载,就可容易得到结构的动力失稳区域,当考虑结构阻尼对不稳定区域的影响时,可将阻尼矩阵表达为Rayleigh阻尼的形式．研究结果表明：采用本文计算方法与已有的理论计算方法得到的连续梁主参数共振的不稳定边界非常吻合,而本文计算方法更为简单,计算结果可靠,计算精度高,可满足工程设计的需要．