Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Twining Poly(polyoxometalate) Chains into Nanoropes

Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non-solvent to its dilute solution is reported. A three-dimensional network of tangled and snake-like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non-solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application.     

Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Spectral boundary controllability of networks of strings

In this Note we give a necessary and sufficient condition for the spectral controllability from one simple node of a general network of strings that undergoes transversal vibrations in a sufficiently large time. This condition asserts that no eigenfunction vanishes identically on the string that contains the controlled node. The proof combines the Beurling–Malliavin's theorem and an asymptotic formula for the eigenvalues of the network. The optimal control time may be characterized as twice the sum of the lengths of all the strings of the network. To cite this article: R. Dáger, E. Zuazua, C. R. Acad. Sci. Paris, Ser. I 334 (2002) 545–550.     

杂多酸催化合成乙酸乙酯

回流吸附法制备的负载型12-钨磷酸(HPW/C)是合成乙酸乙酯的高效催化剂。最佳反应条件下乙醇转化率达96％,酯化选择性100％。催化剂的高活性是由于HPW在活性炭上高度分散,使活性位增多,有效酸量增大。HPW/C还具有热稳定性高和不易流失等优点。     

四角晶相HfO2(001)表面原子和电子结构研究

采用基于第一性原理的密度泛函理论研究了四角晶相二氧化铪(t-HfO₂)体相及 其(001)表面的原子几何与电子结构.理论计算结果表明，t-HfO₂(001)表面不会 产生重构现象.与体相电子结构相比, t-HfO₂(001)表面态密度明显高于体相态 密度.其次，表面原子的态密度更靠近费米能级(E_F)，价带往低能量处移动，并 有表面态产生.计算结果表明了t-HfO₂表面禁带宽度明显低于体相的禁带宽度. t-HfO₂(001)的表面态产生以及表面禁带宽度减小是由于Hf原子与O原子的配位 数减少，表面原子周围的环境发生变化而引起的. 关键词： 密度泛函理论 2(001)')" href="#">t-HfO₂(001) 表面电子结构     

Yb3+掺杂KY(WO4)2激光晶体生长、结构与光谱分析

采用顶部籽晶提拉法(TSSG)生长出Yb:KY(WO₄)₂(Yb:KYW)激光晶体.对预烧后的原料及晶体进行了XRD分析，结果表明，分别在920℃和600℃预烧8h后的熔质和助熔剂基本上形成一相，抑止了实验中的挥发问题；所生长的晶体为β-Yb:KYW，计算其晶格常数为a=1.063nm，b=1.034nm，c=0.755nm，β=130.75°.测得不同厚度样品的吸收光谱，结果表明样品在933nm和981nm有较强的吸收峰，计算出主峰981nm的吸收截面σ关键词： Yb:KYW TSSG法 晶体结构 光谱参数     

非晶态合金薄带与膜的巨磁电阻抗效应理论及计算

通过建立具有平面近横向各向异性场的非晶态合金薄带及膜的磁畴结构模型，利用线性化Maxwell方程组及Landau-Lifshitz方程，推出了在高频交变磁场及外加面内轴向直流磁场H_ex作用下的铁磁材料的与取向相关的磁导率表达式，得到了对方位角平均的相对磁导率及阻抗的计算式，导出了磁导率与张量磁化率分量间的关系，对材料磁导率的实部及虚部随H_ex的变化进行了计算，并给出了对应的磁谱图.建立的磁导率与外磁场的理论关系可将Panina及Kraus给出的理论结果统一起来. 关键词： 非晶态合金薄带及膜 取向相关磁导率 GMI效应理论与计算 近横向各向异性场     

机载稳瞄控制系统模型及仿真分析

瞄准线高精度稳定是机载光电稳瞄系统的主要指标和关键技术。根据四框架稳瞄系统的工作原理，以手动跟踪模式为主要研究对象，建立了稳瞄伺服控制系统模型。考虑到直升机扰动特点，对线扰动、角速率扰动、摩擦力矩、弹性力矩等各种扰动因素也建立相应的数学模型，同时在各种扰动因素作用下利用Matlab对机载高精度稳瞄系统的手动跟踪控制模式进行了仿真设计分析和理论研究，设计出适合的控制器。此模型在实际系统中获得验证，对稳瞄伺服控制系统的设计具有参考意义。