Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

TFSI钝化晶体硅表面性质的第一性原理研究

晶体硅表面钝化是高效率晶体硅太阳能电池的核心技术,直接影响晶体硅器件的性能。本文采用第一性原理方法研究了一种超强酸-双三氟甲基磺酰亚胺(TFSI)钝化晶体硅(001)表面。研究发现,TFSI的四氧原子结构能够与Si(001)表面Si原子有效成键,吸附能达到-5.124 eV。电子局域函数研究表明,TFSI的O原子与晶体硅表面的Si的成键类型为金属键。由态密度和电荷差分密度分析可知,Si表面原子的电子向TFSI转移,从而有效降低了Si表面的电子复合中心,有利于提高晶体硅的少子寿命。Bader电荷显示,伴随着TFSI钝化晶体硅表面的Si原子,表面Si原子电荷电量减少,而TFSI中的O原子和S原子电荷电量相应增加,进一步证明了TFSI钝化Si表面后的电子转移。该工作为第一性原理方法预测有机强酸钝化晶体硅表面的钝化效果提供了数据支撑。     

碳纳米管膜的高温纯化研究

为了获得纯度更高的碳纳米管膜, 保证材料发热稳定性, 需要对通过化学气相沉积法得到的碳纳米管膜进行二次纯化. 通过使用高温纯化炉, 在真空状态下, 从1700℃到3200℃分7挡温度对碳纳米管进行纯化, 并对其含碳量和方块电阻进行比较. 结果表明, 高温纯化后的碳纳米管膜含碳量从95.0%提高到99.9%, 解决了含碳量低的问题. 同时, 在高温纯化中发现碳纳米管膜方块电阻从纯化前3Ω降低到0.5Ω, 方块电阻的降低对碳纳米管膜具有十分重要的意义, 同样对碳纳米管膜后续产品的开发也有重要作用.     

关于两个图的一类新连接图的谱

给定2个图G1和G2，设G1的边集E(G1)={e1,e2,?,em1}，则图G1⊙G2可由一个G1，m1个G2通过在G1对应的每条边外加一个孤立点，新增加的点记为U={u1,u2,?,um1}，将ui分别与第i个G2的所有点以及G1中的边ei的端点相连得到，其中i=?1,2,?,m1。得到：（i）当G1是正则图，G2是正则图或完全二部图时，确定了G1⊙G2的邻接谱（A-谱）。（ii）当G1是正则图，G2是任意图时，给出了G1⊙G2的拉普拉斯谱（L-谱）。（iii）当G1和G2都是正则图时，给出了G1⊙G2的无符号拉普拉斯谱（Q-谱）。作为以上结论的应用，构建了无限多对A-同谱图、L-同谱图和Q-同谱图；同时当G1是正则图时，确定了G1⊙G2支撑树的数量和Kirchhoff指数。     

广西经济增长、金融发展与城乡收入差距的实证研究

探讨了经济增长及金融发展与城乡收入差距之间互动影响,刻画了三者间的逻辑关系,并基于广西1990-2017年的统计数据,运用状态空间模型及卡尔曼滤波算法对三者间动态关系进行了实证分析.结果显示:经济增长对城乡收入差距呈现倒U型曲线形态,而金融发展则显示出具有不断缩小城乡收入差距的趋势.     

Performance evaluation of functionalized ordered mesoporous silica for VOCs adsorption by molecular dynamics simulation

Volatile organic compounds (VOCs) are growing pollutants now that cause the serious environmental pollution and threaten human health. The functionalized ordered mesoporous silica (FOMS) has attracted considerable attention in adsorbing VOCs. In this paper, the molecular dynamics simulation was used to simulate the adsorption performance of FOMS on VOCs (acetone, ethyl acetate and toluene). After simulating different pore sizes (2 nm, 3 nm and 4 nm) adsorption performances of ordered mesoporous silica (OMS) on VOCs, OMS with a pore size of 4 nm was selected to further study the influence of functional groups (vinyl, methyl, and phenyl). The following law was obtained: the saturated adsorption capacities of vinyl-functionalized OMS (V-FOMS) to acetone, ethyl acetate and toluene were 3.045 mmol.g^?1, 2.568 mmol.g^?1 and 1.976 mmol.g^?1 respectively; the saturated adsorption capacities of methyl-functionalized OMS (M-FOMS) to acetone, ethyl acetate and toluene were 2.798 mmol.g^?1, 2.312 mmol.g^?1 and 1.698 mmol.g^?1 respectively; the saturated adsorption capacities of phenyl-functionalized OMS (P-FOMS) to acetone, ethyl acetate and toluene were 2.124 mmol.g^?1, 1.941 mmol.g^?1 and 1.539 mmol.g^?1 respectively. These results show that the adsorption ability of FOMS for different adsorbates follows the sequence of acetone > ethyl acetate > toluene. Furthermore, the interaction between functional groups (vinyl, methyl and phenyl) in FOMS and VOCs was explored. It is found that the interaction between different functional groups and adsorbates is different (interaction energy effect). This interaction energy effect promotes FOMS to better adsorb VOCs. This work would provide fundamental understanding and guidance for the development of novel adsorption materials for the adsorption of VOCs.