气相中CrO2+活化甲烷C—H键的理论研究

用密度泛函UB3LYP/6-311＋＋G**方法计算研究了气相中CrO₂⁺ (²A₁/⁴A")活化甲烷C—H键的微观机理, 找到了四条反应通道. 对其中涉及的两态反应(TSR)进行了分析, 并对影响反应机理和反应速率的势能面交叉现象(potential energy surfaces crossing)进行了详细讨论, 进而运用Hammond假设和Yoshizawa等的内禀坐标单点垂直激发计算的方法找出了一系列势能面交叉点[crossing points (CPs)], 并作了相应的讨论. 进一步用碎片分子轨道理论[fragment molecular orbital (FMO)]对TS1中的轨道相互作用进行了分析, 解释了CrO₂⁺活化甲烷C—H键的机理.     

Dispersion effect on the current voltage characteristic of AlGaN/GaN high electron mobility transistors

The current voltage (IV) characteristics are greatly influenced by the dispersion effects in AlGaN/GaN high electron mobility transistors. The direct current (DC) IV and pulsed IV measurements are performed to give a deep investigation into the dispersion effects, which are mainly related to the trap and self-heating mechanisms. The results show that traps play an important role in the kink effects, and high stress can introduce more traps and defects in the device. With the help of the pulsed IV measurements, the trapping effects and self-heating effects can be separated. The impact of time constants on the dispersion effects is also discussed. In order to achieve an accurate static DC IV measurement, the steady state of the bias points must be considered carefully to avoid the dispersion effects.     

NiY分子筛选择性吸附脱硫性能及作用机理

用液相离子交换法制备了NiY分子筛,并用XRD、TEM、ICP、N2吸附和吡啶吸附原位红外技术等表征手段对其进行了表征. 利用固定床、气相色谱-硫发光检测器（GC-SCD）及傅里叶红外光谱（FT-IR）等方法系统研究了NiY分子筛对噻吩、2-甲基噻吩、3-甲基噻吩、四氢噻吩、苯并噻吩、二苯并噻吩、4-甲基二苯并噻吩、4,6-二甲基二苯并噻吩8种有机硫化物的选择性吸附脱硫性能和吸附机理. 结果表明,NiY分子筛对硫化物的穿透吸附硫容量顺序为四氢噻吩﹥苯并噻吩≈二苯并噻吩≈4,6-二甲基二苯并噻吩﹥4-甲基二苯并噻吩﹥2-甲基噻吩≈3-甲基噻吩﹥噻吩,说明有机硫化物的空间位阻效应不是其在NiY分子筛上吸附的决定因素. 红外结果表明,不同硫化物与NiY分子筛的作用机理并不相同,但主要以硫原子与金属离子配位作用（S-M作用）为主. 噻吩及其烷基取代物在NiY吸附剂上表面酸性作用下发生催化反应,噻吩环的共轭体系遭到破坏形成硫化物大分子或聚合物,导致分子筛孔道的堵塞,严重影响吸附剂的吸附脱硫能力. NiY的选择性吸附脱硫性能是硫化物与吸附中心的作用模式及吸附剂表面酸性综合作用的结果.     

甲醛在金红石型TiO2(100)-(1×1)表面的光解离

We have investigated the photoinduced decomposition of formaldehyde (CH₂O) on a rutile TiO₂(100)-(1×1) surface at 355 nm using temperature-programmed desorption. Products, formate (HCOO^-), methyl radical (CH₃·), ethylene (C₂H₄), and methanol (CH₃OH) have been detected. The initial step in the decomposition of CH₂O on the rutile TiO₂(100)-(1×1) surface is the formation of a dioxymethylene intermediate in which the carbonyl O atom of CH₂O is bound to a Ti atom at the five-fold-coordinated Ti⁴⁺ (Ti_5c) site and its carbonyl C atom bound to a nearby bridge-bonded oxygen (O_b) atom, respectively. During 355 nm irradiation, the dioxymethylene intermediate can transfer an H atom to the O_b atom, thus forming HCOO^- directly, which is considered as the main reaction channel. In addition, the dioxymethylene intermediate can also transfer methylene to the O_b row and break the C-O bond, thus leaving the original carbonyl O atom at the Ti_5c site. After the transfer of methylene, several pathways to products are available. Thus, we have found that O_b atoms are intimately involved in the photoinduced decomposition of CH₂O on the rutile TiO₂(100)-(1×1) surface.     

银纳米光催化4-二乙基对巯基苯胺偶联反应机理的研究

采用密度泛函理论(DFT)对4-二乙基对巯基苯胺在Ag5簇上的光诱导催化偶联反应机理进行了理论研究.在B3LYP/6-311+G(d,p)基组水平上(Ag采用赝势基组Lan L2DZ)对反应过程中所有的过渡态、中间体的几何构型进行了优化,通过能量和振动频率分析以及内禀反应坐标(IRC)计算证实了过渡态和中间体的合理性.研究发现4-二乙基对巯基苯胺吸附在银簇上发生偶联反应生成偶氮苯的关键在氨基端两个乙基的脱去,反应过程中存在交叉点,通过"系间窜越"行为才能完成催化偶联过程.     

基于频散补偿和分数阶微分的多模式兰姆波分离

由于兰姆波的多模和频散特性,实际检测时在同一激发频率下存在多种模式的混合信号,而各模式信号有不同的频散特性,使得在时频混叠的情况下兰姆波的检测变得十分复杂.本文在频散补偿的基础上,通过时延函数建模,依靠不同模式频散趋势的差异性,将时频混叠信号的分离问题转化为部分模式混叠信号的分离问题.基于分数阶微分的理论,用信号幅值谱分数阶微分极大值和对应频率分别与微分阶次拟合多项式实现特征参数的提取并依靠特征参数重建幅值谱.结合相位谱重构时域信号以实现部分混叠信号中频散补偿后的模式的分离.最后恢复频散获得分离后的兰姆波信号.仿真和实验结果表明,本文方法不仅可以实现时频混叠多模式兰姆波信号的分离,更能保证分离精度,有助于复杂多模式频散信号的分离与处理的进一步研究.     

基于自适应阈值正交小波变换兰姆波去噪方法

提出了基于自适应阈值正交小波变换兰姆波去噪方法 （WT-AL）。首先利用正交小波变换降低含噪兰姆波信号的自相关性,然后利用自适应阈值方法自适应地对不同尺度的正交小波变换系数进行阈值处理,最后利用小波重构获得重构信号。实验结果表明：该方法去噪后信号信噪比明显提高,均方误差明显降低。     

A Multiple Resonant Mode Film Bulk Acoustic Resonator Based on Silicon-on-Insulator Structures

With the rapid development of wireless technol- ogy, the demand for integrating multi-band devices has spurred substantial research interest. Research on CMOS compatible radio-frequency （rf） devices has also attracted significant attention. The resonant frequency of film bulk acoustic resonators （FBARs） is mainly determined by the thickness of the piezo- electric film, complicating the integration of differ- ent frequencies on a single chip. One report real- ized multiple resonant frequencies around 2.0 GHz by changing the quality of the electrode. Another re- port obtained the 2.5 GHz main frequency response with a quality factor （Q） of 101.8 and some spuri- ous resonances, while these spurious resonances were irregular.     

K0．8 Fe1．7 SeS超导体内的畴区形貌及三维分布研究

本文利用高角环形暗场像（HAADF）和衍衬像研究了K0．8 Fe1．7 SeS超导样品的超导畴区形貌及三维分布。在[001]带轴下观察到两类形貌的超导畴区,一类畴区尺寸为1μm左右,另一类为由几十纳米大小的小畴区组成的阵列。选区电子衍射和电子能量损失谱结果表明母体区对应Fe空位有序,而超导畴区可能对应K空位有序。STEM-EDS元素Mapping表明超导畴区边缘处K元素含量较多,K0．8 Fe1．7 SeS超导样品中可能至少存在三个相,分别为：K空位有序超导相、畴区外部Fe空位有序基体相以及两种空位有序区的过渡相。在[100]带轴下观察到了超导畴区具有连通性,构建了K0．8 Fe1．7 SeS超导样品中超导畴区的三维分布图。