超小金纳米团簇的电催化氧还原性质

Ultrasmall gold nanoclusters consisting of 2-4 Au atoms were synthesized and their performance in electrocatalytic oxygen reduction reactions (ORR) was examined. These clusters were synthesized by exposing AuPPh₃Cl to the aqueous ammonia medium for one week. Electrospray ionization mass spectrometry (ESI-MS), X-ray absorption fine structure (XAFS), and X-ray photoelectron spectroscopy (XPS) analyses indicate that the as-synthesized gold clusters (abbreviated as Au_x) consist of 2-4 Au atoms coordinated by the triphenylphosphine, hydroxyl, and adsorbed oxygen ligands. A glassy carbon disk electrode loaded with the Au_x clusters (Au_x/GC) was characterized by the cyclic and linear-sweep voltammetry for ORR. The cyclic voltammogram vs. RHE shows the onset potential of 0.87 V, and the kinetic parameters of J_K at 0.47 V and the electron-transfer number per oxygen molecule were calculated to be 14.28 mA/cm² and 3.96 via the Koutecky-Levich equations, respectively.     

Suppression of charge ordering and thermal hysteresis of electronic transport and magnetisation in La0.5Ca0.5Mn1−xNixO3

A series of polycrystalline La_0.5Ca_0.5Mn_1?xNi_xO₃ (x = 0.00, 0.025, 0.050, 0.075, 0.100 and 0.125) was synthesised using solid state reaction. Measurements in a cooling and warming cycle between 300 and 80 K were carried out to study the Ni-doping effects on the electrical resistivity, thermopower and magnetisation of single-phase La_0.5Ca_0.5Mn_1?xNi_xO₃. Partial substitution of Ni for Mn leads to the suppression of charge ordering state, the evidence of which is shown by the dramatic decrease in electrical resistivity and thermal hysteresis width in electrical resistivity, thermopower and magnetisation. However, the magnitude of both electrical resistivity and thermopower increases with increasing Ni content. This can be attributed to an increase in the Mn⁴⁺ concentration, which favours the antiferromagnetic state and leads to a gradual disappearance of ferromagnetic double exchange interaction. Besides, the metal–nonmetal transition temperature decreases with increasing Ni content until x = 0.075, which might arise from increased electron–phonon coupling due to less ordered spins at temperatures above ferromagnetic transition. For samples with x greater than 0.075, no metal–nonmetal transition is observed due to the suppression of double exchange mechanism.     

强流相对论多注电子束研究进展

研制了基于爆炸发射的扇形和圆柱形多注阴极系统,并开展了强流相对论多注电子束的实验研究。研究发现：扇形多注阴极由于发射端面电场分布严重不均,电子束主要由尖端发射,束斑畸变明显,当每注扇形电子束进入到多注扇形漂移管内时,在空间电磁场的作用下电子束会绕束心旋转,导致束斑的畸变和束流的损失;圆柱形多注阴极发射端电场分布相对均匀,电子束斑畸变较小,每注电子束在多注漂移管内绕束心的旋转不会引起束斑的畸变和束流的损失;由于阴极杆和多注阴极柱的发射,多注电子束品质较差,进入多注漂移管时存在电子束轰击管壁现象,造成束流的损失甚至截止。采用大内径磁场可增大阳极筒内半径,明显提高束流的传输效率。目前,采用功率约6.5 GW、传输效率约89%的相对论多注电子束驱动的多注速调管,可实现GW量级的微波输出。     

相对论速调管放大器两腔束流调制的理论与模拟比较分析

采用一维自洽束波互作用的非线性理论,探索了相对论速调管放大器(RKA)的束流调制特性,并与二维PIC结果进行了比较和分析。首先推导了环形电子束的几何因子,然后分别给出了两腔调制时归一化调制电流和电子束动能的积分微分方程。采用调制电子束激励中间腔的非线性理论估算了中间腔间隙电压的幅度和相位,幅度的相对误差为0.07%,相位误差为2.15°。给出了输入腔和中间腔的间隙耦合系数公式,对于束压为715.2 kV、束流为8 kA的电子束,当输入腔和中间腔间隙电压分别为14,315.2 kV,输入腔和中间腔相位差为90.59°时,采用一维非线性理论和二维粒子模拟程序分别计算了基波电流调制系数和距离的关系。对于基波电流调制系数,中间腔之前处于线性区,理论值与模拟值比较一致;在中间腔内部基波电流调制系数出现明显的下降,理论值与模拟值之间的差距较大;中间腔之后处于非线性区,对于基波电流调制系数的最大值和对应的纵向位置,理论值与模拟值基本一致。当束流传输距离为65.8 cm时,计算了归一化电流和归一化电子束动能随时间的变化和电荷守恒参量N(z)与调制电流的n次谐波的电流调制系数随传输距离的变化情况。     

同轴相对论速调管周期永磁聚焦系统的初步研究

为了探索相对论速调管放大器(RKA)的小型化技术,开展了同轴RKA周期永磁聚焦的物理与设计技术研究。周期永磁聚焦系统采用Halbach阵列结构,产生的磁场类型为周期性会切磁场。首先给出该系统的磁场各个分量的表达式,分析该系统磁场分布的特点,并推导得出该系统聚焦强流环形电子束的稳定条件。根据该稳定条件,对Ka波段同轴RKA设计了一个周期永磁聚焦系统,并优化了周期磁场参数,确定了磁场系统设计的最佳周期和幅值。研究结果显示,周期永磁(PPM)聚焦系统在周期长度18 mm和磁场幅值0.33 T的条件下可引导500 kV、6 kA的同轴RKA,得到1 GW的微波输出功率,物理分析确定了周期永磁聚焦系统应用于高功率同轴RKA的技术可能性。     

The improvement of gas-sensing properties of SnO<Subscript>2</Subscript>/zeolite-assembled composite

SnO₂-impregnated zeolite composites were used as gas-sensing materials to improve the sensitivity and selectivity of the metal oxide-based resistive-type gas sensors. Nanocrystalline MFI type zeolite (ZSM-5) was prepared by hydrothermal synthesis. Highly dispersive SnO₂ nanoparticles were then successfully assembled on the surface of the ZSM-5 nanoparticles by using the impregnation methods. The SnO₂ nanoparticles are nearly spherical with the particle size of ~?10 nm. An enhanced formaldehyde sensing of as-synthesized SnO₂-ZSM-5-based sensor was observed whereas a suppression on the sensor response to other volatile organic vapors (VOCs) such as acetone, ethanol, and methanol was noticed. The possible reasons for this contrary observation were proposed to be related to the amount of the produced water vapor during the sensing reactions assisted by the ZSM-5 nanoparticles. This provides a possible new strategy to improve the selectivity of the gas sensors. The effect of the humidity on the sensor response to formaldehyde was investigated and it was found the higher humidity would decrease the sensor response. A coating layer of the ZSM-5 nanoparticles on top of the SnO₂-ZSM-5-sensing film was thus applied to further improve the sensitivity and selectivity of the sensor through the strong adsorption ability to polar gases and the “filtering effect” by the pores of ZSM-5.     

应变纤锌矿ZnO/Mg_xZn_(1-x)O柱形量子点中离子受主束缚激子的光学性质

在有效质量近似下,考虑内建电场效应,采用变分法详细研究了受限于纤锌矿Mg_xZn_(1-x)O/ZnO/Mg_xZn_(1-x)O圆柱形应变量子点中离子受主束缚激子(A~-,X)的带间光跃迁吸收系数随量子点尺寸、Mg含量和离子受主杂质中心位置的变化情况,并和离子施主束缚激子(D~+,X)及自由激子进行了比较.结果表明:随着量子点尺寸的减小,(A~-,X)的光跃迁吸收强度增强,吸收曲线向高能方向移动,出现蓝移现象.随着Mg含量增加,(A~-,X)的光跃迁吸收曲线蓝移,且吸收强度减弱.随着离子受主杂质从量子点的左界面沿材料生长方向移至量子点的右界面,光跃迁吸收曲线向低能方向移动,出现红移现象.此外,与离子施主束缚激子(D~+,X)相比,随着沿材料生长方向掺入杂质位置的变化,光跃迁吸收曲线移动的方向相反.但不管是掺入离子受主杂质还是离子施主杂质,当离子杂质从量子点的左异质界面沿材料生长方向移至右异质界面时,光跃迁吸收峰的移动量大致相同.     

聚氨酯结构与径向分布的分子动力学模拟

采用分子动力学方法计算得到DHI-乙烯醇聚合体系统的结构和径向分布函数.讨论了系统结构和径向分布函数与温度和压力之间的关系.结果表明粘合系统的空间分布一般地随着温度和压力的增加而收窄,对增加聚氨酯系统的粘合性具有积极的意义.     

NO在Ir(111)表面吸附与解离的第一性原理研究

本文系统研究了NO在Ir(111)表面的吸附,解离,以及可能的N_2生成机理.结果表明,顶位吸附的NO,其解离能垒较高(3.17 eV),不会发生解离,而三重Hcp和Fcc空位吸附的NO发生解离,能垒分别为1.23和1.28 eV.N_2是唯一的生成物,不会有副产物N_2O的产生.其最可能的反应路径为N和NO经过N_2O中间体而生成N_2,而不是直接N提取和N-N聚合产生N_2的机理.