A theoretical study of the water gas shift reaction mechanism on Cu(1 1 1) model system

The water gas shift (WGS) reaction is an important reaction system and has wide applications in several processes. However, the mechanism of the reaction is still in dispute. In this paper we have investigated the reaction mechanism on the model Cu(1 1 1) system using the density functional method and slab models. We have characterized the kinetics and the thermodynamics of the four reaction pathways containing 24 elementary steps and computed the reaction potential energy surfaces. Calculations show that the formate (HCOO) intermediate mechanism (CO + OH → HCOO → CO₂ + H) and the associative mechanism (CO + OH → CO₂ + H) are kinetically unlikely because of the high formation barrier. On the other hand, the carboxyl (HOCO) intermediate mechanism (CO + OH → HOCO → CO₂ + H) and the redox mechanism (CO + O → CO₂) are demonstrated to be feasible. Our calculations also indicate that surface oxygen atoms can reduce the barriers of both water dissociation and HOCO decomposition significantly. The calculated potential energy surfaces show that the water dissociation which produces OH groups is the rate-determining step at the initial stage of the reaction or in the absence of surface oxygen atoms. With the development of the reaction or in the presence of oxygen atoms on the surface, CO + OH → HOCO and CO + O → CO₂ become the rate-limiting step for the carboxyl and redox mechanisms, respectively.     

金属-糖胺配合物的合成,光谱表征及催化酯类水解的动力学研究

合成了4种新的糖胺 金属配合物,分别为[Ni(HL) (H2 O) 2 ]2 Cl2 ·CH3OH·2H2 O ,[Cu(HL) ]2 Cl2 ·CH3CH2 OH·3H2 O ,[Zn(HL) ]2 Cl2 ·H2 O ,[Co(HL) (H2 O) (OH) ]2 Cl2 ·CH3OH·2H2 O (HLN ,N′ 二βD 葡萄糖基乙二胺) ,并用元素分析、红外、紫外、核磁共振氢谱对其结构进行了表征。结果表明,Ni(Ⅱ) ,Co(Ⅲ)配合物为八面体构型,而Cu(Ⅱ) ,Zn(Ⅱ)配合物为四面体构型。最后研究了其对对硝基苯吡啶甲酸酯(PNPP)催化水解的催化速率常数。     

R6G单分子表面增强共振拉曼散射光谱探测研究

以共焦显微系统为平台,研究了不同浓度的R6G银溶胶的表面增强共振拉曼散射(SERRS)光谱, 结果表明不同浓度溶液中的R6G分子表现出了不同的光谱特性。在浓度为10-13mol·L-1的R6G银溶胶中 得到了R6G单分子的表面增强共振拉曼散射光谱,观察到了一些光谱非均匀变化现象,如谱色散、谱线的 强度起伏、拉曼谱的偏振化以及分子的闪烁等,并对这些现象进行了分析,证明得到的是R6G单分子的 SERRS光谱。文章还对单分子检测中的一些关键问题进行了分析与讨论,确定了单分子SERRS光谱检测的 适当条件。     

二氢黄酮类化合物的核磁共振碳谱模拟研究

采用表征分子内部化学微环境的结构描述子原子电负性作用矢量(Atomic Electronegativity Interaction Vector, AEIV)对255个共振碳原子进行了结构表征,应用多元线性回归技术建立了结构描述子AEIV与这些碳原子的¹³C NMR化学位移的定量相关模型.该定量结构谱图关系(定量构谱关系/QSSR)模型的复相关系数达到R_MM=0.915,标准偏差为SD_MM=14.879. 采用留一法交互检验的结果为R_CV=0.909,SD_CV=15.324. 结果表明,模型具有良好的估计力和稳定性.     

Effect of Nano-anatase TiO2 on Spectral Characterization of Photosystem Ⅱ Particles from Spinach

The photosystem I (PS Ⅱ) particles were purified by means of nano-anatase TiO2 treatment of spinach and studied by spectroscopy. The results show that the electron transport and the oxygen-evolving rate of PS I are accelerated after it has been treated with nano-anatase TiO2; the UV-Vis absorption spectrum of PS I particles is increased; the red shift of fluorescence emission peak of PS I is 2 nm; the peak intensity is decreased; the PS Ⅱ signal I s of low temperature electron paramagnetic resonanace(EPR) spectrum is intensified under light, and the PS I circular dichroism(CD) spectrum is similar to that of control. It is suggested that nano-anatase TiO2 might bind to the PS I reaction center complex and intensify the function of the PS I electron donor, however, nano-anatase TiO2 treatment does not change the configuration of the PS Ⅱ reaction center complex.     

多普勒漂移对超音速燃气流光辐射特性计算的影响

分析了超音速射流由于高速相对运动产生多普勒谱线漂移效应对光辐射特性计算的影响。通过采用逐线计算法对不同环境压力、气流温度、气流速度条件下超音速燃气射流在不同的红外光谱区(2.7微米谱带和4.3微米谱带)光辐射谱带积分强度的计算结果比较表明:多普勒漂移效应受环境总压影响最大,压力越大多普勒漂移的影响越小;随着温度升高多普勒漂移效应的影响降低;随着相对速度的增加,多普勒漂移效应的影响多数情况下是增加的。     

一种多波长OCDMA解码器方案及其性能分析

提出了一种多波长OCDMA（MW OCDMA）系统的光解码器方案,通过多个光硬限幅器来抑制多用户干扰.分析了使用该解码器的MW OCDMA误码率性能、频谱效率和归一化吞吐量性能.分析结果表明,该方案能有效改善MW OCDMA系统的误码率性能,在要求的误码率条件下增加同时用户数,从而能有效改善MW OCDMA系统的频谱效率.同时,采用光硬限幅器的MW OCDMA 系统的归一化吞吐量性能明显提高,特别是归一化吞吐量峰值提高了约一倍.     

激活台内透射式GaAs光电阴极的光谱响应特性研究

利用在线光谱响应技术,对透射式GaAs光电阴极在高温激活和低温激活后的光谱响应特性进行了测试,计算并比较了高温激活和低温激活后阴极的积分灵敏度和光谱响应特性参数.结果发现,与高温激活相比,低温激活后GaAs光电阴极的积分灵敏度提高了13％,低温激活后阴极的截止波长和峰值波长均向长波有微小偏移.将已获得的测试曲线与铟封后的三代像增强器的光谱响应曲线进行了比较,结果发现铟封前后的光谱响应曲线存在明显差异.     

非均匀性对单层膜光学特性的影响

探讨了不同规律的非均匀性对单层膜的光谱特性的影响,与均匀单层膜对比发现：折射率正变引起透射率的极大值减小,折射率负变引起透射率的极大值变大,当非均匀性很小时,透射率的极小值基本不变.对实验制备的单层膜从实验和理论上进行了对比并给出了较好的拟合,发现在薄膜和基底的界面处存在一过渡层,过渡层可近似为线性,并从理论上给予了分析解释.     

ICP-AES分析铁基样品

采用标准和样品基体匹配的分析条件(1?溶液),有效克服ICP-AES分析时样品中铁基体的光谱干扰,相对标准偏差均小于5%,准确度及精确度均达到满意结果。