TCNQ电荷转移配合物薄膜的制备和表征

TCNQ电荷转移配合物作为一种新型有机材料具有很多特殊的物理、化学性质，由于它在材料研究方面的特殊贡献而成为研究热点。本论文在此领域的主要研究内容如下： 1. C18TCNQ和TMB电荷转移配合物LB膜的制备和表征 利用LB技术制备了TMB•C18TCNQ LB膜，与LB-Doping法相比省略了电子给体的液相掺杂步骤，简单、易行。研究结果表明，与TMB•C18TCNQ LB-Doping膜比较，LB膜的结构和表面形貌都发生了很大变化，LB膜中TMB和C18TCNQ的环面分别垂直于基底表面，脂肪烃链有向垂直于基底表面方向变化的趋势，5层LB膜的表面形貌是由许多堆积在一起的六边形片状微晶组成。所以，通过选择制备方法获得具有不同结构的配合物薄膜是可能的。 2. TMB•TCNQ和硬脂酸混合LB膜的制备和表征 利用LB技术组装了TMB•TCNQ和硬脂酸的混合LB膜。研究发现：本身没有两亲性的TMB•TCNQ可以通过硬脂酸的夹带作用转移到基底上。混合LB膜中硬脂酸与TMB•TCNQ是物理混合，很容易被除去，而且，可以根据实际应用需要来决定混合LB膜中硬脂酸的比例。 3. TMB•TCNQ和硬脂酸混合LB膜的热稳定性研究 利用变温红外光谱研究TMB•TCNQ和硬脂酸的混合LB膜的热稳定性。结果显示，混合LB膜中硬脂酸相变发生70-72 oC，TMB•TCNQ在142-144 oC发生反掺杂（分解）。 4. TCNQ和TMB电荷转移配合物自组装膜的制备和表征 利用layer-by-layer法制备了TMB•TCNQ自组装膜。结果表明，通过三氯锗丙酸的中介作用成功地将TMB和TCNQ组装到基底上并形成电荷转移配合物，电荷转移度约为0.48。 5. 利用红外光谱研究硬脂酸镉LB膜的亚晶胞堆积类型 利用红外光谱研究了沉积在CaF2基底上的1，3，5，7-层硬脂酸镉（CdSt）LB膜的亚晶胞堆积形式，以及交替沉积LB膜中氘代硬脂酸镉（d-CdSt）LB膜对1，2，3-层硬脂酸镉LB膜的亚晶胞堆积的影响。结果表明：1-层CdSt LB膜的亚晶胞是六方堆积，而厚度超过3层的CdSt LB膜的亚晶胞是正交堆积。只有相同种类的CdSt LB膜层与层之间的相互作用才会影响碳氢长链的堆积形式，而不同种类的CdSt LB膜和d-CdSt LB膜之间的相互作用不会影响碳氢长链的堆积形式，不论这种作用是亲水头基之间的还是疏水长链之间的。 6. 近红外光谱分辨率对定量分析的影响 利用近红外光谱分析方法建立了多组分混合物中对乙酰氨基苯酚和乙水杨胺的定量分析模型。研究发现，光谱分辨率对定量分析模型有重要影响，针对具体样品的特定组分，需要选择合适的光谱分辨率，进而获得最佳的定量分析结果。

电荷在液/液界面上的转移反应

针对目前液/液界面电分析化学存在的问题,从三方面研究了电荷在液/液界面上的转移反应.主要结果如下：1将含有氧化还原电对的水相支撑在铂盘电极表面,倒置后插入到有机相中,与参比电极和对电子极构成常规的三电极系统,实现了液/液界面上的电荷转移反应.2应用电化学方法详细探讨了中性载体加速离子在微、纳米管支撑的微、纳米级-水/1,2-二氯乙烷界面上转移反应的机理、热力学和动力学.3研究了手性联萘冠醚与手性酪氨酸在微、纳米管支撑的微、纳米级-水/1,2-二氯乙烷界面上的选择性络合过程的势力学和动力学.研究结果表明R型冠醚易于与D-酪氨酸络合.

应用单、双通道微／纳米管研究液／液界面上电荷转移反应

应用单、双通道微／纳米管研究液／液界面上电荷转移反应过程是目前液／液界面电化学和电分析化学领域的研究热点之一。本文简要地回顾了液／液界面电分析化学研究的发展历程，介绍了液／液界面电分析化学的基本理论和最新进展。围绕着单、双通道微／纳米管技术，分别研究了液／液界面上的电子转移、简单离子转移、加速离子转移和电荷祸合转移过程。主要结果如下：1．应用循环伏安法和微、纳米管系统地研究了二苯并十八冠六（DB18C6）加速二十种氨基酸在水／1，2一二氯乙烷（CE）界面上的转移反应，探讨了其反应机理，测量了其配合常数以及动力学常数。这一研究将对人们理解在生命体中氨基酸在载体蛋白的推动作用下越过生物膜的主动运送过程有较重要意义。2．利用循环伏安法研究了在直接支撑在双通道微米管管尖上的单微一液／液界面上的电荷转移反应，包括简单离子（四甲基按离子TMA+）转移、加速离子转移（DB18C6加速K+离子）和电子转移（二茂铁／铁氰化钾＋亚铁氰化钾体系）反应过程。此装置是目前为止最简单的可用于研究液／液界面上的电荷转移反应的装置之一。3．利用双通道微米管支撑双一微液／液界面作为产生／收集装置考察了液／液界面上的电子转移以及电荷祸合转移过程，包括电子一离子、离子一离子祸合 转移反应。该工作丰富了双通道微米管技术，并且可以通过产生／收集实验观察到一些强亲水或强憎水离子的直接转移的伏安曲线，测得它们在W/DCE界面上的转移式电位以及条件吉布斯转移能。4．初步探讨了双通道微米管作为产生／收集装置所涉及的理论及其传质过程，应用边界元法数值拟合了收集效率与管形之间的关系，通过加速离子转移实验对拟合结果进行了验证。该工作将对于今后进一步深入地应用双通道微米管技术研究液／液界面上的电荷转移反应具有一定的指导作用。

ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

Photostimulated luminescence of silver clusters in zeolite-Y

Upon UV-irradiation at 254 nm, the photoluminescence of silver atoms in zeolite-Y decreases, meanwhile an absorption band shows up around 840 nm. By photostimulation at 840 nm, fluorescence of silver atoms is detected, which is called photostimulated luminescence, and the photoluminescence of silver atoms is increased slightly. These phenomena are attributed to the charge-transfer interaction between the zeolite framework and the entrapped silver atoms. (C) 1997 Published by Elsevier Science B.V.

Electrical bistability and negative differential resistance in diodes based on silver nanoparticle-poly(N-vinylcarbazole) composites

An electrically bistable device has been fabricated using nanocomposite films consisting of silver nanoparticles and a semiconducting polymer by a simple spin-coating method. The current-voltage characteristics of the as-fabricated devices exhibit an obvious electrical bistability and negative differential resistance effect. The current ratio between the high-conducting state and low-conducting state can reach more than 103 at room temperature. The electrical bistability of the device is attributed to the electric-filed-induced charge transfer between the silver nanoparticles and the polymer, and the negative differential resistance behavior is related to the charge trapping in the silver nanoparticles. The results open up a simple approach to fabricate high quality electrically bistable devices by doping metal nanoparticles into polymer.

Theoretical investigation on excitation, ionization and capture in H(1s, 2s)+H(1s, 2s) collisions

Cross sections of electron- loss in H( 1s)+ H( 1s) collisions and total collisional destruction of H( 2s) in H( 1s) + H( 2s) collisions are calculated by four- body classical- trajectory Monte Carlo ( CTMC) method and compared with previous theoretical and experimental data over the energy range of 4 - 100 keV. For the former a good agreement is obtained within di. erent four- body CTMC calculations, and for the incident energy Ep > 10 keV, comparison with the experimental data shows a better agreement than the results calculated by the impact parameter approximation. For the latter, our theory predicts the correct experimental behaviour, and the discrepancies between our results and experimental ones are less than 30%. Based on the successive comparison with experiments, the cross sections for excitation to H( 2p), single- and double- ionization and H- formation in H( 2s)+ H( 2s) collisions are calculated in the energy range of 4 - 100 keV for the. rst time, and compared with those in H( 1s)+ H( 1s) and H( 1s)+ H( 2s) collisions.

The many-particle scattering system He++ on He: Experiment and a complete unified description

Highly differential experimental results of the scattering system He++ on He at 30 keV are presented as well as a complete unified theoretical description where excitation, transfer and ionization are treated simultaneously on an ab initio level. The agreement even for highly differential cross sections is nearly complete although no explicit correlation besides Pauli correlation is included in the calculations.

Average energy loss measured in single and double electron capture collisions of He2 on Ar at low velocities

Employing the recoil ion momentum spectroscopy we investigate the collision between He2+ and argon atoms. By measuring the recoil longitudinal momentum the energy losses of projectile are deduced for capture reaction channels. It is found that in most cases for single- and double-electron capture, the inner electron in the target atom is removed, the recoil ion is in singly or multiply excited states (hollow ion is formed), which indicates that electron correlation plays an important role in the process. The captured electrons prefer the ground states of the projectile. It is experimentally demonstrated that the average energy losses are directly related to charge transfer and electronic configuration.

Excitation and dissociation of tungsten hexacarbonyl W(CO)(6): Statistical and nonstatistical dissociation processes

We have studied the excitation and dissociation processes of the molecule W(CO)(6) in collisions with low kinetic energy (3 keV) protons, monocharged fluorine, and chlorine ions using double charge transfer spectroscopy. By analyzing the kinetic energy loss of the projectile anions, we measured the excitation energy distribution of the produced transient dications W(CO)(6)(2+). By coincidence measurements between the anions and the stable or fragments of W(CO)(6)(2+), we determined the energy distribution for each dissociation channel. Based on the experimental data, the emission of the first CO was tentatively attributed to a nonstatistical direct dissociation process and the emission of the second or more CO ligands was attributed to the statistical dissociation processes. The dissociation energies for the successive breaking of the W-CO bond were estimated using a cascade model. The ratio between charge separation and evaporation (by the loss of CO+ and CO, respectively) channels was estimated to be 6% in the case of Cl+ impact. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3523347]

Identifying the isolated transition metal ions/oxides in molecular sieves and on oxide supports by UV resonance Raman spectroscopy

Isolated transition metal ions/oxides in molecular sieves and on surfaces are a class of active sites for selective oxidation of hydrocarbons. Identifying the active sites and their coordination structure is vital to understanding their essential role played in catalysis and designing and synthesizing more active and selective catalysts. The isolated transition metal ions in the framework of molecular sieves (e.g., TS-1, Fe-ZSM-5, and V-MCM-41) or on the surface of oxides (e.g., MoO3/Al2O3 and TiO2/SiO2) were successfully identified by UV resonance Raman spectroscopy. The charge transfer transitions between the transition metal ions and the oxygen anions are excited by a UV laser and consequently the UV resonance Raman effect greatly enhances the Raman signals of the isolated transition metal ions. The local coordination of these ions in the rigid framework of molecular sieves or in the relatively flexible structure on the surface can also be differentiated by the shifts of the resonance Raman bands. The relative concentration of the isolated transition metal ion/oxides could be estimated by the intensity ratio of Raman bands. This study demonstrates that the UV resonance Raman spectroscopy is a general technique that can be widely applied to the in-situ characterization of catalyst synthesis and catalytic reactions. (C) 2003 Elsevier Science (USA). All rights reserved.

An alternative approach to ascertain the rate-determining steps of TiO2 photoelectrocatalytic reaction by electrochemical impedance spectroscopy

In an attempt to ascertain the rate-determining steps (RDS) of TiO2 photoelectrocatalytic (PEC) reaction, the PEC oxidation of sulfosalicylic acid (SSA) solution in a TiO2-coated electrode reactor system was monitored by applying the electrochemical impedance spectroscopy (EIS) method. In the meantime, an EIS mathematical model was first established to theoretically simulate the PEC reaction. Based on the EIS model, the theoretical simulation indicates three typical reactions in a PEC oxidation process, which include the charge-transfer-dominated reaction, both the charge-transfer- and adsorption-dominated reaction, and the adsorption-dominated reaction. The experimental results of EIS measurement showed that there was only one arc/semicircle on the EIS plane display when the external bias applied was below 200 mV (vs SCE) in the SSA PEC degradation whereas there were two arcs/semicircles when the externally applied bias exceeded 200 mV (vs SCE). The experimental results have a good agreement with the model simulation. The EIS method in this study provides an easier way to determine the RDS in a PEC oxidation process, which would be helpful to better control the reaction in practice.

DFT/TDDFT Studies on the Electronic Structures and Spectral Properties of Rhenium(I) Pyridinybenzoimidazole Complexes

The electronic structures and spectral properties of three Re(I) complexes [Re(CO)(3)XL] (X = Br, Cl; L = 1-(4-5 '-phenyl-1.3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (1), 1-(4-carbazolylbutyl)-2-pyridinylbenzoimidazole (2), and 2-(1-ethyl benzimidazol-2-yl)pyridi ne (3)) were investigated theoretically. The ground and the lowest lying triplet excited states were full optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. TDDFT/PCM calculations have been employed to predict the absorption and emission spectra starting from the ground and excited state geometries, respectively.

Adsorption of 4,4 '-thiobisbenzenethiol on silver surfaces: surface-enhanced Raman scattering study

Adsorption of 4,4'-thiobisbenzenethiol (4,4'-TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface-enhanced Raman scattering (SERS) for the first time, which indicates that 4,4'-TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H-atoms of the S-H bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4'-TBBT in the two systems.