Real Time Monitoring of Electron Transfer Dynamics at Solid/liquid Interfaces by Non-linear Spectroscopy

通过非线性光谱实时监测固/液界面的电子传递动力学

• 批准号: 16072202
• 负责人: UOSAKI Kohei
• 金额: $ 33.66万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16072202/
• 关键词: Non-linear Spectroscopy; electron transfer dynamics; semiconductor nanocluster; pump-probe measurement; solid; liquid interface

To understand the mechanism of electron transfer dynamics at solid/liquid interfaces, information of structures of molecules at electrode/electrolyte interface including short-lived intermediates and solvent at the interface is essential. The determination of the interfacial structures of the intermediate and solvent is, however, difficult by conventional surface vibrational techniques because of small number of molecules compared to bulk molecules. Temporal vibration of vibrational modes induced by electronic excitation is monitored by IR adsorption and surface-specific sum frequecy generation (SFG) techniques. We investigated the relations between interfacial structures and reaction dynamics by using these spectroscopic methods.1. Observation and dynamics of adsorbates at solid/liquid interfaces by SFG spectroscopyDynamics of adsorbed CO on Pt electrode was followed by visible pump SFG probe measurements. An SFG peak due to adsorbed CO at on-top site of Pt was observed at 2064cm-l. T … More he intensity of this peak decreased quickly upon excitation and recovered within few ten of os. A new broad peak was observed at 1980cm-l corresponding to adsorbed CO at multi-fold site, suggesting the site exchange upon excitation. The recovery rate was found to be dependent on potential.2. Carrier and charge transfer dynamics by visible pump-visible and IR techniqueTime-resolved visible-pump visible and infrared-probe techniques, in which very short UV or visible pulse excitation is combined with delayed ultrafast visible and mid-IR absorption, respectively, are powerful tools to monitor the changes in electronic and molecular structure, respectively, as after the photoexcitation. In the present study, (1) a system, which allows these two measurements, was constructed, (2) visible-pump infrared-probe technique was applied to study the effect of size and surface treatment on the carrier dynamics of CdS, and (3) visible-pump visible and infrared-probe techniques were applied to study the photo-induced intra-molecular charge transfer with a triruthenium complex [Ru_3(O)(CH_3CO2)_6(CO)L_2], where L=ligands, containing a strongly IR active ligand, CO, which act as a direct IR probe of the electron density at the metal center.3. Characterization of water structure at biomaterial surfacesMany biological systems such as proteins and enzymes are inactive without water. For a complete understanding of the function of such systems, information of the structure and dynamics of the water is essential. We incestigated the structure of water at several biomaterial surfaces. For example, we monitored the structure of interfacial water at hydro-polymer gel/solid interface by SFG spectroscopy under various pressures. The contribution of weakly hydorogen bonded water in SFG spectra increased with pressure, suggesting the inportant role of weakly hydorogen bonded water to the low friction properties at the hydro-polymer gel/solid interfaces. Less

为了理解固/液界面上的电子转移动力学机制，电极/电解质界面上的分子结构信息，包括界面上的短寿命中间体和溶剂是必不可少的。然而，中间体和溶剂的界面结构的测定是困难的，通过常规的表面振动技术，因为与散装分子相比，分子的数量少。通过红外吸收和表面特异性和频产生（SFG）技术监测电子激发引起的振动模式的时间振动。利用这些光谱方法研究了界面结构与反应动力学之间的关系.固/液界面吸附物的SFG光谱观察和动力学研究用可见泵浦SFG探针测量了CO在Pt电极上的吸附动力学。在2064 cm ~（-1）处观察到Pt顶位吸附CO的SFG峰。不 ...更多信息 在1980 cm ~（-1）处观察到一个新的宽峰，对应于CO在多重位上的吸附，表明激发时发生了位交换。回收率与电位有关.载流子和电荷转移动力学的可见光泵浦可见光和红外技术时间分辨可见光泵浦可见光和红外探测技术，其中非常短的紫外或可见光脉冲激发与延迟超快可见光和中红外吸收相结合，分别是强大的工具，以监测电子和分子结构的变化，分别作为光激发后。本论文的主要工作如下：（1）建立了一套能同时进行这两种测量的系统;（2）利用可见光泵浦红外探针技术研究了CdS的尺寸和表面处理对载流子动力学的影响，（3）利用可见光泵浦、可见光和红外探针技术研究了三钌配合物[Ru_3（O）（CH_3CO_2）_6（CO）L_2]，其中L=配体，含有一个强红外活性配体CO，作为金属中心电子密度的直接红外探针.生物材料表面水结构的表征许多生物系统如蛋白质和酶在没有水的情况下是无活性的。为了全面了解这些系统的功能，水的结构和动力学信息是必不可少的。我们研究了几种生物材料表面的水结构。例如，我们监测的结构在水-聚合物凝胶/固体界面SFG光谱在不同的压力下的界面水。在SFG谱中弱氢键水的贡献随压力的增加而增加，表明弱氢键水对水-聚合物凝胶/固体界面处的低摩擦性能具有重要作用。少

项目成果

Oxidation States an CO Ligand Exchange Kinetics in a Self-Assembled Monolayer of a Triruthenium Cluster Studied by In Situ Infrared Spectroscopy

原位红外光谱研究三钌簇自组装单层中氧化态CO配体交换动力学

• 发表时间: 2005
• 期刊: Chemistry-A European Journal 11,No.17
• 作者: Makoto Sakai;Tsutomu Ohmori;Masaaki Fujii(章著);I. Yagi;H. Wano;Y. Sato;H. Noguchi;W. Zhou;M. Okamura;I. Yagi;I. Yagi;W. Zhou;H. Noguchi;Y. Sato;M. Okamura;H. Wano;I. Yagi;M. Abe;I. Yagi;Hiromi Wano;Yukari Sato;Hidenori Noguchi;Wei Zhou
• 通讯作者: Wei Zhou

Sum Frequency Generation Study at Solid/Liquid Interfaces(Invited)

固/液界面和频产生研究（特邀）

• 发表时间: 2006
• 作者: K. Uosaki;H. Noguchi;T. Okada;M. Ito;K. Uosaki
• 通讯作者: K. Uosaki

分子素子及びその製造方法ならびに集積回路装置およびその製造方法

分子器件及其制造方法集成电路器件及其制造方法；

• 发表时间: 2005

Interfacial Water Structure at As-Prepared and UV-Induced Hydrophilic TiO2 Surfaces Studied by Sum Frequency Generation Spectroscopy and Quartz Crystal Microbalance

• DOI: 10.1021/jp045173f
• 发表时间: 2004-11
• 期刊: Journal of Physical Chemistry B
• 影响因子: 3.3
• 作者: K. Uosaki;and Takanobu Yano;S. Nihonyanagi

Theoretical Analysis of the Potential Distribution and Transportation Behavior of the Ordered Alkyl Monolayer-Silicon Junction.

有序烷基单层-硅结的电势分布和传输行为的理论分析。