CHARACTERIZATION OF TRANSIENT ELECTROCATALYTIC INTERMEDIATES BY SERS

通过 SERS 表征瞬态电催化中间体

• 批准号: 6494797
• 负责人: CHARLES M HOSTEN
• 金额: $ 13.19万
• 依托单位: HOWARD UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-08-01 至 2002-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6494797
• 关键词: Raman spectrometry; active sites; ammonia; atomic absorption spectrometry; catalyst; chemical structure; electrochemistry; enzyme activity; nitrate reductases; nitrites; oxidation reduction reaction; photochemistry; porphyrins; radiochemistry

The net 6-electron, five point reduction of nitrite to ammonia is catalyzed by the enzyme nitrite reductase. Electrochemical studies have shown that a series of water soluble porphyrins are efficient electrocatalyst for the conversion of nitrite to ammonia. The proposed spectro-electrochemical study will couple a number of surface- spectroscopic and electrochemical techniques to obtain data on the molecular structure and lifetimes of the porphyrin intermediates, generated during the electrocatalytic reduction. From this data, a comprehensive mechanism for the porphyrin catalyzed electro-reduction of nitrite to ammonia will be developed. The specific spectroscopic techniques to be employed are solution Raman spectroscopy, surface-enhanced Raman spectroscopy, SERS, and its variant, time-resolved SERS, TRSERS, along with UV/Vis absorption spectroscopy. By linking the large enhancement afforded by SERS, with multi-channel detection, molecular structural information on electro-generated catalytic transients on a SERS active electrode surface will be obtained. Radiation chemical and photochemical studies will also be incorporated and these techniques will provide rat constraints for short-lived iron porphyrin intermediates generated by pulse photochemical processes. The electrochemical techniques to be employed include cyclic voltammetry, differential pulse voltammetry and constant potential electrolysis. Electrochemical techniques provide information regarding the rate of the reaction and the influence of diffusion, concentration and temperature. SERS spectroscopy provides information on the chemical identity, structure, configuration and orientation of the surface species. By coupling electrochemical experiments with SERS scattering spectroscopy, both kinetic and structural characteristics of the surface intermediates will be probed. The conclusion derived from this research will find application in the characterization and design of modified electrode surfaces. These modified surfaces possess potential applications in energy conversion processes, light driven reactions and the activation of small biological molecules.

净6电子，亚硝酸盐降低为5点的氨是 由亚硝酸盐还原酶催化。电化学研究已有 表明一系列水溶性卟啉是有效的 电催化剂，用于将亚硝酸盐转化为氨。提议 光谱电化学研究将融入许多表面 光谱和电化学技术以获取有关该数据的数据 卟啉中间体的分子结构和寿命 在电催化还原过程中产生。从这个数据，一个 卟啉催化电还原的综合机制 将开发亚硝酸盐到氨。 要使用的特定光谱技术是解决方案拉曼 光谱，表面增强的拉曼光谱，SERS及其变体， 时间分辨的SER，TRSER，以及UV/VIS吸收光谱。经过 将SERS提供的大型增强与多通道联系起来 检测，有关电生成催化的分子结构信息 将获得SERS活性电极表面上的瞬变。辐射 化学和光化学研究也将纳入 技术将为短寿命铁卟啉提供大鼠约束 脉搏光化学过程产生的中间体。 要使用的电化学技术包括循环伏安法， 差异脉冲伏安法和恒定电势电解。 电化学技术提供了有关速率的信息 反应和扩散，浓度和温度的影响。 SERS光谱法提供了有关化学身份的信息， 表面物种的结构，构型和方向。经过 将电化学实验与SERS散射光谱进行耦合， 表面中间体的动力学和结构特征 将被探测。这项研究得出的结论将发现 在修饰电极的表征和设计中应用 表面。这些修饰的表面具有潜在的能量应用 转换过程，轻驱动反应和小的激活 生物分子。