Applications of Alkynyl-linked Transition Metal Compounds on Chemically Modified Electrodes

炔基过渡金属化合物在化学修饰电极上的应用

• 批准号: 1565541
• 负责人: William Geiger
• 金额: $ 48万
• 依托单位: University of Vermont & State Agricultural College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-08-01 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1565541&HistoricalAwards=false
• 关键词: Applications; Alkynyl; linked; Transition; Metal

In this project funded by the Chemical Structure, Dynamics and Mechanisms B Program in the Division of Chemistry, Professor William E. Geiger of the University of Vermont is studying electrochemistry in addressing chemical, biochemical, and environmental problems. The most common type of electrochemical cell is one in which two metal electrodes communicate through an electrolyte solution, with chemical reactions taking place at each electrode. Traditionally, the electrodes have been composed of expensive and rare metals such as platinum and gold. In the interest of both cost and sustainability, these traditional metals need to be replaced by cheaper and more common, preferably carbon-based, materials. However, carbon surfaces themselves lack the chemical structure needed to carry out many important reactions, such as those required in efficient fuel cells. The project is designed to molecularly alter the surface structure of carbon, thereby increasing the efficiency of these reactions. These studies provide training in electrochemistry and transition-metal chemistry for undergraduate and graduate students, in addition to high school students. The students are also experiencing other research groups through a number of collaborating arrangements. Professor Geiger is developing a new chemical electrode modification method based on electrochemical oxidation of either an ethynyl-containing molecule or a metal-activated ethynyl molecule. An ethynyl group provides a nearly ideal linkage between a molecular substrate and a carbon surface owing to its ability to offer facile electronic communication between those moieties, its very strong bonding to the surface, and its structural integrity. Both organometallic molecules and porphyrin complexes containing transition metals are being attached to the electrode surfaces. Routes to electrode modification by porphyrins containing a number of different transition metals are being be explored, and one or more electrocatalytic reactions, such as the oxygen reduction reaction, are being probed. Electrodes also are being modified with ethynyl-linked metal photosensitizers and ethynyl-linked multi-electron transfer agents, with the goal of providing new electrode surfaces for efficient biosensors and neural sensors. A new approach to analysis of chemically modified electrodes by magnetic circular dichroism is being studied.

在化学系化学结构、动力学和机理B计划资助的这个项目中，William E.佛蒙特大学的盖革正在研究电化学，以解决化学、生物化学和环境问题。最常见的电化学电池类型是其中两个金属电极通过电解质溶液连通的电池，其中在每个电极处发生化学反应。传统上，电极由昂贵和稀有的金属如铂和金组成。为了成本和可持续性，这些传统金属需要被更便宜和更常见的材料（最好是碳基材料）取代。然而，碳表面本身缺乏进行许多重要反应所需的化学结构，例如高效燃料电池所需的化学结构。该项目旨在分子改变碳的表面结构，从而提高这些反应的效率。这些研究为本科生和研究生以及高中生提供电化学和过渡金属化学方面的培训。学生们还通过一些合作安排体验其他研究小组。盖革教授正在开发一种新的化学电极修饰方法，该方法基于含乙炔基分子或金属活化乙炔基分子的电化学氧化。乙炔基在分子基质和碳表面之间提供了几乎理想的连接，这是由于其能够在那些部分之间提供容易的电子通信、其与表面的非常强的键合以及其结构完整性。有机金属分子和含有过渡金属的卟啉络合物都被附着在电极表面。通过含有许多不同过渡金属的卟啉修饰电极的途径正在探索中，并且一个或多个电催化反应，如氧还原反应，正在探索中。电极也被乙炔基连接的金属光敏剂和乙炔基连接的多电子转移剂修饰，目的是为有效的生物传感器和神经传感器提供新的电极表面。本文研究了一种用磁性圆二色谱分析化学修饰电极的新方法。