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

在这个由化学系化学结构、动力学和机制B计划资助的项目中，佛蒙特州大学的威廉·E·盖格教授正在研究电化学，以解决化学、生化和环境问题。最常见的电化学电池类型是两个金属电极通过电解液进行通信，每个电极上都发生化学反应。传统上，电极一直由贵重和稀有的金属组成，如铂和金。为了成本和可持续性，这些传统金属需要被更便宜、更常见、最好是碳基的材料所取代。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那些反应。该项目旨在从分子上改变碳的表面结构，从而提高这些反应的效率。除了高中生，这些研究还为本科生和研究生提供了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了其他研究小组。盖格教授正在开发一种新的化学电极修饰方法，该方法基于含有乙炔的分子或金属活化的乙炔分子的电化学氧化。乙炔基团在分子底物和碳表面之间提供了近乎理想的连接，因为它能够在分子底物和碳表面之间提供方便的电子通信，它与表面的键合非常强，并且它的结构完整性。有机金属分子和含有过渡金属的卟啉络合物都附着在电极表面。人们正在探索用含有多种不同过渡金属的卟啉修饰电极的途径，并正在探索一种或多种电催化反应，如氧还原反应。乙炔连接的金属光敏剂和乙炔连接的多电子转移剂也在修饰电极，目的是为高效的生物传感器和神经传感器提供新的电极表面。研究了一种用磁性圆二色谱分析化学修饰电极的新方法。

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.