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项目资助的项目中，佛蒙特大学的William E. Geiger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质溶液进行通信，每个电极都发生化学反应。传统上，电极是由昂贵的稀有金属，如铂和金组成的。出于成本和可持续性的考虑，这些传统金属需要被更便宜、更常见的材料（最好是碳基材料）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化学结构。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。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。盖格教授正在开发一种新的化学电极修饰方法，该方法基于对含乙基分子或金属活化的乙基分子的电化学氧化。乙基在分子底物和碳表面之间提供了一种近乎理想的连接，因为它能够在这些部分之间提供方便的电子通信，它与表面的结合非常强，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配合物都附着在电极表面。人们正在探索用含有许多不同过渡金属的卟啉修饰电极的途径，并且正在探索一种或多种电催化反应，例如氧还原反应。电极也被乙基连接的金属光敏剂和乙基连接的多电子转移剂修饰，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。研究了一种用磁圆二色性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.