Electrocatalysis for Electroanalysis: Anodic Oxygen-Transfer Reactions at Doped Metal-Oxide Film Electrodes

该项目由分析和表面化学计划支持 在化学部，由教授丹尼斯C。约翰逊， 爱荷华州州立大学化学系。 作品利用 含有掺杂金属氧化物阳极的电化学电池， 电催化性能将被利用在一项研究中， 涉及极性有机分子的氧转移氧化。 氧 原子调解是由PI提出的， 进行氧化。 实验旨在提供证据支持 或否认这一机制将进行和数字模拟将 用于确认机制。 脂肪胺、氨基酸和小分子 肽，许多具有含硫官能团，是测试 化合物.工作电极被制成适合于 使用旋转圆盘电极组件获得电流-电压曲线 可以分析它们的机械信息。 表面 使用扫描电子探针探索电极的形貌。 显微镜 提供补充资料以支持该机制 研究，对耗尽电解产物进行化学分析 将用气相色谱-质谱联用仪进行分析， 电喷雾质谱法。 电化学电池中的电极反应产生化学变化， 参与反应的离子或分子， 这种变化发生的途径是已知的，科学地使用 过程是有限的。 本项目的目的是了解 在电池阳极发生的反应的性质， 氧原子转移形成产物。的例子很多 可能遵循这种途径的化合物，包括一些生物 利益和其他环境问题。 的潜在应用 所获得的知识是在化学传感器领域， 分析.

This project, supported by the Analytical and Surface Chemistry Program in the Division of Chemistry, is directed by Prof. Dennis C. Johnson of the Chemistry Department at Iowa State University. The work utilizes electrochemical cells containing doped metal oxide anodes whose electrocatalytic properties will be exploited in a study of oxygen-transfer oxidations involving polar organic molecules. Oxygen atom mediation is proposed by the PI as the mechanism by which these oxidations proceed. Experiments designed to provide evidence to support or deny this mechanism will be carried out and digital simulations will be used to confirm mechanisms. Aliphatic amines, amino acids and small peptides, many with functional groups containing sulfur, are the test compounds. Working electrodes fabricated as disks suitable for the rotated disk electrode assembly are used to obtain current-voltage curves which can be analyzed for their mechanistic information. The surface topography of the electrodes is explored using the scanning electron microscope. To provide additional information to support the mechanism studies, chemical analysis of the products of exhaustive electrolysis will be done with gas chromatography-mass spectrometry and electrospray-mass spectrometry. Electrode reactions in electrochemical cells produce chemical changes in the ions or molecules which take part in the reaction but until the pathway is known by which such a change occurs, scientific use of the process is limited. The objective of this project is to understand the nature of reactions taking place at the anode of a cell which involve the transfer of an oxygen atom to form a product. There are many examples of compounds which might follow such a pathway including some of biological interest and others of environmental concern. Potential applications of the knowledge gained are found in the area of sensors for chemical analysis.