International Collaboration in Chemistry: Mechanistic studies of oxygen electrocatalysis by nanoelecrochemical techniques

在这个由化学系化学催化项目支持的国际化学合作项目中，纽约皇后学院的Michael Mirkin教授和他的研究小组正在与巴黎高等师范学院的Christian Amatore教授和他的小组合作，对电化学氧还原反应（ORR）的分子机理进行研究。 ORR过程是许多技术系统的核心（例如，燃料电池、锂和钠电池、催化）以及生物过程，包括肝脏中食物和药物分子的氧化、衰老和许多疾病。 尽管在过去几十年中对ORR进行了广泛的研究，但关于其分子机制的基本问题仍然是开放的。 Mirkin教授正在开发新的实验和计算方法来研究ORR，目的是推进我们对这些基本有趣和实际重要的电催化反应的理解。纳米电化学技术，包括扫描电化学显微镜和伏安法在纳米移液管支持的两种不混溶液体之间的界面上用于ORR的机理分析。 这些技术的非常快速的传质、高灵敏度和选择性使得能够检测和定量ORR过程中产生的短寿命离子物质，例如超氧化物。 借助最近开发的KISSA-2D模拟软件包分析了中间体形成和消耗的动力学。 预期的结果对燃料电池、其他替代能源系统和传感器具有重要意义。 拟议的活动通过促进新仪器的开发，加强了纽约皇后学院的研究和教育基础设施。 已建立的国际合作为两个研究小组的学生提供了额外的培训机会，并使他们接触到广泛的实验和计算方法。 拟议的活动为高中生和本科生提供研究机会。

In this International Collaboration in Chemistry project supported by the Chemical Catalysis Program of the Chemistry Division, Professor Michael Mirkin and his research team at the City University of New York, Queens College is collaborating with Prof. Christian Amatore and his group at the Ecole Normale Superieure, Paris, on molecular mechanistic studies of the electrochemical oxygen reduction reaction (ORR). The ORR process is central to many technological systems (e.g., fuel cells, lithium and sodium batteries, catalysis) as well as biological processes, including oxidation of food and drug molecules in liver, ageing, and numerous diseases. Despite extensive research on the ORR during several decades, basic questions about its molecular mechanism remain open. Professor Mirkin is developing new experimental and computational methods to study the ORR with the aim of advancing our understanding of these fundamentally interesting and practically important electrocatalytic reactions.Nanoelectrochemical techniques, including scanning electrochemical microscopy and voltammetry at the nanopipette-supported interface between two immiscible liquids are used for the mechanistic analysis of the ORR. Very fast mass-transfer, high sensitivity and selectivity of these techniques enable the detection and quantification of short-lived ionic species produced in the course of the ORR, such as superoxide. The kinetics of the intermediate formation and consumption are analyzed with the help of the recently developed KISSA-2D simulation package. The anticipated results have significant implications for fuel cells, other alternative energy systems, and sensors. The proposed activities enhance the infrastructure for research and education at the City University of New York, Queens College by stimulating the development of new instrumentation. The established international collaboration provides additional training opportunities for students in both research groups and exposes them to a wide range of experimental and computational approaches. The proposed activities provide research opportunities to high school students and undergraduate students.