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

在这项由化学部化学催化项目支持的国际化学合作项目中，纽约城市大学皇后学院的Michael Mirkin教授及其研究小组与巴黎高等师范学院的Christian Amatore教授及其小组合作，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（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）的核心。尽管几十年来对ORR进行了广泛的研究，但其分子机制的基本问题仍未解决。Mirkin教授正在开发新的实验和计算方法来研究ORR，目的是促进我们对这些从根本上有趣且在实践中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，在纳米探针支持的两种不混溶液体之间的界面用于ORR的机理分析。这些技术的快速传质，高灵敏度和选择性使得在ORR过程中产生的短寿命离子物种（如超氧化物）的检测和定量成为可能。利用最新开发的KISSA-2D模拟软件包对中间地层和消耗的动力学进行了分析。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。拟议的活动通过刺激新仪器的发展，加强了纽约城市大学皇后学院的研究和教育基础设施。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。建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.