Abstract: Elucidating and controlling the interfacial reactivity of oxygenated intermediates is key to a broad scope of electrochemical studies of catalysts, sensors, and energy storage media. I will present a modern approach to understanding the electrochemical interface using techniques based on small electrodes, new spectroscopic methods, and the use of automated electrochemistry to characterize intermediates such as reactive oxygen species (ROS) and to explore the converstion of oxygenated organics. I will talk about how we use electrochemical microscopy (SECM), a scanned probe technique capable of delivering high spatiotemporal and chemical redox resolution at active surfaces for generating ROS. SECM uses an electrochemical probe to detect and quantify species (e.g. discharged products, homogeneous and heterogeneous intermediates) and the kinetics of processes (e.g. heterogeneous rate constants) through the use of highly localized electrochemical techniques deployed by such probe. In my talk, I will describe the main features of our instrumental setup, applications to interface and bulk nanomaterials used in electrocatalysis and batteries, and emerging directions that amplify the role of hyphenated techniques such as Raman spectroscopy coupled to the SECM. I will highlight recent experiments describing the detection of highly reacting hydroxyl radical intermediates [1] the detection of oxygen evolution in degrading metal-oxide electrodes [2], and the direct detection of singlet oxygen,[3]. Morevoer, using new automated electrochemistry methods to better characterize electrocatalytic transformations involving oxygenated organic compounds, including TEMPO-catalyzed transformations of alcohols.[4] we are opening a new range of experiments where electrochemistry can be strategically used to accelerate discoveries in catalysis and battery science.

[1] Barroso-Martinez, J.S. et al. J. Am. Chem. Soc. 2022, 18896; [2] Mishra, A. J. Electrochem. Soc. 2022, 086501; [3] Mishra, A. et al, J. Am Chem. Soc. 2024, 8847; [4] Pence, M.A. et al. Digital Discovery 2024, 1812.