Electrochemical Imaging of Precisely-Defined Redox and Reactive Interfaces.

Understanding the diverse electrochemical reactions occurring at electrode-electrolyte interfaces (EEIs) is a critical challenge to developing more efficient energy conversion and storage technologies. Establishing a predictive molecular-level understanding of solid electrolyte interphases (SEIs) is challenging due to the presence of multiple intertwined chemical and electrochemical processes occurring at battery electrodes. Similarly, chemical conversions in reactive electrochemical systems are often influenced by the heterogeneous distribution of active sites, surface defects, and catalyst particle sizes. In this mini review, we highlight an emerging field of interfacial science that isolates the impact of specific chemical species by preparing precisely-defined EEIs and visualizing the reactivity of their individual components using single-entity characterization techniques. We highlight the broad applicability and versatility of these methods, along with current state-of-the-art instrumentation and future opportunities for these approaches to address key scientific challenges related to batteries, chemical separations, and fuel cells. We establish that controlled preparation of well-defined electrodes combined with single entity characterization will be crucial to filling key knowledge gaps and advancing the theories used to describe and predict chemical and physical processes occurring at EEIs and accelerating new materials discovery for energy applications.

Ketyl Radical Coupling Enabled by Polycyclic Aromatic Hydrocarbon Electrophotocatalysts.

Herein, we report a new class of electrophotocatalysts, polycyclic aromatic hydrocarbons, that promote the reduction of unactivated carbonyl compounds to generate versatile ketyl radical intermediates. This catalytic platform enables previously challenging intermolecular ketyl radical coupling reactions, including those that classic reductants (e.g., SmI2/HMPA) have failed to promote. More broadly, this study outlines an approach to fundamentally expand the array of reactive radical intermediates that can be generated via electrophotocatalysis by obviating the need for rapid mesolytic cleavage following substrate reduction.

Mapping Localized Peroxyl Radical Generation on a PEM Fuel Cell Catalyst Using Integrated Scanning Electrochemical Cell Microspectroscopy.

Understanding molecular-level transformations resulting from electrochemical reactions is important in designing efficient and reliable energy technologies. In this work, a novel integrated scanning electrochemical cell microspectroscopy (iSECCMS) capability is developed by combining a high spatial resolution electrochemical scanning probe with in situ fluorescence spectroscopy. Using 6-carboxyfluorescein as a fluorescent probe, the iSECCMS platform is employed to measure the effect of the detrimental generation of reactive oxygen species (ROS) formed at the active sites of oxygen reduction reaction (ORR) catalysts. Carbon-supported tantalum-doped titanium oxide (TaTiOx) catalysts, a potential Pt-group-metal-free (PGM-free) cathode material explored for low temperature polymer electrolyte fuel cells (PEFCs), is used as a representative model ORR system, where generation of intermediate H2O2 instead of fully oxidized H2O is a major concern. We establish that the iSECCMS platform provides a novel and versatile capability for spatially resolved mapping of in situ ROS generation and activity during the kinetically-limited ORR and may, therefore, aid the future characterization and development of high-performance PGM-free PEFC cathodes.