Rare Earth Reactive Oxygen Species

With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry Professor Jerome Robinson of Brown University is investigating reactive oxygen species (ROS) of the rare earth elements (RE’s). Rare earth elements (group III + the lanthanides) are a group of critical materials found in a wide range of novel, emerging, and advanced technologies used in society, including applications in energy science, defense, and quantum materials. RE ROS have been proposed as key species in a range of processes; however, our fundamental understanding has been limited by synthetic access and systematic studies of well-defined materials. Through the proposed work, graduate, undergraduate, and high school students will gain specialized experimental and computational training working with critical materials with world-leading experts at academic and national labs. Furthermore, Professor Robinson will develop programs introducing high-school and undergraduate students to the chemistry of RE’s and their applications in technologies to further develop pipelines to a critical materials STEM workforce. RE ROS have been implicated as key species and/or intermediates with reactivity distinct from any other part of the periodic table, yet direct synthesis of many of these materials have yet to be achieved. This research project seeks to synthesize novel RE superoxide and (alkyl/acyl/hydro)peroxide species. Rigorous characterization in the solid- and solution-state and systematic reactivity studies will establish robust structure-function relationships, and elucidate differences from s- and d-block ROS. Additional collaborative efforts to evaluate the electronic structure of these novel compounds (magnetism, XAS/XAFS, computation) will help advance the field’s understanding of the structure and bonding of these materials, including potential applications in quantum information science. Information from this study will inform the identity of active oxidants at bulk and nanoscale materials and the design of novel and selective oxidation catalysts. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.