CAS: Electrocatalytic Oxygen Atom Transfer

With this collaborative project, funded by the Chemical Structure, Dynamics & Mechanism B Program of the Chemistry Division, Ksenija Glusac, Neal Mankad and Jordi Cabana from the Department of Chemistry at the University of Illinois at Chicago (UIC) will investigate new molecular/electrode hybrid electrocatalysts that can perform chemical reactions relevant to energy conversion (e.g. fuel cells) and chemical industry applications (e.g. electrosynthesis of epoxides). The collaboration is synergistic, with each member of the team bringing distinct expertise to the team, ranging from electrochemistry to inorganic catalysis to X-ray spectroscopy.

The multidisciplinary nature of the proposed research will enable the training of graduate students beyond the traditional disciplinary boundaries. Team members aim to leverage the uniquely diverse student body at UIC to enhance the participation of underrepresented groups in STEM research.

Porous graphitic structures functionalized with heteroatoms are excellent carbon-based electrodes for energy storage applications. However, the chemical tunability of catalytic sites in these materials is limited due to extreme pyrolytic temperatures needed for carbon graphitization. Here, the research team will investigate the functionalization of carbon electrodes with chemically tunable molecular catalysts for electrocatalytic oxygen atom transfer (e-OAT).

The planned activities involve: (i) expansion of the chemical toolbox for functionalization of carbon edge and basal planes using covalent linkers and pi-interactions; (ii) electrochemical performance of molecule/carbon hybrids toward e-OAT; (iii) detailed mechanistic studies of reaction intermediates using UV/Vis, mid-IR and X-ray spectro-electrochemical methods. The research is a collaborative effort among the three principal investigators at UIC with synergic expertise in electrocatalysis, transition metal catalysis and chemical characterization of materials, as well as an external collaborator, Dr.

John Keith, University of Pittsburgh, who provides expertise in computational electrochemistry. The lessons learned from his research study could enable future catalyst design, for example, by guiding the incorporation of well-defined catalytic sites via post-pyrolysis modification of the nanocarbon edge and basal plane sites in such systems.

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.