EAGER: Electrocatalysis Modulated by Bifunctional Organic Monolayer: CO2 Reduction to C2

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This Early-concept Grant for Exploratory Research (EAGER) provides proof-of-concept data for a novel technology supporting our nation’s transition to clean energy. Part of the clean energy equation involves the capture and conversion of carbon dioxide (CO2) produced from the combustion of fossil resources. The project further supports progress towards low carbon emission chemical manufacturing by exploring electrochemical conversion of CO2 to small building-block molecules used widely in the manufacture of a broad range of chemical and fuel products. The study focuses on novel catalyst designs that promote highly localized electric fields, thus potentially enabling more efficient energy utilization and greater CO2 conversion efficiency than obtained with conventional catalyst designs. The project also incorporates clean-energy related educational and outreach activities targeted at both pre-college and college level students. A high electric field can rearrange the electronic orbitals of chemical species and alter the electronic interactions between adsorbates and catalytic surfaces. This influences the thermodynamics, kinetics, and mechanisms of (electro)catalytic reactions. The project investigates the effects of local electric fields and exposed-surface sites on the CO2 electroreduction reaction (CO2RR) to C2 products. The concept is investigated using a combination of atomic-scale simulations, electrocatalyst synthesis, spectroscopic characterization, and electrocatalytic performance testing. The catalyst is prepared from a bifunctional thiol-based monolayer (e.g., -S-CnH2n-NH2) immobilized onto a Cu nanowire (NW) array. This catalytic structure enhances local electric fields due to opposing charges in the head and tail functional groups of the monolayer. Surface coverage of thiol molecules is simultaneously tuned to expose Cu step and defect sites. Effectiveness of the combined approach for accelerating CO2RR-to-C2 will be evaluated by (1) deriving relationships between thiol composition/structure and local field strength, (2) determining the thiol surface coverage effects on exposed Cu sites, and (3) investigating the performance and stability of the bifunctional organic monolayer modified Cu NWs under reaction conditions. In parallel with the research, the investigators will involve both graduate students and undergraduate students in their research, and participate in the Immersive Scholar Program at UMass Lowell to promote undergraduate research, including women and underrepresented minorities. The investigators will also convey the importance of clean energy technology and modular electrocatalysis into outreach activities for K-9 students and distribution via various educational media.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.