LEAPS-MPS: Enhancing Polymer Encapsulation Effects on CO2 Reduction by Molecular Electrocatalysts through the Development of Rationally Designed ROMP Polymers

Hamilton College, Clinton NY

Investigators

Abstract

In this project, funded by the MPS-LEAPS (Launching Early-Career Academic Pathways) Program and managed by the Broadening Participation (CHE-BP) Program in the Division of Chemistry, Professor Wesley Kramer and his students at Hamilton College will perform studies aimed at developing new polymer materials that both immobilize molecular electrocatalysts for CO2 reduction on the surface of an electrode, and enhance the performance of the molecular catalyst by optimizing its primary, secondary and outer coordination spheres. This project seeks to address the challenges of precisely controlling the chemical environment around the well-defined active sites of the molecular electrocatalysts through encapsulation in functionalized polymer supports, as opposed to direct modification of the catalyst's structure. Their studies could lead to significant breakthroughs in the practical deployment of earth abundant molecular electrocatalysts for energy conversion reactions that could help accelerate the necessary transition to green energy, renewable fuels, and the development of alternative (non-petroleum derived) sources of chemical feed-stocks. Additionally, this project will support several broader educational initiatives: 1) summer-research opportunities for Hamilton College students from underrepresented backgrounds; 2) research opportunities for Utica area high-school students; 3) the development of K-12 outreach programs with hands-on renewable energy related demonstrations. Professor Kramer and his research group will take advantage of the flexibility of ring-opening metathesis polymerization to develop new polymer materials that are tailored to support specific aspects of the CO2 reduction electrocatalytic mechanism through the incorporation of pendant functional groups. Pendant functional groups will be selected based on their ability to a) act as a ligand for the molecular catalyst; b) facilitate proton movement within the polymer and stabilize catalytic intermediates through H-bonding; c) stabilize catalytic intermediates through electrostatic interactions; and d) concentrate dissolved CO2 in the polymer film. Professor Kramer and his students will prepare new co-polymer materials with a focus on controlling the ratios of the various functional groups within the polymer. Precise control over the polymer composition will allow them to optimize catalyst performance along several different axes. These polymer materials will allow us to leverage the desirable properties of molecular coordination complexes (selective electrocatalysis, tunable coordination environments, earth-abundant metals) while minimize their limitations (organic solvents, diffusion-controlled kinetics, inefficient material use). Insights gained from this project will inform the development of future catalyst-polymer systems for other energy conversion reactions. 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.