Selective Carbon Dioxide to Formate Conversion by Electrolyte Engineering and Tailored Electrocatalytic PCET Strategies

In this project, funded by the Chemical Mechanism, Function, and Properties Program of the Chemistry Division, Professor Jonathan Rochford of the Department of Chemistry at the University of Massachusetts Boston is developing new strategies for the selective conversion of carbon dioxide to formic acid. The global demand for formic acid, and the contribution of its production methods to carbon dioxide emissions, represents a real opportunity for the scientific community to make a tremendous impact on sustainability. Taking inspiration from naturally occurring enzymes (natures catalysts), the catalyst structure and electrolyte will be engineered to harness the redox properties of cheap abundant metals, such as manganese, to facilitate the sustainable conversion of carbon dioxide to formic acid. Two strategic aims will be pursued to achieve this goal. In the first aim, an in-depth understanding of the synergy between second coordination sphere hydrogen-bonding and metal hydride hydricity will be sought to promote highly efficient carbon dioxide insertion at the metal hydride intermediate along the catalytic pathway. In the second aim, selective generation of this critical metal-hydride intermediate will be promoted by utilization of a concerted proton electron transfer reaction pathway, thereby eliminating competing pathways of carbon monoxide and hydrogen production. Success in this project will have a major impact in the fields of artificial photosynthesis and sustainable fuels production. The project lies at the interface of inorganic, organic, physical and analytical chemistry, and represents an excellent opportunity for the multi-disciplinary education and training of scientists at all levels. 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.