title: Design of a Catalytic Active Site for Electrochemical CO2 Reduction with Mn(I)-Tricarbonyl Species.
abstract: The design, synthesis, and assessment of a new manganese-centered catalyst for the electrochemical reduction of CO2 is described. The reported species, MnBr(6-(2-hydroxyphenol)-2,2'-bipyridine)(CO)3, includes a ligand framework with a phenolic proton in close proximity to the CO2 binding site, which allows for facile proton-assisted C-O bond cleavage. As a result of this modification, seven times the electrocatalytic current enhancement is observed compared to MnBr(2,2'-bipyridine)(CO)3. Moreover, reduction is possible at only 440 mV of overpotential. Theoretical computations suggest that the entropic contribution to the activation free energy is partially responsible for the increased catalytic activity. Experimental work, including voltammetry and product quantification from controlled potential electrolysis, suggests a key mechanistic role for the phenolic proton in the conversion of CO2 to CO.
authors.affiliation: †Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.|‡Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: Jay
authors.initials: J
authors.lastname: Agarwal
authors.affiliation: ‡Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: Travis W
authors.initials: TW
authors.lastname: Shaw
authors.affiliation: †Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer
authors.affiliation: ‡Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: Andrew B
authors.initials: AB
authors.lastname: Bocarsly