Design of a catalytic active site for electrochemical CO2 reduction with Mn(I)-tricarbonyl species

Jay Agarwal, Travis W. Shaw, Henry F. Schaefer, Andrew Bruce Bocarsly

Research output: Contribution to journalArticle

99 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)5285-5294
Number of pages10
JournalInorganic Chemistry
Volume54
Issue number11
DOIs
StatePublished - Jun 1 2015

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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