TY - JOUR
T1 - Design of a catalytic active site for electrochemical CO2 reduction with Mn(I)-tricarbonyl species
AU - Agarwal, Jay
AU - Shaw, Travis W.
AU - Schaefer, Henry F.
AU - Bocarsly, Andrew Bruce
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/6/1
Y1 - 2015/6/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84930628338&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84930628338&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b00233
DO - 10.1021/acs.inorgchem.5b00233
M3 - Article
C2 - 25968283
AN - SCOPUS:84930628338
SN - 0020-1669
VL - 54
SP - 5285
EP - 5294
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 11
ER -