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Electrochemical CO2 reduction catalyzed by Mn catalysts: DFT investigations point to strategies for overpotential reduction and activity improvement

Lam, Yan Choi and Nielsen, Robert J. and Goddard, William A. and Gray, Harry B. (2016) Electrochemical CO2 reduction catalyzed by Mn catalysts: DFT investigations point to strategies for overpotential reduction and activity improvement. In: 251st American Chemical Society National Meeting & Exposition, March 13-17, 2016, San Diego, CA. http://resolver.caltech.edu/CaltechAUTHORS:20160414-084344138

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Abstract

Exptl., [(L) Mn(CO)_3]- (where L = bis alkyl- substituted bipyridine) has been obsd. to catalyze the electrochem. redn. of CO_2 to CO in the presence of trifluoroethanol (TFEH). Our DFT calcns. (B3LYP- d3 with continuum solvation) of the free energies of reaction and activation show that the highly exergonic hydrogen bonding between TFEH and TFE (homoconjugation) plays a crit. role in reaction thermodn. and kinetics. The analgous 2,2'- bipyrimidine complex is predicted to have a lower (by ca. 0.5 V) onset overpotential, but at the expense of max. catalytic activity. As a strategy to improve catalytic activity and onset overpotential, a series of 2,2'- and 4,4'- bipyrimidines with tethered alc. or phenol was examd. The major predictions were that: (a) PhOH is not significantly more effective than TFEH at promoting dehydroxylation, due to their similar hydrogen bond acidities; (b) the appended phenols are less effective at promoting catalysis than the appended alc.; and (c) inclusion of one appended phenol arm promotes catalytic turnover by eliminating the entropic penalty of including an external PhOH in the dehydroxylation TS, but inclusion of two phenol arms is detrimental because intramol. hydrogen bonding stabilizes the resting state of the catalytic cycle.


Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription
http://www.acs.org/content/acs/en/meetings/spring-2016.htmlOrganizationConference Website
ORCID:
AuthorORCID
Lam, Yan Choi0000-0001-7809-4471
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A.0000-0003-0097-5716
Additional Information:© 2016 American Chemical Society.
Record Number:CaltechAUTHORS:20160414-084344138
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160414-084344138
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:66149
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:14 Apr 2016 17:09
Last Modified:20 Sep 2017 22:05

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