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Studies of Cobalt-Mediated Electrocatalytic CO_2 Reduction Using a Redox-Active Ligand

Lacy, David C. and McCrory, Charles C. L. and Peters, Jonas C. (2014) Studies of Cobalt-Mediated Electrocatalytic CO_2 Reduction Using a Redox-Active Ligand. Inorganic Chemistry, 53 (10). pp. 4980-4988. ISSN 0020-1669. PMCID PMC4033636. https://resolver.caltech.edu/CaltechAUTHORS:20140505-142420147

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Abstract

The cobalt complex [Co^(III)N_4H(Br)_2]+ (N_4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene) was used for electrocatalytic CO_2 reduction in wet MeCN with a glassy carbon working electrode. When water was employed as the proton source (10 M in MeCN), CO was produced (f_(CO)= 45% ± 6.4) near the Co^(I/0) redox couple for [Co^(III)N_4H(Br)_2]+ (E_(1/2) = −1.88 V FeCp_2^(+/0)) with simultaneous H_2 evolution (f_(H2)= 30% ± 7.8). Moreover, we successfully demonstrated that the catalytically active species is homogeneous through the use of control experiments and XPS studies of the working glassy-carbon electrodes. As determined by cyclic voltammetry, CO_2 catalysis occurred near the formal CoI/0redox couple, and attempts were made to isolate the triply reduced compound (“[Co^0N_4H]”). Instead, the doubly reduced (“Co^I”) compounds [CoN4] and [CoN_4H(MeCN)]+ were isolated and characterized by X-ray crystallography. Their molecular structures prompted DFT studies to illuminate details regarding their electronic structure. The results indicate that reducing equivalents are stored on the ligand, implicating redox noninnocence in the ligands for H_2 evolution and CO_2 reduction electrocatalysis.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1021/ic403122jDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic403122jPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic403122jPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4033636/PubMed CentralArticle
ORCID:
AuthorORCID
McCrory, Charles C. L.0000-0001-9039-7192
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: December 30, 2013; Published: April 28, 2014. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. D.C.L. would also like to acknowledge the National Institutes of Health (Award Number F32GM106726). The authors would also like to thank Tzu-Pin Lin, Michael Takase, and Lawrence Henling for help with crystallography, and Kyle Cummins and Slobodan Mitrovic for help with XPS. Clifford Kubiak is also thanked for many insightful discussions.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
NIH Predoctoral FellowshipF32GM106726
Issue or Number:10
PubMed Central ID:PMC4033636
Record Number:CaltechAUTHORS:20140505-142420147
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140505-142420147
Official Citation:Studies of Cobalt-Mediated Electrocatalytic CO2 Reduction Using a Redox-Active Ligand David C. Lacy, Charles C. L. McCrory, and Jonas C. Peters Inorganic Chemistry 2014 53 (10), 4980-4988
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45504
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:05 May 2014 22:02
Last Modified:03 Oct 2019 06:31

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