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Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO_2 Reduction

Chapovetsky, Alon and Welborn, Matthew and Luna, M. and Haiges, Ralf and Miller, Thomas F., III and Marinescu, Smaranda C. (2018) Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO_2 Reduction. ACS Central Science, 4 (3). pp. 397-404. ISSN 2374-7943. PMCID PMC5879468. http://resolver.caltech.edu/CaltechAUTHORS:20180315-111119688

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Abstract

The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO_2 to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO_2 reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO_2, and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO_2, but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO_2 substrate.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acscentsci.7b00607DOIDOI
https://pubs.acs.org/doi/abs/10.1021/acscentsci.7b00607PublisherArticle
https://pubs.acs.org/doi/suppl/10.1021/acscentsci.7b00607PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5879468PubMed CentralArticle
ORCID:
AuthorORCID
Miller, Thomas F., III0000-0002-1882-5380
Marinescu, Smaranda C.0000-0003-2106-8971
Additional Information:© 2018 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 19, 2017. Published: February 23, 2018. This work was supported by the University of Southern California and the National Science Foundation (NSF) through the CAREER award (CHE-1555387) and the Chemistry of Life Processes Program (CHE-1611581). 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. We are grateful to the USC Wrigley Institute for a Norma and Jerol Sonosky summer fellowship to A.C. M.W. thanks the Resnick Sustainability Institute for a postdoctoral fellowship. We are grateful to NSF (Grant CRIF 1048807) and USC for their sponsorship of NMR spectrometers and an X-ray diffractometer. A.C. and M.W.: equal contribution. CCDC 1590218–1590221 contain the supplementary crystallographic data for this manuscript. The authors declare no competing financial interest.
Group:Resnick Sustainability Institute, JCAP
Funders:
Funding AgencyGrant Number
Resnick Sustainability InstituteUNSPECIFIED
NSFCHE-1555387
NSFCHE-1611581
Department of Energy (DOE)DE-SC0004993
NSFCHE-1048807
University of Southern CaliforniaUNSPECIFIED
PubMed Central ID:PMC5879468
Record Number:CaltechAUTHORS:20180315-111119688
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180315-111119688
Official Citation:Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction Alon Chapovetsky, Matthew Welborn, John M. Luna, Ralf Haiges, Thomas F. Miller III, and Smaranda C. Marinescu ACS Central Science 2018 4 (3), 397-404 DOI: 10.1021/acscentsci.7b00607
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85331
Collection:CaltechAUTHORS
Deposited By: Heidi Rusina
Deposited On:15 Mar 2018 19:57
Last Modified:11 Apr 2018 14:40

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