Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction
Abstract
The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO2 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 CO2 reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO2, 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 CO2, 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 CO2 substrate.
- Authors:
-
- Univ. of Southern California, Los Angeles, CA (United States)
- California Inst. of Technology (CalTech), Pasadena, CA (United States)
- Publication Date:
- Research Org.:
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1498679
- Grant/Contract Number:
- SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chapovetsky, Alon, Welborn, Matthew, Luna, John M., Haiges, Ralf, Miller, Thomas F., and Marinescu, Smaranda C.. Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction. United States: N. p., 2018.
Web. doi:10.1021/acscentsci.7b00607.
Chapovetsky, Alon, Welborn, Matthew, Luna, John M., Haiges, Ralf, Miller, Thomas F., & Marinescu, Smaranda C.. Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction. United States. https://doi.org/10.1021/acscentsci.7b00607
Chapovetsky, Alon, Welborn, Matthew, Luna, John M., Haiges, Ralf, Miller, Thomas F., and Marinescu, Smaranda C.. Fri .
"Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction". United States. https://doi.org/10.1021/acscentsci.7b00607. https://www.osti.gov/servlets/purl/1498679.
@article{osti_1498679,
title = {Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction},
author = {Chapovetsky, Alon and Welborn, Matthew and Luna, John M. and Haiges, Ralf and Miller, Thomas F. and Marinescu, Smaranda C.},
abstractNote = {The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO2 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 CO2 reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO2, 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 CO2, 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 CO2 substrate.},
doi = {10.1021/acscentsci.7b00607},
journal = {ACS Central Science},
number = 3,
volume = 4,
place = {United States},
year = {2018},
month = {2}
}
Web of Science
Figures / Tables:

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