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Title: Reaction mechanism of the selective reduction of CO 2 to CO by a tetraaza [Co IIN 4H] 2+ complex in the presence of protons

Abstract

The tetraaza [Co IIN 4H] 2+complex ( 1) is remarkable for its ability to selectively reduce CO 2 to CO with 45% Faradaic efficiency and a CO to H 2 ratio of 3 : 2. We employ density functional theory (DFT) to determine the reasons behind the unusual catalytic properties of 1 and the most likely mechanism for CO 2 reduction. The selectivity for CO 2 over proton reduction is explained by analyzing the catalyst's affinity for the possible ligands present under typical reaction conditions: acetonitrile, water, CO 2, and bicarbonate. After reduction of the catalyst by two electrons, formation of [Co IN 4H] +–-CO 2 - is strongly favored. Based on thermodynamic and kinetic data, we establish that the only likely route for producing CO from here consists of a protonation step to yield [Co IN 4H] +–CO 2H, followed by reaction with CO 2 to form [Co IIN 4H] 2+–CO and bicarbonate. This conclusion corroborates the idea of a direct role of CO 2 as a Lewis acid to assist in C–O bond dissociation, a conjecture put forward by other authors to explain recent experimental observations. The pathway to formic acid is predicted to be forbidden by highmore » activation barriers, in accordance with the products that are known to be generated by 1. Calculated physical observables such as standard reduction potentials and the turnover frequency for our proposed catalytic cycle are in agreement with available experimental data reported in the literature. The mechanism also makes a prediction that may be experimentally verified: that the rate of CO formation should increase linearly with the partial pressure of CO 2.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Florida A & M Univ., Tallahassee, FL (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1532293
Alternate Identifier(s):
OSTI ID: 1469422
Grant/Contract Number:  
[AC02-05CH11231; SC00004993]
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
[Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 37]; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Garza, Alejandro J., Pakhira, Srimanta, Bell, Alexis T., Mendoza-Cortes, Jose L., and Head-Gordon, Martin. Reaction mechanism of the selective reduction of CO2 to CO by a tetraaza [CoIIN4H]2+ complex in the presence of protons. United States: N. p., 2018. Web. doi:10.1039/c8cp01963k.
Garza, Alejandro J., Pakhira, Srimanta, Bell, Alexis T., Mendoza-Cortes, Jose L., & Head-Gordon, Martin. Reaction mechanism of the selective reduction of CO2 to CO by a tetraaza [CoIIN4H]2+ complex in the presence of protons. United States. doi:10.1039/c8cp01963k.
Garza, Alejandro J., Pakhira, Srimanta, Bell, Alexis T., Mendoza-Cortes, Jose L., and Head-Gordon, Martin. Mon . "Reaction mechanism of the selective reduction of CO2 to CO by a tetraaza [CoIIN4H]2+ complex in the presence of protons". United States. doi:10.1039/c8cp01963k. https://www.osti.gov/servlets/purl/1532293.
@article{osti_1532293,
title = {Reaction mechanism of the selective reduction of CO2 to CO by a tetraaza [CoIIN4H]2+ complex in the presence of protons},
author = {Garza, Alejandro J. and Pakhira, Srimanta and Bell, Alexis T. and Mendoza-Cortes, Jose L. and Head-Gordon, Martin},
abstractNote = {The tetraaza [CoIIN4H]2+complex (1) is remarkable for its ability to selectively reduce CO2 to CO with 45% Faradaic efficiency and a CO to H2 ratio of 3 : 2. We employ density functional theory (DFT) to determine the reasons behind the unusual catalytic properties of 1 and the most likely mechanism for CO2 reduction. The selectivity for CO2 over proton reduction is explained by analyzing the catalyst's affinity for the possible ligands present under typical reaction conditions: acetonitrile, water, CO2, and bicarbonate. After reduction of the catalyst by two electrons, formation of [CoIN4H]+–-CO2- is strongly favored. Based on thermodynamic and kinetic data, we establish that the only likely route for producing CO from here consists of a protonation step to yield [CoIN4H]+–CO2H, followed by reaction with CO2 to form [CoIIN4H]2+–CO and bicarbonate. This conclusion corroborates the idea of a direct role of CO2 as a Lewis acid to assist in C–O bond dissociation, a conjecture put forward by other authors to explain recent experimental observations. The pathway to formic acid is predicted to be forbidden by high activation barriers, in accordance with the products that are known to be generated by 1. Calculated physical observables such as standard reduction potentials and the turnover frequency for our proposed catalytic cycle are in agreement with available experimental data reported in the literature. The mechanism also makes a prediction that may be experimentally verified: that the rate of CO formation should increase linearly with the partial pressure of CO2.},
doi = {10.1039/c8cp01963k},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = [37],
volume = [20],
place = {United States},
year = {2018},
month = {9}
}

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