Reaction mechanism of the selective reduction of CO2 to CO by a tetraaza [CoIIN4H]2+ complex in the presence of protons

Garza, Alejandro J.; Pakhira, Srimanta; Bell, Alexis T.; Mendoza-Cortes, Jose L.; Head-Gordon, Martin

doi:10.1039/c8cp01963k

Reaction mechanism of the selective reduction of CO₂ to CO by a tetraaza [Co^IIN₄H]²⁺ complex in the presence of protons

Journal Article · Mon Sep 03 04:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c8cp01963k· OSTI ID:1532293

Garza, Alejandro J. ^[1]; ^[1]; ^[2]; ^[3]; ^[2]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
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)

The tetraaza [Co^IIN₄H]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 [Co^IN₄H]⁺–-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 [Co^IN₄H]⁺–CO₂H, followed by reaction with CO₂ to form [Co^IIN₄H]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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1532293

Alternate ID(s):: OSTI ID: 1469422

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 37 Vol. 20; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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