An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex
Abstract
The subject of this study [fac-Mn(bqn)(CO)3(CH3CN)]+ (bqn = 2,2'-biquinoline), is of particular interest because the bqn ligand exhibits both steric and electronic influence over the fundamental redox properties of the complex and, consequently, its related catalytic properties with respect to the activation of CO2. While not a particularly efficient catalyst for CO2 to CO conversion, in-situ generation and activity measurements of the [fac-Mn(bqn)(CO)3]- active catalyst allows for a better understanding of ligand design at the Mn center. By making direct comparisons to the related 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen), and 2,9-dimethyl-1,10-phenanthroline (dmphen) ligands via a combination of voltammetry, infrared spectroelectrochemistry, controlled potential electrolysis and computational analysis, the role of steric vs. electronic influences on the nucleophilicity of Mn-based CO2 reduction electrocatalysts is discussed.
- Authors:
-
- Univ. of Massachusetts, Boston, MA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1571410
- Report Number(s):
- BNL-212221-2019-JAAM
Journal ID: ISSN 2296-2646
- Grant/Contract Number:
- SC0012704; CHE-1800062
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Frontiers in Chemistry
- Additional Journal Information:
- Journal Volume: 7; Journal ID: ISSN 2296-2646
- Publisher:
- Frontiers Research Foundation
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; carbon dioxide reduction; electrocatalysis; manganese; carbon monoxide
Citation Formats
McKinnon, Meaghan, Belkina, Veronika, Ngo, Ken T., Ertem, Mehmed Z., Grills, David C., and Rochford, Jonathan. An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex. United States: N. p., 2019.
Web. doi:10.3389/fchem.2019.00628.
McKinnon, Meaghan, Belkina, Veronika, Ngo, Ken T., Ertem, Mehmed Z., Grills, David C., & Rochford, Jonathan. An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex. United States. https://doi.org/10.3389/fchem.2019.00628
McKinnon, Meaghan, Belkina, Veronika, Ngo, Ken T., Ertem, Mehmed Z., Grills, David C., and Rochford, Jonathan. Tue .
"An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex". United States. https://doi.org/10.3389/fchem.2019.00628. https://www.osti.gov/servlets/purl/1571410.
@article{osti_1571410,
title = {An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex},
author = {McKinnon, Meaghan and Belkina, Veronika and Ngo, Ken T. and Ertem, Mehmed Z. and Grills, David C. and Rochford, Jonathan},
abstractNote = {The subject of this study [fac-Mn(bqn)(CO)3(CH3CN)]+ (bqn = 2,2'-biquinoline), is of particular interest because the bqn ligand exhibits both steric and electronic influence over the fundamental redox properties of the complex and, consequently, its related catalytic properties with respect to the activation of CO2. While not a particularly efficient catalyst for CO2 to CO conversion, in-situ generation and activity measurements of the [fac-Mn(bqn)(CO)3]- active catalyst allows for a better understanding of ligand design at the Mn center. By making direct comparisons to the related 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen), and 2,9-dimethyl-1,10-phenanthroline (dmphen) ligands via a combination of voltammetry, infrared spectroelectrochemistry, controlled potential electrolysis and computational analysis, the role of steric vs. electronic influences on the nucleophilicity of Mn-based CO2 reduction electrocatalysts is discussed.},
doi = {10.3389/fchem.2019.00628},
journal = {Frontiers in Chemistry},
number = ,
volume = 7,
place = {United States},
year = {Tue Sep 24 00:00:00 EDT 2019},
month = {Tue Sep 24 00:00:00 EDT 2019}
}
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Figure 1: Molecular structures of complexes investigated.
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Manganese carbonyl complexes for CO 2 reduction
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Mechanistic aspects of CO2 reduction catalysis with manganese-based molecular catalysts
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Correlations between photophysical and electrochemical properties for a series of new Mn carbonyl complexes containing substituted phenanthroline ligands
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Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts
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Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide
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Manganese-Based Catalysts with Varying Ligand Substituents for the Electrochemical Reduction of CO 2 to CO
journal, October 2018
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Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO 2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes
journal, October 2018
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Thermodynamic Aspects of Electrocatalytic CO 2 Reduction in Acetonitrile and with an Ionic Liquid as Solvent or Electrolyte
journal, October 2015
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Density Functionals with Broad Applicability in Chemistry
journal, February 2008
- Zhao, Yan; Truhlar, Donald G.
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Determining the Overpotential for a Molecular Electrocatalyst
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Influence of Weak Brønsted Acids on Electrocatalytic CO 2 Reduction by Manganese and Rhenium Bipyridine Catalysts
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Manganese as a Substitute for Rhenium in CO 2 Reduction Catalysts: The Importance of Acids
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Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO 2 Reduction by fac -Re(bpy)(CO) 3 Cl
journal, October 2013
- Keith, John A.; Grice, Kyle A.; Kubiak, Clifford P.
- Journal of the American Chemical Society, Vol. 135, Issue 42
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis
journal, February 2014
- Sampson, Matthew D.; Nguyen, An D.; Grice, Kyle A.
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Mechanistic Contrasts between Manganese and Rhenium Bipyridine Electrocatalysts for the Reduction of Carbon Dioxide
journal, November 2014
- Riplinger, Christoph; Sampson, Matthew D.; Ritzmann, Andrew M.
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Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
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Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO 2 Reduction using Infrared Spectroelectrochemistry
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In situ study of the low overpotential “dimer pathway” for electrocatalytic carbon dioxide reduction by manganese carbonyl complexes
journal, January 2019
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Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements
journal, January 1987
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The Minnesota Density Functionals and their Applications to Problems in Mineralogy and Geochemistry
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