An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex

McKinnon, Meaghan; Belkina, Veronika; Ngo, Ken T.; Ertem, Mehmed Z.; Grills, David C.; Rochford, Jonathan

doi:10.3389/fchem.2019.00628

Title: An Investigation of Electrocatalytic CO₂ Reduction Using a Manganese Tricarbonyl Biquinoline Complex

Journal Article · 24 September 2019 · Frontiers in Chemistry

DOI: https://doi.org/10.3389/fchem.2019.00628 · OSTI ID:1571410

McKinnon, Meaghan ^[1]; Belkina, Veronika ^[1]; Ngo, Ken T. ^[1]; Ertem, Mehmed Z. ^[2]; Grills, David C. ^[2]; Rochford, Jonathan ^[1]

Univ. of Massachusetts, Boston, MA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1571410

Report Number(s):: BNL--212221-2019-JAAM

Journal Information:: Frontiers in Chemistry, Journal Name: Frontiers in Chemistry Vol. 7; ISSN 2296-2646

Publisher:: Frontiers Research FoundationCopyright Statement

Country of Publication:: United States

Language:: English

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In situ study of the low overpotential “dimer pathway” for electrocatalytic carbon dioxide reduction by manganese carbonyl complexes Neri, Gaia; Donaldson, Paul M.; Cowan, Alexander J. Physical Chemistry Chemical Physics, Vol. 21, Issue 14 https://doi.org/10.1039/c9cp00504h	journal	January 2019
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Manganese-Based Catalysts with Varying Ligand Substituents for the Electrochemical Reduction of CO ₂ to CO Tignor, Steven E.; Kuo, Hsin-Ya; Lee, Tia S. Organometallics, Vol. 38, Issue 6 https://doi.org/10.1021/acs.organomet.8b00554	journal	October 2018
Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO ₂ Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes McKinnon, Meaghan; Ngo, Ken T.; Sobottka, Sebastian Organometallics, Vol. 38, Issue 6 https://doi.org/10.1021/acs.organomet.8b00584	journal	October 2018
Thermodynamic Aspects of Electrocatalytic CO ₂ Reduction in Acetonitrile and with an Ionic Liquid as Solvent or Electrolyte Matsubara, Yasuo; Grills, David C.; Kuwahara, Yutaka ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b00656	journal	October 2015
Density Functionals with Broad Applicability in Chemistry Zhao, Yan; Truhlar, Donald G. Accounts of Chemical Research, Vol. 41, Issue 2 https://doi.org/10.1021/ar700111a	journal	February 2008
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Determining the Overpotential for a Molecular Electrocatalyst Appel, Aaron M.; Helm, Monte L. ACS Catalysis, Vol. 4, Issue 2 https://doi.org/10.1021/cs401013v	journal	December 2013
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Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO ₂ Reduction by fac -Re(bpy)(CO) ₃ Cl Keith, John A.; Grice, Kyle A.; Kubiak, Clifford P. Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja406456g	journal	October 2013
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis Sampson, Matthew D.; Nguyen, An D.; Grice, Kyle A. Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja501252f	journal	February 2014
Mechanistic Contrasts between Manganese and Rhenium Bipyridine Electrocatalysts for the Reduction of Carbon Dioxide Riplinger, Christoph; Sampson, Matthew D.; Ritzmann, Andrew M. Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja508192y	journal	November 2014
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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 Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp063552y	journal	August 2006
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents Isse, Abdirisak A.; Gennaro, Armando The Journal of Physical Chemistry B, Vol. 114, Issue 23 https://doi.org/10.1021/jp100402x	journal	June 2010
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO ₂ Reduction using Infrared Spectroelectrochemistry Machan, Charles W.; Sampson, Matthew D.; Chabolla, Steven A. Organometallics, Vol. 33, Issue 18 https://doi.org/10.1021/om500044a	journal	April 2014
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Carbon monoxide release catalysed by electron transfer: electrochemical and spectroscopic investigations of [Re(bpy-R)(CO)4](OTf) complexes relevant to CO2 reduction Grice, Kyle A.; Gu, Nina X.; Sampson, Matthew D. Dalton Transactions, Vol. 42, Issue 23 https://doi.org/10.1039/c3dt50612f	journal	January 2013
In situ study of the low overpotential “dimer pathway” for electrocatalytic carbon dioxide reduction by manganese carbonyl complexes Neri, Gaia; Donaldson, Paul M.; Cowan, Alexander J. Physical Chemistry Chemical Physics, Vol. 21, Issue 14 https://doi.org/10.1039/c9cp00504h	journal	January 2019
Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements Dolg, M.; Wedig, U.; Stoll, H. The Journal of Chemical Physics, Vol. 86, Issue 2 https://doi.org/10.1063/1.452288	journal	January 1987
The Minnesota Density Functionals and their Applications to Problems in Mineralogy and Geochemistry Zhao, Y.; Truhlar, D. G. Reviews in Mineralogy and Geochemistry, Vol. 71, Issue 1 https://doi.org/10.2138/rmg.2010.71.2	journal	January 2010

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carbon dioxide reduction
carbon monoxide
electrocatalysis
manganese

Title: An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex

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Title: An Investigation of Electrocatalytic CO₂ Reduction Using a Manganese Tricarbonyl Biquinoline Complex