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

Journal Article · · Frontiers in Chemistry
 [1];  [1];  [1];  [2];  [2];  [1]
  1. Univ. of Massachusetts, Boston, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0012704; CHE-1800062
OSTI ID:
1571410
Report Number(s):
BNL-212221-2019-JAAM
Journal Information:
Frontiers in Chemistry, Vol. 7; ISSN 2296-2646
Publisher:
Frontiers Research FoundationCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide journal December 2015
Influence of Weak Brønsted Acids on Electrocatalytic CO 2 Reduction by Manganese and Rhenium Bipyridine Catalysts journal January 2015
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[Mn(bipyridyl)(CO)3Br]: An Abundant Metal Carbonyl Complex as Efficient Electrocatalyst for CO2 Reduction journal September 2011
Pulsed-EPR Evidence of a Manganese(II) Hydroxycarbonyl Intermediate in the Electrocatalytic Reduction of Carbon Dioxide by a Manganese Bipyridyl Derivative journal November 2013
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Mechanistic aspects of CO2 reduction catalysis with manganese-based molecular catalysts journal November 2018
Correlations between photophysical and electrochemical properties for a series of new Mn carbonyl complexes containing substituted phenanthroline ligands journal March 2015
Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts journal January 2018
Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide journal December 2015
Manganese-Based Catalysts with Varying Ligand Substituents for the Electrochemical Reduction of CO 2 to CO 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 journal October 2018
Thermodynamic Aspects of Electrocatalytic CO 2 Reduction in Acetonitrile and with an Ionic Liquid as Solvent or Electrolyte journal October 2015
Density Functionals with Broad Applicability in Chemistry journal February 2008
Determining the Overpotential for a Molecular Electrocatalyst journal December 2013
Influence of Weak Brønsted Acids on Electrocatalytic CO 2 Reduction by Manganese and Rhenium Bipyridine Catalysts journal January 2015
Manganese as a Substitute for Rhenium in CO 2 Reduction Catalysts: The Importance of Acids journal February 2013
Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO 2 Reduction by fac -Re(bpy)(CO) 3 Cl journal October 2013
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis journal February 2014
Mechanistic Contrasts between Manganese and Rhenium Bipyridine Electrocatalysts for the Reduction of Carbon Dioxide journal November 2014
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 journal August 2006
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents journal June 2010
Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO 2 Reduction using Infrared Spectroelectrochemistry journal April 2014
Revealing the secret behind Smo cholesterylation journal March 2022
Carbon monoxide release catalysed by electron transfer: electrochemical and spectroscopic investigations of [Re(bpy-R)(CO)4](OTf) complexes relevant to CO2 reduction journal January 2013
In situ study of the low overpotential “dimer pathway” for electrocatalytic carbon dioxide reduction by manganese carbonyl complexes journal January 2019
Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements journal January 1987
The Minnesota Density Functionals and their Applications to Problems in Mineralogy and Geochemistry journal January 2010

Figures / Tables (16)

Figure 1(p. 5)figure Figure 1
Figure 2(p. 6)figure Figure 2
Figure 3(p. 8)figure Figure 3
Table 1(p. 9)table Table 1
Figure 4(p. 11)figure Figure 4
Figure 5(p. 12)figure Figure 5
Table 2(p. 13)table Table 2
Figure 6(p. 15)figure Figure 6
Figure 7(p. 16)figure Figure 7
Figure 8(p. 18)figure Figure 8
Table 3(p. 19)table Table 3
Table 4(p. 20)table Table 4
Scheme 1(p. 21)figure Scheme 1
Table 5(p. 22)table Table 5
Scheme 2(p. 23)figure Scheme 2
Table 6(p. 24)table Table 6

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