skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A Mn Bipyrimidine Catalyst Predicted To Reduce CO2 at Lower Overpotential

Journal Article · · ACS Catalysis
DOI:https://doi.org/10.1021/cs501963v· OSTI ID:1467633
 [1];  [1];  [1];  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
+ Show Author Affiliations

Experimentally, [(L)Mn(CO)3]- (where L = bis-alkyl-substituted bipyridine) has been observed to catalyze the electrochemical reduction of CO2 to CO in the presence of trifluoroethanol (TFEH). Here we report the atomistic level mechanism of complete catalytic cycles for this reaction, on the basis of DFT calculations (B3LYP-D3 with continuum solvation) of the free energies of reaction and activation, as well as reduction potentials for all catalytically relevant elementary steps. The highly exergonic homoconjugation and carbonation of TFE– play critical roles in reaction thermodynamics and kinetics, the overall half-reaction being 3CO2 + 2TFEH + 2e– → CO + H2O + 2[F3CCH2OCO2]- (calculated standard reduction potential: -1.49 V vs SCE). In the catalytic cycle for CO formation, CO2 coordinates to [(L)Mn(CO)3]- (1a, L = bpy), and the adduct is then protonated to form [(L)Mn(CO)3(CO2H)] (3a). 3a subsequently reacts to form [(L)Mn(CO)4]0 (5a) via one of two pathways: (a) TFEH-mediated dehydroxylation to [(L)Mn(CO)4]+ (4a), followed by one-electron reduction to 5a, or (b) under more reducing potentials, one-electron reduction to [(L)Mn(CO)3(CO2H)]- (3'a), followed by dehydroxylation to 5a. Pathway b has a lower activation energy by 2.2 kcal mol–1. Consequently, the maximum catalytic turnover frequency (TOFmax) is achieved at ~-1.75 V vs SCE (~0.25 V overpotential). For the analogous bipyrimidine compound (not yet studied experimentally), reduction of 3b to 3'b occurs at a potential 0.5 V more positive than that of 3a, and the overpotential required to achieve TOFmax is predicted to be lower by ~0.25 V. This improvement is, however, achieved at the price of a lower TOFmax, and we predict that 1b has superior TOF at potentials above ~-1.6 V vs SCE. In addition, the various factors contributing to product selectivity (CO over H2) are discussed.

Research Organization:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0004993
OSTI ID:
1467633
Journal Information:
ACS Catalysis, Vol. 5, Issue 4; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 58 works
Citation information provided by
Web of Science

References (41)

Syngas production for gas-to-liquids applications: technologies, issues and outlook journal June 2001
High productivity methanol carbonylation catalysis using iridium journal May 2000
Advances in molecular photocatalytic and electrocatalytic CO2 reduction journal November 2012
Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins. Synergistic Effect of Lewis Acid Cations journal January 1996
Ultraefficient selective homogeneous catalysis of the electrochemical reduction of carbon dioxide by an iron(0) porphyrin associated with a weak Broensted acid cocatalyst journal June 1994
Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins:  Synergystic Effect of Weak Brönsted Acids journal January 1996
A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst journal October 2012
Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt journal September 1980
Catalytic reduction of carbon dioxide at carbon electrodes modified with cobalt phthalocyanine journal August 1984
Nickel(II)-cyclam: an extremely selective electrocatalyst for reduction of CO2 in water journal January 1984
Homogeneous CO 2 Reduction by Ni(cyclam) at a Glassy Carbon Electrode journal March 2012
Tetraaza-macrocyclic cobalt(II) and nickel(II) complexes as electron-transfer agents in the photo(electro)chemical and electrochemical reduction of carbon dioxide journal January 1984
Electrochemical reduction of carbon dioxide in the presence of RhCl(CO)(PPh3)2 and IrCl(CO)(PPh3)2 journal October 1989
Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation journal December 2009
Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO) 3 Cl (bipy = 2,2′-bipyridine) journal January 1984
Electrocatalytic reduction of CO2 at a chemically modified electrode journal January 1985
Re(bipy-tBu)(CO) 3 Cl−improved Catalytic Activity for Reduction of Carbon Dioxide: IR-Spectroelectrochemical and Mechanistic Studies journal October 2010
[Mn(bipyridyl)(CO)3Br]: An Abundant Metal Carbonyl Complex as Efficient Electrocatalyst for CO2 Reduction journal September 2011
Manganese as a Substitute for Rhenium in CO 2 Reduction Catalysts: The Importance of Acids journal February 2013
Electrocatalytic reduction of carbon dioxide by associative activation journal January 1988
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis journal February 2014
Electrocatalytic Reduction of Carbon Dioxide with a Manganese(I) Tricarbonyl Complex Containing a Nonaromatic α-Diimine Ligand journal May 2014
Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO journal May 2012
The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO 2 Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry journal March 2013
Direct observation of the reduction of carbon dioxide by rhenium bipyridine catalysts journal January 2013
The effect of weak Brönsted acids on the electrocatalytic reduction of carbon dioxide by a rhenium tricarbonyl bipyridyl complex journal August 1998
Exploring the intermediates of photochemical CO2 reduction: reaction of Re(dmb)(CO)3 COOH with CO2 journal January 2012
Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO 2 Reduction by fac -Re(bpy)(CO) 3 Cl journal October 2013
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
New Model for Calculation of Solvation Free Energies:  Correction of Self-Consistent Reaction Field Continuum Dielectric Theory for Short-Range Hydrogen-Bonding Effects journal January 1996
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal January 1980
Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F journal October 1983
Ab initio effective potentials for use in molecular quantum mechanics journal November 1974
Fe and Ni AB initio effective potentials for use in molecular calculations journal October 1974
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg journal January 1985
Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe journal February 2001
Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide journal January 2007
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents journal June 2010
H 2 Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation journal November 2010
Mechanistic insights into hydride transfer for catalytic hydrogenation of CO 2 with cobalt complexes journal January 2014

Cited By (8)

Mono- and bimetallic manganese–carbonyl complexes and clusters bearing imidazol(in)ium-2-dithiocarboxylate ligands journal January 2017
Detection of catalytic intermediates at an electrode surface during carbon dioxide reduction by an earth-abundant catalyst journal October 2018
Vibrational sum-frequency generation spectroscopy of electrode surfaces: studying the mechanisms of sustainable fuel generation and utilisation journal January 2019
Computational Design of Quaterpyridine‐Based Fe/Mn–Complexes for the Direct Hydrogenation of CO 2 to HCOOH: A Direction for Atom‐Economic Approach journal May 2018
In situ study of the low overpotential “dimer pathway” for electrocatalytic carbon dioxide reduction by manganese carbonyl complexes journal January 2019
A rational design of manganese electrocatalysts for Lewis acid-assisted carbon dioxide reduction journal January 2019
Proton–hydride tautomerism in hydrogen evolution catalysis journal May 2016
Solvent and Ligand Substitution Effects on the Electrocatalytic Reduction of CO 2 with [Mo(CO) 4 ( x,x ′-dimethyl-2,2′-bipyridine)] ( x =4-6) Enhanced at a Gold Cathodic Surface journal August 2018

Similar Records

Steric and Lewis Basicity Influence of the Second Coordination Sphere on Electrocatalytic CO2 Reduction by Manganese Bipyridyl Complexes
Journal Article · Mon Sep 26 00:00:00 EDT 2022 · Inorganic Chemistry · OSTI ID:1467633
+6 more
Developing Scaling Relationships for Molecular Electrocatalysis through Studies of Fe-Porphyrin-Catalyzed O2 Reduction
Journal Article · Mon Apr 13 00:00:00 EDT 2020 · Accounts of Chemical Research · OSTI ID:1467633
+1 more
Identifying and Breaking Scaling Relations in Molecular Catalysis of Electrochemical Reactions
Journal Article · Wed Jul 19 00:00:00 EDT 2017 · Journal of the American Chemical Society · OSTI ID:1467633
+1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY