Dihydropteridine/pteridine as a 2H+/2e– redox mediator for the reduction of CO2 to methanol: A computational study

Lim, Chern -Hooi; Holder, Aaron M.; Hynes, James T.; Musgrave, Charles B.

doi:10.1021/acs.jpcb.7b01224

Title: Dihydropteridine/pteridine as a 2H⁺/2e^– redox mediator for the reduction of CO₂ to methanol: A computational study

Abstract

Conflicting experimental results for the electrocatalytic reduction of CO₂ to CH₃OH on a glassy carbon electrode by the 6,7-dimethyl-4-hydroxy-2-mercaptopteridine have been recently reported. In this study, we have used computational chemistry to examine the issue of this molecule's ability to act as a hydride donor to reduce CO₂.

Authors:

^[1]; Holder, Aaron M. ^[2];

^[3];

^[1]

Univ. of Colorado, Boulder, CO (United States)
Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Univ. of Colorado, Boulder, CO (United States); Univ. Sorbonne Univ.-UPMC, Paris (France)

Publication Date:: Tue Apr 04 00:00:00 EDT 2017

Research Org.:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:: 1355143

Report Number(s):: NREL/JA-5K00-68432
Journal ID: ISSN 1520-6106

Grant/Contract Number:: AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 121; Journal Issue: 16; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; computational chemistry; electrocatalytic reduction

Citation Formats


                    Lim, Chern -Hooi, Holder, Aaron M., Hynes, James T., and Musgrave, Charles B. Dihydropteridine/pteridine as a 2H+/2e– redox mediator for the reduction of CO2 to methanol: A computational study.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.jpcb.7b01224.

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                    Lim, Chern -Hooi, Holder, Aaron M., Hynes, James T., & Musgrave, Charles B. Dihydropteridine/pteridine as a 2H+/2e– redox mediator for the reduction of CO2 to methanol: A computational study.  United States.  https://doi.org/10.1021/acs.jpcb.7b01224

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                    Lim, Chern -Hooi, Holder, Aaron M., Hynes, James T., and Musgrave, Charles B. Tue .  
"Dihydropteridine/pteridine as a 2H+/2e– redox mediator for the reduction of CO2 to methanol: A computational study".  United States.  https://doi.org/10.1021/acs.jpcb.7b01224.  https://www.osti.gov/servlets/purl/1355143.

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@article{osti_1355143,

  title        = {Dihydropteridine/pteridine as a 2H+/2e– redox mediator for the reduction of CO2 to methanol: A computational study},

  author       = {Lim, Chern -Hooi and Holder, Aaron M. and Hynes, James T. and Musgrave, Charles B.},

  abstractNote = {Conflicting experimental results for the electrocatalytic reduction of CO2 to CH3OH on a glassy carbon electrode by the 6,7-dimethyl-4-hydroxy-2-mercaptopteridine have been recently reported. In this study, we have used computational chemistry to examine the issue of this molecule's ability to act as a hydride donor to reduce CO2.},

  doi          = {10.1021/acs.jpcb.7b01224},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 16,

  volume       = 121,

  place        = {United States},

  year         = {Tue Apr 04 00:00:00 EDT 2017},

  month        = {Tue Apr 04 00:00:00 EDT 2017}

}

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Title: Dihydropteridine/pteridine as a 2H+/2e– redox mediator for the reduction of CO2 to methanol: A computational study

Abstract

Citation Formats

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation journal, June 2013

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Attempts To Catalyze the Electrochemical CO 2 -to-Methanol Conversion by Biomimetic 2e – + 2H + Transferring Molecules journal, January 2016

Reduction of CO 2 to Methanol Catalyzed by a Biomimetic Organo-Hydride Produced from Pyridine journal, November 2014

Electrocatalytic hydrogenation of pyridinium enabled by surface proton transfer reactions journal, January 2017

Electrochemical Reduction of Carbon Dioxide to Methanol in the Presence of Benzannulated Dihydropyridine Additives journal, February 2017

Mechanism of Homogeneous Reduction of CO 2 by Pyridine: Proton Relay in Aqueous Solvent and Aromatic Stabilization journal, December 2012

Simultaneous Two-Hydrogen Transfer as a Mechanism for Efficient CO 2 Reduction journal, October 2010

Proton relay and electron flow in the O–O single bond formation in water oxidation by the ruthenium blue dimer journal, January 2012

A Theoretical Study of the Formation of the Aminoacetonitrile Precursor of Glycine on Icy Grain Mantles in the Interstellar Medium journal, January 2008

Hydrogen transfer from 4-R and 4-S (4-3H) NADH in the reduction of d,l-cis-6,7-dimethyl-6,7(8H)-dihydropterin with dihydropteridine reductase from human liver and sheep liver journal, July 1979

A New Enzyme, NADPH-Dihydropteridine Reductase in Bovine Liver journal, March 1977

Neurotransmitter Synthesis by Neuroblastoma Clones journal, January 1972

Tryptophan Hydroxylation: Measurement in Pineal Gland, Brainstem, and Carcinoid Tumor journal, January 1967

The role of tetrahydropteridines in the enzymatic conversion of tyrosine to 3,4-dihydroxyphenylalanine journal, September 1964

Electrochemistry of some substituted pteridines journal, February 1973

Electrochemistry of Reduced Pterin Cofactors book, June 1982

Redox chemistry of reduced pterin species journal, November 1981

Electrochemical, spectral and kinetic characterization of the 5,8-dihydro compound formed on electrochemical reduction of 2-dimethylamino-3,6,7-trimethylpterin journal, October 1983

The solution electrochemistry of tetrahydrobiopterin revisited journal, March 2009

Electronic Structure, Ionization Potential, and Electron Affinity of the Enzyme Cofactor (6 R )-5,6,7,8-Tetrahydrobiopterin in the Gas Phase, Solution, and Protein Environments journal, November 2006

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal, July 2007

The influence of polarization functions on molecular orbital hydrogenation energies journal, January 1973

Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: New energy gradients and molecular surface tessellation journal, January 2004

Benchmark calculations of proton affinities and gas-phase basicities of molecules important in the study of biological phosphoryl transfer journal, January 2005

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

Standard hydrogen electrode and potential of zero charge in density functional calculations journal, September 2011

Computational Electrochemistry: The Aqueous Ru 3+ |Ru 2+ Reduction Potential journal, April 2007

Computational electrochemistry: prediction of liquid-phase reduction potentials journal, January 2014

GROMACS: A message-passing parallel molecular dynamics implementation journal, September 1995

Geometry optimization with QM/MM, ONIOM, and other combined methods. I. Microiterations and constraints journal, April 2003

UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations journal, December 1992

The pyridinium-dihydropyridine system. Reduction potentials and the mechanism of oxidation of 1,4-dihydropyridines by a Schiff base journal, February 1982

Tautomeric equilibria of 2- and 4-thiouracil in gas phase and in solvent: A density functional study journal, January 2001

Infrared spectra of thiouracils: experimental matrix isolation and ab initio Hartree-Fock, post-Hartree-Fock and density functional theory studies journal, December 1996

Thiouracils. 2. Tautomerism and infrared spectra of thiouracils. Matrix-isolation and ab initio studies journal, March 1990

Proton-Coupled Electron Transfer journal, November 2007

The kinetics of the dehydration of methylene glycol journal, June 2000

Kinetics of the dehydration of methylene glycol in aqueous solution journal, April 1966

Towards a Comprehensive Hydride Donor Ability Scale journal, November 2012

Hydride-Donor Abilities of 1,4-Dihydropyridines: A Comparison with π Nucleophiles and Borohydride Anions journal, March 2009

Catalytic Reduction of CO 2 by Renewable Organohydrides journal, December 2015

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals journal, August 2019

Title: Dihydropteridine/pteridine as a 2H⁺/2e^– redox mediator for the reduction of CO₂ to methanol: A computational study

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO ₂ Fixation
journal, June 2013

Photoelectrochemical cells
journal, November 2001

Solar Water Splitting Cells
journal, November 2010

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities
journal, April 2001

Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels
journal, December 2009

Anthropogenic Chemical Carbon Cycle for a Sustainable Future
journal, August 2011

Non-Metal-Mediated Homogeneous Hydrogenation of CO2 to CH3OH
journal, December 2009

Roles of the Lewis Acid and Base in the Chemical Reduction of CO ₂ Catalyzed by Frustrated Lewis Pairs
journal, August 2013

Room Temperature Reduction of CO ₂ to Methanol by Al-Based Frustrated Lewis Pairs and Ammonia Borane
journal, February 2010

Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More
journal, December 2009

Electrocatalytic and Photocatalytic Conversion of CO ₂ to Methanol using Ruthenium Complexes with Internal Pyridyl Cocatalysts
journal, June 2014

An Organic Hydride Transfer Reaction of a Ruthenium NAD Model Complex Leading to Carbon Dioxide Reduction
journal, September 2012

Selective Solar-Driven Reduction of CO ₂ to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell
journal, May 2008

Photochemical Reduction of Carbon Dioxide to Methanol and Formate in a Homogeneous System with Pyridinium Catalysts
journal, October 2013

Reversible Hydride Generation and Release from the Ligand of [Ru(pbn)(bpy)2](PF6)2 Driven by a pbn-Localized Redox Reaction
journal, September 2005

Electrochemistry of Aqueous Pyridinium: Exploration of a Key Aspect of Electrocatalytic Reduction of CO ₂ to Methanol
journal, September 2013

CO ₂ Reduction Catalyzed by Mercaptopteridine on Glassy Carbon
journal, August 2014

Attempts To Catalyze the Electrochemical CO ₂ -to-Methanol Conversion by Biomimetic 2e ^– + 2H ⁺ Transferring Molecules
journal, January 2016

Reduction of CO ₂ to Methanol Catalyzed by a Biomimetic Organo-Hydride Produced from Pyridine
journal, November 2014

Electrocatalytic hydrogenation of pyridinium enabled by surface proton transfer reactions
journal, January 2017

Electrochemical Reduction of Carbon Dioxide to Methanol in the Presence of Benzannulated Dihydropyridine Additives
journal, February 2017

Mechanism of Homogeneous Reduction of CO ₂ by Pyridine: Proton Relay in Aqueous Solvent and Aromatic Stabilization
journal, December 2012

Simultaneous Two-Hydrogen Transfer as a Mechanism for Efficient CO ₂ Reduction
journal, October 2010

Proton relay and electron flow in the O–O single bond formation in water oxidation by the ruthenium blue dimer
journal, January 2012

A Theoretical Study of the Formation of the Aminoacetonitrile Precursor of Glycine on Icy Grain Mantles in the Interstellar Medium
journal, January 2008

Hydrogen transfer from 4-R and 4-S (4-3H) NADH in the reduction of d,l-cis-6,7-dimethyl-6,7(8H)-dihydropterin with dihydropteridine reductase from human liver and sheep liver
journal, July 1979

A New Enzyme, NADPH-Dihydropteridine Reductase in Bovine Liver
journal, March 1977

Neurotransmitter Synthesis by Neuroblastoma Clones
journal, January 1972

Tryptophan Hydroxylation: Measurement in Pineal Gland, Brainstem, and Carcinoid Tumor
journal, January 1967

The role of tetrahydropteridines in the enzymatic conversion of tyrosine to 3,4-dihydroxyphenylalanine
journal, September 1964

Electrochemistry of some substituted pteridines
journal, February 1973

Electrochemistry of Reduced Pterin Cofactors
book, June 1982

Redox chemistry of reduced pterin species
journal, November 1981

Electrochemical, spectral and kinetic characterization of the 5,8-dihydro compound formed on electrochemical reduction of 2-dimethylamino-3,6,7-trimethylpterin
journal, October 1983

The solution electrochemistry of tetrahydrobiopterin revisited
journal, March 2009

Electronic Structure, Ionization Potential, and Electron Affinity of the Enzyme Cofactor (6 R )-5,6,7,8-Tetrahydrobiopterin in the Gas Phase, Solution, and Protein Environments
journal, November 2006

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007

The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973

Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: New energy gradients and molecular surface tessellation
journal, January 2004

Benchmark calculations of proton affinities and gas-phase basicities of molecules important in the study of biological phosphoryl transfer
journal, January 2005

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

Standard hydrogen electrode and potential of zero charge in density functional calculations
journal, September 2011

Computational Electrochemistry: The Aqueous Ru ³⁺ |Ru ²⁺ Reduction Potential
journal, April 2007

Computational electrochemistry: prediction of liquid-phase reduction potentials
journal, January 2014

GROMACS: A message-passing parallel molecular dynamics implementation
journal, September 1995

Geometry optimization with QM/MM, ONIOM, and other combined methods. I. Microiterations and constraints
journal, April 2003

UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992

The pyridinium-dihydropyridine system. Reduction potentials and the mechanism of oxidation of 1,4-dihydropyridines by a Schiff base
journal, February 1982

Tautomeric equilibria of 2- and 4-thiouracil in gas phase and in solvent: A density functional study
journal, January 2001

Infrared spectra of thiouracils: experimental matrix isolation and ab initio Hartree-Fock, post-Hartree-Fock and density functional theory studies
journal, December 1996

Thiouracils. 2. Tautomerism and infrared spectra of thiouracils. Matrix-isolation and ab initio studies
journal, March 1990

Proton-Coupled Electron Transfer
journal, November 2007

The kinetics of the dehydration of methylene glycol
journal, June 2000

Kinetics of the dehydration of methylene glycol in aqueous solution
journal, April 1966

Towards a Comprehensive Hydride Donor Ability Scale
journal, November 2012

Hydride-Donor Abilities of 1,4-Dihydropyridines: A Comparison with π Nucleophiles and Borohydride Anions
journal, March 2009

Catalytic Reduction of CO ₂ by Renewable Organohydrides
journal, December 2015

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals
journal, August 2019