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Title: Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

Abstract

Here, the hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)
Publication Date:
Research Org.:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1348826
Grant/Contract Number:  
SC0009758
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 111; Journal Issue: 42; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; renewable; solar fuels; electrocatalysis

Citation Formats

Bediako, D. Kwabena, Solis, Brian H., Dogutan, Dilek K., Roubelakis, Manolis M., Maher, Andrew G., Lee, Chang Hoon, Chambers, Matthew B., Hammes-Schiffer, Sharon, and Nocera, Daniel G. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins. United States: N. p., 2014. Web. doi:10.1073/pnas.1414908111.
Bediako, D. Kwabena, Solis, Brian H., Dogutan, Dilek K., Roubelakis, Manolis M., Maher, Andrew G., Lee, Chang Hoon, Chambers, Matthew B., Hammes-Schiffer, Sharon, & Nocera, Daniel G. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins. United States. https://doi.org/10.1073/pnas.1414908111
Bediako, D. Kwabena, Solis, Brian H., Dogutan, Dilek K., Roubelakis, Manolis M., Maher, Andrew G., Lee, Chang Hoon, Chambers, Matthew B., Hammes-Schiffer, Sharon, and Nocera, Daniel G. Wed . "Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins". United States. https://doi.org/10.1073/pnas.1414908111. https://www.osti.gov/servlets/purl/1348826.
@article{osti_1348826,
title = {Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins},
author = {Bediako, D. Kwabena and Solis, Brian H. and Dogutan, Dilek K. and Roubelakis, Manolis M. and Maher, Andrew G. and Lee, Chang Hoon and Chambers, Matthew B. and Hammes-Schiffer, Sharon and Nocera, Daniel G.},
abstractNote = {Here, the hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring.},
doi = {10.1073/pnas.1414908111},
url = {https://www.osti.gov/biblio/1348826}, journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 42,
volume = 111,
place = {United States},
year = {2014},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 35 works
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Figures / Tables:

Figure 1 Figure 1: Crystal structure of 1-Ni with thermal ellipsoids set at 50% probability. Selected internuclear distances (Å) and angles (°): Ni(1)−N(1) 1.951(3), Ni(1)−N(2) 1.940(3), Ni(1)−N(3) 1.951(3), Ni(1)−N(4) 1.951(3), Ni(1)−O(1) 4.510(6), N(1)−Ni(1)−N2 89.83(12), N(1)−Ni(1)−N(4) 90.31(12), N(2)−Ni(1)− N(3) 90.06(12), N(3)−Ni(1)−N(4) 89.87(13).

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Works referenced in this record:

Catalysis of the electrochemical reduction of carbon dioxide
journal, January 2013


Proton-coupled electron transfer: classification scheme and guide to theoretical methods
journal, January 2012


Electocatalytic Water Oxidation by Cobalt(III) Hangman β-Octafluoro Corroles
journal, June 2011


Substituent Effects on Cobalt Diglyoxime Catalysts for Hydrogen Evolution
journal, November 2011


Molecular Catalysis of Electrochemical Reactions. Mechanistic Aspects
journal, July 2008


Theoretical studies of the mechanism of catalytic hydrogen production by a cobaloxime
journal, January 2011


A survey of Hammett substituent constants and resonance and field parameters
journal, March 1991


Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006


Oxygen reduction reactivity of cobalt(ii) hangman porphyrins
journal, January 2010


Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014


Concerted proton-coupled electron transfers in aquo/hydroxo/oxo metal complexes: Electrochemistry of [OsII(bpy)2py(OH2)]2+ in water
journal, July 2009


Role of Proton-Coupled Electron Transfer in O–O Bond Activation
journal, July 2007


Proton-coupled electron transfer kinetics for the hydrogen evolution reaction of hangman porphyrins
journal, January 2012


Coupled electron transfers in artificial photosynthesis
journal, October 2007


Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays
journal, March 2012


Porphyrin Architectures Bearing Functionalized Xanthene Spacers
journal, February 2002


Photosynthetic energy conversion: natural and artificial
journal, January 2009


Manganese as a Substitute for Rhenium in CO 2 Reduction Catalysts: The Importance of Acids
journal, February 2013


Hydrogen Generation by Hangman Metalloporphyrins
journal, June 2011


A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s-1 for H2 Production
journal, August 2011


Proton-Coupled Electron Transfer
journal, November 2007


Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere
journal, June 2013


Keeping the Energy Debate Clean: How Do We Supply the World's Energy Needs?
journal, January 2010


Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic
journal, February 2012


Does one-electron transfer to nickel(II) porphyrins involve the metal or the porphyrin ligand?
journal, January 1989


Efficient Synthesis of Hangman Porphyrins
journal, March 2010


Digital simulations on unequally spaced grids.
journal, February 2003


Theory of Coupled Electron and Proton Transfer Reactions
journal, December 2010


Energy implications of future stabilization of atmospheric CO2 content
journal, October 1998


Proton-Directed Redox Control of O−O Bond Activation by Heme Hydroperoxidase Models
journal, April 2007


Opportunities and challenges for a sustainable energy future
journal, August 2012


Proton-Coupled Electron Transfer
journal, October 1998


Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010


Proton-Coupled O−O Activation on a Redox Platform Bearing a Hydrogen-Bonding Scaffold
journal, February 2003


Chemistry of Personalized Solar Energy
journal, November 2009


Efficient Reduction of CO 2 to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials
journal, May 2014


Thermodynamics and kinetics of CO2, CO, and H+ binding to the metal centre of CO2reductioncatalysts
journal, January 2012


Hydrogen-Bond Relays in Concerted Proton–Electron Transfers
journal, October 2011


Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II
journal, March 2008


PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View
journal, June 2004


A Synthetic Nickel Electrocatalyst with a Turnover Frequency above 100 000 s−1 for H2 Production
journal, November 2011


Digital simulations on unequally spaced grids.
journal, July 2002


Does one-electron transfer to nickel(II) porphyrins involve the metal or the porphyrin ligand ?
journal, August 1989


    Works referencing / citing this record:

    Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic
    journal, February 2012


    Digital simulations on unequally spaced grids.
    journal, February 2003


    Hydrogen-Bond Relays in Concerted Proton–Electron Transfers
    journal, October 2011


    Role of Proton-Coupled Electron Transfer in O–O Bond Activation
    journal, July 2007


    A survey of Hammett substituent constants and resonance and field parameters
    journal, March 1991


    Proton-Coupled Electron Transfer
    journal, November 2007


    Molecular Catalysis of Electrochemical Reactions. Mechanistic Aspects
    journal, July 2008


    Theory of Coupled Electron and Proton Transfer Reactions
    journal, December 2010


    Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
    journal, November 2010


    Does one-electron transfer to nickel(II) porphyrins involve the metal or the porphyrin ligand?
    journal, January 1989


    Manganese as a Substitute for Rhenium in CO 2 Reduction Catalysts: The Importance of Acids
    journal, February 2013


    Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II
    journal, March 2008


    Chemistry of Personalized Solar Energy
    journal, November 2009


    Proton-Coupled O−O Activation on a Redox Platform Bearing a Hydrogen-Bonding Scaffold
    journal, February 2003


    Proton-Directed Redox Control of O−O Bond Activation by Heme Hydroperoxidase Models
    journal, April 2007


    Hydrogen Generation by Hangman Metalloporphyrins
    journal, June 2011


    Electocatalytic Water Oxidation by Cobalt(III) Hangman β-Octafluoro Corroles
    journal, June 2011


    Substituent Effects on Cobalt Diglyoxime Catalysts for Hydrogen Evolution
    journal, November 2011


    Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays
    journal, March 2012


    Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere
    journal, June 2013


    Efficient Reduction of CO 2 to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials
    journal, May 2014


    Porphyrin Architectures Bearing Functionalized Xanthene Spacers
    journal, February 2002


    Efficient Synthesis of Hangman Porphyrins
    journal, March 2010


    Energy implications of future stabilization of atmospheric CO2 content
    journal, October 1998


    Opportunities and challenges for a sustainable energy future
    journal, August 2012


    Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
    journal, April 2014


    Accelerating proton-coupled electron transfer of metal hydrides in catalyst model reactions
    journal, July 2018


    Photosynthetic energy conversion: natural and artificial
    journal, January 2009


    Oxygen reduction reactivity of cobalt(ii) hangman porphyrins
    journal, January 2010


    Theoretical studies of the mechanism of catalytic hydrogen production by a cobaloxime
    journal, January 2011


    Thermodynamics and kinetics of CO2, CO, and H+ binding to the metal centre of CO2reductioncatalysts
    journal, January 2012


    Catalysis of the electrochemical reduction of carbon dioxide
    journal, January 2013


    Proton-coupled electron transfer: classification scheme and guide to theoretical methods
    journal, January 2012


    Proton-coupled electron transfer kinetics for the hydrogen evolution reaction of hangman porphyrins
    journal, January 2012


    A polypyridyl Co( ii ) complex-based water reduction catalyst with double H 2 evolution sites
    journal, January 2016


    Proton switching as a driving force for the metal–organic complex-mediated growth of gold colloids
    journal, January 2016


    Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles
    journal, January 2017


    Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reduction
    journal, January 2019


    Cobalt-based molecular electrocatalysis of nitrile reduction: evolving sustainability beyond hydrogen
    journal, January 2019


    Powering the planet: Chemical challenges in solar energy utilization
    journal, October 2006


    Concerted proton-coupled electron transfers in aquo/hydroxo/oxo metal complexes: Electrochemistry of [OsII(bpy)2py(OH2)]2+ in water
    journal, July 2009


    Coupled electron transfers in artificial photosynthesis
    journal, October 2007


    Keeping the Energy Debate Clean: How Do We Supply the World's Energy Needs?
    journal, January 2010


    A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s-1 for H2 Production
    journal, August 2011


    Proton-Coupled Electron Transfer
    journal, October 1998


    PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View
    journal, June 2004


    Proton-coupled electron transfer chemistry of hangman macrocycles: Hydrogen and oxygen evolution reactions
    journal, January 2015


    Accelerating proton-coupled electron transfer of metal hydrides in catalyst model reactions
    journal, July 2018


    A polypyridyl Co( ii ) complex-based water reduction catalyst with double H 2 evolution sites
    journal, January 2016


    Proton switching as a driving force for the metal–organic complex-mediated growth of gold colloids
    journal, January 2016


    Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles
    journal, January 2017


    Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reduction
    journal, January 2019


    Cobalt-based molecular electrocatalysis of nitrile reduction: evolving sustainability beyond hydrogen
    journal, January 2019


    Proton-coupled electron transfer chemistry of hangman macrocycles: Hydrogen and oxygen evolution reactions
    journal, January 2015


    A comparative study of electrocatalytic hydrogen evolution by iron complexes of corrole and porphyrin from acetic acid and water
    journal, February 2019


    Electrochemical and spectroscopic methods for evaluating molecular electrocatalysts
    journal, May 2017


    Molecular engineered nanomaterials for catalytic hydrogen evolution and oxidation
    journal, January 2016


    A molecular approach to an electrocatalytic hydrogen evolution reaction on single-layer graphene
    journal, January 2017


    Hydrogen evolution by cobalt hangman porphyrins under operating conditions studied by vibrational spectro-electrochemistry
    journal, January 2018


    Reversible intramolecular hydrogen transfer: a completely new mechanism for low impact sensitivity of energetic materials
    journal, January 2019


    Artificial photosynthesis: opportunities and challenges of molecular catalysts
    journal, January 2019


    Remote ion-pair interactions in Fe-porphyrin-based molecular catalysts for the hydrogen evolution reaction
    journal, January 2019


    Intrinsic hydrogen evolution capability and a theoretically supported reaction mechanism of a paddlewheel-type dirhodium complex
    journal, January 2019


    Hydrogen gas generation using a metal-free fluorinated porphyrin
    journal, January 2018


    Hydrogen evolution from water catalyzed by cobalt-mimochrome VI*a, a synthetic mini-protein
    journal, January 2018


    Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides
    journal, January 2019


    Promoting proton coupled electron transfer in redox catalysts through molecular design
    journal, January 2019


    Chicken fat for catalysis: a scaffold is as important for molecular complexes for energy transformations as it is for enzymes in catalytic function
    journal, January 2019