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

This content will become publicly available on April 8, 2020

Title: Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides

Abstract

Electrochemical regeneration of organic hydrides is often hindered by the rapid dimerization of organic radicals produced as the first intermediates of these electrochemical transformations. Here, we utilize proton-coupled electron transfer to outcompete the undesired dimerization and achieve successful hydride regenerations of two groups of organic hydrides – acridines and benzimidazoles. An analysis of the critical factors that control the regeneration pathways of organic hydrides is demonstrated in this report.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Colorado, Boulder, CO (United States)
  3. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Petroleum Research Fund (PRF); Kuwait University Fellowship; USDOE; Advanced Cyberinfrastructure for Education and Research (ACER)
OSTI Identifier:
1544430
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 55; Journal Issue: 39; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ilic, Stefan, Alherz, Abdulaziz, Musgrave, Charles B., and Glusac, Ksenija D. Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides. United States: N. p., 2019. Web. doi:10.1039/c9cc00928k.
Ilic, Stefan, Alherz, Abdulaziz, Musgrave, Charles B., & Glusac, Ksenija D. Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides. United States. doi:10.1039/c9cc00928k.
Ilic, Stefan, Alherz, Abdulaziz, Musgrave, Charles B., and Glusac, Ksenija D. Mon . "Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides". United States. doi:10.1039/c9cc00928k.
@article{osti_1544430,
title = {Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides},
author = {Ilic, Stefan and Alherz, Abdulaziz and Musgrave, Charles B. and Glusac, Ksenija D.},
abstractNote = {Electrochemical regeneration of organic hydrides is often hindered by the rapid dimerization of organic radicals produced as the first intermediates of these electrochemical transformations. Here, we utilize proton-coupled electron transfer to outcompete the undesired dimerization and achieve successful hydride regenerations of two groups of organic hydrides – acridines and benzimidazoles. An analysis of the critical factors that control the regeneration pathways of organic hydrides is demonstrated in this report.},
doi = {10.1039/c9cc00928k},
journal = {ChemComm},
number = 39,
volume = 55,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on April 8, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

The Possible Role of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by Photosystem II
journal, July 2007

  • Meyer, Thomas J.; Huynh, My Hang V.; Thorp, H. Holden
  • Angewandte Chemie International Edition, Vol. 46, Issue 28
  • DOI: 10.1002/anie.200600917

Proton-Coupled Electron Transfer
journal, November 2007

  • Huynh, My Hang V.; Meyer, Thomas J.
  • Chemical Reviews, Vol. 107, Issue 11
  • DOI: 10.1021/cr0500030

Proton-Coupled Electron Transfer
journal, April 2012

  • Weinberg, David R.; Gagliardi, Christopher J.; Hull, Jonathan F.
  • Chemical Reviews, Vol. 112, Issue 7
  • DOI: 10.1021/cr200177j

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

  • Zimmerman, Paul M.; Zhang, Zhiyong; Musgrave, Charles B.
  • Inorganic Chemistry, Vol. 49, Issue 19
  • DOI: 10.1021/ic100454z

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

  • Lim, Chern-Hooi; Holder, Aaron M.; Hynes, James T.
  • Journal of the American Chemical Society, Vol. 136, Issue 45
  • DOI: 10.1021/ja510131a

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

  • Lim, Chern-Hooi; Holder, Aaron M.; Hynes, James T.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 24
  • DOI: 10.1021/acs.jpclett.5b01827

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

  • Helm, M. L.; Stewart, M. P.; Bullock, R. M.
  • Science, Vol. 333, Issue 6044, p. 863-866
  • DOI: 10.1126/science.1205864

Electrocatalytic Hydrogen Evolution at Low Overpotentials by Cobalt Macrocyclic Glyoxime and Tetraimine Complexes
journal, July 2007

  • Hu, Xile; Brunschwig, Bruce S.; Peters, Jonas C.
  • Journal of the American Chemical Society, Vol. 129, Issue 29
  • DOI: 10.1021/ja067876b

Potential-Dependent Electrocatalytic Pathways: Controlling Reactivity with p K a for Mechanistic Investigation of a Nickel-Based Hydrogen Evolution Catalyst
journal, October 2015

  • Rountree, Eric S.; Dempsey, Jillian L.
  • Journal of the American Chemical Society, Vol. 137, Issue 41
  • DOI: 10.1021/jacs.5b08297

An Iron Electrocatalyst for Selective Reduction of CO 2 to Formate in Water: Including Thermochemical Insights
journal, November 2015


Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid
journal, March 2017

  • Roy, Souvik; Sharma, Bhaskar; Pécaut, Jacques
  • Journal of the American Chemical Society, Vol. 139, Issue 10
  • DOI: 10.1021/jacs.6b11474

A pendant proton shuttle on [Fe 4 N(CO) 12 ] alters product selectivity in formate vs. H 2 production via the hydride [H–Fe 4 N(CO) 12 ]
journal, January 2016

  • Loewen, Natalia D.; Thompson, Emily J.; Kagan, Michael
  • Chemical Science, Vol. 7, Issue 4
  • DOI: 10.1039/C5SC03169A

Electrocatalytic Hydrogen Evolution from Water by a Series of Iron Carbonyl Clusters
journal, October 2013

  • Nguyen, An D.; Rail, M. Diego; Shanmugam, Maheswaran
  • Inorganic Chemistry, Vol. 52, Issue 21
  • DOI: 10.1021/ic4023882

Linear Free Energy Relationships in the Hydrogen Evolution Reaction: Kinetic Analysis of a Cobaloxime Catalyst
journal, April 2016


Kinetic Analysis of Competitive Electrocatalytic Pathways: New Insights into Hydrogen Production with Nickel Electrocatalysts
journal, January 2016

  • Wiedner, Eric S.; Brown, Houston J. S.; Helm, Monte L.
  • Journal of the American Chemical Society, Vol. 138, Issue 2
  • DOI: 10.1021/jacs.5b10853

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins
journal, October 2014

  • Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 42
  • DOI: 10.1073/pnas.1414908111

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

  • Muckerman, James T.; Fujita, Etsuko
  • Chemical Communications, Vol. 47, Issue 46
  • DOI: 10.1039/c1cc15330g

Reaction Parameters Influencing Cobalt Hydride Formation Kinetics: Implications for Benchmarking H 2 -Evolution Catalysts
journal, December 2016

  • Elgrishi, Noémie; Kurtz, Daniel A.; Dempsey, Jillian L.
  • Journal of the American Chemical Society, Vol. 139, Issue 1
  • DOI: 10.1021/jacs.6b10148

Electrochemical Approach to the Mechanistic Study of Proton-Coupled Electron Transfer
journal, July 2008


Hydrogen-Bonding and Protonation Effects in Electrochemistry of Quinones in Aprotic Solvents
journal, July 1997

  • Gupta, Neeraj; Linschitz, Henry
  • Journal of the American Chemical Society, Vol. 119, Issue 27
  • DOI: 10.1021/ja970028j

Model Systems for Flavoenzyme Activity. Stabilization of the Flavin Radical Anion through Specific Hydrogen Bond Interactions
journal, May 1995

  • Breinlinger, Eric; Niemz, Angelika; Rotello, Vincent M.
  • Journal of the American Chemical Society, Vol. 117, Issue 19
  • DOI: 10.1021/ja00124a029

The Kinetic Effect of Internal Hydrogen Bonds on Proton-Coupled Electron Transfer from Phenols: A Theoretical Analysis with Modeling of Experimental Data
journal, December 2009

  • Johannissen, Linus O.; Irebo, Tania; Sjödin, Martin
  • The Journal of Physical Chemistry B, Vol. 113, Issue 50
  • DOI: 10.1021/jp9048633

Nickel phlorin intermediate formed by proton-coupled electron transfer in hydrogen evolution mechanism
journal, December 2015

  • Solis, Brian H.; Maher, Andrew G.; Dogutan, Dilek K.
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 3
  • DOI: 10.1073/pnas.1521834112

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

  • Ohtsu, Hideki; Tanaka, Koji
  • Angewandte Chemie International Edition, Vol. 51, Issue 39
  • DOI: 10.1002/anie.201204348

Reactivity of a fac-ReCl(α-diimine)(CO) 3 complex with an NAD + model ligand toward CO 2 reduction
journal, January 2014

  • Matsubara, Yasuo; Hightower, Sean E.; Chen, Jinzhu
  • Chem. Commun., Vol. 50, Issue 6
  • DOI: 10.1039/C3CC47699E

Mechanism of Hydride Donor Generation Using a Ru(II) Complex Containing an NAD + Model Ligand: Pulse and Steady-State Radiolysis Studies
journal, May 2008

  • Polyansky, Dmitry E.; Cabelli, Diane; Muckerman, James T.
  • Inorganic Chemistry, Vol. 47, Issue 10
  • DOI: 10.1021/ic702139n

Atomic structure of ferredoxin-NADP+ reductase: prototype for a structurally novel flavoenzyme family
journal, January 1991


Theoretical Analysis of Cobalt Hangman Porphyrins: Ligand Dearomatization and Mechanistic Implications for Hydrogen Evolution
journal, November 2014

  • Solis, Brian H.; Maher, Andrew G.; Honda, Tatsuhiko
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs501454y

The Role of Homolytic Bond Dissociation Energy in the Deprotonation of Cation Radicals. Examples in the NADH Analogues Series
journal, April 1998

  • Anne, Agnès; Fraoua, Sylvie; Grass, Valérie
  • Journal of the American Chemical Society, Vol. 120, Issue 12
  • DOI: 10.1021/ja973725k

Direct Observation of NADH Radical Cation Generated in Reactions with One-Electron Oxidants
journal, November 2003

  • Zielonka, Jacek; Marcinek, Andrzej; Adamus, Jan
  • The Journal of Physical Chemistry A, Vol. 107, Issue 46
  • DOI: 10.1021/jp035803y

Stable free radicals. 12. New aspects of the behavior of 1-alkyl-4-(carboalkoxy)- and 1-alkyl-4-carbamidopyridinyl radicals in solution and in thin films
journal, August 1981

  • Hermolin, Joshua; Levin, Menachem; Kosower, Edward M.
  • Journal of the American Chemical Society, Vol. 103, Issue 16
  • DOI: 10.1021/ja00406a023

Electrosynthesis of Imidazolium Carboxylates
journal, August 2013

  • de Robillard, Guillaume; Devillers, Charles H.; Kunz, Doris
  • Organic Letters, Vol. 15, Issue 17
  • DOI: 10.1021/ol401949f

Electrochemistry of synthetic analogues of NAD dimers
journal, January 1992


Electrochemistry of NADH/NAD+ analogs. A detailed mechanistic kinetic and thermodynamic analysis of the 10-methylacridan/10-methylacridinium couple in acetonitrile
journal, February 1990

  • Hapiot, Philippe; Moiroux, Jacques; Saveant, Jean Michel
  • Journal of the American Chemical Society, Vol. 112, Issue 4
  • DOI: 10.1021/ja00160a007

Thermodynamic Hydricities of Biomimetic Organic Hydride Donors
journal, March 2018

  • Ilic, Stefan; Pandey Kadel, Usha; Basdogan, Yasemin
  • Journal of the American Chemical Society, Vol. 140, Issue 13
  • DOI: 10.1021/jacs.7b13526

Thermodynamic and kinetic hydricities of metal-free hydrides
journal, January 2018

  • Ilic, Stefan; Alherz, Abdulaziz; Musgrave, Charles B.
  • Chemical Society Reviews, Vol. 47, Issue 8
  • DOI: 10.1039/C7CS00171A

Renewable Hydride Donors for the Catalytic Reduction of CO 2 : A Thermodynamic and Kinetic Study
journal, October 2018

  • Alherz, Abdulaziz; Lim, Chern-Hooi; Kuo, Yu-Ching
  • The Journal of Physical Chemistry B, Vol. 122, Issue 44
  • DOI: 10.1021/acs.jpcb.8b08536

Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy
journal, January 2018

  • Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T.
  • The Journal of Physical Chemistry B, Vol. 122, Issue 3
  • DOI: 10.1021/acs.jpcb.7b12093

Benzimidazoles as Metal-Free and Recyclable Hydrides for CO 2 Reduction to Formate
journal, November 2018

  • Lim, Chern-Hooi; Ilic, Stefan; Alherz, Abdulaziz
  • Journal of the American Chemical Society, Vol. 141, Issue 1
  • DOI: 10.1021/jacs.8b09653

Sensitization of p-GaP with Monocationic Dyes: The Effect of Dye Excited-State Lifetime on Hole Injection Efficiencies
journal, February 2016

  • Ilic, Stefan; Brown, Elizabeth S.; Xie, Yun
  • The Journal of Physical Chemistry C, Vol. 120, Issue 6
  • DOI: 10.1021/acs.jpcc.5b10474

Photoregeneration of Biomimetic Nicotinamide Adenine Dinucleotide Analogues via a Dye-Sensitized Approach
journal, November 2018

  • Hargenrader, George N.; Weerasooriya, Ravindra B.; Ilic, Stefan
  • ACS Applied Energy Materials, Vol. 2, Issue 1
  • DOI: 10.1021/acsaem.8b01574

Thermodynamic Hydricity of Transition Metal Hydrides
journal, June 2016


Kinetic Effects of Increased Proton Transfer Distance on Proton-Coupled Oxidations of Phenol-Amines
journal, November 2011

  • Markle, Todd F.; Rhile, Ian J.; Mayer, James M.
  • Journal of the American Chemical Society, Vol. 133, Issue 43
  • DOI: 10.1021/ja2056853

One-Electron Oxidation of a Hydrogen-Bonded Phenol Occurs by Concerted Proton-Coupled Electron Transfer
journal, October 2004

  • Rhile, Ian J.; Mayer, James M.
  • Journal of the American Chemical Society, Vol. 126, Issue 40
  • DOI: 10.1021/ja031583q

Hydride affinities of organic radicals in solution. A comparison of free radicals and carbenium ions as hydride ion acceptors
journal, June 1993

  • Handoo, Kishan L.; Cheng, Jin Pei; Parker, Vernon D.
  • Journal of the American Chemical Society, Vol. 115, Issue 12
  • DOI: 10.1021/ja00065a017