Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Increasing the rate of hydrogen oxidation without increasing the overpotential: A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay

Abstract

Oxidation of hydrogen (H₂) to protons and electrons for energy production in fuel cells is catalyzed by platinum, but its low abundance and high cost present drawbacks to widespread adoption. Precisely controlled proton delivery and removal is critical in hydrogenase enzymes in nature that catalyze H₂ oxidation using earth-abundant metals (iron and nickel). Here we report a synthetic iron complex, (CpC5F4N)Fe(PEtN(CH2)3NMe2PEt)(Cl), that serves as a precatalyst for the oxidation of H₂, with turnover frequencies of 290 s⁻¹ in fluorobenzene, under 1 atm of H₂ using 1,4-diazabicyclo[2.2.2]octane (DABCO) as the exogenous base. The cooperative effect of the primary, secondary and outer coordination spheres for moving protons in this remarkably fast catalyst emphasizes the key role of pendant amines in mimicking the functionality of the proton pathway in the hydrogenase enzymes.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1203861
Report Number(s):
PNNL-SA-105708
Journal ID: ISSN 2041-6520; CSHCBM; KC0307010
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 5; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 30 DIRECT ENERGY CONVERSION; homogeneous catalysis; hydrogen oxidation; proton transport; iron; diphosphine; outer coordination sphere

Citation Formats

Darmon, Jonathan M., Kumar, Neeraj, Hulley, Elliott B., Weiss, Charles J., Raugei, Simone, Bullock, R. Morris, and Helm, Monte L. Increasing the rate of hydrogen oxidation without increasing the overpotential: A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay. United States: N. p., 2015. Web. doi:10.1039/C5SC00398A.
Copy to clipboard
Darmon, Jonathan M., Kumar, Neeraj, Hulley, Elliott B., Weiss, Charles J., Raugei, Simone, Bullock, R. Morris, & Helm, Monte L. Increasing the rate of hydrogen oxidation without increasing the overpotential: A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay. United States. https://doi.org/10.1039/C5SC00398A
Copy to clipboard
Darmon, Jonathan M., Kumar, Neeraj, Hulley, Elliott B., Weiss, Charles J., Raugei, Simone, Bullock, R. Morris, and Helm, Monte L. Thu . "Increasing the rate of hydrogen oxidation without increasing the overpotential: A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay". United States. https://doi.org/10.1039/C5SC00398A. https://www.osti.gov/servlets/purl/1203861.
Copy to clipboard
@article{osti_1203861,
title = {Increasing the rate of hydrogen oxidation without increasing the overpotential: A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay},
author = {Darmon, Jonathan M. and Kumar, Neeraj and Hulley, Elliott B. and Weiss, Charles J. and Raugei, Simone and Bullock, R. Morris and Helm, Monte L.},
abstractNote = {Oxidation of hydrogen (H₂) to protons and electrons for energy production in fuel cells is catalyzed by platinum, but its low abundance and high cost present drawbacks to widespread adoption. Precisely controlled proton delivery and removal is critical in hydrogenase enzymes in nature that catalyze H₂ oxidation using earth-abundant metals (iron and nickel). Here we report a synthetic iron complex, (CpC5F4N)Fe(PEtN(CH2)3NMe2PEt)(Cl), that serves as a precatalyst for the oxidation of H₂, with turnover frequencies of 290 s⁻¹ in fluorobenzene, under 1 atm of H₂ using 1,4-diazabicyclo[2.2.2]octane (DABCO) as the exogenous base. The cooperative effect of the primary, secondary and outer coordination spheres for moving protons in this remarkably fast catalyst emphasizes the key role of pendant amines in mimicking the functionality of the proton pathway in the hydrogenase enzymes.},
doi = {10.1039/C5SC00398A},
journal = {Chemical Science},
number = 5,
volume = 6,
place = {United States},
year = {Thu Mar 05 00:00:00 EST 2015},
month = {Thu Mar 05 00:00:00 EST 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C5SC00398A
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: (a) Observable catalytic intermediates from the reaction of 1-Cl with NaBAr4F under 1 atm H2. (b) Representation of the solid-state structure of 1-FeH(NH) with 30% probability ellipsoids. The BArF4 anion and all hydrogen atoms with the exception of the proton and the hydride are omitted for clarity.
All figures and tables (6 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Mechanistic insights into hydride transfer for catalytic hydrogenation of CO 2 with cobalt complexes
journal, January 2014

  • Kumar, N.; Camaioni, D. M.; Dupuis, M.
  • Dalton Trans., Vol. 43, Issue 31
  • DOI: 10.1039/C4DT01551G

Catalytic Turnover of [FeFe]-Hydrogenase Based on Single-Molecule Imaging
journal, October 2011

  • Madden, Christopher; Vaughn, Michael D.; Díez-Pérez, Ismael
  • Journal of the American Chemical Society, Vol. 134, Issue 3
  • DOI: 10.1021/ja207461t

Universal Solvation Model Based on the Generalized Born Approximation with Asymmetric Descreening
journal, August 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 9
  • DOI: 10.1021/ct900312z

Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H⋅⋅⋅H-N Dihydrogen Bond Characterized by Neutron Diffraction
journal, April 2014

  • Liu, Tianbiao; Wang, Xiaoping; Hoffmann, Christina
  • Angewandte Chemie International Edition, Vol. 53, Issue 21
  • DOI: 10.1002/anie.201402090

Catalysis of chemical reactions by electrodes
journal, September 1980

  • Saveant, Jean Michel
  • Accounts of Chemical Research, Vol. 13, Issue 9
  • DOI: 10.1021/ar50153a005

Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile
journal, June 2012

  • Roberts, John A. S.; Bullock, R. Morris
  • Inorganic Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/ic302461q

Iron Complexes for the Electrocatalytic Oxidation of Hydrogen: Tuning Primary and Secondary Coordination Spheres
journal, March 2014

  • Darmon, Jonathan M.; Raugei, Simone; Liu, Tianbiao
  • ACS Catalysis, Vol. 4, Issue 4
  • DOI: 10.1021/cs500290w

Dihydrogen Bonding:  Structures, Energetics, and Dynamics
journal, July 2001

  • Custelcean, Radu; Jackson, James E.
  • Chemical Reviews, Vol. 101, Issue 7
  • DOI: 10.1021/cr000021b

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992

  • Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463096

Toward Molecular Catalysts by Computer
journal, January 2015

  • Raugei, Simone; DuBois, Daniel L.; Rousseau, Roger
  • Accounts of Chemical Research, Vol. 48, Issue 2
  • DOI: 10.1021/ar500342g

Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation
journal, June 2014

  • Ginovska-Pangovska, Bojana; Dutta, Arnab; Reback, Matthew L.
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar5001742

Structure-Function Relationships in [FeFe]-Hydrogenase Active Site Maturation
journal, March 2012

  • Nicolet, Yvain; Fontecilla-Camps, Juan C.
  • Journal of Biological Chemistry, Vol. 287, Issue 17
  • DOI: 10.1074/jbc.R111.310797

Development of Molecular Electrocatalysts for Energy Storage
journal, February 2014

A modular, energy-based approach to the development of nickel containing molecular electrocatalysts for hydrogen production and oxidation
journal, August 2013

  • Shaw, Wendy J.; Helm, Monte L.; DuBois, Daniel L.
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1827, Issue 8-9
  • DOI: 10.1016/j.bbabio.2013.01.003

Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions
journal, January 2013

  • Thoi, V. Sara; Sun, Yujie; Long, Jeffrey R.
  • Chem. Soc. Rev., Vol. 42, Issue 6
  • DOI: 10.1039/C2CS35272A

Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: Recent progress and future challenges
journal, January 2012

  • Du, Pingwu; Eisenberg, Richard
  • Energy & Environmental Science, Vol. 5, Issue 3
  • DOI: 10.1039/c2ee03250c

Properties of Bases in Acetonitrile as Solvent. IV. Proton Acceptor Power and Homoconjugation of Mono- and Diamines
journal, November 1965

  • Coetzee, J. F.; Padmanabhan, G. R.
  • Journal of the American Chemical Society, Vol. 87, Issue 22
  • DOI: 10.1021/ja00950a006

Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Combining acid–base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase
journal, October 2011

  • Camara, James M.; Rauchfuss, Thomas B.
  • Nature Chemistry, Vol. 4, Issue 1
  • DOI: 10.1038/nchem.1180

Determining the Overpotential for a Molecular Electrocatalyst
journal, December 2013

  • Appel, Aaron M.; Helm, Monte L.
  • ACS Catalysis, Vol. 4, Issue 2
  • DOI: 10.1021/cs401013v

A Functional [NiFe]Hydrogenase Mimic That Catalyzes Electron and Hydride Transfer from H2
journal, February 2013

Will Solar-Driven Water-Splitting Devices See the Light of Day?
journal, September 2013

  • McKone, James R.; Lewis, Nathan S.; Gray, Harry B.
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm4021518

An iron complex with pendent amines as a molecular electrocatalyst for oxidation of hydrogen
journal, February 2013

  • Liu, Tianbiao; DuBois, Daniel L.; Bullock, R. Morris
  • Nature Chemistry, Vol. 5, Issue 3
  • DOI: 10.1038/nchem.1571

Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986

Protonation of Ferrous Dinitrogen Complexes Containing a Diphosphine Ligand with a Pendent Amine
journal, June 2012

  • Heiden, Zachariah M.; Chen, Shentan; Mock, Michael T.
  • Inorganic Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/ic4000704

p K a Measurements of P(RNCH 2 CH 3 ) 3 N
journal, August 2000

  • Kisanga, Philip B.; Verkade, John G.; Schwesinger, Reinhard
  • The Journal of Organic Chemistry, Vol. 65, Issue 17
  • DOI: 10.1021/jo000427o

Production of hydrogen by electrocatalysis: making the H–H bond by combining protons and hydrides
journal, January 2014

  • Bullock, R. Morris; Appel, Aaron M.; Helm, Monte L.
  • Chem. Commun., Vol. 50, Issue 24
  • DOI: 10.1039/C3CC46135A

Energy-adjustedab initio pseudopotentials for the second and third row transition elements
journal, January 1990

  • Andrae, D.; H�u�ermann, U.; Dolg, M.
  • Theoretica Chimica Acta, Vol. 77, Issue 2
  • DOI: 10.1007/BF01114537

Basicity of substituted 2-phenyl-1,1,3,3- tetramethylguanidines and other bases in acetonitrile solvent
journal, April 1989

  • Leffek, Kenneth T.; Pruszynski, Przemyslaw; Thanapaalasingham, Kohila
  • Canadian Journal of Chemistry, Vol. 67, Issue 4
  • DOI: 10.1139/v89-089

Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
journal, April 1964

  • Nicholson, R. S.; Shain, Irving
  • Analytical Chemistry, Vol. 36, Issue 4, p. 706-723
  • DOI: 10.1021/ac60210a007

Small molecule mimics of hydrogenases: hydrides and redox
journal, January 2009

  • Gloaguen, Frédéric; Rauchfuss, Thomas B.
  • Chem. Soc. Rev., Vol. 38, Issue 1
  • DOI: 10.1039/B801796B

Structural and Functional Analogues of the Active Sites of the [Fe]-, [NiFe]-, and [FeFe]-Hydrogenases †
journal, June 2009

  • Tard, Cédric; Pickett, Christopher J.
  • Chemical Reviews, Vol. 109, Issue 6
  • DOI: 10.1021/cr800542q

Catalytic Activation of H 2 under Mild Conditions by an [FeFe]-Hydrogenase Model via an Active μ-Hydride Species
journal, September 2013

  • Wang, Ning; Wang, Mei; Wang, Ying
  • Journal of the American Chemical Society, Vol. 135, Issue 37
  • DOI: 10.1021/ja408376t

Hydrogenases
journal, March 2014

  • Lubitz, Wolfgang; Ogata, Hideaki; Rüdiger, Olaf
  • Chemical Reviews, Vol. 114, Issue 8
  • DOI: 10.1021/cr4005814

Merging the old with the new
journal, December 2011

  • Darensbourg, Marcetta Y.; Bethel, Ryan D.
  • Nature Chemistry, Vol. 4, Issue 1
  • DOI: 10.1038/nchem.1228

Synthetic Models for the Active Site of the [FeFe]-Hydrogenase: Catalytic Proton Reduction and the Structure of the Doubly Protonated Intermediate
journal, November 2012

  • Carroll, Maria E.; Barton, Bryan E.; Rauchfuss, Thomas B.
  • Journal of the American Chemical Society, Vol. 134, Issue 45
  • DOI: 10.1021/ja309216v

Homogeneous Ni Catalysts for H 2 Oxidation and Production: An Assessment of Theoretical Methods, from Density Functional Theory to Post Hartree−Fock Correlated Wave-Function Theory
journal, December 2010

  • Chen, Shentan; Raugei, Simone; Rousseau, Roger
  • The Journal of Physical Chemistry A, Vol. 114, Issue 48
  • DOI: 10.1021/jp106800n

Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H⋅⋅⋅H-N Dihydrogen Bond Characterized by Neutron Diffraction
journal, April 2014

  • Liu, Tianbiao; Wang, Xiaoping; Hoffmann, Christina
  • Angewandte Chemie, Vol. 126, Issue 21
  • DOI: 10.1002/ange.201402090
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines
    journal, February 2016

    • Egbert, Jonathan D.; Labios, Liezel A.; Darmon, Jonathan M.
    • European Journal of Inorganic Chemistry, Vol. 2016, Issue 8
    • DOI: 10.1002/ejic.201501477

    Dinitrogen Activation and Functionalization Using β-Diketiminate Iron Complexes: Dinitrogen Activation and Functionalization Using β-Diketiminate Iron Complexes
    journal, April 2019

    • Bhutto, Samuel M.; Holland, Patrick L.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 14
    • DOI: 10.1002/ejic.201900133
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 3)figure
      Figure 2 (p. 4)figure
      Scheme 1 (p. 5)figure
      Table 1 (p. 5)table
      Figure 3 (p. 6)figure
      Figure 4 (p. 6)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections:

        Other research related to this record: