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

Jonathan M. Darmon, Neeraj Kumar, Elliott B. Hulley, Charles J. Weiss, Simone Raugei, R Morris Bullock, Monte Helm

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Oxidation of hydrogen (H2) to protons and electrons for energy production in fuel cells is currently catalyzed by platinum, but its low abundance and high cost present drawbacks to widespread adoption. Precisely controlled proton removal from the active site 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 inclusion of a properly tuned outer coordination sphere proton relay results in a cooperative effect between the primary, secondary and outer coordination spheres for moving protons, increasing the rate of H2 oxidation without increasing the overpotential when compared with the analogous complex featuring a single pendant base. This finding emphasizes the key role of pendant amines in mimicking the functionality of the proton pathway in the hydrogenase enzymes.

Original languageEnglish
Pages (from-to)2737-2745
Number of pages9
JournalChemical Science
Volume6
Issue number5
DOIs
Publication statusPublished - May 1 2015

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Electrocatalysts
Protons
Hydrogen
Iron
Oxidation
Hydrogenase
Fluorobenzenes
Enzymes
Platinum
Nickel
Amines
Fuel cells
Metals
Earth (planet)
Electrons
Costs

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Increasing the rate of hydrogen oxidation without increasing the overpotential : A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay. / Darmon, Jonathan M.; Kumar, Neeraj; Hulley, Elliott B.; Weiss, Charles J.; Raugei, Simone; Bullock, R Morris; Helm, Monte.

In: Chemical Science, Vol. 6, No. 5, 01.05.2015, p. 2737-2745.

Research output: Contribution to journalArticle

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