Molecular Electrocatalysts for the Oxidation of Hydrogen and the Production of Hydrogen - The Role of Pendant Amines as Proton Relays
Electrocatalysts for efficient conversion between electricity and chemical bonds will play a vital role in future systems for storage and delivery of energy. Our research on functional models of hydrogenase enzymes uses nickel and cobalt, abundant and inexpensive metals, in contrast to platinum, a precious metal used in fuel cells. A key feature of our research is a focus on the use of pendant amines incorporated into diphosphine ligands. These pendant amines function as proton relays, lowering the barrier to proton transfers to and from the catalytically active metal site. The hydride acceptor ability of metal cations, along with the basicity of pendant amines, are key thermochemical values that determine the thermodynamics of addition of H2 to a metal complex with a pendant amine incorporated into its ligand. Nickel catalysts for oxidation of H2 have turnover frequencies up to 50 s-1 (at 1 atm H2 and room temperature). Nickel and cobalt catalysts for production of H2 by reduction of protons are studied, one of which has a turnover frequency over 1000 s-1. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1010463
- Report Number(s):
- PNNL-SA-75690; KC0307010
- Journal Information:
- European Journal of Inorganic Chemistry, 2011(7):1017-1027, Journal Name: European Journal of Inorganic Chemistry, 2011(7):1017-1027 Journal Issue: 7 Vol. 2011; ISSN EJICFO; ISSN 1434-1948
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
30 DIRECT ENERGY CONVERSION
AMINES
CATALYSTS
CATIONS
CHEMICAL BONDS
COBALT
ELECTRICITY
ELECTROCATALYSTS
ENZYMES
Electrochemistry
FUEL CELLS
FUNCTIONAL MODELS
HYDRIDES
HYDROGEN
HYDROGENASES
Homogeneous catalysis
Hydrides
Hydrogen
NICKEL
OXIDATION
PLATINUM
PRODUCTION
PROTONS
Proton Transport
STORAGE
THERMODYNAMICS