Solar and wind are carbon-neutral, sustainable energy sources, but their intermittent nature requires reliable energy storage. Catalysts that efficiently interconvert between electrical energy and chemical bonds (fuels) are needed for sustainable, secure energy in the future. Electrocatalysts based on inexpensive, earth-abundant metals (“Cheap Metals for Noble Tasks”) are needed since low-temperature fuel cells generally use platinum, an expensive, precious metal. Nickel catalysts for production of H2 and oxidation of H2 have been developed using pendant amines as proton relays. Iron complexes with pendant amines on the diphosphine ligand are also being studied, showing that it is possible to rationally design catalysts based on abundant, inexpensive metals as alternatives to precious metals. Organometallic Fe(II) complexes derived from CpFe(diphosphine)H, with pendant amines in the diphosphine ligands are electrocatalysts for oxidation of H2 (1 atm) at room temperature. The equilibrium between a Fe(H2) dihydrogen complex and the product of heterolytic cleavage can be altered by changing the substituents on the diphosphine ligands. The product of heterolytic cleavage has a Fe-H • • • H-N dihydrogen bonding interaction between the hydridic Fe-Hδ- and the acidic N-Hδ+ on the pendant amine. Mn(I) complexes containing pendant amines on the diphosphine ligand exhibit unusually fast (&gt;107 s-1 at 22 °C) reversible heterolytic cleavage of H2. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

Molecular electrocatalysts for the oxidation of hydrogen: Pendant amines as proton relays

249th National Meeting (2015)

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