Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere

George M. Jacobsen, Jenny Y. Yang, Brendan Twamley, Aaron D. Wilson, R. Morris Bullock, M. Rakowski Dubois, Daniel L. Dubois

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The cobalt analogue of a highly active nickel electrocatalyst for hydrogen production has been synthesized and characterized as [Co(PPh 2NPh2)2(CH3CN)](BF 4)2. In the presence of triflic acid in acetonitrile solution, the complex loses one cyclic diphosphine ligand to form [Co(P Ph2NPh2)(CH3CN) 3](BF4)2, which has been synthesized independently and stucturally characterized. The latter complex serves as an electrocatalyst for hydrogen formation with a turnover frequency of 90 s -1 and an overpotential of 285 mV using bromoanilinium tetrafluoroborate as the acid. A similar cobalt complex with a related diphosphine ligand that does not contain a pendant base is not catalytically active, confirming an important role for the pendant amine in the catalytic reaction.

Original languageEnglish
Pages (from-to)167-174
Number of pages8
JournalEnergy and Environmental Science
Issue number1
Publication statusPublished - Dec 1 2008


ASJC Scopus subject areas

  • Environmental Chemistry
  • Renewable Energy, Sustainability and the Environment
  • Nuclear Energy and Engineering
  • Pollution

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