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

Research output: Contribution to journalArticle

122 Citations (Scopus)

Abstract

The cobalt analogue of a highly active nickel electrocatalyst for hydrogen production has been synthesized and characterized as [Co(PPh 2NPh 2)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 Ph 2NPh 2)(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
Volume1
Issue number1
DOIs
Publication statusPublished - 2008

Fingerprint

Electrocatalysts
Hydrogen production
Cobalt
cobalt
ligand
Protons
catalyst
Ligands
hydrogen
Catalysts
Acids
acid
Nickel
Acetonitrile
Amines
Hydrogen
nickel
turnover
co-ordination
trifluoromethanesulfonic acid

ASJC Scopus subject areas

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

Cite this

Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere. / Jacobsen, George M.; Yang, Jenny Y.; Twamley, Brendan; Wilson, Aaron D.; Bullock, R Morris; Rakowski Dubois, M.; DuBois, Daniel L.

In: Energy and Environmental Science, Vol. 1, No. 1, 2008, p. 167-174.

Research output: Contribution to journalArticle

Jacobsen, George M. ; Yang, Jenny Y. ; Twamley, Brendan ; Wilson, Aaron D. ; Bullock, R Morris ; Rakowski Dubois, M. ; DuBois, Daniel L. / Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere. In: Energy and Environmental Science. 2008 ; Vol. 1, No. 1. pp. 167-174.
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