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

doi:10.1039/b805309j

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

Energy & Environmental Science & Technology

Research output: Contribution to journal › Article › peer-review

179 Scopus citations

Abstract

The cobalt analogue of a highly active nickel electrocatalyst for hydrogen production has been synthesized and characterized as [Co(P^Ph ₂N^Ph₂)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 ^Ph₂N^Ph₂)(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 language	English
Pages (from-to)	167-174
Number of pages	8
Journal	Energy and Environmental Science
Volume	1
Issue number	1
DOIs	https://doi.org/10.1039/b805309j
State	Published - 2008

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

abstract = "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.",

author = "Jacobsen, \{George M.\} and Yang, \{Jenny Y.\} and Brendan Twamley and Wilson, \{Aaron D.\} and Bullock, \{R. Morris\} and \{Rakowski Dubois\}, M. and Dubois, \{Daniel L.\}",

year = "2008",

doi = "10.1039/b805309j",

language = "English",

volume = "1",

pages = "167--174",

journal = "Energy and Environmental Science",

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TY - JOUR

T1 - Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere

AU - Jacobsen, George M.

AU - Yang, Jenny Y.

AU - Twamley, Brendan

AU - Wilson, Aaron D.

AU - Bullock, R. Morris

AU - Rakowski Dubois, M.

AU - Dubois, Daniel L.

PY - 2008

Y1 - 2008

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/57649152244

U2 - 10.1039/b805309j

DO - 10.1039/b805309j

M3 - Article

AN - SCOPUS:57649152244

SN - 1754-5692

VL - 1

SP - 167

EP - 174

JO - Energy and Environmental Science

JF - Energy and Environmental Science

IS - 1

ER -

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

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