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

被引:165
作者
Jacobsen, George M. [1 ]
Yang, Jenny Y. [2 ]
Twamley, Brendan [3 ]
Wilson, Aaron D. [1 ]
Bullock, R. Morris [2 ]
DuBois, M. Rakowski [2 ]
DuBois, Daniel L. [2 ]
机构
[1] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA
[2] Pacific NW Natl Lab, Div Chem & Mat Sci, Richland, WA 99352 USA
[3] Univ Idaho, Dept Chem, Moscow, ID 83844 USA
关键词
D O I
10.1039/b805309j
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The cobalt analogue of a highly active nickel electrocatalyst for hydrogen production has been synthesized and characterized as [Co((P2N2Ph)-N-Ph)(2)(CH3CN)](BF4)(2). In the presence of triflic acid in acetonitrile solution, the complex loses one cyclic diphosphine ligand to form [Co((P2N2Ph)-N-Ph)(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.
引用
收藏
页码:167 / 174
页数:8
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