A Cobalt-Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons

被引：362

作者：

McNamara, William R. ^{[1
]}

Han, Zhiji ^{[1
]}

Alperin, Paul J. ^{[1
]}

Brennessel, William W. ^{[1
]}

Holland, Patrick L. ^{[1
]}

Eisenberg, Richard ^{[1
]}

机构：

[1] Univ Rochester, Dept Chem, Rochester, NY 14627 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 39期

关键词：

RAY-ABSORPTION SPECTROSCOPY; HYDROGEN EVOLUTION; VISIBLE-LIGHT; ARTIFICIAL PHOTOSYNTHESIS; HOMOGENEOUS CATALYSIS; FUNCTIONAL MODELS; PHOTO-REDUCTION; METAL-COMPLEXES; ACTIVE-SITE; WATER;

D O I：

10.1021/ja207842r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The complex [Co(bdt)(2)](-) (where bdt = 1,2-benzenedithiolate) is an active catalyst for the visible light driven reduction of protons from water when employed with Ru(bpy)(3)(2+) as the photosensitizer and ascorbic acid as the sacrificial electron donor. At pH 4.0, the system exhibits very high activity, achieving >2700 turnovers with respect to catalyst and an initial turnover rate of 880 mol H-2/mol catalyst/h. The same complex is also an active electrocatalyst for proton reduction in 1:1 CH3CN/H2O in the presence of weak acids, with the onset of a catalytic wave at the reversible redox couple of -1.01 V vs Fc(+)/Fc. The cobalt-dithiolene complex [Co(bdt)(2)](-) thus represents a highly active catalyst for both the electrocatalytic and photocatalytic reduction of protons in aqueous solutions.

引用

页码：15368 / 15371

页数：4

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