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
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
收藏
页码:15368 / 15371
页数:4
相关论文
共 40 条
[1]  
[Anonymous], 2001, ELECTROCHEMICAL METH
[2]   Some general principles for designing electrocatalysts with hydrogenase activity [J].
Artero, V ;
Fontecave, M .
COORDINATION CHEMISTRY REVIEWS, 2005, 249 (15-16) :1518-1535
[3]   CHARACTERIZATION AND ELECTRONIC STRUCTURES OF METAL COMPLEXES CONTAINING BENZENE-1,2-DITHIOLATE AND RELATED LIGANDS [J].
BAKERHAW.MJ ;
BILLIG, E ;
GRAY, HB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (21) :4870-&
[4]   ARTIFICIAL PHOTOSYNTHESIS - SOLAR SPLITTING OF WATER TO HYDROGEN AND OXYGEN [J].
BARD, AJ ;
FOX, MA .
ACCOUNTS OF CHEMICAL RESEARCH, 1995, 28 (03) :141-145
[5]   A Nickel(II)-Sulfur-Based Radical-Ligand Complex as a Functional Model of Hydrogenase [J].
Begum, Ameerunisha ;
Moula, Golam ;
Sarkar, Sabyasachi .
CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (41) :12324-12327
[6]   Hydrogen evolution by cobalt tetraimine catalysts adsorbed on electrode surfaces [J].
Berben, Louise A. ;
Peters, Jonas C. .
CHEMICAL COMMUNICATIONS, 2010, 46 (03) :398-400
[7]   Electrocatalytic reduction of protons to hydrogen by a water-compatible cobalt polypyridyl platform [J].
Bigi, Julian P. ;
Hanna, Tamara E. ;
Harman, W. Hill ;
Chang, Alicia ;
Chang, Christopher J. .
CHEMICAL COMMUNICATIONS, 2010, 46 (06) :958-960
[8]  
BOSWICK CI, 2004, PROG INORG CHEM, V55, P55
[9]   HOMOGENEOUS CATALYSIS OF THE PHOTO-REDUCTION OF WATER BY VISIBLE-LIGHT - MEDIATION BY A TRIS(2,2'-BIPYRIDINE)RUTHENIUM(II)-COBALT(II) MACROCYCLE SYSTEM [J].
BROWN, GM ;
BRUNSCHWIG, BS ;
CREUTZ, C ;
ENDICOTT, JF ;
SUTIN, N .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (05) :1298-1300
[10]   COBALT-CATALYZED EVOLUTION OF MOLECULAR-HYDROGEN [J].
CONNOLLY, P ;
ESPENSON, JH .
INORGANIC CHEMISTRY, 1986, 25 (16) :2684-2688