Hydrogen Generation by Hangman Metalloporphyrins

被引：267

作者：

Lee, Chang Hoon ^{[1
]}

Dogutan, Dilek K. ^{[1
]}

Nocera, Daniel G. ^{[1
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 23期

关键词：

MOLECULAR ELECTROCATALYSTS; EFFICIENT SYNTHESIS; H-2; EVOLUTION; ACTIVE-SITE; COMPLEXES; REDUCTION; OVERPOTENTIALS; XANTHENE; HYDRIDE; MODELS;

D O I：

10.1021/ja202136y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A cobalt(II) hangman porphyrin with a xanthene backbone and a carboxylic acid hanging group catalyzes the electrochemical production of hydrogen from benzoic and tosic acid in acetonitrile solutions. We show that (CoH)-H-II is exclusively involved in the generation of H-2 from weak acids. In a stronger acid, a (CoH)-H-III species is observed electrochemically, but it still needs to be further reduced to (CoH)-H-II before H-2 generation occurs. Overpotentials for H-2 generation are lowered as a result of the hangman effect.

引用

收藏

页码：8775 / 8777

页数：3

相关论文

共 23 条

[1] Cobaloximes as functional models for hydrogenases. 2. proton electroreduction catalyzed by difluoroborylbis(dimethylglyoximato)cobalt(II) complexes in organic media [J].

Baffert, Carole ;

Artero, Vincent ;

Fontecave, Marc .

INORGANIC CHEMISTRY, 2007, 46 (05) :1817-1824

[2] Hydride-Containing Models for the Active Site of the Nickel-Iron Hydrogenases [J].

Barton, Bryan E. ;

Rauchfuss, Thomas B. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (42) :14877-14885

[3] 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

[4] COFACIAL BISORGANOMETALLIC DIPORPHYRINS - SYNTHETIC CONTROL IN PROTON REDUCTION CATALYSIS [J].

COLLMAN, JP ;

HA, YY ;

WAGENKNECHT, PS ;

LOPEZ, MA ;

GUILARD, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (20) :9080-9088

[5] Solar Energy Supply and Storage for the Legacy and Non legacy Worlds [J].

Cook, Timothy R. ;

Dogutan, Dilek K. ;

Reece, Steven Y. ;

Surendranath, Yogesh ;

Teets, Thomas S. ;

Nocera, Daniel G. .

CHEMICAL REVIEWS, 2010, 110 (11) :6474-6502

[6] Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime [J].

Dempsey, Jillian L. ;

Winkler, Jay R. ;

Gray, Harry B. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (47) :16774-16776

[7] Hangman Corroles: Efficient Synthesis and Oxygen Reaction Chemistry [J].

Dogutan, Dilek K. ;

Stoian, Sebastian A. ;

McGuire, Robert, Jr. ;

Schwalbe, Matthias ;

Teets, Thomas S. ;

Nocera, Daniel G. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (01) :131-140

[8] Efficient Synthesis of Hangman Porphyrins [J].

Dogutan, Dilek K. ;

Bediako, D. Kwabena ;

Teets, Thomas S. ;

Schwalbe, Matthias ;

Nocera, Daniel G. .

ORGANIC LETTERS, 2010, 12 (05) :1036-1039

[9] H2 Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation [J].

Fourmond, Vincent ;

Jacques, Pierre-Andre ;

Fontecave, Marc ;

Artero, Vincent .

INORGANIC CHEMISTRY, 2010, 49 (22) :10338-10347

[10] Electrochemical generation of rhodium porphyrin hydrides. Catalysis of hydrogen evolution [J].

Grass, V ;

Lexa, D ;

Saveant, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (32) :7526-7532