(5,10,15,20-tetramethylporphyrinato)cobalt(II):: A remarkably active catalyst for the electroreduction of O2 to H2O

被引:116
作者
Shi, CN [1 ]
Anson, FC [1 ]
机构
[1] CALTECH, Div Chem & Chem Engn, Arthur Amos Noyes Labs, Pasadena, CA 91125 USA
关键词
D O I
10.1021/ic971255p
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Unlike most simple, monomeric cobalt porphyrins, the cobalt tetramethylporphyrin identified in the title catalyzes the electroreduction of O-2 to H2O instead of H2O2. On graphite electrodes, coatings of the porphyrin prepared by irreversible adsorption from chloroform solutions catalyze the electroreduction of O-2 in aqueous HClO4 at unusually positive potentials. Both the title porphyrin and the corresponding unsubstituted cobalt porphine are argued to derive their activity as four-electron reduction catalysts from their propensity to form dimers (or higher aggregates) in solution and, presumptively, on the surface of graphite electrodes.
引用
收藏
页码:1037 / 1043
页数:7
相关论文
共 27 条
[1]  
Albery W.J., 1971, Ring-disc electrodes
[2]  
[Anonymous], 1980, Electrochemical Methods
[3]   CYCLIC AND DIFFERENTIAL PULSE VOLTAMMETRIC BEHAVIOR OF REACTANTS CONFINED TO ELECTRODE SURFACE [J].
BROWN, AP ;
ANSON, FC .
ANALYTICAL CHEMISTRY, 1977, 49 (11) :1589-1595
[4]   Reactions of hydroxylamine with metal porphyrins [J].
Choi, IK ;
Liu, YM ;
Wei, ZC ;
Ryan, MD .
INORGANIC CHEMISTRY, 1997, 36 (14) :3113-3118
[5]   MOLECULAR CATALYSTS FOR MULTIELECTRON REDOX REACTIONS OF SMALL MOLECULES - THE COFACIAL METALLODIPORPHYRIN APPROACH [J].
COLLMAN, JP ;
WAGENKNECHT, PS ;
HUTCHISON, JE .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (15-16) :1537-1554
[6]   ELECTRODE CATALYSIS OF THE 4-ELECTRON REDUCTION OF OXYGEN TO WATER BY DICOBALT FACE-TO-FACE PORPHYRINS [J].
COLLMAN, JP ;
DENISEVICH, P ;
KONAI, Y ;
MARROCCO, M ;
KOVAL, C ;
ANSON, FC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (19) :6027-6036
[7]  
DOLPHIN D, 1978, PORPHYRINS, V5, P303
[8]  
DURAND RR, 1984, THESIS CALTECH
[9]   SYNTHESIS OF MESOTETRAMETHYLCHLORIN [J].
EISNER, U .
JOURNAL OF THE CHEMICAL SOCIETY, 1957, (FEB) :854-858
[10]   SOLUTION ELECTRON-TRANSFER REACTIONS IN ORGANIC AND ORGANOMETALLIC ELECTROCHEMISTRY [J].
EVANS, DH .
CHEMICAL REVIEWS, 1990, 90 (05) :739-751