Electrode catalysis of the four-electron reduction of oxygen to water by dicobalt face-to-face porphyrins. [Acid electrolyte fuel cells]

Journal Article · Wed Sep 10 00:00:00 EDT 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00539a009· OSTI ID:6927798

Collman, J P ^[1]; Denisevich, P; Konai, Y; Marrocco, M; Koval, C; Anson, F C

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1. Stanford Univ., CA

A series of dimeric metalloporphyrin molecules has been synthesized in which the two porphyrin rings are constrained to lie parallel to one another by two amide bridges of varying length that link the rings together. These cofacial metalloporphyrins have been applied to the surface of graphite electrodes and tested for catalytic activity toward the electroreduction of dioxygen to water in aqueous acidic electrolytes. All molecules tested exhibited some catalytic activity, but hydrogen peroxide rather than water was the chief reduction product. However, the dicobalt cofacial porphyrin linked by four-atom bridges produced a catalyzed reduction almost exclusively to water and at exceptionally positive potentials. Rotating ring-disk voltametric measurements were employed to diagnose the electrode reaction pathway and a possible mechanism for the observed catalysis is suggested. The results seem to demonstrate the participation of two metal centers in controlling the course of a multiple-electron process.

• OSTI ID: 6927798
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

30 DIRECT ENERGY CONVERSION
300505 -- Fuel Cells-- Electrochemistry
Mass Transfer & Thermodynamics
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
ACID ELECTROLYTE FUEL CELLS
CARBON
CARBOXYLIC ACIDS
CATALYSTS
CATALYTIC EFFECTS
CATHODES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
COBALT COMPLEXES
COMPLEXES
CURRENTS
DATA
DIMERS
DIRECT ENERGY CONVERTERS
ELECTRIC CURRENTS
ELECTRIC POTENTIAL
ELECTROCATALYSTS
ELECTROCHEMICAL CELLS
ELECTROCHEMISTRY
ELECTRODES
ELECTROLYSIS
ELECTRON SPIN RESONANCE
ELEMENTS
EXPERIMENTAL DATA
FUEL CELLS
GRAPHITE
GRAPHS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
INFORMATION
LYSIS
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN
OXYGEN COMPOUNDS
PERFORMANCE TESTING
PEROXIDES
PORPHYRINS
REDOX REACTIONS
REDUCTION
RESONANCE
SPECTROSCOPY
SYNTHESIS
TESTING
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
WATER