PHYSICAL, CHEMICAL AND ELECTROCHEMICAL CHARACTERIZATION OF HEAT-TREATED TETRACARBOXYLIC COBALT PHTHALOCYANINE ADSORBED ON CARBON-BLACK AS ELECTROCATALYST FOR OXYGEN REDUCTION IN POLYMER ELECTROLYTE FUEL-CELLS

Tetracarboxylic cobalt phthalocyanine (CoPcTc) has been adsorbed on ca rbon black (C). The resulting CoPcTc/C has been heat-treated in Ar at various temperatures ranging from 100 to 1100 degrees C in order to pr oduce catalysts for the electroreduction of oxygen in polymer electrol yte fuel cells. Heat-treated CoPcTc/C materials have been characterize d by TGA, DSC, bulk elemental analyses, XRD, XPS and ToF SIMS. Their e lectrocatalytic properties have been evaluated by rde and gde measurem ents. The highest activity is found for CoPcTc/C heat-treated between 500 and 700 degrees C. In this temperature range, the catalytic site c an be traced back either to the intact polymer (< 600 degrees C) or to phthalocyanine fragments still containing Co, even as CoN4 chelates. However, short term life tests on the initially most active catalysts indicate that these catalysts are not stable compared to those obtaine d after pyrolysis of CoPcTc/C at 900 degrees C. The active site of the latter catalysts is related to inorganic cobalt present as metal and oxides. TEM reveals that inorganic cobalt is surrounded by a protectin g graphite shell rendering it chemically stable in acidic media.