E. Rios et al., Mixed valency spinel oxides of transition metals and electrocatalysis: case of the MnxCo3-xO4 system, ELECTR ACT, 44(8-9), 1998, pp. 1491-1497
Correlations between solid state chemistry, surface properties and electroc
atalytical reactivities towards the reaction of oxygen are investigated on
powder electrodes of cobalt and manganese spinel type oxides MnxCo3-xO4 (0
less than or equal to x less than or equal to 1). The cationic distribution
s have been computed from X-ray diffractometry, magnetism and oxidation pow
er:data, showing the occurrence of the Mn4+/Mn3+ solid state redox couple i
n octahedral sites. The change of the Mn4+/Mn3+ content as a function of x
have been correlated to pH of zero charge, pH(z), rest potential, E-i=0, ac
tivation-energy of conductance, E-a, and to the electrocatalytical paramete
rs of the oxygen reduction reaction (ORR) and evolution reaction (OER). Man
ganese catalyzes the ORR but inhibits the OER. (C) 1998 Published by Elsevi
er Science Ltd. All rights reserved.