Electrocatalytic oxygen reduction using transition metal substituted sandwich type polyoxometalates in pH=5 acetate buffer (original) (raw)

Abstract

Transition metal substituted polyoxometalates have been employed as oxygen reduction catalysts in the past decade. However, sandwich type polyoxometalates have very little representation in literature, save a couple of works in Fe and Cu substituted Wells Dawson polyoxometalate structures(1,2). In this work, substitution of some of the first-group transition metals V, Mn, Fe, Co, Ni, Cu & Zn together with Ru, Ir & Pd have been accomplished in a Weakley type sandwich polyoxometalate; {(WZnM2)[ZnW9O34]2}n-.These bimetallic-substituted polyoxometalates have been tested for electrocatalytic oxygen reduction in a pH=5 buffer solution (chosen due to stability issues of sandwich). There is a systematic trend in the position of oxygen reduction peak (E1/2) as a function of transition metal substitution. An attempt has been made to address the functionality of oxygen reduction peak to the thermodynamic redox potentials of the substituted transition metal. In this exercise, the central belt of transition metals is considered to be the electrocatalytic active site and the enveloping Keggin structures behave as electron transfer mediators.

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