Fe-substituted cobalt-phosphate polyoxometalates as enhanced oxygen evolution catalysts in acidic media

All-inorganic and earth-abundant bi-/trimetallic hydr(oxy)oxides are widely used as oxygen evolution electrocatalysts owing to their remarkable performance. However, their atomically precise structures remain undefined, complicating their optimization and limiting the understanding of their enhanced performance. Here, the underlying structure-property correlation is explored by using a well-defined cobalt-phosphate polyoxometalate cluster [{Co4(OH)3(PO4)}4(SiW9O34)4]32− (1), which may serve as a molecular model of multimetal hydr(oxy)oxides. The catalytic activity is enhanced upon replacing Co by Fe in 1, resulting in a reduced overpotential (385 mV) for oxygen evolution (by 66 mV) compared to that of the parent 1 at 10 mA cm−2 in an acidic medium; this overpotential is comparable to that for the IrO2 catalyst. These abundant-metal-based polyoxometalates exhibit high stability, with no evidence of degradation even after 24 h of operation.