Abstract
A wide variety of electrocatalytic processes taking place at either functionalized surfaces or “metal” surfaces, are , in fact, surface redox mediated . This means that the electrode potential defines the steady state population of active sites and suggests that the role of the potential in active site generation must be incorporated in the pre-exponential factor of the overall rate expression. In fact, the potential driven active site generation serves to “ignite” the faradaic process. This explains why the E0 redoc system of M/Mox , or MOX+n/MOX+n+m surface couples , must be as close as possible to E0 cell process , to enable high conversion efficiency as well as higher rates at low overpotentials. The coinage metals are active ORR catalysts at high pH apparently because a different early step in the faradaic process results in highlighting of the benefit of active site generation at the lowest possible overpotential .
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