While our results reveal p(NDI-T2 P75) reacts directly with oxygen to form hydro(gen) peroxide, our operando spectroscopy results do not demonstrate evidence for a surface-bound intermediate expected for a catalytic, or "inner-sphere," pathway. In this regard, we briefly describe the energetic contributions to ORR reactivity, highlighting the non-catalytic outersphere pathways for oxygen reduction which may occur at low overpotentials at high pH. Figure presents a general, though not necessarily universal, framework to understand oxygen reduction to the 2-electron product in alkaline electrolytes (pH > 11.7) involving the commonly hypothesized surface adsorbate and solvated intermediates. (Electro)catalysis occurs through the adsorption of reaction intermediates (chemisorption/surface bond formation), which modulates their reduction voltages by -ΔGads/F, where ΔGads is the Gibbs energy of adsorption and F is Faraday's constant. In the Alternative non-catalytic pathways for the 2-electron oxygen reduction, however, may occur without adsorption. In these outer-sphere pathways, the first electron transfer reaction to oxygen is crucial. This initial reduction reaction is generally considered the rate-limiting step (RLS) due to its very negative standard reduction voltage. At pH > 4.88 (pKa of HO2), this step yields the superoxide radical, O2 •-, as shown in Reaction [1]: