Synergy between Fe and Ni in the optimal performance of (Ni, Fe)OOH catalysts for the oxygen evolution reaction

The oxygen evolution reaction (OER) is critical to solar production of fuels, but the reaction mechanism underlying the performance for a best OER catalyst, Fe-doped NiOOH [(Ni, Fe)OOH], remains highly controversial. We used grand canonical quantum mechanics to predict the OER mechanisms including kinetics and thus overpotentials as a function of Fe content in (Ni, Fe) OOH catalysts. We find that density functional theory (DFT) without exact exchange predicts that addition of Fe does not reduce the overpotential much. However, DFT with exact exchange predicts dramatic improvement in performance for (Ni, Fe) OOH, leading to an overpotential of 0.42 V and a Tafel slope of 23 mV/decade (dec), in good agreement with experiments, 0.3-0.4 V and 30 mV/dec. We reveal that the high spin d(4) Fe(IV) leads to efficient formation of an active O radical intermediate, while the closed shell d(6) Ni(IV) catalyzes the subsequent O-O coupling, and thus it is the synergy between Fe and Ni that delivers the optimal performance for OER.