Manipulating Intermetallic Charge Transfer for Switchable External Stimulus‐Enhanced Water Oxidation Electrocatalysis

Abstract Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear‐scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co−Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm −2 ), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli‐sensitive spin crossover‐based pathway, which opens the way for switchable electrocatalytic devices.