Fleeting-Active-Site-Thrust Oxygen Evolution Reaction by Iron Cations from the Electrolyte

Oxygen evolution reaction (OER) is key to sustainable energy and environmental engineering, thus necessitating rational design of high-performing electrocatalysts that requires understanding the structure–performance relationship with a possible dynamic nature under working conditions. Herein, we uncover a novel type of OER mechanisms thrust by the fleeting active sites (FASs) dynamically formed on Ni-based layered double hydroxides (Ni-LDHs) by Fe cations from the electrolyte under OER potentials. We employ grand-canonical ensemble methods and microkinetic modeling to elucidate the potential-dependent structures of FASs on Ni-LDHs and demonstrate that the fleeting-active-site-thrust (FAST) mechanism delivers superior OER activity via the FAST intramolecular oxygen coupling pathway, which also suppresses the lattice oxygen mechanism, leading to improved operando stability of Ni-LDHs. We further reveal that introducing only trace-level loadings (10–100 ppm) of FASs on Ni-LDHs can significantly boost and govern the catalytic performance for OER. This underscores the crucial importance of considering the novel FAST mechanism in OER and also suggests the electrolyte as a key part of the structure–performance relationship as well as an effective design strategy via engineering the electrolyte.