Fe site regulation and activity deciphering by selective phase transformation in the confined FeNi nanoparticles for oxygen evolution reaction

Given its initially low activity and difficulty in active phase formation, Fe site regulation is rarely touched in FeNi-based oxygen evolution reaction (OER) catalysts. Herein, the Fe sites regulation and activity deciphering are demonstrated by selective phase transformation taking nitrogen-doped carbon confined FeNi nanoparticles derived from Fe 2 Ni-MIL-MOF pyrolysis as an example; driven by the reduction atmosphere and Kirkendall effect assisted by melamine pyrolysis, some Fe and Ni sites were separated to form metallic Fe and FeNi alloy and the subsequent fluorination process induced the ionic compound FeF 2 formation rather than NiF 2 , offering a good platform to evaluate the influence of active Fe phase for OER catalysis. Theoretical calculations combined with ex-situ and in-situ spectral characterization techniques proved the complete convention of FeF 2 into a high-valent and reactive intermediate state of FeOOH. Considering the stable metallic state of Ni, the largely improved catalytic performance could be attributed to the Fe site regulation and the subsequent synergistic catalysis effect. Compared to the traditional iron-based catalyst, theoretically, the electronic structure of FeF 2 was more conducive to the active FeOOH phase formation and significantly lowered the reaction energy barrier for OER. By addressing the aforementioned problems, low overpotential and good stability for OER catalysts were realized. The current work showed valid proof of the FeNi-based catalysts regulation via Fe sites for energy-relevant catalysis reactions.