Coordination Tuning of FeNi‐HMT Frameworks Derived Effective Hybrid Catalysts for Water Oxidation

Abstract FeNi‐based hybrid materials are promising oxygen evolution reaction (OER) catalysts for water electrolysis in hydrogen generation. In this work, the coordination tuning of FeNi‐HMT frameworks was achieved by simply changing the Fe/Ni ratios using hexamethylenetetramine (HMT) as an organic ligand, and the derived hybrid FeNi catalysts with varied compositions were probed for OER. Incorporating varying amounts of Fe 3+ by adjusting the Ni/Fe ratio results in different metal‐organic framework (MOF) structures, and higher Fe feed leads to the formation of amorphous structures due to the coordination structure destruction from the weaker coordination capacity of Fe 3+ compared to Ni 2+ combining with the tertiary amine ligand. Among them, the FeNi‐HMT (with the Fe/Ni molar ratio of 1/1) derived catalyst, consisting of Fe 0.36 Ni 0.64 alloy/Ni 0.4 Fe 2.6 O 4 spinel oxide heterostructures supported by graphitized carbon matrix, exhibits the highest OER performance. The unique structure facilitates significant electron transfer at the alloy/spinel interface due to the large work function difference between each phase. This strong electronic effect downshifts the d‐band center of the catalyst and optimizes the binding energies to the crucial oxygenated intermediates, thereby promoting the OER kinetics. This work highlights the importance of the coordination tuning of FeNi‐HMT frameworks for highly efficient catalyst development.