Modulating 3d Charge State via Halogen Ions in Neighboring Molecules of Metal–Organic Frameworks for Improving Water Oxidation

Abstract Modulating the coordination environment of the metal active center is an effective method to boost the catalytic performances of metal–organic frameworks (MOFs) for oxygen evolution reaction (OER). However, little attention has been paid to the halogen effects on the ligands engineering. Herein, a series of MOFs X─FeNi‐MOFs (X = Br, Cl, and F) is constructed with different coordination microenvironments to optimize OER activity. Theoretical calculations reveal that with the increase in electronegativity of halogen ions in terephthalic acid molecular (TPA), the Bader charge of Ni atoms gets larger and the Ni‐3d band center and O‐2p bands move closer to the Fermi level. This indicates that an increase in ligand negativity of halogen ions in TPA can promote the adsorption ability of catalytic sites to oxygen‐containing intermediates and reduce the activation barrier for OER. Experimental also demonstrates that F─FeNi‐MOFs exhibit the highest catalytic activity with an ultralow overpotential of 218 mV at 10 mA cm −2 , outperforming most otate‐of‐the‐art Fe/Co/Ni‐based MOFs catalysts, and the enhanced mass activity by seven times compared with that for the sample before ligands engineering. This work opens a new avenue for the realization of the modulation of NiFe─O bonding by halogen ion in TPA and improves the OER performance of MOFs.