Introducing non-bridging ligand in metal-organic framework-based electrocatalyst enabling reinforced oxygen evolution...

Using seawater as the replacement of freshwater for electrolysis, with the integration of renewable energy, is deemed as an attractive manner to harvest green hydrogen. However, the complexity of seawater puts forward stricter requirement to the electrocatalyst to alleviate the chlorine electrochemistry and corrosion. Herein, a nanosheet array of NiFe-MOF@Ni₂P/Ni(OH)₂ is devised by partially substituting terephthalic acid (H₂BDC) ligand by ferrocenecarboxylic acid (FcCA). Tailoring the active site into an under-coordinated fashion affords NiFe-MOF@Ni₂P/Ni(OH)₂ excellent performance towards oxygen evolution reaction (OER), only requiring the overpotentials of 302 mV and 394 mV in alkaline seawater to drive the current densities of 100 and 1000 mA cm^-2, respectively. Moreover, the as-obtained electrocatalyst showed robust durability for operating more than 120 h at 500 mA cm^-2 under harsh condition (6 M KOH + 1.5 M NaCl, 60 ℃). Density functional theory (DFT) calculations confirmed that tuning the coordination environment of Ni in NiFe-MOF by incorporating the non-bridging FcCA ligands could boost the formation of more active catalytic sites, which can simultaneously enhance the electronic conductivity and accelerate OER kinetics. This work provides beneficial enlightenment of combining MOF-based electrocatalyst with direct electrolysis of seawater.