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Updated: Oct 22, 2026

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
Synergistic d-Orbital Interactions and Interfacial Coupling in Metal-Organic Framework-Based Electrocatalysts for
Sofiu Mahmud1, Hafiz Adil Qayyum2,3, Sharafadeen Gbadamasi4
1School of Engineering, RMIT University, Melbourne, Victoria, Australia.
Abstract:
The structural versatility of metal-organic frameworks (MOFs) makes them attractive platforms for electrocatalyst design, but with limited active site density. Here, Fe-MOF is decorated with Ni-, Mo-, and W-based oxides via electrochemical deposition, avoiding high-temperature carbonization. The short interlayer distances (1.88-2.67 Å) and more negative binding energies (-4.09 to -4.88 eV) indicate intimate interfacial contact and strong adhesion between the deposited metal oxides and the Fe-MOF. Synergistic interactions between Ni 3d and Mo/W non‑3d orbitals modulate electronic structure and optimize adsorption of reaction intermediates. Electron localization values <0.5 and charge density difference analysis reveal substantial electron redistribution and interfacial charge transfer. DFT studies show that NiMoW@Fe-MOF with the lowest ɳOER (0.68 V) preferentially adsorbs OH- over Cl- (-1.14 and -1.09 eV, respectively), promoting selective OER. The NiW@Fe-MOF (cathode) exhibits the most favorable ΔGH* (-1.64 eV) and suppresses Ca(OH)2 and Mg(OH)2 precipitation via WO2-mediated OH- consumption. Consequently, the NiW@Fe-MOF‖NiMoW@Fe-MOF enables selective inhibition of chlorine evolution and mitigation of scaling. The NiW@Fe-MOF‖NiMoW@Fe-MOF operates stably in alkaline seawater at 0.5 A cm-2 for 500 h and delivers 1 A cm-2 at 1.84 V, well below the 2.35 V required by a 20% Pt/C‖RuO2 benchmark, demonstrating strong potential for direct seawater splitting.
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