Synergistic d-Orbital Interactions and Interfacial Coupling in Metal-Organic Framework-Based Electrocatalysts for Direct Seawater Electrolysis.
5 affiliations
- 1School of Engineering, RMIT University, Melbourne, Victoria, Australia.
- 2Department of Physics, College of General Studies, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia.
- 3Interdisciplinary Research Center for Hydrogen Technologies and Carbon Management (IRC-HTCM), King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia.
- 4School of Sciences, RMIT University, Melbourne, Victoria, Australia.
- 5School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu, China.
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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BibTeX
@article{mahmud2026synergistic,
title = {{Synergistic d-Orbital Interactions and Interfacial Coupling in Metal-Organic Framework-Based Electrocatalysts for Direct Seawater Electrolysis.}},
author = {Sofiu Mahmud and Hafiz Adil Qayyum and Sharafadeen Gbadamasi and Muhammad Waqas Khan and Suraj Loomba and Muhammad Haris and Chamali Malaarachchi and Seyed Mousavi and Babar Shabbir and Jian Xian and Nasir Mahmood},
journal = {ChemSusChem},
year = {2026},
month = oct,
doi = {10.1002/cssc.71154},
url = {https://europepmc.org/article/MED/42899500},
note = {CC BY-NC-ND},
}
RIS
TY - JOUR
TI - Synergistic d-Orbital Interactions and Interfacial Coupling in Metal-Organic Framework-Based Electrocatalysts for Direct Seawater Electrolysis.
AU - Sofiu Mahmud
AU - Hafiz Adil Qayyum
AU - Sharafadeen Gbadamasi
AU - Muhammad Waqas Khan
AU - Suraj Loomba
AU - Muhammad Haris
AU - Chamali Malaarachchi
AU - Seyed Mousavi
AU - Babar Shabbir
AU - Jian Xian
AU - Nasir Mahmood
PY - 2026
DA - 2026/10/01
JO - ChemSusChem
DO - 10.1002/cssc.71154
UR - https://europepmc.org/article/MED/42899500
AB - 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.
SN - 1864-5631
SN - 1864-564X
ER -